Springer Series in

CHEMICAL PHYSICS 74

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Springer Series in
CHEMICAL PHYSICS
Series Editors: A.W. Castleman, Jr. J.P. Toennies K. Yamanouchi W. Zinth
The purpose of this series is to provide comprehensive up-to-date monographs
in both well established disciplines and emerging research areas within the broad
fields of chemical physics and physical chemistry. The books deal with both fun-
damental science and applications, and may have either a theoretical or an exper-
imental emphasis. They are aimed primarily at researchers and graduate students
in chemical physics and related fields.

75 Basic Principles 84 Progress in Ultrafast

in Applied Catalysis Intense Laser Science I
By M. Baerns Editors: K. Yamanouchi, S.L. Chin,
76 The Chemical Bond P. Agostini, and G. Ferrante
A Fundamental 85 Quantum Dynamics
Quantum-Mechanical Picture Intense Laser Science II
By T. Shida Editors: K. Yamanouchi, S.L. Chin,
77 Heterogeneous Kinetics P. Agostini, and G. Ferrante
Theory of Ziegler-Natta-Kaminsky 86 Free Energy Calculations
Polymerization Theory and Applications
By T. Keii in Chemistry and Biology
78 Nuclear Fusion Research Editors: Ch. Chipot
Understanding Plasma-Surface and A. Pohorille
Interactions
87 Analysis and Control of
Editors: R.E.H. Clark
Ultrafast Photoinduced Reactions
and D.H. Reiter
Editors: O. Kühn and L. Wöste
79 Ultrafast Phenomena XIV
Editors: T. Kobayashi, 88 Ultrafast Phenomena XV
T. Okada, T. Kobayashi, Editors: P. Corkum, D. Jonas,
K.A. Nelson, S. De Silvestri D. Miller, and A.M. Weiner
80 X-Ray Diffraction 89 Progress in Ultrafast Intense Laser
by Macromolecules Science III
By N. Kasai and M. Kakudo Editors: K. Yamanouchi, S.L. Chin,
81 Advanced Time-Correlated Single P. Agostini, and F. Ferrante
Photon Counting Techniques 90 Thermodynamics
By W. Becker and Fluctuations
82 Transport Coefficients of Fluids Far from Equilibrium
By B.C. Eu By J. Ross
83 Quantum Dynamics 91 Progress in Ultrafast Intense Laser
of Complex Molecular Systems Science IV
Editors: D.A. Micha Editors: K. Yamanouchi, A. Becker,
and I. Burghardt R. Li, and S.L. Chin
Rudolf Holze

Surface
and Interface Analysis
An Electrochemists Toolbox

With 207 Figures

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Professor Dr. Rudolf Holze
Technische Universität Chemnitz
Institut für Chemie
09107 Chemnitz, Germany
E-Mail: rudolf.holze@chemie.tu-chemnitz.de

Series Editors:
Professor A.W. Castleman, Jr.
Department of Chemistry, The Pennsylvania State University
152 Davey Laboratory, University Park, PA 16802, USA

Professor J.P. Toennies

Max-Planck-Institut für Strömungsforschung
Bunsenstrasse 10, 37073 Göttingen, Germany

Professor K. Yamanouchi
University of Tokyo, Department of Chemistry
Hongo 7-3-1, 113-0033 Tokyo, Japan

Professor W. Zinth
Universität München, Institut für Medizinische Optik
Öttingerstr. 67, 80538 München, Germany

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ISBN 978-3-540-00859-0 e-ISBN 978-3-540-49829-2

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Preface

As undertaken by electrochemists, spectroscopic, topographical and numerous other

non-electrochemical methods extensively covered in this book have driven the in-
vestigation of structure and dynamics at phase boundaries between condensed mat-
ter influenced by the presence and action of both an electric field and charged par-
ticles (like ions in solution or electrons in a metal) towards significant advances in
recent years. They are based in particular upon an intense use of spectroscopic and
surface sensitive methods adapted to the particular needs of in situ investigations
of these electrochemical interfaces. Consequently the area is called (not completely
exactly) spectroelectrochemistry. More recently, scanning probes capable of map-
ping the interface and providing a more or less topographic image have become
available.
Numerous reviews covering single methods or families of related methods have
appeared in journals, monographs and volumes of series. In addition, books contain-
ing collected review papers have been published. The articles were written by spe-
cialists and experts in the respective methods and describe fundamental and applied
aspects, including examples of successful applications. Unfortunately this approach
cannot provide the full picture because coherence is lacking between methods and
different but related properties and other aspects of a given system investigated
with various methods. In addition, the papers are generally of a somewhat differ-
ent level; sometimes they are filled with a flood of details or extensive repetitions
of fundamental information already provided in standard textbooks. The present
book attempts to close this gap by providing the generalist’s view. It offers a broad
collection of spectroscopic and surface sensitive techniques currently employed in
investigations of electrochemical systems. Relationships between different methods
pertaining both to the principles of the methods and the properties of the investi-
gated systems are highlighted. In many cases examples illustrating the power and
the potential of a combined use of several spectroelectrochemical techniques are
discussed in detail.
As presumably nobody can be an expert in all discussed methods and techniques,
this book will not cover all methods with the same intensity and expertise. Never-
theless, all reported methods are described in sufficient detail, enabling the reader to
access the current literature, to evaluate the methods and to choose methods of po-
tential use for his given problem. This is the main purpose of the book: to serve as a

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vi

guide to the successful application of spectroelectrochemistry and surface analytical

methods in electrochemistry—just like a toolbox.
This book is based on numerous original papers and reviews. Because of the
immense number of original papers and reviews, I have only provided references
to those that I have assumed to be of particular importance as an introduction or
that offer essential details not covered in this text. I wish to express my sincere
apologies to all authors who have published important results and are not quoted
explicitly within this book. Their contributions are nevertheless highly esteemed.
Personal communications and experience with several methods in the laboratory
of our research group and numerous contributions from coworkers and colleagues
added to the base of this book. Some of them provided papers and preprints, ex-
amined experimental details, supplied original data or checked parts of the manu-
script. Help and contributions from V. Brandl, M. Bron, C.H. Hamann, J. Lippe,
A. Malinauskas, M. Probst, S. Schomaker, B. Speiser and B. Westerhoff are grate-
fully acknowledged. W. Vielstich introduced me to electrochemistry, E.B. Yeager
provided inspiring access to new areas of research and to new methods during my
postdoctoral stay at his laboratory, G. Comsa initiated a continuing interest in sur-
face science and C.H. Hamann was an inspiring discussion partner. Without their
stimulating support this book would have remained unwritten. Close cooperation
and helpful assistance in planning and preparing this book by the staff of Springer-
Verlag (Heidelberg), in particular by Claus Ascheron, Angela Lahee and Adelheid
Duhm, are gratefully appreciated. My wife’s tolerance for many hours spent in front
of computer terminals and scientific papers was the essential prerequisite. The book
would have been impossible without this.

Chemnitz, September 2008 R. Holze

The best books are those which make the reader supplement them.
(Voltaire, Philosophical Dictionary, Foreword)

It is vain to do with more what can be done with less (Entia non sunt multiplicanda
praeter necessitatem).
(William of Occam)
Contents

List of Acronyms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

List of Symbols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxi

Part I Introduction and Overview

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2 Structure and Dynamics of Electrochemical Phase Boundaries . . . . . . 7

3 Scope and Limitations of Classical Electrochemical Methods . . . . . . . . 9

4 Spectroscopy and Surface Analysis at Interfaces Between

Condensed Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

Part II Methods and Applications

5 Spectroscopy at Electrochemical Interfaces . . . . . . . . . . . . . . . . . . . . . . . 35

5.1 Optical Spectroscopy in the Visible Range . . . . . . . . . . . . . . . . . . . . . . 37
5.1.1 UV-Vis Spectroscopy with Optically Transparent Electrodes 38
5.1.2 External Reflectance Spectroscopy . . . . . . . . . . . . . . . . . . . . . . 43
5.1.3 Attenuated Total Reflectance Spectroscopy . . . . . . . . . . . . . . . 45
5.1.4 Luminescence Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5.1.5 Fluorescence Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
5.1.6 Electroreflectance Spectroscopy (ERS) . . . . . . . . . . . . . . . . . . 50
5.1.7 Diffuse Reflectance Spectroscopy . . . . . . . . . . . . . . . . . . . . . . 57
5.1.8 Reflection Anisotropy Spectroscopy . . . . . . . . . . . . . . . . . . . . 58
5.1.9 Photoacoustic Spectroscopy (PAS) . . . . . . . . . . . . . . . . . . . . . . 60
5.1.10 Photothermal Spectroscopy (PTS) . . . . . . . . . . . . . . . . . . . . . . 62
5.1.11 Circular Dichroism (CD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
5.1.12 Near Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

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viii Contents

5.2 Optical Spectroscopy in the Infrared Range . . . . . . . . . . . . . . . . . . . . . 71

5.2.1 Infrared Transmission Spectroscopy with Thin Layer Cells . 74
5.2.2 Infrared Reflection Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 75
5.2.3 External Reflection Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 76
5.2.4 Attenuated Total Reflection Spectroscopy . . . . . . . . . . . . . . . . 91
5.2.5 Surface Enhanced Infrared Absorption Spectroscopy
(SEIRAS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.2.6 Diffuse Reflectance Infrared Spectroscopy (DRIFT) . . . . . . . 100
5.2.7 Photothermal Deflection Spectroscopy (PDS) . . . . . . . . . . . . . 100
5.2.8 Infrared Emission Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . 101
5.2.9 Far Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.2.10 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.2.11 Surface Raman Spectroscopy (SRS) . . . . . . . . . . . . . . . . . . . . 104
5.2.12 Surface Enhanced Raman Spectroscopy (SERS) . . . . . . . . . . 104
5.2.13 Surface Enhanced Hyper-Raman Spectroscopy (SEHRS) . . . 123
5.2.14 Surface Resonance Raman Spectroscopy (SRRS) . . . . . . . . . 125
5.2.15 Confocal Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 128
5.2.16 Near Field Raman Microscopy (Micro-Spectroscopy) . . . . . . 130
5.3 Spectroscopy in the X-ray Range . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.3.1 Mössbauer Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
5.3.2 X-Ray Absorption Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 137
5.3.3 X-Ray Absorption Fine Structure Spectroscopy . . . . . . . . . . . 137
5.4 Magnetic Resonance Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
Further Reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5.5 Magnetooptic and Magnetic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5.5.1 Magnetic Circular Dichroism . . . . . . . . . . . . . . . . . . . . . . . . . . 159
5.5.2 Magneto-Optical Kerr Effect (MOKE) . . . . . . . . . . . . . . . . . . 160
5.5.3 Alternating Gradient Field Magnetometry (AGFM) . . . . . . . . 162
5.5.4 SQUID Magnetometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
5.6 Photoelectrochemical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.6.1 Photoemission Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
5.6.2 Photocurrent Spectroscopy (PCS) . . . . . . . . . . . . . . . . . . . . . . 165
5.6.3 Photovoltage Spectroscopy (PVS) . . . . . . . . . . . . . . . . . . . . . . 170
5.6.4 Photoluminescence (PL) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
5.6.5 Micro-Optical Ring Electrode (MORE) . . . . . . . . . . . . . . . . . . 172
5.7 Nonlinear Optical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
5.7.1 Second Harmonic Generation (SHG) . . . . . . . . . . . . . . . . . . . . 173
5.7.2 Sum and Difference Frequency Generation . . . . . . . . . . . . . . . 175
5.8 Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
5.8.1 Differential Electrochemical Mass Spectrometry (DEMS) . . 178
5.8.2 Electrospray Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . 180
5.8.3 Thermospray Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . 182
5.8.4 Inductively Coupled Plasma Mass Spectrometry (ICPMS) . . 183
5.8.5 Thermodesorption Mass Spectrometry (TDMS) . . . . . . . . . . . 183
 Contents ix

5.9 Miscellaneous Spectroscopies and Methods . . . . . . . . . . . . . . . . . . . . . 184

5.9.1 Probe beam deflection (PBD) . . . . . . . . . . . . . . . . . . . . . . . . . . 184
5.9.2 Light Reflection Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
5.9.3 Phase-Shift Interferometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
5.9.4 Photoacoustic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
5.9.5 Ellipsometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
5.9.6 Surface Plasmon Resonance Spectroscopy . . . . . . . . . . . . . . . 195
5.9.7 Surface Plasmon Excitation and Related Methods . . . . . . . . . 199
5.9.8 Inductively Coupled Plasma Atomic Emission
Spectroelectrochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
5.9.9 Positron Annihilation Spectroscopy (PAS) . . . . . . . . . . . . . . . 201
5.9.10 Neutron Reflectivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
5.9.11 Neutron Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204

6 Diffraction and Other X-Ray Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233

6.1 X-Ray Diffraction Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
6.1.1 X-Ray Diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
6.1.2 Surface X-Ray Diffraction (SXD) . . . . . . . . . . . . . . . . . . . . . . 239
6.1.3 Surface Differential X-Ray Diffraction (SDD) . . . . . . . . . . . . 240
6.1.4 Neutron Diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
6.2 Miscellaneous Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
6.2.1 X-ray Standing Wave Fluorescence Analysis (XSW) . . . . . . . 241
6.2.2 Surface X-ray Scattering (SXS) . . . . . . . . . . . . . . . . . . . . . . . . 242
6.2.3 Small Angle X-ray Scattering (SAXS) . . . . . . . . . . . . . . . . . . 245
6.2.4 Specular X-ray Reflection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247

7 Surface Analytical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251

7.1 Topographic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
7.2 Scanning Probe Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
7.2.1 Scanning Tunneling Microscopy (STM) . . . . . . . . . . . . . . . . . 253
7.2.2 Differential Conductance Tunneling Spectroscopy (DCTS) . 260
7.2.3 Atomic Force Microscopy (AFM) . . . . . . . . . . . . . . . . . . . . . . 260
7.2.4 Scanning Kelvin Probe Force Microscopy (SKPFM) . . . . . . . 263
7.2.5 Scanning Electrochemical Microscopy (SECM) . . . . . . . . . . . 264
7.2.6 pH-Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
7.2.7 Scanning Ion-Conductance Microscopy . . . . . . . . . . . . . . . . . 271
7.2.8 Scanning Reference Electrode Technique (SRET) . . . . . . . . . 271
7.2.9 Scanning Vibrating Electrode Technique (SVET) . . . . . . . . . 272
7.2.10 Scanning Kelvin Probe (SKP) . . . . . . . . . . . . . . . . . . . . . . . . . . 273
7.2.11 Scanning Tunneling Spectroscopy and Related Methods . . . . 277
7.3 Near Field and Confocal Optical Methods . . . . . . . . . . . . . . . . . . . . . . 279
7.3.1 Near Field Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
7.3.2 Confocal Optical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280

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7.4 Surface Conductivity Measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

7.5 Interfacial Conductivity Measurements . . . . . . . . . . . . . . . . . . . . . . . . 285
7.6 Microradiology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 295
List of Acronyms

Commonly used acronyms in surface analysis, surface spectroscopy and spectro-

electrochemistry

aSNOM Apertureless scanning near field optical microscopy

AAS Atomic absorption spectroscopy
AC-SECM Alternating current scanning electrochemical microscopy
ADXD Angular dispersive X-ray diffraction
AEAPS Auger electron appearance potential spectroscopy
AES Auger electron spectroscopy
AES-SAM Auger electron spectroscopy scanning Auger microscopy
AFM Atomic force microscopy
AGFM Alternating gradient field magnetometry
AIRS Absorption infrared spectroscopy, also: abnormal infrared effect
AIS Atom inelastic scattering
ALE Atomic layer epitaxy
APD Azimuthal photoelectron diffraction
APS Appearance potential spectroscopy
ARAES Angle-resolved Auger electron spectroscopy
ARPEFS Angle-resolved photoemission extended fine structure
ARUPS Angle-resolved ultraviolet photoelectron spectroscopy
ATR Attenuated total reflection (spectroscopy), see also: FTIR
AXAFS Atomic X-ray absorption fine structure spectroscopy
BAW Bulk acoustic wave
BB-SFG Broad band sum frequency generation
CD Circular dichroism
CDAD Circular dichroism photoelectron angular distribution
CDP Current density probe
CELS Characteristic energy loss spectroscopy
CER Contact electric resistance
CFM Chemical force microscopy
CL Cathodoluminescence, Chemiluminescence
CLSM Confocal laser scanning microscopy
CTR Crystal truncation rod
CV Cyclic voltammetry
DAPS Disappearance potential spectroscopy

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xii List of Acronyms

DCTS Differential conductance tunneling spectroscopy

DEMS Differential electrochemical mass spectroscopy
DESERS Deenhanced surface enhanced Raman spectroscopy
DFT Density functional theory
DPDS Differential photothermal deflection spectroscopy
DRIFT Diffuse reflection infrared Fourier transform spectroscopy
DRIFTS same as DRIFT
DS Desorption spectroscopy
DXAFS Dispersive X-ray absorption fine structure (spectroscopy, mea-
surement)
DTS Distance tunneling spectroscopy
EBMA Electron beam micro analysis, see EMMA
EBSD Electron backscatter diffraction
ECESR Electrochemical ESR spectroscopy
ECL Electrochemiluminescence
ECTDMS Electrochemical thermal desorption mass spectrometry
EC-STM Electrochemical scanning tunneling microscopy
EDX Energy dispersive X-ray (analysis)
EDXD Energy dispersive X-ray diffraction
EELS Electron energy loss spectroscopy
EER Electrolyte electroreflectance
EFM Electric force microscopy
EFTEM Energy filtered transmission electron microscopy
EIS Electron impact spectroscopy (also: electrochemical impedance
spectroscopy)1
ECALE Electrochemical atomic layer epitaxy
ELEED Elastic low energy electron diffraction
ELL Ellipsometry
ELS Energy loss spectroscopy
EMIRS Electrode potential modulated infrared spectroscopy
EMLC Electrochemically modulated liquid chromatography
EM(MA) Electron microprobe (mass analysis)
EMP Electron micro probe, see EMMA
EMSI Ellipsomicroscopy
EQCB Electrochemical quartz crystal balance
EQCM Electrochemical quartz crystal microbalance
EQMB Electrochemical quartz (crystal) microbalance
ERS Electroreflectance spectroscopy
ESCA Electron spectroscopy for chemical analysis
ESD Electron stimulated desorption
ESDIAD Electron stimulated desorption ion angular distribution
ESI Electrospray ionization
1 The use of spectroscopy in connection with impedance measurements is not reasonable,
thus it is frequently discouraged.
 List of Acronyms xiii

ESI-FTMS Electrospray ionization Fourier transform mass spectrometry

ESID Electron stimulated ion desorption
ESI-MS Electrospray ionization mass spectroscopy
ESR Electron spin resonance (spectroscopy)
EXAFS Extended X-ray absorption fine structure (analysis), see also:
NEXAFS, SEXAFS
EXELFS Extended electron loss fine structure spectroscopy
FAB Fast atom bombardment
FAB-MS Fast atom bombardment mass spectrometry
FCS Fluorescence correlation spectroscopy
FD Flash desorption
FDS Flash desorption spectroscopy
FES Field emission spectroscopy
FFC Filiform corrosion
FIM Field ion microscopy
FIS Field ion spectroscopy
FMIR Frustrated multiple internal reflectance (spectroscopy)
FSCV Fast scan cyclic voltammetry
FSCV–SECM Fast scan cyclic voltammetry scanning electrochemical micro-
scope
FT-EMIRS Fourier transform electrode potential modulated infrared spec-
troscopy
FTIR2 Fourier transform infrared (spectroscopy), see also: FTIRRAS,
MIRFTIRS, PMFTIRRAS, SNIFTIRS, SPAIRS
FTIR Frustrated total internal reflection3
FT-IR Fourier transform infrared (spectroscopy)
FTIR-DRS Fourier transform infrared diffuse reflection spectroscopy
FTIRRAS Fourier transform infrared reflection absorption spectroscopy
FT-SERS Fourier transform surface enhanced Raman spectroscopy
GAIRS Grazing angle absorption infrared spectroscopy
GC Glassy carbon
GISAXS Grazing incidence small angle X-ray scattering
μGISAXS Microbeam grazing incidence small angle X-ray scattering
GIXAFS Grazing incidence X-ray absorption fine structure spectroscopy
GI-XAS Grazing incidence X-ray absorption spectroscopy
GIX(R)D Grazing incidence X-ray diffraction
HAADF High angle angular dark field (imaging in TEM)
HEED High energy electron diffraction
HEIS High energy ion scattering
HIID Heavy ion induced desorption
HIKE High kinetic energy photoemission spectroscopy
HIXE Proton induced X-ray emission spectroscopy
2 Sometimes also written FT-IR, see there.
3 This term is hardly used anymore, see instead ATR.

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xiv List of Acronyms

HOPG Highly ordered pyrolytic graphite

HOPG Highly oriented pyrolytic graphite
HPXPS High pressure X-ray photoelectron spectroscopy
HREELS High resolution electron energy loss spectroscopy
HRSKP Height-regulated scanning Kelvin probe (also: HR-SKP)
ICP-AES Inductively coupled plasma atomic emission spectrometry
ICP-AESE Inductively coupled plasma atomic emission spectroelectro-
chemistry
ICP-MS Inductively coupled plasma mass spectrometry
IES Inelastic electron tunneling spectroscopy
IETS same as IES
ILEED Inelastic low energy electron diffraction
ILIT Indirect laser-induced temperature jump (technique)
IMMA Ion microprobe mass analysis
IMXA Ion microprobe X-ray analysis
IMPS Intensity modulated photocurrent spectroscopy
IMVS Intensity modulated photovoltage spectroscopy
INS Ion neutralisation spectroscopy
INSEX In situ X-ray reflection/transmission diffraction
IPS Inverse photoelectron spectroscopy
IR Infrared spectroscopy, see also: EMIRS, IRRAS, LPSIRS
IRD Information rich detection
IRE Infrared emission spectroscopy, internal reflection element
IRPDS Infrared photothermal deflection spectroscopy
IRRAS Infrared reflection absorption spectroscopy, see also:
PMFTIRRAS
IRS Internal reflectance spectroscopy
IS Ionisation spectroscopy
ISS Ion surface scattering (spectroscopy)
IES Inelastic tunneling spectroscopy
ITIES Interface between two immiscible electrolyte solutions
ITO Indium (doped) tin oxide
KFM Kelvin force microscopy
LAMMA Laser microprobe mass analysis
LD Laser desorption, see also: linear dichroism
LEED Low energy electron diffraction
LEEM Low energy electron microscopy
LEIS Low energy ion scattering
LEIS Localized (scanning) electrochemical impedance spectroscopy
LFM Lateral force microscopy
LIBS Laser induced breakdown spectroscopy
LID Laser induced fluorescence
LIMS Laser ionisation mass spectroscopy
LIPS Laser induced plasma spectroscopy
 List of Acronyms xv

LPSIRS Linear potential scan infrared spectroscopy

LRS Laser Raman spectroscopy
LSM Layered synthetic microstrucutures
LSPR Localized surface plasmon resonance
MBRS Molecular beam relaxation spectroscopy
MBS Mössbauer spectroscopy
MBSS Molecular beam surface scattering
MCD Magnetic circular dichroism
MCT Mercury cadmium telluride (detector)
MEF Metal enhanced fluorescence
MEIS Medium energy ion scattering
MER(S) Multiple external reflectance (spectroscopy)
MFM Magnetic force microscopy
MFON Metal film over nanospheres
MFTIRS Microscope Fourier transform infrared spectroscopy
MIR(S) Multiple internal reflectance (spectroscopy)
MIRFTIRS Multiple internal reflection Fourier transform infrared spec-
troscopy
MMC Metal matrix composite
MOKE Magneto-optical Kerr effect
MORE Micro-optical ring electrode
MR Micro Raman (spectroscopy)
MSHG Magnetization induced second harmonic generation
MSS Molecule-surface scattering
NEXAFS Near edge X-ray absorption fine structure spectroscopy
NIR Near infrared (spectroscopy)
NIR-SERS Near infrared surface enhanced Raman spectroscopy
NIS Neutron inelastic scattering
NR(S) Normal Raman (spectroscopy)
NPD Neutron powder diffraction
NSOM Near field scanning optical microscope
OLEMS Online electrochemical mass spectrometry
ORC Oxidation-reduction electrode potential cycling
OPG Ordinary pyrolytic graphite
OSEE Optically stimulated exoelectron spectroscopy
OTE Optically transparent electrode
PAM Photoacoustic method
PAS Photoacoustic spectroscopy
PASCA Positron annihilation spectroscopy for chemical analysis
PAX Photoelectron spectroscopy with adsorbed xenon
PBD Probe beam deflection
PCS Photocurrent spectroscopy
PD Photodesorption
PDATRFTIRS Potential dependent attenuated total reflectance Fourier trans-
form infrared spectroscopy

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xvi List of Acronyms

PDBS Photothermal beam deflection spectroscopy

PDFTIRRAS Potential difference Fourier transform infrared reflection ab-
sorption spectroscopy
PDFTIRES Potential difference Fourier transform infrared emission spec-
troscopy
PDIRS Potential difference infrared spectroscopy
PDMS Plasma desorption mass spectrometry
PDS Photothermal deflection spectroscopy
PECM Photoelectrochemical microscope
PEEM Photoelectron emission microscopy
PEIS Photoelectrochemical impedance spectroscopy4
PEM Photoelastic modulator
PEM Photoelectrochemical measurement
PES Photoelectron spectroscopy, see also: ESCA, UPS, XPS
PFM-AFM Pulsed-force mode atomic force microscopy
PG Pyrolytic graphite
PhD Photoelectron diffraction
PHEEM Photoemission electron microscopy
PI Penning ionization
PIG Paraffin-impregnated graphite
PIGME Particle induced gamma ion emission
PIXE Particle induced X-ray emission spectroscopy
PMFTIRRAS Polarisation modulated Fourier transform infrared reflection ab-
sorption spectroscopy
PMFS Potential modulated fluorescence spectroscopy
PMR Potential modulated reflectance
PMRS Potential modulated reflectance spectroscopy
PPES Photopyroelectric (photothermal) spectroscopy
PSD Photon-stimulated desorption
PSI Phase-shift interferometry
PSP Plasmon surface polaritons
PSTM Photon scanning-tunneling microscope
PTS Photothermal spectroscopy
PVS Photovoltage spectroscopy
QEXAFS Quick-scanning extended X-ray absorption fine structure (analy-
sis)
RAIRS Reflection absorption infrared spectroscopy
RAS Raman spectroscopy [also NR(S)], see also: DESERS,SERRS,
SERS, SRS, SRRS, SUERS
RAS Reflection anisotropy spectroscopy, see also: RDS
RBS Rutherford backscattering
RDE-EIS Rotating disc electrode electrochemical impedance spec-
troscopy
4 See footnote on p. xii.
 List of Acronyms xvii

RDS Reflectance difference spectroscopy, see also: RAS

RC-SECM Redox competition mode scanning electrochemical microscopy
ReflEXAFS EXAFS at a grazing angle below the critical angle of total re-
flection
REMPI Resonance enhanced multiphoton ionization
RHEED Reflected high energy electron diffraction
RIBS Rutherford ion backscattering spectroscopy
RRS Resonance Raman spectroscopy
RTIL Room temperature ionic liquid
SAES Scanning Auger electron spectroscopy
SAM Scanning Auger microprobe
SAM Self-assembled monolayer
SANS Small angle neutron scattering
SAPG Stress-annealed pyrolytic graphite
SAXS Small angle X-ray scattering
SC Surface conductivity (measurement)
SDD Surface differential X-ray diffraction
SDEMS Scanning differential electrochemical mass spectroscopy
SECM Scanning electrochemical microscope
SEF Surface enhanced fluorescence
SEI Solid electrolyte interface
SEIDAS Surface enhanced infrared difference absorption spectroscopy
SEIRAS Surface enhanced infrared absorption spectroscopy
SEIRRAS Surface enhanced infrared reflection absorption spectroscopy
SEM Scanning electron microscope
SERS Surface enhanced Raman spectroscopy
SEHRS Surface enhanced hyper-Raman spectroscopy scattering
SERHRS Surface enhanced resonance hyper-Raman spectroscopy
SERRS Surface enhanced resonance Raman spectroscopy
SES Surface enhanced spectroscopy
SESHG Surface enhanced second harmonic generation
SEVS Surface enhanced vibrational spectroscopy
SEXAFS Surface extended X-ray absorption fine structure (analysis)
spectroscopy
SFG Sum frequency generation
SFIRS Synchrotron far infrared spectroscopy
SFM Scanning force microscopy, see also: AFM
SG/TC Substrate generation/tip collection (mode)
SHEED Surface high energy electron diffraction
SHG Second harmonic generation
SI Surface ionisation
SICM Scanning ion conductance microscopy
SIET Scanning ion-sensitive electrode technique
SIMS Secondary ion mass spectroscopy

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xviii List of Acronyms

SKP Scanning Kelvin probe

SKPFM Scanning Kelvin probe force microscopy
SMD Single molecule detection
SMOKE Surface magneto-optical Kerr effect
SMS Single molecule spectroscopy
sm-SERS Single molecule surface enhanced Raman spectroscopy
SMS-SERS Single molecule surface enhanced Raman spectroscopy
SNMS Secondary (sputtered) neutral (ion) mass spectroscopy
SNIFTIRS Subtractively normalized interfacial Fourier transform infrared
spectroscopy
SNIM Scanning near field infrared microscopy
SNOM Scanning near field optical microscopy
SORS Spatially offset Raman spectroscopy
SP Surface plasmon
SPAIR(S) Single potential alteration infrared (spectroscopy)
SPFELS Surface plasmon field enhanced light scattering
SPLS Surface plasmon enhanced light scattering (see also SPFELS)
SPM Scanning probe microscopy, see also: STM, EFM, MFM, AFM,
SEM
SPPL Surface plasmon enhanced photoluminescence
SPR Surface plasmon resonance
SPS Surface photovoltage spectroscopy
SQUID Superconducting quantum interference device
SRET Scanning reference electrode technique
SR-GIX(R)D Synchrotron radiation grazing incidence X-ray diffraction
SRRS Surface resonance Raman spectroscopy
SRS Surface Raman spectroscopy
SRS Specular reflectance spectroscopy
STEM Scanning transmission electron microscopy
STM Scanning tunneling microscopy
STS Scanning tunneling spectroscopy
SUERS Surface unenhanced Raman spectroscopy
SVET Scanning vibrating electrode technique
SW-FTIRS Square wave Fourier transform infrared reflection spectroscopy
SWNT Single-wall carbon nanotube
SXAPS Soft X-ray appearance potential spectroscopy
SXES Soft X-ray emission spectroscopy
SXS Surface X-ray scattering
TDMS Thermodesorption mass spectroscopy
TDS same as TDMS
TEAS Thermal energy atom scattering
TEF Tip enhanced fluorescence
TERS Tip enhanced Raman scattering
THG Third harmonic generation
 List of Acronyms xix

TLC Thin layer cell

TPD Temperature-programmed desorption
TPRS Temperature-programmed reaction spectroscopy
TR-SFG Time-resolved sum frequency generation
TRBD Total reflection Bragg diffraction
UME Ultramicroelectrode
UPS Ultraviolet photoelectron spectroscopy
UV-Vis Spectroscopy with UV and visible light
VASE Variable angle spectroscopic ellipsometry
VSF Visible sum frequency
VSFG Vibrational sum frequency generation
VTS Voltage tunneling spectroscopy
WAXS Wide-angle X-ray scattering
WDX Wavelength dispersive X-ray (analysis)
XANES X-ray absorption near edge structure
XES X-ray emission spectroscopy
XPD X-ray photoelectron diffraction
XPS X-ray photoelectron spectroscopy
XRD X-ray diffraction
XRR X-ray reflection
XSW X-ray standing wave

α Accommodation coefficient measurement

σ Adsorption isotherm measurement
θ Degree of coverage
∅ Work function
∅PE Work function determination by photoemission measurement
∅TE Work function determination by thermoemission measurement
∅FE Work function determination by field emission measurement
∅FERP Work function determination by field emission retarding poten-
tial measurement
∅DTERP Work function determination by diode thermoemission retarding
potential measurement
∅K Work function determination by Kelvin method

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List of Symbols

Common symbols and abbreviations used in electrochemistry1

A Area, constant, optical absorption

a Activity, absorption coefficient
ai Debye length
CV Cyclic voltammogram
C Capacitance / μF
CD Double layer capacity / μF
Cdiff Differential double layer capacity
Cint Integral double layer capacity
c Concentration / M
cs Surface concentration
c0 Bulk concentration / M
D Diffusion coefficient / cm2 s−1
d Distance
E Electrode potential / V
E Electrical field strength
EA Activation energy / kJ mol−1
EF Fermi energy
EH Electrode potential vs. standard hydrogen electrode, see also: ENHE
EHg2 SO4 = EMSE
EMSE electrode potential vs. mercurous sulfate electrode, csulfate = 0.1 M
Em Electrode potential of measurement, also: Emeas
ENCE Electrode potential vs. normal calomel electrode
ENHE Electrode potential vs. normal (i.e. standard) hydrogen electrode2
Epzc Electrode potential of zero charge
Eref Reference electrode potential, electrode potential of reference mea-
surement, see also: Er
Er Reference electrode potential, electrode potential of reference mea-
surement, also: Eref
1 For further details of electrochemical symbols, see R. Parsons, Pure Appl. Chem. 37
(1974) 499.
2 The term “normal electrode” should be avoided because normal may be misunderstood as
a designation of a certain concentration.
xxii List of Symbols

ESCE Electrode potential vs. saturated calomel electrode

ESHE Electrode potential vs. standard hydrogen electrode
E0 Electrode potential at rest (i.e. I = 0 mA cm−2 )
E00 Standard electrode potential
ΔE Difference of electrode potentials, e.g. peak potentials
e0 Elementary charge
F Faraday constant
I Ionic strength
I Current / A
Ict Charge transfer current / A
jct Charge transfer current density / A cm−2
k Extinction coefficient
M Molarity / mol·l−1
M Molar mass
m Molality
NL Loschmidt number
n Number of mols, electrode reaction valency, refractive index
R Resistance, universal gas constant, reflected intensity of light
RCT Charge transfer resistance
Rf Roughness factor
Rsol Electrolyte solution resistance
RHE Relative hydrogen electrode
T Absolute temperature
u Ionic mobility
upd Underpotential deposit
V Volume
v dE/dt, scan rate in cyclic voltammetry

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 Part I

Introduction and Overview

1 Introduction

Electrochemistry is an extremely interdisciplinary area of science closely related to

chemistry, physics, materials science, biology, surface science and a host of other
fields. It is basically devoted to investigations of structures and dynamics as being
present at interfaces between phases containing different types of mobile charged
particles. Thus the process of electrochemical production of chlorine proceeding
at the surface of a metal electrode in contact with a halide-containing solution in
chlorine-alkali electrolysis is a typical case of electrochemistry at work. In the elec-
trode the mobile charges are electrons, which are withdrawn from the chloride an-
ions that are the mobile charged species in the solution phase. The interface es-
tablished between molten iron and the fairly complicated mixture of molten metal
oxides floating on top of the molten metal is another example. The stimulation of
nerves and the propagation of information along nerves is another, totally different
case. One more different case is the delamination of an organic coating applied to
a metal surface for corrosion protection that occurs because of processes occurring
at the metal-coating interface in the presence of a thin solution film on top of the
coating containing small concentrations of electrolyte salts. In all of the examples
just mentioned charged particles and large electric fields at interfaces play a piv-
otal role in establishing the structure at the interface and in controlling the various
processes occurring at the interface. These examples share an additional feature that
may possibly complicate their investigation: All interfaces are “buried” between two
condensed phases (liquid or solid). Electrochemical investigations have focused in
recent decades on elucidating their static and dynamic features exactly. The breadth
of the few listed examples illustrates the need for intense research. Beyond these
aspects of interfacial electrochemistry, the processes and structures within a con-
densed phase containing ions far away from the interface with their particular prop-
erties are the other main topics of electrochemistry. They are related to ionic con-
duction, thermodynamics of perfect (ideal) and real phases and other topics that
are of only peripheral interest within the scope of this book. Initial investigations
of electrochemical interfaces were limited to the measurements of electrical and
chemical quantities, e.g. current, voltage, potential, charge or concentration. Kinet-
ics could be elucidated by performing these measurements as a function of time,
concentration and temperature. Unfortunately the obtained results provided in most
cases only a very rough and macroscopic picture. A complete understanding, in par-
ticular at the microscopic level, was impossible or only highly speculative. With the

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4 1 Introduction

increasing importance and breadth of the application of electrochemistry in indus-

try, technology and daily life, this has become a considerable obstacle. Optimization
of a given system or process and the understanding of the failure of a product with
electrochemical features is possible only based on a deeper understanding of the
electrochemical interface.
The advent of a broad variety of methods in vacuum physics, surface and ma-
terials science and analytical chemistry has provided a rich zoo of methods that
have been converted for use in experimental electrochemistry. In contrast to the ex-
perimental methods briefly touched upon before, these methods are summarized as
“non-traditional methods”.
The overwhelming abundance of available methods is a tremendous possibility
and a considerable seduction. Reasonable use of available methods and selection of
the most suitable ones is possible only based on at least a minimum knowledge of
the available methods, their strengths and weaknesses and their known pitfalls. So
far the researcher has to consult either the original literature, including numerous
more or less strongly focused reviews, or quite a few books that provide overviews
of some subfamilies of the large number of available methods. The present book
attempts to provide a broad overview delving into the depth of a certain method
only as far as necessary to provide an initial understanding. It attempts to include
all known methods of investigation applied to electrochemical interfaces that have
arrived at a stage where a useful application has become visible to a broader audi-
ence.
In the following chapters and sections this will be done in a way that will hope-
fully be useful for the researcher looking for a method for his particular problem
and for the graduate student looking for possible methods to treat the task of his
masters thesis. In the second chapter, the structure and dynamics of electrochem-
ical interfaces will be reviewed briefly. The term “interphase” will be introduced,
stressing the fact that the topmost layers or regions of both phases that are in contact
at the interface are different from layers and regions within the bulk of the phases.
The third chapter pays a closer look at the possibilities of classical electrochemi-
cal methods and stresses the limitations beyond which traditional electrochemical
methods provide only the basis for speculative interpretation of experimental data.
In Chap. 4, spectroscopic and surface analytical methods that form the bulk of
this book are treated in the form of a general overview. This chapter will be of inter-
est for a reader with an already established background in traditional electrochem-
istry who is looking for a general introduction. Chapter 5 provides the complete pic-
ture of spectroscopic methods. Chapters 6 and 7 treat X-ray and surface topographic
methods. A brief introduction explains the way methods are assigned to various
families. Descriptions of the available methods as known to the author are provided
together with instructive examples of their applications. The structure of a descrip-
tion always follows the same scheme. The fundamentals are presented briefly. The
electrochemical system properties that can be investigated with the method are in-
dicated. A description of the experimental setup is provided. Some examples serve
as illustration. References are provided especially for methods and experimental de-
 1 Introduction 5

tails that cannot be treated exhaustively within the limited scope of this book. No
attempt is made to provide a complete listing of all reported applications of a given
technique.
A generous list of acronyms is provided, giving the reader access to fast explana-
tions of the myriad of examples of the modern letter soup omnipresent in scientific
papers. The subject index will serve as a fast access lane especially for those readers
searching for information about a particular method.

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2 Structure and Dynamics
of Electrochemical Phase Boundaries

In our environment surfaces, phase boundaries and interfaces are omnipresent. A liv-
ing cell, a crystal of salt, a living organism, a cutting tool or a sheet of metal are
separated from the surroundings by surfaces—and thus interfaces are established.
At a first glance this may be accepted as a trivial and obvious fact of life without
much importance. The properties and activities of a biological cell are presumably
controlled by its structure and the processes occurring in its interior; density and
the chemical and physical properties of a crystal depend on the chemical identity of
its constituents and their arrangement in the crystal. The same may be said of the
other examples. A closer look at this understanding leaves a number of open ques-
tions, because many processes of central importance are occurring at the interface.
By just looking at the bulk properties of the adjacent systems these properties may
be understood improperly or, sometimes, not at all.
This quickly becomes evident when we take another look at our examples: The
exchange of all materials (nutrients, water, waste, etc.) of a cell with the environ-
ment occurs via the membrane enclosing the cell, wherein a liquid/liquid interface
is established. The permeability of the membrane is of vital importance for a proper
functioning of these transport processes. It depends upon the structure of the mem-
brane itself and the structure and composition of the interface between the mem-
brane and the surrounding atmosphere. The selective permeability for toxins of the
cells and membranes constituting an animal’s skin may be a reason for the mas-
sive die-off among amphibians. The practical applicability and the many mechani-
cal properties of a cutting tool certainly depend on the bulk properties of the used
raw material. But the durability of the cutting edge, its hardness and stability even
under demanding operating conditions, depend mostly upon the chemical composi-
tion and structure of its surface, which basically forms a solid/gas interface. Surface
hardening or treatment by, for example, ion implantation or galvanic deposition of
additional material, may considerably change and improve the bulk material’s ini-
tial properties. The corrosion stability of the metal sheet depends of course upon
the chemical identity or, in the case of an alloy, the composition of the metal. But
corrosion takes place only on the outermost layer of the sheet, and consequently
the surface properties once more control the process occurring at this solid/liquid
interface.
These apparently unrelated examples have one feature in common: Structure or
dynamics or even both at the interface are strongly influenced by electronic charges
8 2 Structure and Dynamics of Electrochemical Phase Boundaries

that are present as ions in the liquid around the membrane or the corroding metal.
Sometimes the participation of charged particles in chemical processes as necessary
in the surface treatment of the cutting tool is essential. The investigation of the
structure and dynamics of interfaces influenced by electric charges or by charged
particles is the task of electrochemists. Traditional methods and their limits will be
reviewed briefly in the following chapter.

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3 Scope and Limitations
of Classical Electrochemical Methods

The experimental tools of electrochemists were, until a few years ago, mainly rather
simple measurements of electrical, physical and chemical quantities. Using a broad
variety of experimental methods today called “classical electrochemical methods”,
they were able to provide models of electrified interfaces with respect to both struc-
ture and dynamics. Unfortunately their results were in many cases of a very macro-
scopic nature, any interpretations of the model with respect to the microscopic struc-
ture and mechanistic aspects of the dynamics and reaction were only more or less
reasonable derivations. This gap, which caused many misunderstandings of puz-
zling features in electrochemical processes and interfaces, has started to close. The
use of an enormous variety of spectroscopic and surface analytical tools in inves-
tigations of these interfaces has considerably broadened our knowledge. In many
cases microscopic models based on the results of these studies with “non-traditional
electrochemical methods” have enabled us to understand many hitherto strange phe-
nomena in a convincing way.
The “traditional methods” generally are based upon measuring the potential of
a working electrode and the current necessary to establish this potential. In many
cases the registration of these data is done as a function of time, concentration or
some other additional experimental variable. The relationship between current and
potential, in particular the deviation of the actual electrode potential established dur-
ing the flow of a current from the rest potential at nil current, can be explained by
assuming a variety of hindrances impeding the flow of current or increasing the elec-
trode potential actually necessary to obtain the desired current. This difference of
potentials is called overpotential and the various contributing hindrances are named
according to the cause of the hindrance: A charge transfer overpotential is caused by
a sluggish charge transfer needing additional activation energy in order to proceed at
appreciable rates. The slow mass transport caused by limited rates of diffusion, con-
vection or migration generates a concentration overpotential (sometimes it is more
precisely called “diffusion overpotential”). The name implies that an insufficient
concentration of a reactant needed in the electrochemical reaction is the cause. Of
course a small concentration of the reactant in the bulk of the solution enhances this
effect. Slow removal of reaction products will also result in diffusion overpotentials.
Chemical reactions preceding or following the charge transfer as heterogeneous re-
actions on the electrode surface or as homogeneous reactions in the solution phase
produce reaction overpotentials. As both transport and reaction tend to impede the
10 3 Scope and Limitations of Classical Electrochemical Methods

overall rate of the electrochemical reaction by limiting either the supply of reac-
tants or the removal of products, they are sometimes summarized as concentration
overpotentials. Finally, adsorption or desorption of reactants and crystallization in
the case of metal deposition or dissolution may be slow, resulting in adsorption or
crystallization overpotentials. Numerous electrochemical methods have been used
to separate these various overpotentials in order to get a handle for further improve-
ments of the reaction rate for practical applications or to get a better understanding
of the reaction kinetics. Of course, it was always tempting to deduce mechanis-
tic models describing the reaction on a molecular-microscopic level. Unfortunately,
such deductions must be mostly tentative because they generally are not based on
direct molecular or atomic evidence of the actual identity of the species proposed as
participants in the electrochemical reaction sequence.
This lack of evidence has stimulated intense efforts to modify known methods
in order to comply with the specific requirements of measurements in the presence
of an electrolyte solution or other specifics of electrochemical investigations.
At any given interface between two phases the properties of both phases close to
the interface and, in particular, those of the topmost layers are different from those in
the bulk. In order to separate this special portion of a system from both bulk phases
the term interphase has been coined for this quasi-phase in between the bulk phases.
This term considerably expands the two-dimensional view of the phase boundary
as a simple interface between two completely homogenous phases. The particular
properties of these interphases are of pivotal importance for their behavior in many
areas of science and technology. In applied sciences an improvement of these prop-
erties is possible only with knowledge of these properties that is as broad and deep
as possible. In electrochemistry the interphase properties are further complicated by
the involvement of charged particles and extremely high electric fields. A broader
overview of the electrochemical interface will identify further adjacent domains:
• The electrolyte solution
• Diffusion and/or reaction layers
• The electrochemical double layer comprised of the diffuse (Gouy-Chapman)
and the inner (Helmholtz) layer
• Space charge layers and surface states (with semiconducting electrodes)
• Adsorbed species on the electrode surface
• Molecular or polymer films
• The bulk of the electrode material
Properties of interphases relevant for an understanding of structures and dynam-
ics therein can be grouped into atomic (microscopic) and macroscopic ones. Nev-
ertheless the close relationships between both types of properties have allowed us
to infer conclusions with respect to atomic models from macroscopic information.
Investigations of these properties have gained tremendously in recent years from the
application of a broad variety of spectroscopic methods. Certainly many properties,
in particular macroscopic ones, can be studied by measuring surface properties (like
conductivity, hardness, etc.) with non-spectroscopic methods. In most cases the re-
sults will be rather general and a complete understanding of relationships between

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 3 Scope and Limitations of Classical Electrochemical Methods 11

the surface properties of interest, any structural features of the surface and the inter-
phase on an atomic level will not be accessible. This will seriously obstruct further
improvements of the knowledge of these properties.
4 Spectroscopy and Surface Analysis at Interfaces
Between Condensed Phases

The need for further methods to study electrochemical interfaces and interphases
has been indicated in the preceding chapter. Spectroscopic methods in particular
were suggested as suitable tools [1–3]. The major advantage was considered to be
their capability to provide information on a microscopic level by probing the subject
of interest, resulting in signals that contain the desired information specifically from
the place of interest. In this chapter a first overview is given of available methods and
possible approaches for a typical selection of experimental tasks, which are taken
predominantly from electrochemical investigations. All methods will be dealt with
in detail in the sections of the following chapters; thus the immediately following
text is addressed preferably at the reader looking for a general introduction.
The broad variety of methods suitable for spectroscopy at surfaces and other
kinds of surface analysis has been touched upon already in the preceding chapter.
The term “surface” referred mostly to solids being exposed to a vacuum or even ul-
tra high vacuum environment. Few methods can be used under ambient conditions
and at atmospheric pressure or even in the presence of condensed phases as encoun-
tered in electrochemical systems because of the strong interactions between several
probes and signals with particles in condensed phases or in the gas phase at am-
bient temperature and pressure. The same line of argument applies to the interface
between immiscible liquids.
The application of spectroscopic methods to surface studies always involves a
probe used to stimulate or perturb the interphase in a well-defined way. This causes
a signal to be emitted from the interphase. In many cases the signal is simply the
modulated probe. Special care has to be exercised in order to obtain information ex-
clusively from those parts of the interface as close as possible to the interface. Many
techniques are essentially surface sensitive (i.e. selective). In some cases methods
or sample systems have to be modified in order to achieve this surface sensitivity.
The broad range of energies (or wavelengths, frequency or any other equivalent
unit) as depicted in Fig. 4.1 provides ample opportunities to develop methods.
Various probes available for surface studies are depicted in Fig. 4.2. Electromag-
netic radiation (h · ν), neutral atom beams (i 0 ), ion beams (i ± ), magnetic (H ) or
electric (E) fields and thermal excitation (W ) can be used as probes.
Because of the numerous different types of interactions and resulting signals, the
possible combinations of probes and signals are myriad. A simple matrix indicating
some of these combinations and the resulting methods is provided in Table 4.1.

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14 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

Fig. 4.1. The electromagnetic spectrum (approximate values and numbers only) with typical
applications

Fig. 4.2. Probes and signals in electrochemical interfacial investigations; for explanation of
symbols, see text

The explanation of the acronyms is listed above (p. xi). No distinction is made
here between methods applicable in situ or ex situ. Suggestions for names and ab-
breviations provided in the literature have been taken into account [4]. Once the
effect of the interaction of the probe with the surface or the intensity of the mea-
sured signal is investigated as a function of either the energy of the probe or the
signal, the method becomes a spectroscopy.
A very rich family of methods is based on electron or particle beams ranging in
kinetic energy from a few electron volts (eV) up to several thousand eV (keV). As
spectroscopic studies of electrochemical systems should be done preferably in situ,
i.e. in the presence of the electrolyte solution (or molten electrolyte in some cases),
electrons, ions and neutral particle beams cannot be used at these conditions; they
can only be used ex situ after an appropriate sample transfer. The same applies
to short wavelength UV-radiation [5]. Even the remaining combinations are mani-
fold. Despite the inherent drawbacks of ex situ methods some ex situ techniques are
used because of the valuable answers they can provide and/or because the neces-
sary transfer is very well understood and does not result in artifacts. The spectro-
scopic methods for electrochemical applications developed from methods of vari-
ous origins by adapting them to electrochemical requirements, in particular for their
use under in situ conditions, are commonly summarized as spectroelectrochemical
methods. Various authors have reviewed the combination of electrochemistry and
spectroscopic methods, e.g. [6, 7]. Obviously the applicability of any method de-
pends on the compatibility of the employed probes and signals with the components
of the electrochemical cell. The advent of new sources for the generation of probes
and new means for analysing and detecting signals from the interface/interphase has
frequently changed the possibilities of methods considerably. This applies in partic-
 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases 15

Table 4.1. Probes and signals in surface analysis

Probe Signal
e− h·ν i0 i± W E; H
e− AES-SAM APS ESD ESD ∅FERP
EELS SXAPS ESDIAD ESDIAD ∅DTERP
ELS DAPS
EXELFS EM/MA
AEAPS
LEED
RHEED
SEM, STM
IETS
h·ν UPS IR, ELL PD PD
XPS UV-Vis LD LIMS
ESCA RAS
∅PE MBS
ARUPS SHG
PCS ESR
EXAFS INSEX
SEXAF EXAFS
XANES SEXAFS
XANES
i0 CL MBSS SI
MBRS
TEAS
FAB
α, σ
i± INS IMXA ISS
SIMS
HIID
RBS
LEIS, HEIS
W ∅TE FD SI
DS
TDS
E; H FES FIS ∅K
∅FE FIM

ular to the use of synchrotrons as sources of electromagnetic radiation. Synchrotrons

are circular electron beam accelerators. Electrons travelling on a circular orbit emit
radiation, the energy distribution of which depends on the energy of the travelling
electrons. By adjusting the electron energy, electromagnetic radiation with a broad
range of frequencies extending from the far infrared into the range of hard X-rays

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16 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

can be generated; in a typical setup the energy can be continuously varied from
10 eV to 2700 eV. In addition, this radiation shows a defined time structure; it is
completely polarized [8–13].
A brief overview of available methods can be obtained easily by looking at the
various interface and interphase properties and grouping the methods with respect to
their ability to provide information relevant to a particular property. In electrochem-
ical systems where an electrode is in contact with an electrolyte and has possibly
been modified by an adsorbed species or a surface layer, these properties are:
macroscopic properties
• Optical absorptivity (color)
• Optical reflectivity
• Electrical conductivity
• Crystallographic structure of the interphase
• Concentration of adsorbed species, see also: microscopic properties
microscopic properties
• Chemical identity of atoms and molecules in the interface, state of oxidation, co-
ordination with further ligands, distance from interacting atoms in the electrode
surface
• Type, strength and orientation of interaction between these particles and the
electrode and their environment
These various properties are collected together with a selection of methods suit-
able for their investigation in Fig. 4.3.
The explanation of the acronyms is provided above (see p. xi). Only methods
applicable under ex situ conditions are emphasized in the figure (italics). As al-
ready indicated, a sample transfer from the electrochemical cell into a ultrahigh
vacuum (UHV) analysis system accompanied by drying of the sample and exposure
to the atmosphere is necessary and any conceivable influence of this step may result
in artifacts. This is most impressively demonstrated in studies of corrosion layers
on iron electrodes. Ex situ methods have repeatedly yielded erroneous results; for
example, because of dehydration of the corrosion products [14].
Macroscopic Properties. In many cases macroscopic properties of molecular and
thick adsorbate layers or electrode coatings are closely related to their chemical
composition and thickness. They are also related to several application-related pa-
rameters, e.g. color, conductivity or state of passivity.
The optical absorption in the UV-Vis region of the electromagnetic spectrum can
be measured as a function of electrode potential and wavelength in external reflec-
tion or in transmission. In the latter case the use of optically transparent electrodes
(OTE) made of glass coated with indium-doped tin oxide (ITO) or sputtered with
gold or platinum is required. In order to minimize absorption, especially of colored
electrolyte solutions, thin layer cells with short optical pathlengths are preferred.
Nevertheless, in many cases simple cells made of standard cuvets, working elec-
trodes cut from coated glass, metal wires serving as counter electrodes and small
 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases 17

Fig. 4.3. Spectroelectrochemical methods applied to an electrochemical interface composed

of an electrode with an adsorbate ZXY; for explanation of acronyms, etc., see text

Fig. 4.4. Transmission spectra of glass sheets with different ITO-coatings as indicated

reference electrodes mounted without protruding into the optical beam can be man-
ufactured easily [15, 16]. Experiments can be performed in standard double beam
spectrometers. A complete cell is placed in the reference beam with a working elec-
trode and without the electrochemically active species present in the other cell. Any
absorption of the electrolyte solution or the OTE will be canceled out by the nulling
procedure of the spectrometer. Typical UV-Vis spectra of ITO coated electrodes are
shown in Fig. 4.4.
Electronic transitions in thin films of conducting polymers deposited on the OTE
have been investigated with UV-Vis spectroscopy. As an example, in Fig. 4.5, UV-

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18 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

Fig. 4.5. UV-Vis spectra of a conducting polymer layer of poly(2-propylaniline) deposited on

a gold sputtered glass slide electrode; electrode potentials as indicated

Vis absorption spectra of a film of poly(2-propylaniline) on an ITO electrode as a

function of electrode potential (i.e. degree of doping) are shown.
Various electronic transitions caused by excitation of electrons from π into π ∗
states and from binding into antibinding polaron1 and bipolaron2 states that change
as a function of electrode potential can be seen.
In the case of dissolved reaction intermediates or products, the use of a trans-
mission arrangement and OTE results in the detection of these species in the elec-
trolyte solution. This method is, of course, not surface sensitive; it has been used fre-
quently for the investigation of organic electrochemical reactions involving various
species of distinctly different UV-Vis-absorption [17, 18]. In the case of optically
active dissymmetric organic species, circular dichroism (CD) may be observed. The
stereoselectivity of heterogeneous electron transfer processes can be studied using
a spectrometer with linear polarized light [19].
In the case of interphases on top of opaque or thick electrodes, external reflec-
tion of the probe light beam arriving at the electrode surface under investigation
after passage through the adjoining electrolyte film is possible. Because no refer-
ence as necessary in the conventional two-beam spectrometers is available, some
other parameter has to be modulated in order to get a spectrum that can be put into
relationship with defined states of the interphase. Generally, the electrode potential
is modulated. Consequently, the method is called electroreflectance spectroscopy
(ERS). As the interaction of species in the interphase with the light depends upon
the plane of polarization of the incoming light spectra obtained with p-polarized
and s-polarized light are different in many cases, differences between correspond-
1 In solid state physics, “polarons” are electrostatically induced local lattice distortions
caused by an electron in a ionic crystal. In conducting polymers radical cations (lone electrons
associated with positively charged holes) have a similar effect.
2 Recombination of two polarons (similar to recombination of two electrons resulting in
Cooper pairs in superconductors) leads to spinless bipolarons with a formal charge of two.
Conversion between polaron and bipolaron states as a function of electrode potential is asso-
ciated with changes in the spectra.
 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases 19

ing spectra obtained therewith can be used in the interpretation. Molecular adsor-
bates [20], their orientations [21] and electronic transitions that depend on the crys-
tallographic orientation of the electrode have been studied [22]. Measurements with
internal reflectance have been reported infrequently [23]. The electrode is deposited
on a transparent crystal and the probe light is guided into the crystal under an an-
gle resulting in attenuated total reflectance (ATR) at the electrode-coated surface.
Light absorption can be attributed to properties of species on top of the electrode.
Unfortunately, self-absorption of the crystal complicates the spectra.
Besides different absorption of s- and p-polarized light by adsorbates or sur-
face layers on electrodes, the phase shift between both is influenced during the
passage. Simultaneous measurements of both are done with ellipsometry. Recent
experimental developments of automatic ellipsometers have greatly simplified ex-
perimental procedures; nevertheless, the interpretation of results is difficult. Passive
layers [24–33], underpotential metal deposits [34–36], organic adsorbates [37] and
surface modifying films [38] have been investigated. The range of accessible wave-
lengths has been extended from the UV-Vis into the infrared region [39].
The overall reflectance of an electrode surface measured without respect to the
wavelength of the incoming light is of small experimental importance. The use of
light sources of high intensity in narrow energy intervals may induce nonlinear ef-
fects at the surface. The generation of light at the second (SHG) or the third har-
monic frequency (THG) is a possible result. In the presence of molecular adsorbates,
sum frequency generation (SFG) with light frequency that combines the frequency
of the incoming light and molecular vibrations can be detected. The former tech-
niques have been used in studies of electrode coverage with simple adsorbates and
of surface crystallographic structure [40, 41]; the latter is suitable for investigations
of organic adsorbates [42, 43].
In the previous discussion, only reflection and absorption of light have been
considered. In many cases the interaction of light with species in the interphase
may cause further processes by exciting electrons into upper states and forming
electron–hole pairs. Photovoltages measured directly (photovoltage spectroscopy
PVS) or photocurrents detected by applying a potential difference across the in-
terphase (photocurrent spectroscopy PCS) as a function of exciting wavelength can
be used to investigate optoelectronic properties of semiconductors [44].
Although the electronic conductivity of an interphase that is present on an elec-
trode can be related to various optoelectronic properties that are also measurable
with spectroscopic techniques, the direct measurement of surface conductivities is
not a spectroelectrochemical method. It is nevertheless a surface sensitive method
that provides results closely related to those of other methods discussed in this book.
Data on the electrosorption of alcohols on gold electrodes [45] or the electrode po-
tential dependent conductivity of intrinsically conducting polymers [46] have been
obtained with in situ surface conductivity measurements. Figure 4.4 shows the elec-
trical resistance of a poly(2-propylaniline) film measured in situ under experimental
conditions suppressing any influence of solution phase conduction. The influence of

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20 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

the electrode potential upon the resistance is obvious. A detailed discussion of this
relationship has been presented elsewhere [7].
The crystallographic structure of interphases can be investigated with various
methods. In situ, the application of X-ray diffraction INSEX is possible. Because of
the depth of penetration of X-ray beams both in the transmission and the external
reflection arrangement, the sample has to be made very thin in order to minimize
unwanted contributions from the bulk of the electrode. Crystalline products of cor-
rosion processes [47, 48], surface films [49], surface reconstruction [50] and catalyst
systems [51] have been investigated.
Dynamic diffraction of an X-ray beam at lattice planes close to the surface of a
perfect single crystal can result in standing X-ray waves (XSW). Measurements of
the geometry of the standing wave or of photoelectrons released by the XSW can
yield information on the position of atoms relative to the diffracting lattice plane in
the interphase [52, 53].
The surface morphology of both crystalline and amorphous electrode surfaces or
interphase layers can be studied in situ with scanning tunneling microscopy STM.
The method is based upon the very pronounced dependency of the tunneling current
between a sharp tip and a conducting surface. Scanning a surface with such a tip at a
constant mechanical (macroscopic) distance morphological features of microscop-
ically (atomically) different distance from the tip will result in dramatic changes
of the tunnel current. This in turn can be used to map the atomic morphology of
the surface. Numerous studies pertaining to processes involving metal deposition,
dissolution, corrosion and reconstruction have been reported [54–64]. The investi-
gation of organic adsorbates has been hampered so far by considerable difficulties
during interpretation of the obtained tunneling current vs. surface topography data.
The conceivable use of the STM arrangement in tunneling spectroscopy [65] may
provide additional information on vibrational properties of organic adsorbates and
thus ease the interpretation of STM data. The first experiments with intrinsically
conducting polymers have been described [66].
The morphology, including features of adsorbates, can be determined with a
small tip that scans the electrode surface mechanically using a very low contact
pressure. This method is termed atomic force microscopy (AFM) [67] because van
der Waals force interactions are probed. The first applications in metal deposition
studies have been reported [68–71].
Ex situ macroscopic properties of adsorbates and interphases not sensitive to-
wards a transfer of the sample from the electrochemical cell into an analysis system
(in most cases a UHV chamber) can be studied with additional techniques. The crys-
tallographic data can be derived from low energy electron diffraction (LEED) [72];
this is possible only if the sample has a minimum degree of ordering.
Surface concentrations of adsorbed or deposited species can be derived from a
number of methods discussed previously. In the case of absorption spectroscopies,
the extinction of the probing light corresponds more or less directly to the degree of
coverage and an independent way of calibrating is generally necessary. The intensity
 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases 21

of SHG signals corresponds to the coverage. Further details have been reviewed
elsewhere [73].
Microscopic Properties. In most electrochemical experiments involving complex
adsorption and/or reaction steps, the identification of adsorbates, intermediates and
reaction products and their relationship to the environment are of central impor-
tance. As has been pointed out in the previous chapter some information about the
chemical identity of species involved in the reaction can be gleaned indirectly from
macroscopic properties of the interphase. Unambiguous identification is neverthe-
less possible almost exclusively only with additional spectroscopic techniques.
As shown in Fig. 4.3, a broad array of methods is available for this task. Direct
identification of volatile molecular species present on or near an electrode is possi-
ble with differential electrochemical mass spectrometry (DEMS) [74–81]. For this
method the electrode has to be porous and gas permeable. It is mounted on the inlet
port of a mass spectrometer. Because of the pressure gradient between the vacuum
and the electrochemical cell with the porous electrode operated at ambient pressure,
volatile species can be sucked into the mass spectrometer and analysed therein.
Sometimes reactive intermediates—particularly, of electroorganic reactions—
have unpaired electrons and consequently show the typical properties of a radical.
Although the free spin of the electron is generally quenched upon strong adsorp-
tive interaction with a metallic surface and consequently not detectable, sometimes
the electrochemical reaction sequence allows detection of these radicals by electro-
chemical electron spin resonance spectroscopy (ECESR). This is possible when the
radical desorbs and is present in the electrolyte phase in a concentration sufficient for
detection by electron spin resonance spectroscopy or when the radical is separated
from the metal by a suitable spacer (i.e. incorporated in an insulating interphase on
the surface). A variety of radical intermediates generated electrochemically has been
studied in situ with various different electrochemical cells [82–84]. Radical cations
formed during electrooxidation of electrochemically active polymers can also be
studied with ECESR [7, 82]. As an example, ECESR spectra of polyindoline are
displayed as a function of the electrode potential in Fig. 4.6.
With an increase of the electrode potential towards anodic values, the polymer
is oxidized (p-doped). The unpaired electron causes a radical–cation-like behavior.
The high degree of delocalization results in the single line spectrum. A higher degree
of doping corresponds to a larger concentration of free spins and, accordingly, the
twice-integrated ECESR signal shows a well-defined dependency upon the electrode
potential.
These radical cations are termed polarons based on the physical description of
similar states in solid state physics. Their relevance to the electronic conduction
mechanism in these films has been discussed elsewhere [86].
The chemical identity of molecular adsorbates on electrode surfaces can be de-
rived from their vibrational behavior. In situ infrared (IR) and Raman spectroscopy
are possible. Because of the strong IR absorption of most electrolyte solvents, mod-
ulated techniques are necessary. Potential and polarization modulation have been
employed [53] and the methods are named correspondingly. Modulation is not nec-

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22 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

Fig. 4.6. ECESR spectra of a film of polyindoline in an aqueous solution of 1 N H2 SO4 at

E SCE = −100 and −150 mV [85]

essary with Raman spectroscopy in the case of aqueous electrolyte solutions because
water is a very poor scatterer. The low efficiency of the Raman process makes sim-
ple surface Raman spectroscopy (SRS) rather insensitive. Giant enhancements of
the scattered signal intensity have been observed after various surface treatments,
particularly of coinage metal surfaces (Cu, Ag and Au). The resulting microstruc-
ture of the sample surface and additional surface-specific enhancement effects re-
sult in a 106 -fold increase in the intensity of the scattered signal. The effect and
numerous applications have been reviewed extensively [87]. Besides identification
of the adsorbate, these methods also provide information about the orientation of the
adsorbate and the interaction with the environment. A combined use of both meth-
ods sometimes provides complementary information that yields a more complete
model of the adsorbate structure. This can be demonstrated with selected data of a
study of the adsorption of 2-buten-1,4-diol on a polycrystalline gold electrode. Pre-
vious electrosorption studies with classical electrochemical methods have indicated
a rather strong physisorption of the alcohol from a neutral aqueous solution [88].
With respect to the orientation of the molecule on the surface and the influence of
the electric field in the double layer upon the intramolecular binding, no informa-
tion could be derived from these electrochemical measurements. Various vibrational
modes were detected using both vibrational spectroscopies (see Figs. 4.7 and 4.8).
Interpretation of the spectra based on a comparison with vibrational spectra of
the alcohol in pure form and dissolved in the electrolyte solution resulted in a pro-
posed adsorbate structure with the π-bond system of the unsaturated alcohol in-
teracting strongly with the electrode-side on (vibrational mode of the C=C bond
around 1598 cm−1 ) and with the C–OH bond (vibrational mode of the C–OH bond
around 1030 cm−1 ) at a tilted or perpendicular orientation with respect to the elec-
trode surface towards the electrolyte solution. This information is helpful for under-
standing the mechanism of the electrooxidation of this alcohol [89].
 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases 23

Fig. 4.7. Potential dependent IR spectra (PDIR) of a gold electrode in an aqueous solution of
2 mM 2-buten-1,4-diol and 0.1 M KClO4 in water, electrode potentials as indicated, 256 or
512 scans at each electrode potential, resolution 8 cm−1

Fig. 4.8. SER spectra of a polycrystalline gold electrode in a solution of 0.1 M KClO4 in
water, concentration of 2-buten-1,4-diol indicated in the figure, E SCE = 0 V (upper trace),
0.245 V (lower trace), resolution 7 cm−1

Besides these techniques that are applicable to solid electrodes with a smooth or,
in the case of IR spectroscopy, carefully polished surface, technologically important
rough or porous samples are sometimes of interest. Vibrational spectroscopy at the
surfaces of rough or porous samples is possible with photoacoustic and photother-
mal spectroscopy (PAS, PTS) [90–94].
After identification of an adsorbate, an intermediate or a reaction product by one
of the methods discussed above or based on further information about the electro-
chemical process, additional information may be required.
Of course vibrational spectroscopies generally yield data suitable not only for
identification of the adsorbate, but also indicative of intramolecular changes affected

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24 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

by the interaction with the electrode surface or the interactions within the interphase.
These data may even contain information pertaining to the type and strength of
interaction with the electrode surface.
In the case of metallic adsorbates (metal deposits, underpotentially deposited
upd-layers, catalytically active metal deposits), the type of coordination to surface
sites (one-, two- or three-fold) and the distance to these sites may be of interest.
Vice versa the same type of data may be of importance in the case of adsorbed
ions on metal electrodes or about the atomic environment of a given atom/ion in
an interphase. Analysis of the fine structure of X-ray absorption (EXAFS, XANES)
close to the X-ray absorption edge of the species (atom) of interest will yield this
data provided the sample can be prepared in a very thin layer in order to exclude
unwanted bulk interference. Otherwise the experiment can be done in reflection
(SEXAFS). Information about the distance between the atom of interest and its first
and sometimes even second shell of surrounding species can be derived from the
spectra [95]. Availability of a suitable light source, generally a synchrotron (for
details see p. 15), is an experimental prerequisite. The method has been applied in
studies of passive and corrosion layers on various metals [96–102] and of molecular
and ionic adsorbates on single crystal surfaces [103].
Very similar information can be obtained with the experimentally less demand-
ing Mössbauer spectroscopy. The resonant absorption of gamma radiation by certain
atomic nuclei (57 Fe, 119 Sn and several other isotopes of technical interest, e.g. 57 Co,
can also be studied in the emission mode) yields information about the electromag-
netic environment of this atom. By comparison with standard samples the chemical
environment of a given atom, the specific type of chemical compound wherein it is
incorporated and further morphological information can be derived from the Möss-
bauer spectra [104–113].
Local electron densities characteristic of a chemical environment can be studied
with in situ positron annihilation spectroscopy (PASCA) [114].
Ex situ identification and investigation of adsorbed species is possible provided
the interaction between adsorbate and electrode is strong enough to keep the inter-
face unchanged even after moving the electrode into an ultrahigh vacuum cham-
ber. Elemental identification is possible with various electron spectroscopies. Auger
electron spectroscopy (AES) is particularly popular and can be used for quantitative
measurements (degree of coverage), too [115–121]. The state of oxidation can be
studied with photoelectron spectroscopy ESCA [122] or XPS [123].
Various mass spectroscopies are applicable ex situ in order to obtain molecu-
lar information. Secondary ion mass spectroscopy (SIMS) can be used [124, 125].
Thermal desorption mass spectroscopy is a viable alternative as a less intrusive and
more surface sensitive tool [126, 127]. So far, the latter method has been applied ex-
clusively to adsorbed hydrogen and carbon monoxide formed in an electrochemical
reaction of organic CHO-compounds.
A general feature of practically all spectroscopic and surface sensitive meth-
ods described in the following chapters should be kept in mind: Compared to many
electrochemical methods, in many cases these techniques provide information on a
 Further Reading 25

quite different time scale whereas fast electrochemical methods, instationary ones
in particular, will yield data pertaining to processes occurring in microseconds and
beyond. Most techniques described in the following chapters operate more slowly
and will give information on a second or even slower time scale. Only in a few cases
do some spectroscopies acquire data fast enough to provide time resolved informa-
tion on a second or even millisecond time scale. This difference should always be
kept in mind when comparing results obtained with these nontraditional methods
with those of traditional electrochemical methods. Somewhat related to this general
statement is the fact that many nontraditional methods yield particularly those data
and results that can be obtained most easily with a given method. A simple example
helps to explain this: When several intermediates are present during an electrochem-
ical reaction measurement with infrared spectroscopy, we may identify preferable
species with a large IR absorption cross section that are not necessarily the most
important intermediates at all. Quite the contrary, these species may be formed at
the dead end of a side reaction pathway. With another method, e.g. with a mass
spectroscopy, those species in particular that can be ionized and detected most eas-
ily will be found. Such species may be different from those identified with infrared
spectroscopy. Already this simple example illustrates the need for a careful selection
and combination of experimental methods and for a careful interpretation.
The following chapters are devoted to single methods or to closely related fam-
ilies of methods. A brief overview, including some joint features of a given method,
will precede the description of the individual techniques. The principle of organiza-
tion of methods and techniques is a common feature. These are either probes shared
by several techniques or particular surface/interphase properties studied with the
methods. An introduction to spectroelectrochemistry in molecular inorganic chem-
istry is available [128].

Further Reading
A.W. Adamson, Physical Chemistry of Surfaces, 5th edn. (Wiley, New York, 1997)
K. Kolasinski, Surface Science (VCH/Wiley, Weinheim, 2002)
V.G. Bordo, H.-G. Rubahn, Optics and Spectroscopy at Surfaces and Interfaces (Wiley/VCH,
Weinheim, 2005)
J.C. Rivière, S. Myhra (eds.), Handbook of Surface and Interface Analysis (Dekker, New
York, 1998)
G. Ertl, J. Küppers, Low Energy Electron Diffraction and Surface Chemistry, 2nd edn. (Verlag
Chemie, Weinheim, 1985)
R. Caudano, J.-M. Gilles, A.A. Lucas (eds.), Vibrations at Surfaces (Plenum, New York,
1982)
T.N. Rhodin, G. Ertl (eds.), The Nature of the Surface Chemical Bond (North-Holland, Am-
sterdam, 1979)
R.S. Mikhail, E. Robens, Microstructure and Thermal Analysis of Surfaces (Wiley, Chich-
ester, 1983)
R.B. Hall, A.B. Ellis (eds.), Chemistry and Structures at Interfaces (Verlag Chemie, Deerfield
Beach, 1986)

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26 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

J.O’M. Bockris, A. González-Martin, in Spectroscopic and Diffraction Techniques in Inter-

facial Electrochemistry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320
(Kluwer Academic, Dordrecht, 1990), p. 1
F. MacRitchie, Chemistry at Interfaces (Academic Press, San Diego, 1990)
R. Hoffmann, Solids and Surfaces (VCH, Weinheim, 1988)
J.T. Yates Jr., (ed.), Vibrational Spectroscopy of Molecules on Surfaces (Plenum, New York,
1987)
J.C. Vickerman (ed.), Surface Analysis – The Principal Techniques (Wiley, Chichester, 1997)
A.W. Czanderna, D.M. Hercules (eds.), Progress in Techniques and Instrumentation: Meth-
ods of Surface Analysis (Plenum, New York, 1991)
H.-H. Perkampus, Encyclopedia of Spectroscopy (VCH, Weinheim, 1995)
T. Owen, Fundamentals of UV-Visible Spectroscopy (Hewlett&Packard, 1996)
D. Brune, R. Hellborg, H.J. Whitlow, O. Hunderi (eds.), Surface Characterization (Wiley/VCH,
Weinheim, 1997)
G.E. McGuire, J. Fuchs, P. Han, J.G. Kushmerick, P.S. Weiss, S.J. Simko, R.J. Nemanich,
D.R. Chopra, Anal. Chem. 71, 373R (1999)
K. Seibold, P. Albers, GIT Fachz. Lab. 1989 637; 706
R.Parsons, Chem. Rev. 90, 813 (1990)

References
1. H. Gerischer, Ber. Bunsenges. Phys. Chem. 92, 1436 (1988)
2. J.O’M. Bockris, M. Gamboa-Aldeco, in Spectroscopic and Diffraction Techniques in
Interfacial Electrochemistry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C,
vol. 320 (Kluwer Academic, Dordrecht, 1990), p. 55
3. D.M. Kolb, Surf. Sci. 500, 722 (2002)
4. I. Mills, T. Cvitas, K. Homann, N. Kelley, K. Kuchitsu, Quantities, Units and Symbols
in Physical Chemistry, 2nd edn. (Blackwell Scientific, Oxford, 1993)
5. D.E. Eastman, F.J. Himpsel, Phys. Today 5, 64 (1981)
6. K. Rajeshwar, R.O. Lezna, N.R. de Tacconi, Anal. Chem. 64, 429A (1991)
7. H. Gerischer, Angew. Chem. 100, 63 (1988)
8. E.E. Koch (ed.), Handbook of Synchrotron Radiation, vol. 1 (North-Holland, Amster-
dam, 1983)
9. E.E. Koch (ed.), Handbook of Synchrotron Radiation, vol. 2 (North-Holland, Amster-
dam, 1983)
10. G.V. Marr (ed.), Handbook of Synchrotron Radiation, vol. 3 (North-Holland, Amster-
dam, 1987)
11. C. Kunz, Synchrotron Radiation – Techniques and Applications (Springer, Berlin,
1979)
12. H. Winick, S. Doniach (eds.), Synchrotron Radiation Research (Plenum, New York,
1980)
13. G. Margaritondo, Introduction to Synchrotron Radiation (Oxford University Press, Ox-
ford, 1988)
14. J.A. Bardwell, G.I. Sproule, M.J. Graham, J. Electrochem. Soc. 140, 50 (1993)
15. J. Lippe, PhD Dissertation. Universität Oldenburg, 1991
16. M.B.G. Pilkington, B.A. Coles, R.G. Compton, Anal. Chem. 61, 1787 (1989)
17. A.J. Bard, L.R. Faulkner, Electrochemical Methods (Wiley, New York, 1980), or Elec-
trochemical Methods, 2nd edn. (Wiley, New York, 2000)
 References 27

18. B.-S. Kim, S.-M. Park, J. Electrochem. Soc. 140, 115 (1993)
19. J. Daub, J. Salbeck, I. Aurbach, Angew. Chem. 100, 278 (1988)
20. J.A. Caram, C. Gutierrez, J. Electroanal. Chem. 323, 213 (1992)
21. P.H. Schmidt, W. Plieth, J. Electroanal. Chem. 201, 163 (1986)
22. D.M. Kolb, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New York, 1988),
p. 87
23. W.N. Hansen, Adv. Electrochem. Electrochem. Eng. 9, 1 (1973)
24. B.D. Cahan, R.F. Spanier, Surf. Sci. 16, 166 (1969)
25. B.D. Cahan, Surf. Sci. 56, 354 (1976)
26. C.T. Chen, B.D. Cahan, J. Electrochem. Soc. 129, 17 (1982)
27. R. Parsons, W.H.M. Visscher, J. Electroanal. Chem. 36, 329 (1972)
28. J.L. Ord, F.C. Ho, J. Electrochem. Soc. 118, 46 (1971)
29. J. Horkans, B.D. Cahan, E. Yeager, Surf. Sci. 46, 1 (1974)
30. J.M.M. Droog, P.T. Alderliesten, G.A. Bootsma, J. Electroanal. Chem. 99, 173 (1979)
31. S. Gottesfeld, S. Srinivasan, J. Electroanal. Chem. 86, 89 (1978)
32. T. Ohtsuka, K.E. Heusler, J. Electroanal. Chem. 100, 319 (1979)
33. J.L. Ord, J. Electrochem. Soc. 129, 335 (1982), 767
34. R. Adzic, E. Yeager, B.D. Cahan, J. Electrochem. Soc. 121, 474 (1974)
35. R. Adzic, B.D. Cahan, E. Yeager, J. Chem. Phys. 58, 1780 (1973)
36. J. Horkans, B.D. Cahan, E. Yeager, J. Electrochem. Soc. 122, 1585 (1975)
37. K. Kunimatsu, R.H. Parsons, J. Electroanal. Chem. 100, 335 (1979)
38. F. Chao, M. Costa, E. Museux, E. Levart, Elektrokhimiya 29, 57 (1993)
39. R.C. Kainthla, J.O’M. Bockris, J. Electrochem. Soc. 135, 143C (1988)
40. R.M. Corn, in Adsorption of Molecules at Metal Electrodes, ed. by J. Lipkowski, P.N.
Ross (VCH, New York, 1992), p. 347, and references therein
41. G.L. Richmond, in Electroanalytical Chemistry, vol. 17, ed. by A.J. Bard (Dekker, New
York, 1991), p. 87
42. Y.R. Shen, J. Electrochem. Soc. 135, 142C (1988)
43. Y.R. Shen, in Chemistry and Structures at Interfaces, ed. by R.B. Hall, A.B. Ellis (Ver-
lag Chemie, Deerfield Beach, 1986)
44. M.W. Peterson, B.A. Parkinson, J. Electrochem. Soc. 135, 1424 (1988)
45. R.I. Tucceri, D. Posadas, Electrochim. Acta 32, 27 (1987)
46. R. Holze, J. Lippe, Synth. Met. 38, 99 (1990)
47. J. McBreen, W.E. O’Grady, D.E. Sayers, C.Y. Yang, ECS-Meeting, Philadelphia, USA,
10–15 May 1987, Ext. Abstr. #523
48. M. Fleischmann, P. Graves, I. Hill, J. Robinson, A. Oliver, ECS-Meeting, Cincinnati,
USA, 6–11 May 1984, Ext. Abstr. #427
49. T. Ikashoji, T. Iwasaki, Inorg. Chem. 27, 1123 (1988)
50. M. Fleischmann, B.W. Mao, J. Electroanal. Chem. 247, 311 (1988)
51. J. McBreen, Electrochemical society meeting, St. Louis, USA, May 17–22, 1992, Ext.
Abstr. #35 and references therein
52. G. Materlik, J. Zegenhagen, W. Uelhoff, Phys. Rev. B32, 5502 (1985)
53. J.H. White, in Electrochemical Interfaces, ed. by H.D. Abruna (VCH, New York, 1991),
p. 133
54. M.H. Dean, A. Pinkowski, U. Stimming, J. Electrochem. Soc. 135, 143C (1988)
55. C.L. Li, L.D. Bell, C.P. Bankston, W.J. Kaiser, ECS-Meeting, Honolulu, 18–
23.10.1987, Ext. Abstr. #1472
56. O. Lev, F.-R. Fan, A.J. Bard, J. Electrochem. Soc. 135, 783 (1988)
57. F.F. Fan, A.J. Bard, Anal. Chem. 60, 751 (1988)

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28 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

58. D.H. Craston, C.W. Lin, A.J. Bard, J. Electrochem. Soc. 135, 785 (1988)
59. L.D. McCormick, M.H. Dean, U. Stimming, T. Thundat, L. Nagahara, S.M. Lindsay,
J. Electrochem. Soc. 135, 144C (1988)
60. R.S. Robinson, J. Electrochem. Soc. 135, 143C (1988)
61. L.-L. Ni, L.D. Bell, C.P. Bankston, W.J. Kaiser, J. Electrochem. Soc. 135, 144C (1988)
62. R. Christoph, H. Rohrer, H. Siegenthaler, H. Wiese, Hauptversammlung der Bunsenge-
sellschaft, Passau, 12–14.5.1988
63. P. Lustenberger, H. Rohrer, R. Christoph, H. Siegenthaler, J. Electroanal. Chem. 243,
225 (1988)
64. K.M.H. Dean, A. Pinkowski, U. Stimming, J. Electrochem. Soc. 135, 143C (1988)
65. for an introduction see: P.K. Hansma, in Vibrational Spectroscopy of Molecules on Sur-
faces, ed. by J.T. Yates, T.E. Madey (Plenum, New York, 1987), p. 135
66. R. Yang, W.H. Smyrl, D.F. Evans, J. Phys. Chem. 96, 1428 (1992)
67. A.A. Gewirth, K.J. Hanson, Interface 2, 37 (1993)
68. R. Mohr Rynders, R.C. Alkire, Electrochemical Society Meeting, St. Louis, USA, May
17–22, 1992, Ext. Abstr. #475
69. C.-C. Chen, S.M. Vesecky, A.A. Gewirth, J. Am. Chem. Soc. 114, 451 (1992)
70. B.J. Cruickshank, A.A. Gewirth, R. Mohr Rynders, R.C. Alkire, J. Electrochem. Soc.
139, 2829 (1992)
71. S. Manne, P.K. Hansma, J. Massie, V.B. Elings, A.A. Gewirth, Science 251, 183 (1991)
72. D.M. Kolb, G. Lehmpfuhl, M.S. Zei, in Spectroscopic and Diffraction Techniques in
Interfacial Electrochemistry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C,
vol. 320 (Kluwer Academic, Dordrecht, 1990), p. 361
73. R. Holze, J. Schneider, C.H. Hamann, Ber. Bunsenges. Phys. Chem. 92, 1319 (1988)
74. O. Wolter, J. Heitbaum, Ber. Bunsen. Phys. Chem. 88, 2, 6 (1984)
75. B. Bittins-Cattaneo, E. Cattaneo, P. Königshoven, W. Vielstich, in Electroanalytical
Chemistry, vol. 17, ed. by A.J. Bard (Dekker, New York, 1991), p. 181
76. S. Wasmus, E. Cattaneo, W. Vielstich, Electrochim. Acta 35, 771 (1990)
77. D. Tegtmeier, A. Heindrichs, J. Heitbaum, Ber. Bunsenges. Phys. Chem. 93, 201 (1989)
78. K. Nishimura, R. Ohnishi, K. Kunimatsu, M. Enyo, J. Electroanal. Chem. 258, 219
(1989)
79. H. Nakajima, H. Kita, K. Kunimatsu, A. Aramata, J. Electroanal. Chem. 201, 175
(1986)
80. Y. Hirata, K. Suga, M. Fujihira, Chem. Lett. 1990, 1155
81. M. Fujihira, T. Noguchi, J. Electroanal. Chem. 347, 457 (1993)
82. R. Holze, Habilitationsschrift. Universität Oldenburg, 1988
83. R.G. Compton, A.M. Waller, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum,
New York, 1988), p. 87
84. L. Dunsch, A. Petr, Ber. Bunsenges. Phys. Chem. 97, 436 (1993)
85. J. Lippe, PhD Thesis. Universität Oldenburg, 1991
86. R. Holze, J. Lippe, Bull. Electrochem. 8, 516 (1992)
87. for a complete list see: R. Holze, Electroanalysis 5, 497 (1993)
88. T. Luczak, M. Beltowska-Brzezinska, R. Holze, Electrochim. Acta 38, 717 (1993)
89. R. Holze, T. Luczak, M. Beltowska-Brzezinska, Electrochim. Acta 39, 991 (1994)
90. R.E. Malpas, A.J. Bard, Anal. Chem. 52, 109 (1980)
91. G.H. Brilmyer, A.J. Bard, Anal. Chem. 52, 685 (1980)
92. S. Yoshihara, M. Ueno, Y. Nagae, A. Fujishima, J. Electroanal. Chem. 243, 475 (1988)
93. J. Rappich, J.K. Dohrmann, Hauptversammlung der Bunsengesellschaft. Passau, 12.–
15.5.1988
 References 29

94. C.E. Vallet, S. Berns, J.J. Hendrickson, C.W. White, J. Electrochem. Soc. 135, 387
(1988)
95. M.F. Toney, J. McBreen, Interface 2, 22 (1993)
96. H. Baumgärtel, H.-W. Jochims, B. Brutschy, Z. Phys. Chem. NF 154, 1 (1987)
97. A. Michalowicz, J. Huet, A. Gaudemer, Nouv. J. Chim. 1982, 79
98. M.S. Co, W.A. Hendrickson, K.O. Hodgson, S.A. Doniach, J. Am. Chem. Soc. 105,
1144 (1983)
99. J.C. Poncet, R. Guilard, Polyhedron 2, 417 (1983)
100. W.H. Liu, X.F. Wang, T.Y. Teng, H.W. Huang, Rev. Sci. Instr. 54, 1653 (1983)
101. J. Goulon, P. Friant, J.L. Poncet, R. Guilard, J. Fischer, L. Ricard, Springer Ser. Chem.
Phys. 27, 100 (1983)
102. C. Goulon-Ginet, J. Goulon, J.P. Battioni, D. Mansuy, J.C. Chottard, Springer Ser.
Chem. Phys. 27, 349 (1983)
103. L. Blum, A.D. Abruna, J. White, J.G. Gordon II, G.L. Borges, M.G. Samant, O.R.
Melroy, J. Chem. Phys. 85, 6732 (1986)
104. W.E. O’Grady, J. Electrochem. Soc. 127, 555 (1980)
105. C. Fierro, R.E. Carbonio, D. Scherson, E.B. Yeager, J. Phys. Chem. 91, 6579 (1987)
106. D.A. Corrigan, R.S. Conell, C. Fierro, D.A. Scherson, J. Chem. Phys. 86, 5009 (1987)
107. D.A. Scherson, C. Fierro, D. Tryk, S.L. Gupta, E.B. Yeager, J. Eldridge, R.W. Hoffman,
J. Electroanal. Chem. 184, 419 (1985)
108. D.A. Scherson, S.B. Yao, E.B. Yeager, J. Eldridge, M.E. Kordesch, R.W. Hoffman,
J. Electroanal. Chem. 150, 535 (1983)
109. D. Scherson, S.B. Yao, E.B. Yeager, J. Eldridge, M.E. Kordesch, R.W. Hoffman, Appl.
Surf. Sci. 10, 325 (1982)
110. D.A. Scherson, S.B. Yao, E.B. Yeager, J. Eldridge, M.E. Kordesch, R.W. Hoffman,
J. Phys. Chem. 87, 932 (1983)
111. H. Leidheiser, J. Electrochem. Soc. 135, C5 (1988)
112. M.V. Ananth, N.V. Parthasaradhy, J. Sci. Ind. Res. 47, 28 (1988)
113. D.A. Scherson, S.L. Gupta, C. Fierro, E.B. Yeager, M.E. Kordesch, J. Eldridge, R.W.
Hoffman, J. Blue, Electrochim. Acta 28, 1205 (1983)
114. Y.C. Jean, K.C. Cheng, ECS-Meeting. Toronto, 12–17 May 1985, Ext. Abstr. #676
115. A.T. Hubbard, Europ. Spec. 78, 28 (1988)
116. J.A. Schoeffel, A.T. Hubbard, Anal. Chem. 49, 2370 (1977)
117. A.T. Hubbard, J. Electroanal. Chem. 168, 43 (1984)
118. V.K.F. Chia, J.L. Stickney, M.P. Soriaga, S.B. Rosasco, G.N. Salaita, A.T. Hubbard,
J.B. Benziger, K.W.P. Pang, J. Electroanal. Chem. 163, 407 (1984)
119. A.T. Hubbard, Acc. Chem. Res. 13, 177 (1980)
120. J. Aberdam, in Spectroscopic and Diffraction Techniques in Interfacial Electrochem-
istry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Acad-
emic, Dordrecht, 1990), p. 383
121. H.J. Mathieu, in Surface Analysis – The Principal Techniques, ed. by J.C. Vickerman
(Wiley, Chichester, 1997), p. 99
122. B. Ratner, D. Castner, in Surface Analysis – The Principal Techniques, ed. by J.C.
Vickerman (Wiley, Chichester, 1997), p. 43
123. R. Kötz, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 409
124. H.W. Buschmann, S. Wilhelm, W. Vielstich, Electrochim. Acta 31, 939 (1986)

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30 4 Spectroscopy and Surface Analysis at Interfaces Between Condensed Phases

125. J.C. Vickerman, A. Swift, in Surface Analysis – The Principal Techniques, ed. by J.C.
Vickerman (Wiley, Chichester, 1997), p. 135
126. S. Wilhelm, W. Vielstich, H.W. Buschmann, T. Iwasita, J. Electroanal. Chem. 229, 377
(1987)
127. S. Wilhelm, H.W. Buschmann, W. Vielstich, DECHEMA Monographie, vol. 112 (VCH,
Weinheim, 1988), p. 113
128. E. Alessio, S. Daff, M. Elliot, E. Iengo, L.A. Jack, K.G. Macnamara, J.M. Pratt, L.J.
Yellowlees, in Trends in Molecular Electrochemistry, ed. by A.J.L. Pombeiro, C. Ama-
tore (FontisMedia/Dekker, Lausanne/New York, 2004), p. 339
 Part II

Methods and Applications

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 References 33

In this part the various non-traditional methods employed in electrochemical in-

vestigations are described in three chapters. The description follows a very simply
outline in order to facilitate readability. Fundamentals of methods are provided in
detail only where the author believes that these fundamentals cannot be assumed to
be generally known or where a detailed knowledge is necessary for understanding
the displayed examples and results.
The term “electrode”, according to W. Nernst, refers to the electron (or hole)
conducting part of an electrochemical system (a half cell) together with the ion
conducting part (electrolyte solution, molten salt, solid electrolyte). Commonly, the
term is used frequently with reference to the former part only. Although the Nern-
stian description is certainly the more precise one, experimental methods mostly
serve to investigate the interface (or interphase) between both phases with the for-
mer part of the system being the focus of interest. Consequently, in the following
text the term “electrode” will be used to designate the former part only. Electro-
chemical symbols are used as suggested by IUPAC [1].
As already pointed out, the myriad of conceivable combinations of probes and
signals and the experimental ingenuity of researchers adapting a given method to
an encountered problem has resulted in a considerable wealth of spectroelectro-
chemical and surface analytical methods established as non-traditional methods of
investigation. Organizing these methods in a reasonable way as a means of orienta-
tion to help the reader poses a problem almost as large as the breadth of the methods
to be described.
Based on the traditional designation of spectroscopy as a method wherein either
absorption or scattering of electromagnetic radiation independently of the type and
energy of the radiation is the central feature, spectroscopic methods are collected in
Chap. 5. Methods wherein diffraction of any kind is the central aspect are collected
in Chap. 6. In a still rapidly growing collection of methods, the topography of a sur-
face or an interface is visualized using a scanning probe method. In addition, some
of these methods provide additional information on the surface with spatial resolu-
tion. These methods are collected together with further techniques, wherein already
established methods are adapted in a way enabling the acquisition of localized infor-
mation in the final chapter. Because these methods are essentially not spectroscopic
techniques but surface analytical tools, some additional non-spectroscopic methods
used to study surface properties like surface conductivity are added to this chapter.
Collections of reviews of single methods or small selections of methods have
been published; as already indicated, they do not provide the broad picture of the
complementary use of spectroelectrochemical methods or deal with too much detail
[2–10].

References
1. R. Parsons, Pure Appl. Chem. 37, 499 (1974)
2. E. Yeager, B.D. Cahan, D. Scherson, M. Hanson, Nav. Res. Rev. 37, 13 (1985)
3. W. Plieth, G.S. Wilson, C.G. de la Fe, Pure Appl. Chem. 70, 1395, 2409 (1998)
34 Part II

4. H.D. Abruna (ed.), Electrochemical Interfaces (VCH, New York, 1991)

5. A. Wieckowski (ed.), Interfacial Electrochemistry (Dekker, New York, 1999)
6. M. Hunger, J. Weitkamp, Angew. Chem. 113, 3040 (2001)
7. J.F. Haw (ed.), In-Situ Spectroscopy in Heterogeneous Catalysis (VCH/Wiley, Wein-
heim, 2002)
8. B.M. Weckhuysen, Chem. Commun. 2002, 97
9. J.C. Lindon, G.E. Tranter, J.L. Holmes (eds.), Encyclopedia of Spectroscopy and Spec-
trometry (Academic Press, New York, 2000)
10. F. Hoffman, Surf. Sci. Rep. 3, 107 (1983)

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5 Spectroscopy at Electrochemical Interfaces

The following section provides a systematic overview of spectroscopic methods as

applied in electrochemical investigations. They are grouped according to the type
and energy of the employed probe, i.e. according to the type of electromagnetic ra-
diation used. (Suggestions for a subdivision of the electromagnetic spectrum have
been provided elsewhere [1].) In a few cases, the light returning as the signal from
the investigated interphase is not analysed with respect to energy, but with respect
to some other experimental parameter, e.g. the plane of polarization or intensity.
Sometimes the overall intensity is measured only as a function of another experi-
mental parameter. These techniques are, strictly speaking, not spectroscopic ones;
they are nevertheless incorporated in appropriately designated sections together with
the real spectroscopic methods. Further experimental developments underway when
this text was prepared made these assignments preliminary ones, anyway. In the case
of ellipsometry, only measurements at fixed wavelengths were done initially. In the
meantime, spectroscopic ellipsometry, i.e. measurements of optical constants of the
investigated interface as a function of the wavelength of the sample light beam, have
become standard. In some cases (e.g. photothermal measurements), investigations
with and without taking into account the actual wavelength of the sampling light
have been done.
As already pointed out, the number of known and conceivable interfaces and
interphases where electrochemical processes may proceed is overwhelmingly large.
The following listing of methods deals exclusively with those which are the subject
of electrochemical investigations. No methods used exclusively for bioelectrochem-
ical systems and samples are included. Semiconductor electrodes are included de-
spite the fact that the understanding of their spectroelectrochemical investigations
requires a deeper understanding beyond the knowledge of the metal/solution inter-
face. (For a broad introduction and overview see [2].)
Obviously the increasing importance of solid electrolytes as employed in solid
oxide or polymer membrane fuel cells calls for experimental methods adapted specif-
ically to the needs of these experimental setups, which are considerably different
from those employing liquid electrolyte solutions. The number of experimental
methods beyond classical electrochemical ones adapted specifically to these require-
ments was fairly low when preparing this chapter. In most cases standard surface
analytical or solid state analytical techniques were employed; for an introductory
overview see [3]. Nevertheless, these electrochemical systems are not taken into
36 5 Spectroscopy at Electrochemical Interfaces

consideration in the following overview when a standard technique has been modi-
fied and adopted substantially.
Besides solid electrolytes of various types, molten salts and ionic liquids1 [4–7]
have attracted considerable interest as electrolyte systems. Although their practi-
cal application is currently focused almost entirely on a number of electrolytical
processes (production of aluminum, fluorine), advanced systems for electrochemi-
cal energy conversion and storage and electrochemical production using both molten
salt electrolytes and ionic liquids are under investigation. The specific properties
of molten salts, their high viscosity and, in many cases, extreme chemical aggres-
siveness pose specific challenges in cell design and the selection of appropriate
materials. Reported experimental setups are consequently of only limited general
applicability. Spectroelectrochemical and surface analytical methods as employed
exclusively with molten salt electrolytes are not covered in this book. Fortunately
the state of the art has been reviewed previously and the reader will find helpful
introductory overviews elsewhere [8, 9]. Liquid/liquid interfaces between immis-
cible liquid solutions are not treated broadly for basically the same reasons. There
have been a considerable number of reports on electrochemical investigations, but
spectroscopic methods have been applied infrequently only. An overview has been
provided elsewhere [10].
In the following sections spectroscopic methods and related surface analytical
methods are treated in detail. They are grouped according to the probe employed by
the method. Sometimes this organizational scheme failed and thus a few methods
are collected at the end of this section. Most experimental setups reported in the
literature are included. Their advantages and limitations are commented upon only
briefly; in many cases judgments may differ, anyway. In order to enable the reader
and potential user to get an idea of the essentials of the setup and its connection to
a spectrometer, simplified and schematic drawings are provided. Detailed pictures
containing even the most minute aspects (including sometimes the most obvious)
are not included because these additions tend to detract from the essentials. Further
information about details can be obtained from the original papers always quoted
with the figures.
Growing interest in detailed information related to particular locations at an elec-
trochemical interface (e.g. steps on a single crystal surface or particular features at a
modified electrode surface) combined with instrumental developments have resulted
in experimental methods providing localized information. In cases where this infor-
mation is obtained point-by-point (sequentially), the procedure is called a scanning
one and the method may be called mapping. In some cases (e.g. with focal plane
1 The particular advantages of ionic liquids (extremely low vapor pressure, not combustible,
physico-chemical properties can be adjusted easily by variation of mixing ratios, good solva-
tion capabilities without specific coordination, broad electrochemical window between an-
odic/cathodic decomposition, good electrolytic conductivity, high thermal stability, broad
temperature range of the liquid state) seem to imply a promising future for their applica-
tion. These properties may nevertheless turn into serious drawbacks when separation of polar
or ionic products from the liquid is required or when low solubility of frequently encountered
reactands (methanol) or gases (hydrogen, oxygen) is becoming effective.

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 5.1 Optical Spectroscopy in the Visible Range 37

detectors in infrared spectroscopy), large parts of the surface under investigation

can be imaged onto a detector built of numerous elements. This approach is called
imaging.
General information about preparation, purification, etc. of solvents for elec-
trolyte solutions is provided by Mann [11]. Suggestions for further reading are pro-
vided only where texts deemed suitable are available.

5.1 Optical Spectroscopy in the Visible Range

Fundamentals. Species involved in electrochemical reactions that show optical ab-
sorption caused by electronic transitions in the UV-Vis region of the electromagnetic
spectrum can be studied in situ with a variety of spectroelectrochemical techniques.
The choice of a suitable technique depends on the type of species to be investigated
and upon the exact location of the species (e.g. directly adsorbed on the metallic
electrode surface, incorporated in a film attached to the electrode surface, dissolved
in the electrolyte solution). Basically, two families of spectroelectrochemical tech-
niques have been established so far (see Fig. 5.1):
• Measurement in the transmission mode using optically transparent or semitrans-
parent electrodes
• Measurement in the reflectance mode using either external specular reflection,
internal reflection [attenuated total reflection (ATR)] or diffuse reflection
We will describe these techniques in detail. Methods where absorption of light
causes emission of species, e.g. photons or electrical currents across the electro-
chemical interface, are treated in Sects. 5.1.6 and 5.1.9.

Fig. 5.1. Typical spectroelectrochemical arrangements for in situ measurements in the UV-
Vis range; from left to right: standard arrangement; arrangement with thin layer of electrolyte
solution (TLC) only; external reflection, internal reflection at the backside of the electrode
38 5 Spectroscopy at Electrochemical Interfaces

5.1.1 UV-Vis Spectroscopy with Optically Transparent Electrodes

Fundamentals. A species generated electrochemically or formed in an electro-

chemical reaction sequence by a chemical reaction with an electronic absorption
in the UV-Vis range of the electromagnetic spectrum can be detected by means of
its optical absorption provided that the actual extinction (based on the molar ex-
tinction coefficient and the concentration) is sufficient. Detection can be achieved
very simply by putting the electrochemical cell into the beam of a suitable spec-
trometer. Species to be detected may interact with the light beam when the beam is
passing in parallel just in front of the electrode surface; this requires tedious opti-
cal adjustment and is not commonly used. For a development with two-dimensional
spectroscopy, see p. 44. A very simple approach is the passage of the beam per-
pendicular through the electrode and the electrolyte solution. This works only with
electrodes that have a sufficient transparency for the used light. Very thin layers of
noble metals, metal oxides or carbon will have this property. Fine metal grids or
metal meshes that are either made from metal wires or micromachined in various
ways (e.g. LIGA technique2 ) will have an optical transparency of zero where the
wires are; between them, passage of the beam is unimpeded. Species formed at the
transparent layers or at the grids can cause the desired optical absorption. The rather
complicated transport processes of these three-dimensional systems can be simpli-
fied considerably when the time scale of the electrochemical experiments is long
enough to allow the diffusion layer thickness to become larger than the openings in
the electrode. In this case the diffusion process feeding the electrode reaction be-
comes one-dimensional. Further details of investigated electrochemical systems in
particular with respect to the use of thin layer cells are provided elsewhere [12–14].
The evaluation of a typical thin layer cell with respect to electrochemical response
behavior has been discussed [15].
Instrumentation. Various materials are optically transparent in the UV-Vis range
of the electromagnetic spectrum while maintaining a considerable electronic con-
ductivity. Thin sputtered or vapour deposited metal layers (e.g. gold, platinum) and
indium-doped tin oxide (ITO) on glass are typical examples. Their absorption spec-
tra depend on the thickness, degree of doping, state of oxidation and other variables.
Typical absorption spectra are displayed in Figs. 5.2 and 5.3.
These coated glasses can be used as working electrodes [optically transparent
electrodes (OTE)] in standard three-electrode arrangements provided that both glass
and coating are chemically and electrochemically stable and inert in the used elec-
trolyte solution and the applied range of electrode potentials. The use of a modified
infrared spectroscopy transmission cell equipped with quartz windows for UV-Vis
spectroelectrochemistry has been described [18]. Platinum layers deposited onto the
quartz served as an optically transparent working electrode and an additional plat-
inum layer served as a pseudo-reference electrode. A counter electrode outside the
thin layer zone (in one of the tubes used for solution supply) served as a counter
2 LIGA = lithographic-galvanic; this term refers to the manufacturing process applied for
making microstructured honeycomb electrodes.

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 5.1 Optical Spectroscopy in the Visible Range 39

Fig. 5.2. Absorption spectra of ITO-coated glass and of a glass sheet coated with a gold
sputter layer [16]

Fig. 5.3. Absorption spectra of ITO-coated glass with coatings of various electrical conduc-
tivities [17]

electrode. Chemical modifications of ITO surfaces have been discussed [19] and the
electrochemistry of ITO has been investigated in various media [20]. Recently, free-
standing synthetic diamond discs that were highly doped with boron have been used
as transparent electrodes [21]. Transparent carbon films obtained by pyrolysis of di-
luted commercial photoresist spin-coated onto glass slides have been described [22].
Compared with ITO-coated glass, diamond shows a significantly higher chemical
stability in various environments, has a fairly well-defined surface chemistry, with-
stands cathodic polarization (where ITO is reduced), has a wide electrochemical
potential window and shows a small background current in this range.
The optical arrangement is fairly simple. The working electrode is mounted in
an electrochemical cell, in most cases consisting just of a standard cuvet fitted with a
tight lid providing feedthroughs for the electrodes and for a gas purge. As a counter
electrode, a piece of metal wire (e.g. platinum or gold) is mounted in the cuvet
without protruding into the light beam. A reference electrode of any type can be
connected to the electrolyte solution via a salt bridge (e.g. a liquid-filled thin plas-
tic tube closed with a porous glass or ceramic plug). The cell is arranged with the
working electrode perpendicular to the light beam in the UV-Vis spectrometer; in
the case of a two-beam instrument in the sample beam path. A cuvet filled with the
40 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.4. Cell arrangement for in situ UV-Vis spectroelectrochemistry with optically transpar-
ent electrodes

electrolyte solution to be investigated and an electrode of the same kind as the work-
ing electrode (without connection to the potentiostat) are mounted in the reference
beam. In a single-beam instrument, the desired UV-Vis-spectra showing changes of
optical absorption as a function of electrode potential, time, etc., are obtained by
using a defined spectrum (e.g. at an initial potential value, at the spontaneously es-
tablished rest potential of the electrode, at time zero) as the background spectrum in
the standard spectral calculations. A typical arrangement showing the major parts is
displayed in Fig. 5.4.
Beyond numerous studies of soluble reaction intermediates and products (as an
example see a study of electroreduction of nitrosobenzene [23] or investigations of
chromium aryl complexes [24]) this design has also been employed successfully in
studies of polymer films deposited onto these electrodes. Films showing redox ac-
tivity and, in many cases, intrinsic electronic conductivity [intrinsically conducting
polymers (ICPs)] have been studied; for an overview see [25, 26]. In a typical set
of spectra (Fig. 5.5) obtained with a film of polyaniline, optical absorptions cor-
responding to the π → π ∗ transition (around 330 nm) and to further transitions
involving species like radical cations (polarons) and dications (bipolarons) formed
in the sequence of electrooxidation of the film are observed.
Solid materials showing electrochemical activity can be studied by mechanically
attaching them as small particles to an ITO-electrode [27]. The electroreduction of
indigo has been studied using this approach.
A considerably different approach employs a mini-grid electrode. This type of
electrode can be made of a variety of metals (gold, platinum, etc.) and is basically
a very fine mesh. Expanded metal-like structures, finely woven wires [28] or struc-
tures prepared via the LIGA-process [29, 30] are currently in use [31–33]. They
are inserted into electrochemical cells of basically the same type as that used with
OTE. The light beam passes the grid or the honeycomb structure of the LIGA ele-
ment. Because the wires or the structural LIGA elements are extremely fine, only

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 5.1 Optical Spectroscopy in the Visible Range 41

Fig. 5.5. UV-Vis spectra of a polyaniline film deposited on an ITO electrode in contact with
an aqueous solution of 1 M HClO4 , electrode potentials as indicated

a tiny fraction of the light is stopped. The light passing the open parts will inter-
act with species in the solution phase. Consequently, this method is not surface
sensitive; rather, it is only sensitive to species present in the solution phase. Nev-
ertheless, these species are essentially close to the electrode surface because of the
fine structure. A cell design employing a completely sealed cell with connectors
for electrolyte solution flow has been described elsewhere [34]. A cell suitable for
work at low temperatures has been described by Hartl et al. [35]. Because carbon, as
an electrode material, has some advantages over metallic materials (higher hydro-
gen overpotential, low chemical reactivity, corrosion resistance), graphite-coatings
of metal mesh electrodes have been developed and employed [36, 37].
The length of the optical pathway through electrolyte solution-filled portions
of the setup might cause problems when nonaqueous solvents with considerable
light absorption in the investigated spectral range are used, when further optically
absorbing species besides the species of interest (e.g. educts) are present at con-
siderably concentrations, when electrolyte solutions of poor conductivity are em-
ployed or when complete electrochemical conversion of a species is desired. High
absorbance might result in a poor signal-to-noise ratio in spectral ranges of low
transmission, poor conductivity may cause a sluggish response of the electrochem-
ical cell to rapid potential changes used e.g. in potential scan or potential step elec-
trochemistry. A thin layer cell as depicted in Fig. 5.6 has been suggested [38]; for
another design, see [39].
A Pyrex culture tube fitting into a standard 10-mm cuvet for UV-Vis spec-
troscopy is equipped with two holes. One hole is closed with a fused silica window
permitting entrance of the light beam and a piece of NMR-tube closed with an ITO
glass disc is fitted into the second one. The latter serves as a working electrode.
Contact is made via a platinum wire touching the ITO surface that also serves as a
spacer between the working electrode and the silica window. The counter electrode
is a platinum wire loop. The cell has shown no distortions of cyclic voltammograms
up to scan rates of 25 mV s−1 . A similar cell design suitable for NIR spectroscopy
42 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.6. Spectroelectrochemical cell for in situ UV-Vis spectroelectrochemistry with opti-
cally transparent electrodes [39]

Fig. 5.7. Spectroelectrochemical thin layer cell for in situ UV-Vis spectroelectrochemistry
with a mini-grid electrode [40]

will be discussed below. A considerably more simple design employing two glass
sheets kept at a fixed distance by thin PTFE tape strips has been suggested [40, 41].
A metal wire grid mounted between the plates acts as a working electrode. The
setup is immersed with its bottom edge into a beaker filled with an electrolyte so-
lution. A metal wire counter electrode and a reference electrode are also immersed
into this reservoir. The solution is sucked into the gap by applying a vacuum at
the top edge and capillary action keeps the solution in place. With sufficiently hy-
drophilic glass surfaces, the capillary action takes place without additional suction.
The light beam passes through the glass plate arrangement at the position where
the grid working electrode is placed. Further simplification of the design is possible
with glass plates (one or both of them coated with ITO) as the working electrode, as
was initially suggested elsewhere [42]. For a schematic cell design of this type, see
Fig. 5.7.
With only weakly absorbing solvents, low concentrations of the species to be
detected or weak effects (i.e. small extinction coefficient), a long optical pathlength
might be desirable. In a design described by Zak et al. [43], a cell body holding both
the counter and the reference electrode is manufactured from PTFE. The working
electrode is attached to the cell body with a spacer of about 0.1-mm thickness. The

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 5.1 Optical Spectroscopy in the Visible Range 43

light beam of the spectrometer passes through the gap between the working elec-
trode and the cell body via quartz glass windows. The pathlength is equivalent to
the distance between the windows, i.e. the length of the working electrode (up 1–2
cm). The beam width is given by the thickness of the spacers and the distance be-
tween them (e.g. 0.1–7 mm). Very small reactand concentrations can be detected.
A long optical path cell employing standard 10-mm cuvets has been described [44].
A gold-coated PTFE-block is positioned 0.5 mm above the bottom of the cuvet.
A hole through the block provides access for the counter and reference electrode.
The fairly large working electrode surface and the small active electrolyte volume
enclosed by the cuvet and the PTFE-block (in the microliter range) allow fast con-
version of reactants. A similar design employing optical fibres for coupling a spec-
troelectrochemical thin layer cell to a spectrometer has been described by Brewster
and Anderson [45]. A cell design employing reticulated vitreous carbon and provid-
ing a long optical pathlength and simplified handling has been reported [46]. Cell
designs for experiments with molten salts have been provided elsewhere [13, 47].
Recording optical absorption at selected wavelengths as a function of electrode
potential or recording the first derivative (dA/dE vs. E) are useful methods for
identification of electrochromic sites in electroactive polymers [48, 49] and for cal-
culating formal Nernst potentials E0 [50, 51].
UV-Vis spectroscopy with TLC and OTE can be used beyond the identifica-
tion of species to determine redox potentials, particularly with complicated systems
showing multiple electron transfers [52].

5.1.2 External Reflectance Spectroscopy

Fundamentals. UV-Vis spectroscopic measurements with solid electrodes of a

thickness beyond that of transparent films (e.g. metal or glassy carbon discs) are
possible in the external reflection mode. A beam of light is directed through a win-
dow in the electrochemical cell and the electrolyte solution towards the electrode
surface. This surface is polished in order to maintain a high reflectivity. The use
of rough surfaces is also possible; techniques employing the diffuse reflectance ob-
served in this case are treated in the following section (see p. 57). After a single
specular reflection, the beam is directed through the electrolyte solution and the cell
window towards the detector. Alternatively, multiple reflections are possible (see
also p. 46). No influence of the electrooptical properties of the electrode material
itself (e.g. electrode potential or wavelength dependent reflectivity) or of any modi-
fication on the electrode (e.g. a polymer film or a thin metal deposit) is assumed to
be effective; these effects are studied with electroreflectance spectroscopy (see p. 56
for the former case and the previous section for the latter case). Measurements with
films or layers deposited onto the electrode are also possible.
Instrumentation. A straightforward design of an electrochemical cell enabling si-
multaneous electrochemical and spectroscopic measurements (in both the UV-Vis
44 5 Spectroscopy at Electrochemical Interfaces

and the NIR region3 of the spectrum) with near normal incidence specular reflec-
tion has been described by Salbeck [53]. A smooth metal disc acting as a working
electrode is pressed against an optically transparent cell window. The electrolyte so-
lution layer of about 15 μm thickness thus formed establishes semi-infinite diffusion
conditions. Light from the spectrometer source is guided towards the electrode sur-
face at near normal incidence with fiber optics. The reflected light is picked up with
a second fiber and piped to the detector. Combined with fast multichannel detectors
(e.g. diode arrays) or intensified multichannel detectors, spectra can be acquired in
a rapid sequence, enabling real time experiments for kinetic and mechanistic stud-
ies [54–56]. A setup that is similar in design and suitable in a broad range of temper-
atures (−55 to 80°C) and which has an external reflectance attachment (i.e. without
fiber optics) has been described [57].
Besides cell designs that employ metals or other electrode materials in disc
shape for external reflection spectroscopy, Robinson and McCreery have success-
fully employed cylindrical carbon fibers of 12 μm diameter [58, 59]. The carbon
fiber was illuminated with a tunable dye laser. Scattered light was collected with
fiber optics and guided to a photomultiplier detector. Because no thin layer arrange-
ment and consequently poor electrochemical cell response were involved, fast ex-
periments on a microsecond time scale were possible. Studies of polyaniline films
deposited on platinum discs have been described [60].
A combination of transmission and external reflectance spectroscopy resulting
in a cell for bidimensional4 UV-Vis spectroelectrochemistry has been described [61].
With an optically transparent electrode (OTL), the schematic setup shown in Fig. 5.8
illustrates the different pathways of the light. One beam passes through the electrode
and the electrolyte solution in front of it and the second beam passes only through
the solution in front of the electrode close to it, guided strictly in parallel to the
surface. Thus the former beam carries information pertaining to both the solution
and the electrochemical interface (e.g. polymer films or other modifications on the
electrode surface), whereas the latter beam carries only information about the solu-
tion phase. Proper data treatment enables separation of both parts. Identification of

Fig. 5.8. Schematic setup of bidimensional UV-Vis spectroelectrochemistry (based on [62])

3 The accessible section of the spectrum depends on the actual optical transparency of the
employed components (cell window, fiber optics, etc.).
4 In other spectroscopies, the term “two-dimensional” is substituted for “bidimensional”.

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 5.1 Optical Spectroscopy in the Visible Range 45

insoluble species attached to the electrode and soluble species is easily possible and
the setup has been applied to numerous systems (for a review, see [62]).
In a modified setup using a solid platinum electrode modified by depositing an
intrinsically conducting polymer, one beam of light impinges on the polymer/elec-
trode surface at almost normal incidence and the second beam is passed along the
electrode surface through the electrolyte solution. As a function of the electrode
potential, two different UV-Vis absorption spectra are acquired. Because different
locations in the electrolyte solution and, in case of the former beam, the deposited
polymer are probed, complex processes can be elucidated. In the case of electro-
chemically controlled release of hexacyanoferrate from a film of polypyrrole, the
simultaneous release of pyrrole oligomers could be verified [62].

5.1.3 Attenuated Total Reflectance Spectroscopy5

Fundamentals. A plane wave of electromagnetic radiation (i.e. light) impinging

upon an interface between two media of different optical density from the medium
√
with the higher refractive index np = ε p will be reflected totally (internally) pro-
vided the angle of incidence (see Fig. 5.9) is larger than a critical value θ c [63]. At
smaller angles most of the light is transmitted and the reflectivity decreases abruptly
(see Fig. 5.10). The actual value of θ c depends on the refractive indices n of both
media according to Snell’s law sin θ c = nd /np with d indicating the more dense
medium. The intensity of the electromagnetic wave along the z-axis decays at val-
ues of θ above θ c exponentially with a decay length l = λ/(2π(n sin θ )2 − 1) (see
Fig. 5.9) and the wave extending beyond the phase boundary is called an evanescent
wave. Only the interfacial range is illuminated and only within this range can light
and absorbing species interact. The intensity of the incoming light I in is enhanced
by a factor of about 4 at θ c (Fig. 5.11).
Instrumentation. A setup employing an ITO-coated glass sheet as the working
electrode and ATR element as shown in Fig. 5.12 has been proposed for studies of
thin films deposited on the ITO layer [64]. Light is piped through an optical fiber to

Fig. 5.9. Schematics of total internal reflection; for details, see text
5 For further details, see the corresponding section in Sect. 5.1.2 on infrared spectroscopy.
46 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.10. Reflectivity I out /I in as a function of the angle of incidence θ calculated for ε p =
3.4036 and εp = 1.778 (based on data in [64])

Fig. 5.11. Intensity enhancement I s /I in at the interface (z = 0) as a function of the angle of

incidence θ (based on data in [64])

Fig. 5.12. Spectroelectrochemical ATR cell for in situ UV-Vis spectroelectrochemistry [65]

a prism that couples the light into the ATR element. A second prism guides the light
into an optical fiber connected to the spectrometer.
Spectral information is gathered from species within the range of the evanes-
cent wave penetration length at the ITO-solution interface. The reported cell design

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 5.1 Optical Spectroscopy in the Visible Range 47

allows measurements with polarized light. Results reported so far deal with neu-
tral copper phthalocyanine bilayers [65]. The use of colloidal gold nanoparticles
deposited onto ITO as a working electrode has been described [65].

5.1.4 Luminescence Spectroscopy

Fundamental. Luminescence is the emission of electromagnetic radiation, partic-

ularly light in the visible range of the electromagnetic spectrum, which is effected
by a supply of energy. Numerous forms of luminescence caused by a host of dif-
ferent forms of energy have been observed. Chemiluminescence is the emission of
light by energetically excited species formed in the course of a chemical reaction.
For example, the reacting species may be radicals generated by electrolysis [66].
In this case it may be called more specifically electrochemiluminescence (ECL).
Photoluminescence is caused by the absorption of light, see Sect. 5.1.6. When the
emission of light (luminescence) follows rapidly after absorption, the phenomenon
is generally called fluorescence [67] (see p. 48). Delayed emission is called phos-
phorescence. An introduction to the luminescent properties of semiconductors in
contact with electrolyte solutions has been provided elsewhere [68].
Instrumentation. A cell design employing reticulated vitreous carbon as the work-
ing electrode material that enables both UV-Vis absorption and luminescence mea-
surements has been described [47]. A thin-layer cell with a platinum working elec-
trode has been developed [69]. The luminescence of the electrooxidation products
of o-tolidine as a function of electrode potential was studied. A simplified flow cell
design has been reported [70]. Luminescence spectra and fluorescence intensity6 for
various aromatic compounds and their electrochemical and photochemical reaction
products were observed as a function of flow rate, current and time after the poten-
tial step. In the latter study the electrooxidation of p-phenylenediamine (PPD) was
examined. The cyclic voltammogram showed two oxidation peaks; the first one is
assumed to be caused by the formation of the radical cation according to

PPD → PPD+ + e−

Upon excitation with light of about λ = 245 nm, a luminescence peak of the
parent compound at λ = 391 nm (trace (a) in Fig. 5.13) was observed. During
electrooxidation a different spectrum with a peak around λ = 342 nm (trace (b) in
Fig. 5.13) was seen. The latter spectrum was initially assigned to the radical cation,
but no agreement between experimental data and this assumption could be reached.
In a second step it was assigned to the dication formed according to

PPD+ → PPD2+ + e−

This assumption was discarded when experiments with an electrode potential

beyond the second voltammetric oxidation peak where the dication is generated
6 The terms fluorescence and luminescence are unfortunately somewhat mixed up in this
report.
48 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.13. Luminescence spectra of a solution of 0.777 mM p-phenylenediamine in ace-

tonitrile with 0.1 M tetra-n-butylammonium perchlorate; (a): no electrode potential applied;
(b): electrode potential positive to the voltammetric peak where the radical cation is generated
applied (based on data in [71])

directly via electrooxidation yielded essentially the same spectrum. Based on evi-
dence obtained from literature, the spectrum was finally assigned to a dimeric cation
species formed according to

2PPD+  (PPD+ )2

The photoelectrooxidation of bis(benzylidene)acenaphthene has been studied by

Compton et al. [71] using the cell described above [71]; a highly fluorescent product
was identified.
Photoluminescence data of numerous semiconductors in contact with various
electrolyte solutions have been reviewed [69].
Luminescence generated by chemical reactions [chemiluminescence (CL)] that,
in turn, are initiated by electrogenerated species [electrogenerated chemilumines-
cence (ECL)] has also been studied in simple setups, including flow cells. Reported
examples include ECL of acridinium esters reacting with peroxide formed upon
reduction of dissolved dioxygen in solution [72]. Electrogenerated chemilumines-
cence may simply be used to report the rate of electrochemical reactions. As an al-
ternative, the use of light-emitting diodes suitably coupled to the working or counter
electrode to measure electrochemical activity without the need to make actual cur-
rent measurements [73] has been proposed.

5.1.5 Fluorescence Spectroscopy

Fundamentals. Fluorescence is the spontaneous emission of light after excitation

of a species with light (see also p. 47). Fluorescence spectra of molecules provide
valuable information about structural features [74].

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 5.1 Optical Spectroscopy in the Visible Range 49

Instrumentation. A universal cell design also useful here has been reported [75,
45]. It is similar to the cell design previously described by Salbeck [76]. The disc-
shaped electrode under investigation, which is embedded in an inert sheath, is situ-
ated closely behind an optically transparent window. Its surface and the electrolyte
solution volume immediately in front of the electrode are illuminated with exciting
light from a monochrome source using a fiber optic cable at an angle of approx. 45◦ .
Fluorescence is detected with a second fiber optic cable mounted perpendicularly in
front of the window and connected to a fluorometer. The feasibility of fluorescence
spectroelectrochemistry has been demonstrated using perylene dipentylimide [76]:

In its neutral state the molecule shows strong fluorescence with bands at 425,
480 and 520 nm when excited with light of λ0 = 480 nm. Cyclic voltammetry
showed two reversible one-electron reduction processes (Fig. 5.14).
The fluorescence of the molecule disappeared during the first reduction process;
this could not be evidenced at the low concentration of the reactand with UV-
Vis absorption spectroscopy. The potential-dependent fluorescence of various 5-
substituted indole trimer films has been investigated [77].

Fig. 5.14. Cyclic voltammogram and fluorescence intensity plotted vs. time of perylene
dipentylimide at 0.1 mM concentration in a solution of 0.5 M TBAHP in methylene chlo-
ride (based on data in [76])
50 5 Spectroscopy at Electrochemical Interfaces

Potential-modulated fluorescence spectroscopy at liquid/liquid interfaces

between immiscible liquids has been reported and a cell design has been provided
[78]. The dependence of the adsorption of the free, bare or the water-soluble por-
phyrins at the polarized water/1,2-dichloroethane interface has been studied [79].
Observed spectral differences suggest a solvation structure at the interface that is
different from that inside the bulk of the respective solution phases. For further
studies with related porphyrins at the same interface, see [79]. Details of the transfer
mechanism of the rose bengal dianion across the water/1,2-dichloroethane interface
have been elucidated [80].

5.1.6 Electroreflectance Spectroscopy7 (ERS)

Fundamentals. Beyond probing species that are more or less strongly absorbing in
solution or that are adsorbed/attached to the electrode surface UV-Vis spectroscopy
can be used to study electrooptical properties of the electrode material itself. (For
a thorough introduction, see [81–83]; the fundamentals have been introduced else-
where [84, 85].) The complex refractive index of a medium containing its refractive
index and its extinction coefficient can be used in good approximation to describe
the wavelength-dependent response of a medium to an impinging beam of elec-
tromagnetic radiation. Further consideration of the complex refractive index leads
to the complex dielectric function. Contributions from free and bound electrons as
well as from plasmon excitations result in frequency dependencies of the real and
the imaginary part of the dielectric constant typical for any given material. The re-
flectivity of an interface can be calculated using Fresnel’s equations. With polarized
light (as most commonly used in this type of spectroscopy), the reflectivities for
light polarized perpendicular or parallel to the plane of incidence are characteristi-
cally different depending again on the wavelength. They can be derived by taking
into account the strength of the electric field vectors of the incoming and the re-
flected beam at the reflecting interface for various angles. In the infrared region,
most metals are almost perfect reflectors; only parallel polarized light will interact
with species attached to the metal surface (for surface selection rules, see Sect. 5.2).
Because of the more complicated situation in the UV-Vis-range, interaction (i.e.
absorption) between light and species at the interface may occur even at normal in-
cidence. As already pointed out before, the interface solution/electrode is actually
composed of three phases:
1. The bulk solution
2. The bulk electrode
3. The interphase
Thus a complete description of the system under study has to take into account prop-
erties of these three phases. Optical properties of the interphase can be obtained from
measurements of the reflectivity as a function of wavelength; with systems showing
no pronounced interphase, the optical properties of the metal can be studied.
7 Initially, this method was called the electrolyte electro reflectance (EER) technique.

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 5.1 Optical Spectroscopy in the Visible Range 51

Instrumentation. The measurement of absolute reflectance values for a given in-

terface is difficult because numerous contributions of components in the optical
beam path will contribute. It is more convenient to measure relative changes of
reflectivity ΔR/R as a function of wavelength (or energy). This result is directly
related to ΔI /I , with I being the intensity of light. Typical values of ΔR/R are
10−1 to 10−5 . The change in reflectivity (i.e. in intensity) has to be effected by
some well-defined electrochemical manipulation. Most frequently this is a modula-
tion of the electrode potential. Combined with lock-in amplification, the necessary
signal-to-noise ratio can be obtained. Measurements in a range of electrode poten-
tials wherein no faradaic reactions occur and the change in reflectivity is assumed to
be caused directly by the change of the modulated electrode potential are called elec-
troreflectance spectroscopy (ERS). The experimental setup includes a light source
(frequently a xenon lamp) coupled with a monochromator and a polarizer. The light
is guided to the interface under investigation at a selected angle of incidence; the
reflected light is detected by a photomultiplier. The signal from the photomultiplier
is processed using the lock-in amplifier, yielding the desired electroreflectance spec-
trum (for a typical setup, see [86]).
The design of spectroelectrochemical cells is strongly simplified by the fact that
the most commonly used electrolyte solutions are highly transparent in the UV-Vis
range. Cells with the working electrode placed in the center of a cylindrical cell body
provide perfect electrochemical response; the use of bent quartz windows permits
investigations at various angles of incidence by just rotating the cell. Measurements
with single crystal electrodes in the dipping (hanging meniscus) technique are also
possible. Typical examples are shown in Fig. 5.15 and a review of experimental
setups is available [84].
The spectral range accessible for measurements is limited by the transmission
properties of the electrolyte solution and the optical components, the intensity dis-
tribution of the used light source and the spectral sensitivity of the detector to values
of about 220 < λ < 1400 nm.
The broad variety of investigated systems includes single- and polycrystalline
metal electrodes (for an overview, see [84]), adlayers of metal atoms, ions and mole-
cular species and films like metal oxides of nanometric thickness. Overviews of
studies of anodic oxides (including corrosion, passivation and electrochromic lay-
ers) on various metals have been provided [84, 87]. Thick corrosion layers on 304
stainless steel have been investigated [88]. Polarization anisotropy with a polycrys-
talline gold electrode was observed by Zhao et al. [89] and data pertaining to a
Ag(110) electrode surface have been presented and reviewed in a broader context
by Furtak and Lynch [90, 91]. Semiconductor/electrolyte solution interfaces have
been studied by Shaklee et al. [92]. In a study of the n-GaAs/electrolyte solution
interface, changes in the potential distribution in the semiconductor depletion layer
were identified [93]. The possible advantages of a simultaneous (double beam) ap-
plication of electroreflectance spectroscopy and second harmonic generation have
been pointed out [94].
52 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.15. Schematics of spectroelectrochemical cells for electroreflectance spectroscopy.

Top: Arrangement for measurements at various angles of incidence; bottom: Cell for mea-
surement with electrodes in the dipping technique

Fig. 5.16. Normal incidence electroreflectance spectra of two reconstructed Au(100) surfaces
in contact with a solution of 0.01 M HClO4 , potential step from E SCE = −0.2 V to 0.3 V
(based on data in [98])

The optical properties of a Au(100) surface in its reconstructed state differ

markedly because of the participation of electronic surface states in the optical ex-
citation; these states depend on the crystallographic surface structure [95]. Surface
band structure calculations have revealed the existence of empty surface states [96].
These surface states can be shifted in their energy by the electrode potential (Stark
shift) [97]. Optical transitions into these states thus become potential dependent.
In Fig. 5.16 the electroreflectance spectrum of the Au(100)–(1 × 1) surface
shows two derivative-like features around 3 and 4.2 eV assigned to transitions from
the bulk d-band into the aforementioned unoccupied surface states [98]. These fea-

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 5.1 Optical Spectroscopy in the Visible Range 53

Fig. 5.17. Reflectance spectra of Ag(111) single crystal electrodes in contact with a solution
of 0.1 M KCl, potential step from E SCE = −0.2 V, reference spectrum recorded before
oxidation-reduction cycle (based on data in [98])

tures are absent in the ER spectrum of a Au(100)–(5 × 20) surface. This difference
can be used to monitor structural transitions between these reconstructions. The in-
fluence of the surface anisotropy of single crystal silver electrodes has been studied
with ERS [87]; for an introductory overview, see [84]. Since the electric field vector
of the impinging light is perpendicular to the (111) direction, the effect is twice as
large as that of the orientation parallel to this direction. A somewhat less metallic
character of the surface, when it is oriented in the former direction, can be deduced
from surface plasmon dispersion curves measured with an air gap.
Optical properties of gold nanorod arrays have been studied and were found to
be dominated by surface plasmon modes superimposed on interference effects [99].
The formation of a surface complex composed of molecules (e.g. pyridine or pyr-
azine) strongly bound to silver formed during oxidation-reduction electrode poten-
tial cycles is evident in ER spectra shown in Fig. 5.18. They show pronounced ab-
sorptions not found with the respective molecules in solution.
This approach works also with adsorption/desorption-induced changes of reflec-
tivity, provided the sorption kinetics are fast enough to follow the potential modula-
tion. In this case absorption features in the obtained spectra are attributed to changes
in coverage (no influence of the electrode potential is presumed). Precisely speaking,
these spectra should not be called electroreflectance spectra (see also [88] concern-
ing this classification).
The derivative-like feature around λ = 600 nm in Fig. 5.18 indicates an elec-
trode potential induced shift of this absorption.
54 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.18. Electroreflectance spectra of a Ag(111) single crystal electrode in contact with a
solution of 0.1 M KCl + 0.05 M pyrazine before (- - -) and after (——) oxidation-reduction
cycles, potential step from E SCE = −0.5 V to 0.0 V (based on data in [83])

Fig. 5.19. Electroreflectance spectra of a polycrystalline platinum electrode in contact with a

solution of 0.5 M Na2 SO4 + 5 × 10−5 M p-nitroaniline, E MSE = 440 mV, ΔE = 100 mV,
(based on data in [101])

The structure of the electrochemical double layer in the presence of adsorbed

molecules can be investigated with ERS.8 In a typical study, Schmidt and Pli-
eth [100] have investigated the adsorption of p-nitroaniline on a polycrystalline
platinum electrode from sulfuric acid solution. The ER spectrum as displayed in
Fig. 5.19 shows two distinct bands when light polarized parallel to the plane of re-
flection is used (with light polarized perpendicular, only a flat baseline was found).
8 This should not be confused with UV-Vis spectroscopy of dissolved species in the elec-
trolyte solution more or less close to the surface, but not necessarily adsorbed onto the surface,
as discussed above.

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 5.1 Optical Spectroscopy in the Visible Range 55

Fig. 5.20. Electroreflectance spectra of a Au(110) electrode in contact with an aqueous solu-
tion of 0.1 M NaClO4 and 10−3 M pyridine, potential modulation between E SCE = −0.3 V
and 0.1 V, modulation frequency 18 Hz (based on data in [102])

Peak 1 is assigned to the π → π ∗ transition of the adsorbed molecule, peak 2

is caused by intermolecular interactions in the adsorbate layer. A perpendicular ori-
entation of the molecule with the nitro-group interacting with the platinum surface
was concluded.
The adsorption of pyridine on a Au(110) electrode surface has been studied
with ERS [101]. Spectra obtained in the absence and in the presence of pyridine
in solution show marked differences (see Fig. 5.20). The electrode potential was
modulated between two values (E SCE = −0.3 V and 0.1 V) where the coverage
was constant (i.e. in the flat range of the adsorption isotherm). Thus the ER spectra
do not show any coverage effect; rather, they show only electrode potential induced
changes of the adsorbate layer. In the absence of pyridine, a rather flat spectrum
is obtained. With pyridine in solution, the spectrum shows a derivative-like feature
around 257 nm and a further absorption around 197 nm collides with the onset of
water absorption.
Both bands are caused by electronic transitions (absorptions) of pyridine. The
derivative-like structure indicates a small electrode potential induced shift of the
transition energy assigned to a Stark effect. From the polarity of the lobes (when go-
ing from longer to shorter wavelength: first an increase, then a decrease in reflectiv-
ity) a redshift can be concluded. The orientation of pyridine adsorbed on a Au(110)
electrode surface has been deduced from ER spectra measured subsequently with
light of p- and s-polarization (see Fig. 5.21) [102]. When the plane of polarization
is switched from p to s the band at 257 nm shows a dramatic increase. This band is
z-polarized and is associated with the molecular dipole moment along the molecular
axis intersecting the nitrogen atom and the p-C atom. Consequently, the molecule
is adsorbed in a perpendicular orientation as already tentatively deduced from the
comparison of spectra obtained with p-polarized light in the presence/absence of
56 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.21. Electroreflectance spectra of a Au(110) electrode in contact with an aqueous solu-
tion of 0.1 M NaClO4 and 10−3 M pyridine, potential modulation between E SCE = −0.3 V
and 0.1 V, modulation frequency 18 Hz (based on data in [102])

Fig. 5.22. Electroreflectance spectra of a polycrystalline gold electrode in contact with a

buffer solution; A and B: absorption spectra of MBred ; C: after electrode transferred from
MB-containing solution into solution without MB, EAg/AgCl = −190 mV, ΔE = 80 mV;
(based on data in [104])

pyridine in solution (see p. 55). A similar study pertaining to the Au(100) surface
has been reported [102].
In a study of the redox spectroelectrochemistry of methylene blue (MB),9 ER
spectra as displayed in Fig. 5.22 were recorded [103].
The bipolar structure of the ER spectrum (A) cannot be explained by considering
the optical absorption of MV in its reduced and oxidized forms. The reduced form
(leuco-MB) is colorless. The spectrum displayed in Fig. 5.22 (trace B) shows only
a single-sided band attributed to the oxidized form MBox . Thus the ER spectrum A
is not caused simply by species in solution phase in front of the electrode. This as-
sumption is confirmed in spectrum C, which was obtained after transfer of the gold
electrode from the MB-containing solution into a solution containing no MB. The
observation of an ER spectrum implies that irreversibly adsorbed MB is still present
9 MB = 3,7-bis(dimethylamino)phenothiazin-5-ium chloride.

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 5.1 Optical Spectroscopy in the Visible Range 57

on the gold surface and its surface state differs from the state in the presence of MB
in solution as indicated by the changes in the observed ER spectra A and C. Re-
dox properties of polypyrrole-modified electrodes doped with metalloporphyrines
have been studied [104]. Results permitted the localization of the proceeding re-
dox process and determination of their redox potential. Gold nanorods embedded
in a porous alumina matrix have been investigated with simple reflectance measure-
ments and ERS [105]. Depending on the plane of polarization of the incident light,
the transverse or both the transverse and the longitudinal plasmon mode could be
identified.
With slow kinetics of the involved processes or with interfaces where electrode
potential modulation might be detrimental because of crystallographic changes in
the metal surface, other spectroscopic techniques have to be used. The whole spec-
trum of interest can be scanned or registered within a few milliseconds with a rapid
scan spectrometer or a multichannel (diode array) spectrometer. Repeated acquisi-
tion provides the required signal-to-noise ratio. After a potential step, the acquisition
is repeated and spectral calculation yields ΔR/R. This single potential step proce-
dure allows investigation of systems where repeated potential modulation has failed.
Using pyrolytically prepared graphite films, the intercalation of Li+ and K+ has
been monitored with ERS [106]. For a review on ERS, see also [107].

5.1.7 Diffuse Reflectance Spectroscopy

Fundamentals. Measurement of the radiation diffusively (i.e. not specularly) re-
flected from a surface as a function of wavelength results in a diffuse reflectance
spectrum. This method is applied frequently in the various ranges of the electro-
magnetic spectrum for investigations of powders or other poorly reflecting sub-
stances (see also Sect. 5.1.2). Combining a fiber optics spectrometer with an op-
tical microscope, this method can be applied to spectroelectrochemical investiga-
tions of small amounts of electrochemically active colored materials deposited on
a soft electrode surface by mechanical embedding (abrasive stripping voltamme-
try technique) [108]. Results will be displayed as Kubelka–Munk functions of the
wavelength.
Instrumentation. A suitable electrochemical cell is displayed in Fig. 5.23. The
material to be investigated is embedded in the front surface of the working electrode
(e.g. a soft graphite electrode). Visual inspection of the surface is feasible via an op-
tical microscope attached to the cell bottom via a transparent window. Illumination
of the surface is affected by a halogen lamp incorporated in the microscope. The
working electrode is connected to a potentiostat, counter and reference electrode,
yielding the standard three-electrode arrangement. The fiber optics spectrometer is
also coupled with the microscope and great care must be exercised in order to keep
specularly reflected light from the microscope illumination lamp from entering the
spectrometer.
Figure 5.24 shows the Kubelka–Munk function of silver octacyanomolybdate(IV)
and (V). Upon oxidation of the molybdenum ion, a silver ion is released into solu-
tion and the optical absorption of the solid compound increases drastically [110].
58 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.23. Spectroelectrochemical cell for diffuse reflectance spectroscopy [109]

Fig. 5.24. Kubelka–Munk function of silver octacyanomolybdate(IV) and (V) immobilized

on a graphite electrode in contact with an aqueous solution of 0.1 M AgNO3 [110]

The change of the oxidation state of the central ion can be effected electrochem-
ically, as evident in the cyclic voltammogram displayed in Fig. 5.25. The corre-
sponding change of reflectance indicating the change of the Mo(IV) complex into
the Mo(V) complex is included, too.
The considerable hysteresis between the reflectance values recorded in the ca-
thodic- and anodic-going scans already implies more complicated features of the
ongoing process beyond a mere change of the state of oxidation. Displaying the
first derivative thus provides further information about kinetics and topology of the
electrochemical processes.

5.1.8 Reflection Anisotropy Spectroscopy10

Fundamentals. When the reflectivity at normal or near normal incidence is mea-
sured relative to various crystallographic directions, anisotropies may be observed.
10 This method is sometimes called reflectance difference spectroscopy (RDS) and, because
of considerable overlap, this method is sometimes also considered to be a variation of
electroreflectance spectroscopy (see p. 50 for further details).

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 5.1 Optical Spectroscopy in the Visible Range 59

Fig. 5.25. Cyclic voltammogram of silver octacyanomolybdate(IV) and (V) immobilized on

a graphite electrode in contact with an aqueous solution of 0.1 M AgNO3 at a scan rate of
1 mV/s; change of the reflectance at λ = 550 nm (dotted line) [110]

For a bulk isotropic crystal, this reflects anisotropies of the surface optical response.
Various theories and models describing the physical fundamentals of this observa-
tion have been reported; for an overview, see [110]. For a silver single crystal, a
simple explanation was proposed [111] for the differences between the dispersion
relations of surface plasmons on different crystal faces and along the two principal
symmetry directions on Ag(110). A relationship between the energy of the surface
plasmon and the packing of silver atoms was found. This was explained by assum-
ing that the free electrons have a smaller optical effective mass along the denser
surfaces. This is closely related to different free-electron conductivities along the
crystallographic orientations. Based on a simple examination, this explanation was
found to be insufficient [111]. Further developments, including interband and intra-
band electronic transitions [112, 113], have been described [111].
Instrumentation. An RDS setup (as commercially supplied [111, 114]) is equiva-
lent to a normal incidence ellipsometer. It directly delivers the real and the imaginary
parts (or their ratio) of r11̄0 and r001 . These are the complex reflectances along the
respective crystallographic directions.
Results are displayed as
   
Δr r1 − r2
Re = Re
r r

with the indices referring to orientation of the light detection with respect to crys-
tallographic orientation. Sometimes the real and the imaginary parts are displayed
separately.
Various possible optical configurations have been compared elsewhere [115].
In order to record reflectance-difference spectra beyond a light source (e.g. a Xe
60 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.26. Reflectance anisotropy spectrum of a Au(110) surface in contact with an aqueous
solution of 0.1 M Na2 SO4 at EAg/AgCl = 0.6 V (based on data in [119])

lamp), a monochromator (if wavelength dependencies are to be studied), a detector

(a photomultiplier), a polarizer and a photoelastic modulator or a rotating polarizer
are needed [116]. A multichannel spectrometer design-enabling rapid acquisition of
RA spectra has been described [117].
RA spectra obtained with a Au(110) surface exposed to an aqueous solution of
0.1 M Na2 SO4 [118] are displayed in Fig. 5.26.
At the applied electrode potential, the gold surface shows the 1 × 1 arrangement.
The observed features around 2.5, 2.8, 3.5 and 4.5 eV have been assigned to inter-
band transitions from the filled d-band into empty states above the Fermi level; for
further details, see [119].
Further results reported so far deal with surface reconstruction [119], metal de-
position [118, 120] and adsorbate layers (including molecular orientation) [121].
The electrochemical oxidation of a Au(110) surface has been studied with RAS
[122]. Evidence for surface oxidation and adsorption of hydroxyl ions was obtained
and both processes destroy surface states of the Au(110)(1 × 2) in a reversible man-
ner. No significant kinetic barriers for any of these processes were found.

5.1.9 Photoacoustic Spectroscopy11 (PAS)

Fundamentals. Illumination of a surface with electromagnetic radiation will result

in absorption of this radiation provided the surface is capable of interacting with
the radiation in a way that results in absorption of energy. Recording the absorption
as a function of the wavelength of the incident radiation will provide an absorption
spectrum that, in turn, may yield information about structural, electrooptical or other
properties of the surface and of regions of the material close to the surface. When
light in the visible range of the electromagnetic spectrum is used, the spectrum will
give information about optical transitions of species adsorbed on the surface or opti-
cal transitions in surface layers (e.g. in semiconducting oxide layers). Measuring the
11 See also Sect. 5.9.4, p. 190.

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 5.1 Optical Spectroscopy in the Visible Range 61

Fig. 5.27. Principle of photoacoustic spectroscopy according to [123]

amount of absorbed radiation can be accomplished in various fashions. In various

techniques that employ reflection or attenuated total reflection setups, the intensity
of the light before and after the interaction is measured. These techniques cannot be
used with rough or dull surfaces because these surfaces tend to scatter the incident
radiation in a diffuse way. With these surfaces, photoacoustic detection will provide
the required information, as already established in infrared spectroscopy (see also
Sect. 5.1.9, p. 60).
Instrumentation. The light of a Xe-lamp is passed through a monochromator and
a mechanical chopper. Part of the monochromatic light is directed towards a carbon
black sample fitted with a microphone that serves as a reference sample.
The other part of the radiation passes the beamsplitter and enters the electro-
chemical cell via a quartz glass window. The electrode surface to be investigated
is mounted close to the window in order to minimize absorption of radiation in the
electrolyte solution. The electrode and the microphone head enclose a small gas vol-
ume. Changes in the pressure of the enclosed gas, which is affected by absorption
of electromagnetic radiation that is converted into thermal energy, are detected by
this microphone. Since detection of the absorption proceeds on the back side of the
investigated surface in a manner contrary to that employed with conventional pho-
toacoustic spectroscopy, the applicability of this mode had to be checked. This was
done successfully by Vallet et al. [124]. The signal of both microphones was passed
via a lock-in amplifier and displayed as a function of incident light wavelength. In
a simplified setup, a piezoelectric detector was used instead of a microphone [124].
In this arrangement, the electrode material under investigation was glued directly
onto the piezoelectric detector. As an example, the photoacoustic response obtained
during electroreduction of diheptyl viologen (DHV2+ ) at a platinum electrode in an
aqueous solution of 0.3 M KBr is shown in Fig. 5.28.
Upon reduction of DHV2+ a deeply colored film of the salt DHVBr is formed on
the electrode surface. This becomes clearly evident in the photoacoustic spectrum,
when the electrode potential is switched from an initial value positive to the reduc-
tion potential to a value negative of the reduction potential. The recorded spectrum
was found to be in good agreement with spectra of HVBr films previously recorded.
For further details, see [125].
62 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.28. Piezoelectric signal of a platinum electrode in contact with an aqueous solution of
10−2 M DHV2+ and 0.3 M KBr at an electrode potential positive (1) and negative (2) to the
reduction potential (based on data in [125])

5.1.10 Photothermal Spectroscopy (PTS)

Fundamentals. As already described in the preceding section (p. 23), absorption

of electromagnetic radiation that illuminates an electrode surface by a surface layer
or in particular by adsorbates on the electrode surface can result in thermal effects.
These can be detected by various means as described below.
Instrumentation. A rather simple approach is the measurement of the temperature
change of the investigated electrode. Using a differential thermistor setup, this was
accomplished in a very simple fashion by Brilmyer and Bard [126]. Two identical
thermistors were used. One thermistor was glued to the backside of the working
electrode and the other was inserted into the electrolyte solution close to the work-
ing electrode but without thermal contact with the electrode. Both thermistors were
incorporated into differential amplifier circuits based on standard operational am-
plifiers. The output signal was passed through a lock-in amplifier connected to the
chopper and displayed as a function of incident light wavelength. As an example,
the photothermal spectrum of a film of DHVBr deposited by electroreduction on a
platinum electrode is displayed in Fig. 5.29.
It closely resembles corresponding spectra recorded with other methods, includ-
ing photoacoustic spectroscopy.
Measurements of the deflection of a light beam caused by local heating at the
solid/solution interface as a function of the wavelength of light illuminating this
interface are an alternative possibility; the resulting method is called photother-
mal deflection spectroscopy (PDS) [127, 128]. The experimental setup as depicted
in Fig. 5.30 closely resembles the arrangement for probe beam deflection studies
treated in Sect. 5.1.9.
Local heating of the electrode surface that is caused by the impinging mono-
chromatic light results in density gradients in the electrolyte solution in front of the

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 5.1 Optical Spectroscopy in the Visible Range 63

Fig. 5.29. Photothermal spectrum of a platinum electrode in contact with an aqueous solution
of DHV2+ at an electrode potential negative to the reduction potential [127]

Fig. 5.30. Probe beam deflection setup for photothermal spectroscopy [129]

electrode surface. A laser light beam passing close to the interface through this part
of the solution will be deflected (“mirage effect”). Its actual position can be detected
with a position sensitive detector. Recording the deflection as a function of the illu-
minating wavelength results in the desired absorption spectrum of the electrode sur-
face. Submonolayer studies of adsorbate layers on a platinum surface in contact with
a solution of perchloric acid [129] and on copper electrodes [129] as well as results
on photocorrosion of semiconductors [130] have been reported. A slightly modified
procedure known as differential photothermal deflection spectroscopy (DPDS) has
been suggested by Barbero et al. [131]. It is based on the acquisition of photother-
mal deflection spectra at two different states of the electrode/solution interface (e.g.
two different electrode potentials). Subsequent spectral ratioing results in spectra
independent of the intensity fluctuation of the employed lamp, spectral intensity dis-
tribution of the lamp, etc. Physical parameters of conducting polymer layers have
been studied with various types of photothermal spectroscopies [132].
64 5 Spectroscopy at Electrochemical Interfaces

5.1.11 Circular Dichroism (CD)

Fundamentals. Optically active molecules show different extinction coefficients
for circularly polarized light εL and ε R as a function of wavelength (circular dichro-
ism (CD) [133, 134]). The observed difference Δε = ε L − ε R is small compared to
the extinction coefficient ε—generally about Δε/ε ≤ 10−3 [135]. The name of the
effect derives from the fact that plane-polarized light becomes elliptically polarized
upon passage through a sample showing CD. Together with optical rotary dispersion
(ORD, anomalous dispersion), CD is grouped under the term “Cotton effect”.
Instrumentation. The standard optical device for transforming light into circularly
polarized light is a quarter-wave plate. Unfortunately this device produces the de-
sired kind of light only at a single wavelength—at all other wavelengths, elliptically
polarized light is produced. Circular dichroism spectroscopy became possible only
with the advent of the Pockels cell. Its optical properties can be adjusted properly
at every wavelength. More recently the Pockels cell has been replaced by photoe-
lastic modulators (PEM). With suitable crystals used as PEM, the accessible range
of wavelengths could be extended into the infrared; with synchrotron radiation, the
vacuum UV range can be studied.
A first spectroelectrochemical setup employing an optically transparent (ITO-
coated) electrode in a thin layer three-electrode arrangement was described by Daub
et al. [136–138]. Two ITO-coated glass sheets were mounted at a distance of 0.1 mm
at a PTFE body. This body was used as the head of an electrochemical glass cell. The
counter electrode, reference electrode and the purge gas inlet and outlet were also at-
tached to the cell head. The volume of electrolyte solution in the cell was adjusted to
maintain an upper level just reaching the lower edge of the two ITO-electrodes. Cap-
illary action sucked the solution into the tiny gap. The cell was placed in the beam
of an UV-Vis spectrometer with the ITO-electrodes positioned perpendicularly in
the beam. The CD spectroelectrochemistry of the optically active esters depicted in
Fig. 5.31 has been studied [139].
The electrochemical reduction proceeds via a radical anion, a subsequently
formed diradical dianion and a tetraanion formed after intramolecular rearrange-
ment. The CD spectra of the two enantiomeric forms of the diradical dianion, as
shown in Fig. 5.32, are distinctly different.

Fig. 5.31. The two forms of an optically active bianthraquinone ester

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 5.1 Optical Spectroscopy in the Visible Range 65

Fig. 5.32. Bottom: Conventional UV-Vis absorption spectrum of the (S)-(+)-diradical dian-
ion of the bianthraquinone ester (see Fig. 5.31). Top: CD spectrum of the (S)-(+)-diradical
dianion (—) and the (R)-(−)-diradical dianion (—) (based on data in [139])

No racemization was observed when the electrode potential was scanned only to
a value where the dianion is formed. Upon formation of the tetraanion, subsequent
chemical reactions were found. With a slightly different electrolyte salt (Me4 NBF4
instead of Bu4 NF6 ), reversibility without racemization was found even up to the
tetraanion formation. Further examples include the spectroelectrochemistry of vi-
tamin D2 [139], which has been studied with a long pathlength cell similar to the
design described by Zak et al. [44]. Optical rotary dispersion and CD of optically
active polybithiophene that has been electropolymerized in a cholesteric electrolyte
have been studied [140]. The optical rotation of this chiral polymer could be con-
trolled via the electrode potential.

5.1.12 Near Infrared Spectroscopy

Fundamentals: Besides optical absorption in the UV-Vis region of the electromag-

netic spectrum, absorption in the near infrared region can be employed to study
electrochemical processes. This part of the electromagnetic spectrum12 between ca.
900 nm and 3000 nm (10000 cm−1 to 3333 cm−1 ) shows predominant overtone
bands of electronic absorptions already seen in the UV-Vis region. In addition, ab-
sorptions caused by mobile charge carriers are seen [26, 27]. Thus, this part of the
spectrum has not attracted much attention. Investigations of intrinsically conduct-
ing polymers and transition metal complexes showing large absorptions in the NIR
12 The actual limits, particularly the lower wavelength one, seem to be subject to arbitrary

definition. Spectra showing absorptions around 12000 cm−1 have been designated NIR spec-
tra, whereas sometimes the range from 4000 cm−1 to 14000 cm−1 has been called NIR.
66 5 Spectroscopy at Electrochemical Interfaces

because of intramolecular charge transfers have caused an increased interest in NIR

spectroelectrochemistry. For an introductory overview see [141, 142].
Instrumentation. Numerous spectrometers for the NIR range are basically either
UV-Vis or infrared spectrometers with suitable additional optics and light sources.
They come with two-beam arrangements or single beam setups with internal sample
chambers or with fiber optics used for coupling the spectrometer with a cuvet, i.e.
a spectroelectrochemical cell. Depending on the type of instrument and the spec-
tral range actually to be investigated, optical components and materials used in the
construction of the spectroelectrochemical cell have to be selected. For investiga-
tions extending only slightly into the NIR range with an electrolyte solution con-
taining only weakly absorbing solvents, most components (i.e. cuvets and optically
transparent electrodes) as used with in situ UV-Vis spectroelectrochemistry can be
used. Optics made of fused silica with a low hydroxyl group content will cause no
significant optical absorption. An overview of the NIR absorption of common sol-
vents used in spectroelectrochemical investigations in this spectral range is shown
in Figs. 5.33–5.35.

Fig. 5.33. NIR transmission spectrum of propylene carbonate

Fig. 5.34. NIR transmission spectrum of acetonitrile

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 5.1 Optical Spectroscopy in the Visible Range 67

Fig. 5.35. NIR transmission spectrum of water

Fig. 5.36. NIR transmission of various fused silica fibers

A cell suitable for measurements at low temperatures that employs a platinum

gauze working electrode inside a cuvet that is used as a cell with counter and ref-
erence electrode placed in a tubular extension on top of the cuvet has been de-
scribed [143]. Measurements extending up to the limit of a lead sulfide detector (i.e.
3000 nm) require particularly careful selection of materials and cell design. Because
of the strong and very pronounced optical absorption of glass fibers used in the UV-
Vis and lower NIR range, these fibers are not suitable for investigations at higher
wavelengths. Figure 5.36 provides information on the optical transparency of typi-
cal fibers with very low (UV-Vis–NIR fiber) and slightly higher hydroxyl (UV-Vis
fiber) content. Near infrared spectrometers with fiber optics allow a simpler experi-
mental setup.
The absorption of commonly used solvents in this spectral range requires the
use of thin layer cells in order to avoid spectra with poor signal-to-noise ratios.
68 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.37. NIR-transmission of standard glass and ITO-coated glass; top: reference air; bot-
tom: reference glass; 1, 2 and 3: different coating conditions, resulting layer thickness, con-
ductivity, etc.

The design described above for use with UV-Vis spectroelectrochemistry can be
used here provided that both the glass used as cell window (cuvet) and the ITO-
coated glass have sufficiently low NIR absorption. As shown in Fig. 5.37, the optical
absorption of ITO-coated glass shows some major bands where the signal-to-noise
ratio might be worse than in other parts of the spectrum.
Highly absorbing electrolyte solutions require thin layer arrangements. In the
simplest setup, two glass sheets (one of which is coated with ITO and is slightly
longer) are clamped together with narrow PTFE strips acting as spacers at the edges.
The bottom edge of the assembly is immersed into the electrolyte solution. Most so-
lutions will penetrate into the gap because of capillary action. A more sophisticated
setup, including a cell body and provisions for reference and counter electrode, is
depicted in Fig. 5.38.
A setup suitable for work with highly reflective solid electrodes (e.g. platinum,
gold or glassy carbon discs) has been described by Salbeck [145]. As shown in the
cross section in Fig. 5.39, the polished electrode surface is mounted close to the
NIR-transparent cell bottom, leaving only a thin layer of electrolyte solution in the
narrow gap. Connection to the NIR spectrometer is accomplished with a fiber optic

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 5.1 Optical Spectroscopy in the Visible Range 69

Fig. 5.38. Thin layer cell for NIR spectroelectrochemistry in the transmission mode according
to [142, 144]

Fig. 5.39. Thin layer cell for NIR spectroelectrochemistry in the external reflection mode
according to [145]

cable containing bundled cables that extend from the light source to the detector.
The light coming via one fiber from the source passes through the window and the
solution. It is externally reflected at the electrode surface back into the fiber that
leads to the detector. The cell can be thermostatted down to −40°C and it shows
both thin layer and semi-infinite diffusion behavior.
Investigated systems include a broad variety of dissolved organometallic species,
electrochemically active organic molecules and redox active polymers like polyani-
line (for a review, see [142]). Both dissolved species and species attached by ad-
sorption, covalent bonding or film-forming deposition have been studied. Dissolved
polyaniline dispersions as prepared by chemical oxidation [145] show various tran-
sitions in the NIR, as depicted in a set of NIR spectra in Fig. 5.40. The bands around
λ = 1490 nm and 1950 nm are overtones of the N–H stretch mode of an aromatic
amine, whereas the band around λ = 2300 nm is caused by the oligomer itself,
which presumably indicates the presence of mobile charge carriers.
NIR spectra of polyaniline films (see Fig. 5.41) that are deposited on optically
transparent ITO-coated glass sheets and recorded in the same spectral range show
70 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.40. NIR spectra of a polyaniline dispersion prepared with various concentrations of
aniline (dispersion prepared according to [146]; for further details, see [146])

Fig. 5.41. NIR spectra of a polyaniline film in a solution of 0.5 M sulfuric acid at E RHE = 1 V
at various times of electropolymerization (for further details, see [147])

similar features. Depending on the reference (or background) spectrum, the ob-
served features can be assigned to the film and its changes (with the film in the
spectroelectrochemical cell at a fixed electrode potential taken as a reference), to
the growing film (with a spectroelectrochemical cell filled with supporting elec-
trolyte solution that contains the monomer) or to the aniline in the system being
present as dissolved monomer or as a building block in the polymer film (with a
spectroelectrochemical cell that is only filled with supporting electrolyte solution).
The bands discussed above are again present, although very weak. A distinction
between absorption caused by the aniline in solution and the aniline in the polymer is
impossible. With the electrolyte solution containing the monomer as a background,
a different result is observed.
The broad absorption already seen above is present again, implying that it must
be caused by species in the film. These are most likely mobile charge carriers (for a
detailed discussion, see [147]).

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 5.2 Optical Spectroscopy in the Infrared Range 71

Fig. 5.42. NIR spectra of a polyaniline film in a solution of 0.5 M sulfuric acid and 1 M aniline
at E RHE = 1 V at various times of electropolymerization (for further details, see [147])

5.2 Optical Spectroscopy in the Infrared Range

Rotational and vibrational modes of molecules and polyatomic ions are probed
with infrared and Raman spectroscopy. Energies needed to promote a species into
a higher vibrational or rotational state are generally in the mid-infrared (approx.
400–4000 cm−1 ) and in the far infrared (10–400 cm−1 ). Transitions can be stud-
ied by supplying the needed energy and measuring the absorption by the species
under study; this is done with infrared absorption spectroscopy. Alternatively, the
species under investigation can be exposed to monochromatic light. The inelasti-
cally scattered light is shifted in wavelength (Stokes and anti-Stokes shift) and the
shift again yields the desired information about the energies of rotational and vibra-
tional transitions. Although this method, known as Raman spectroscopy, works with
light in the visible or NIR range, it is nevertheless treated in this chapter because the
results provide information about rotational and vibrational properties of species at
the interface under investigation. Furthermore, both spectroscopies can be employed
in a complementary manner, i.e. results of one spectroscopy can be enhanced and
complemented (e.g. with respect to the accessible range of wavelength or the ob-
served vibrational modes that might show up with one spectroscopy only because
of symmetry reasons) by the other one. In addition, results of one spectroscopy
can be used to support and confirm data obtained with the other one. This com-
plementary approach is also expressed in monographs treating both spectroscopies
almost simultaneously [147]. A general overview of symmetry, selection rules and
nomenclature in various surface spectroscopies has been provided by Bradshaw and
Richardson [148].
Beyond intramolecular modes of species present in the electrolyte solution or in-
teracting with an electrode surface, modes caused by adsorptive interaction between
the adsorbed species and the electrode surface can be studied (e.g. the silver-halide
stretching mode with surface enhanced Raman spectroscopy (SERS); for details,
72 5 Spectroscopy at Electrochemical Interfaces

see p. 104). These modes that appear mostly at fairly low wavenumbers provide
particularly useful information about mode and strength of interaction.
Fundamentals, applications and experimental details of both infrared and Ra-
man spectroscopy are treated in numerous textbooks and handbooks [149–157];
thus only a few general details of these spectroscopies, which are of particular im-
portance for applications in electrochemistry, are treated here.
Infrared spectroscopy, as applied in numerous different experimental setups for
electrochemical investigations, is at first glance seriously hampered by the fact that
most electrolyte systems (including both the solvent and the dissolved supporting
electrolyte) tend to absorb infrared radiation strongly. Thus the detection of absorp-
tion of radiation of species present in an adsorbate layer or dissolved in this elec-
trolyte solution is difficult. Various approaches have been described to overcome
this problem.
In thin layer cells similar to those used in UV-Vis spectroscopy, the absorp-
tion by the electrolyte solution is kept low by keeping the electrolyte volume that is
passed by the beam of light thin. Unfortunately this also limits the number of species
under investigation that can be probed by the light. Strongly absorbing species and
solvents with supporting electrolytes that show absorptions in a range of the spec-
trum far away from absorption bands of interest can nevertheless be studied suc-
cessfully.
Species adsorbed on surfaces can be probed with radiation in external or attenu-
ated total reflection mode. In the former mode, a beam of infrared light is directed at
the surface of interest. The reflected light is measured and attenuated by absorption
caused by the species under investigation. In an in situ study in the external reflection
mode, the light beam has to pass through the electrolyte solution in contact with the
surface under investigation and the window of the electrochemical cell; thus the light
also contains information about radiation absorption by these components. This in-
formation is mostly unwanted. Unfortunately even a very thin electrolyte solution
film and an almost completely transparent cell window will absorb more energy than
the rather small number of adsorbed species. This poses a problem in the detection
of only these absorptions. Modulation or differential techniques have to be applied.
Recording spectra with the electrode at different electrode potentials yields only
bands influenced by the electrode potential after spectral ratioing. All unwanted ab-
sorptions listed above are eliminated. A similar approach employs the surface selec-
tion rules, i.e. the differences in interaction between light of various types of polar-
ization with adsorbed species. Details of these methods are discussed below (p. 76).
With attenuated total reflection spectroscopy, the light absorption by the elec-
trolyte solution and the cell window is no obstacle. The probe beam enters a crystal
transparent for infrared light. It is directed to the outer surface of the crystal, which
is coated with a thin layer of the electrode material under investigation. The beam
is reflected, but a small part (the evanescent wave) penetrates the surface and thus
can probe species located immediately on the electrode surface. The returning beam
contains exactly this information. As discussed below (p. 91) in detail, this approach
shows also serious limitations.

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 5.2 Optical Spectroscopy in the Infrared Range 73

Spectrometers used for this investigation are in most cases commercial instru-
ments equipped with accessories for the desired mode of spectroscopy. Because of
the strong absorptions already mentioned, instruments with powerful light sources
and high optical throughput are preferred and sensitive detectors are desirable. Be-
sides commonly known infrared light sources, synchrotron radiation provides a
source of high intensity polarized light of variable frequency [158]. Both disper-
sive and Fourier transform instruments can be used. In the former case custom-built
spectrometers have been used in practically all reported studies, whereas in the latter
case mostly commercial instruments can be used after only minor adaptations.
The design of a spectroelectrochemical setup for in situ infrared studies and for
all methodologies described below is rather straightforward. The light provided by
a glowbar or a Nernst glower is collected and guided towards the electrochemical
cell. The transmitted or reflected light (depending on the method) is sent towards the
entrance slit of the monochromator. At the exit slit an infrared detector connected
to data processing electronics is positioned. In most cases, a chopper in the light
beam and a lock-in amplifier are used in combination to enhance the sensitivity of
the method when applying a modulation technique light; e.g. electrode potential
modulation. A typical experimental setup with computer-based data processing is
described in [159].
The use of a Fourier transform infrared (FTIR) spectrometer has provided a
completely different methodological approach to this spectroscopy [160, 161]. The
central component of any FTIR spectrometer is an interferometer. No dispersive
elements are used. Based on the construction, various advantages in comparison
with dispersive instruments are achieved:
• The Jacquinot advantage: Light from the source does not pass through a slit,
but only through a large circular hole (the Jacquinot stop) at the entrance of the
interferometer optics. Thus a much larger fraction of the light from the source is
used.
• The Felgett advantage:13 Light of all wavelengths emitted from the source is
passed through the spectrometer simultaneously and reaches the detector, re-
sulting in a much stronger signal. In a dispersive instrument, only light of the
selected wavelength reaches the detector. Thus, in the former case, the signal
level is way above the detector noise level.
• The Connes advantage: Because of the way data points (intensities) are mea-
sured at any given position of the moving mirror in the interferometer, superpo-
sition of two subsequently recorded interferograms (i.e. coaddition of measured
signals) is easily possible. This results in a greatly improved signal-to-noise ra-
tio.
Raman spectroscopy is not hampered by most of the problems described above.
Water, as the most frequently used electrolyte solvent, is a very weak Raman scat-
terer. Both incident light and scattered light are in the visible or NIR range, wherein
cell windows of common glass are transparent. Unfortunately the yield of scattered
13 This advantage is also called the multiplex advantage.
74 5 Spectroscopy at Electrochemical Interfaces

light is very low (10−6 ) [162] and this makes detection of Raman light a challeng-
ing task, even with liquid or solid samples in standard Raman spectroscopy. The
number of scatterers adsorbed on a metal surface is extremely small by comparison;
thus detection of light that is scattered by them seems to be almost impossible. En-
hancement of scattered intensity by surface effects outlined (p. 104) and significant
advances in detector and data processing technology allow detection of even very
weak scattered light [163, 164].
Localized vibrational spectra can be obtained with various microspectroscopic
setups that employ near field optics and other tools (see Sect. 7.3). Tunneling spec-
troscopy performed with a scanning tunneling microscopy can also be used (see
Sect. 7.2.11).
Electron energy loss spectroscopy (EELS) and high resolution electron energy
loss spectroscopy (HREELS) can also provide vibrational information of adsorbates
on surfaces [165]. Because these methods employ electrons instead of electromag-
netic radiation, surface selection rules (see p. 76) are not effective; this allows inves-
tigation of modes not observed with infrared spectroscopy. Unfortunately the use of
electrons both as probe and signal prevents in situ application. Studies of electrode
surfaces are feasible with these methods after emersion of the electrode from the
solution, but they have been reported only infrequently.

5.2.1 Infrared Transmission Spectroscopy with Thin Layer Cells

Fundamentals. Dissolved species formed or changed during electrochemical re-

actions that show infrared absorption can be studied in solution using a thin layer
cell that only has optically transparent components in the spectral range of inter-
est. By recording the spectral absorption at various electrode potentials or at time
intervals and subsequent spectra ratioing changes of infrared absorption and the
corresponding composition of solution as a function of electrode potential or time
can be identified. This method provides information about species in solution and
thus it is not surface sensitive. The same information can be obtained in an external
reflection setup operated in a non-surface sensitive manner (see p. 76).
Instrumentation. Construction materials that are optically transparent in the mid-
infrared range are limited to various salt crystals (KBr, NaCl, ZnSe, etc.) and semi-
conductors (Si, Ge). These materials have to be used as cell windows. Aqueous
electrolyte solutions are obviously unsuitable. Electrodes can be made of opaque
materials and, in this case, have to be placed out of the light beam. This results in a
sluggish cell response, i.e. optical absorption will be detected only after considerable
time lags caused by slow diffusion of products from the electrode into the beam. Op-
tically transparent electrodes can be made from metal minigrids or fine metal mesh.
Handling of these fragile metal materials can be simplified by embedding them into
melt-sealed polyethylene sheets. A design reported by Krejcik et al. [166] is shown
in Fig. 5.43.
A gold or platinum wire mesh or minigrid acting as the working electrode and
located in the beam path, an additional metal grid serving as the counter electrode

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 5.2 Optical Spectroscopy in the Infrared Range 75

Fig. 5.43. Schematic design of the three-electrode arrangement embedded in polyethylene

melt-seal laminate according to [169]

and a silver chloride coated silver wire as reference electrode are embedded into
the melt-seal polyethylene laminate. Using PTFE seals, this laminate is mounted
between two KBr-plates as cell windows with suitable steel pressure plates and
screws. The whole assembly is placed into a standard FTIR spectrometer. By spec-
tral ratioing single beam spectra, changes caused by electrochemical processes can
be detected as functions of time or electrode potential. A cell employing a mesh
electrode has been used in studies of the spectroelectrochemistry of hydrogenase en-
zymes and related compounds [167]. A cell design with adjustable thickness of the
electrolyte solution layer has been presented [168]. Alternative designs employing
preferable standard components for transmission infrared spectroscopy have also
been described [169]. In a typical study, the electrochemical conversion of substi-
tuted phosphine complexes was monitored [170]. A thin layer cell micromachined
from silicon has been developed [171]. Because of limitations in the use of ATR
crystals (see p. 91) in in situ investigations of lithium ion batteries, a transmission
cell for studies of LiFePO4 as a cathode material for these batteries has been devel-
oped and applied [172, 173].

5.2.2 Infrared Reflection Spectroscopy

Any species showing infrared active vibrational modes adsorbed on a reflecting sur-
face can be studied with infrared spectroscopy. The beam of light will interact ab-
sorptively with the species when passing through the adsorbate layer before and after
the point of reflection. This enables studies of all kinds of adsorbates on many sur-
faces. Of particular interest in electrochemistry are surfaces of metals and semicon-
ductors employed as electrodes. Thus the following text deals only with reflection
at these surfaces; other surface and interfaces are not treated. Attempts to record in-
frared spectra of emersed electrodes (i.e. ex situ measurements) have been reported
infrequently in studies of adsorption of hydroquinone and benzoquinone on a poly-
crystalline platinum electrode [174–177]. Further development of this approach has
76 5 Spectroscopy at Electrochemical Interfaces

obviously stopped due to the need for large electrodes, a cumbersome experimen-
tal setup and the lack of any particular advantage in comparison to spectroscopies
employing working electrodes immersed in the electrolyte solution.

5.2.3 External Reflection Spectroscopy

Fundamentals. Infrared light impinging at an angle of incidence θ (according to

convention and as depicted in Fig. 5.44, this is the angle between the surface nor-
mal and the beam of light) onto a reflecting surface (for example, at the interface
metal/dielectric) will be reflected specularly at the same angle θ. The impinging
and reflected waves form a node at the point of reflection. At small values of θ ,
the resulting amplitude of the electric field vector will be zero and absorption of
radiation by species showing infrared active vibration (modes with a change of the
dipole moment different from zero during a normal vibration) is not possible. At
larger angles of incidence the behavior depends strongly upon the polarization of
the incoming light with respect to the plane of reflection, which is defined by the
incoming and the reflected beam of light. The phase shift of the electric field vector
is of particular interest. It suffices to discuss the case of p-polarized light with the
vector of the electric light in the plane of reflection and s-polarized light with this
vector being perpendicular to the plane. With s-polarized light the phase shift is an
almost constant 180◦ at all angles of incidence and the effective field vector (which
would have been parallel to the reflecting surface) is zero, as shown in Fig. 5.44.
With p-polarized light the phase shift varies from 0 to 180◦ depending on the
actual value of θ. Vectorial addition of the electric field vectors of the impinging
and reflected rays yields the effective electric field at the point of reflection. In the
case of s-polarized light, the phase shift of approx. 180◦ will result in practical
zero field strength at all values of θ. At a 90◦ phase shift the effective field will be

Fig. 5.44. Schematic illustration of phase shift of the electric field vector of polarized light
reflected at a surface; top: s-polarized light; bottom: p-polarized light

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 5.2 Optical Spectroscopy in the Infrared Range 77

Fig. 5.45. Calculated phase shift for s- and p-polarized light at a reflecting surface (based on
data in [181])

Fig. 5.46. Calculated absorption coefficients As and Ap for a layer of 1 nm thickness of ace-
tone on a reflecting surface as a function of the angle of incidence θ (based on data in [179])

maximal for p-polarized radiation; at lower and higher values the phase shift will
differ [178]. The calculated phase shift for both cases is depicted in Fig. 5.45.
At angles close to 90◦ the phase shift is at the value yielding a maximum effec-
tive field strength. Calculation of absorption coefficients Ap for p-polarized and As
for s-polarized light based on the Maxwell equations, assuming a layer of 1 nm of
acetone on a reflecting surface, show basically the close relationship between angle
of incidence and phase shift (see Fig. 5.46).
In ex situ studies of CO adsorbed on palladium sheets at grazing incidence,
considerable discrepancies between the behavior predicted by Greenler and the ac-
tual results were observed [180, 181]. The actual plane of polarization of the in-
coming light was without influence on the obtained spectra. This contradiction was
explained by invoking surface microroughness in the subnanometer range. Calcu-
lations have indeed indicated that a roughness of 2.5 to 5 nm is enough to provide
statistically distributed orientations of the adsorbed CO dipoles. This again recom-
mends perfect polishing of the electrode surface. Further details have been reviewed
previously [182–184].
78 5 Spectroscopy at Electrochemical Interfaces

Utilization of the differences in interaction between infrared light of the two

possible types of polarization with species at the interface (or in the interphase)
allows the dedicated design of setups for measurements of surface species or of
solution phase species. The latter possibility has already been discussed and will be
considered again briefly at the end of this section (p. 90); the former case will be
treated below.
Surface enhanced infrared absorption (SEIRA) has been observed in external
reflection spectroscopy [185], for further details, see Sect. 5.2.5.
Instrumentation. The subsequent discussion focuses initially on surface sensitive
setups; the use of external reflection spectroscopy for solution phase studies is re-
viewed afterwards. Because the size of the illuminated surface area is given by
the—mostly elliptically deformed—infrared beam and the reflected beam contains
information averaging surface properties, no particular spatial resolution is possible.
With infrared microscopy this would be possible; the geometric arrangement for ex-
ternal reflection based on an FTIR spectrometer and an attached infrared microscopy
as applied to studies of a variety of individually addressable arrays (combinatorial
chemistry) of nanostructured platinum as electrocatalyst for methanol oxidation has
been described [186]. A study has been reported of interfacial processes and species
at the tin/organic solvent-based electrolyte solution as employed in lithium batteries
using an infrared microscope [187] and the results indicate alloying/dealloying of
lithium with tin.
Taking into account the general considerations outlined above the spectroelec-
trochemical cell has to be of a thin layer design. A typical example is shown in a
cross section in Fig. 5.48; another view is presented in Fig. 5.49, showing major
features of the cell. In cases where a standard spectrometer is used, the cell has to
be mounted in the optical beam using an external reflection attachment as schemat-
ically depicted in Fig. 5.47.
A fundamental problem of thin layer cells is the fairly high ionic solution resis-
tance even when aqueous solutions of strong electrolytes are used. (Values of layer
thickness vary considerably; Parry et al. [189] have estimated a thickness of less
than 10 μm, whereas Bae et al. [190] have claimed a value below 1.5 μm.) This can
result in ionic migration, which in turn might cause spurious bands in the observed
spectra not caused by adsorbed species but by migrating dissolved ones. A quan-
titative treatment has been reported [191]. The sensitivity of the method can be
improved considerably, as already suggested by the calculations of Greenler [192],
by using infrared radiation impinging on the electrode surface at a large angle of
incidence (grazing angle). The use of hemispherical or prismatic windows allows
such arrangement [193]. A cell mounted perpendicularly in the sample chamber has
been described [194]. For a general review, see [195], an early overview of exper-
imental setups including data acquisition and processing has been provided [196].
The influence of interference effects in the thin layer arrangement, particularly on
the sensitivity, has been discussed thoroughly [197]. A cell suitable for measure-
ments in a wide range of temperatures from T = −100 to 25°C with rather pre-
cise temperature control (±0.5°C) has been described [198]. Its capabilities were

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 5.2 Optical Spectroscopy in the Infrared Range 79

Fig. 5.47. Optical path of IR light in an external reflection attachment equipped with an elec-
trochemical cell; a: polarizer; b, e, f : plane mirrors; c: concave mirror; d: cell with working
electrode

Fig. 5.48. Axial cross section of a spectroelectrochemical cell for external reflection mea-
surement according to [188]

demonstrated with the identification of the electrooxidation reaction intermediate of

1,4-bis(2-ferrocenylvinyl)benzene.
A spectroelectrochemical cell has been described that allows investigations of
electrochemically active species in an electrolyte solution that interact with gaseous
reactands dissolved in this solution at elevated pressure [199]. Results obtained with
organometallic nickel complexes interacting with dissolved CO imply the forma-
tion of various carbonyl adducts [202]. Special requirements of measurements at
active materials for lithium ion batteries have been considered in a cell described
elsewhere [200] for SNIFTIRS studies. The incorporation of a gold electrode that
80 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.49. Glass body of the cell depicted in Fig. 5.48; a: reference electrode compartment
with Luggin capillary; b: counter electrode compartment; c: gas inlet; d: gas outlet, according
to [191]

is evaporated onto a piezoelectric quartz crystal as employed in a quartz crystal

microbalance in the spectroelectrochemical cell in an FTIR spectrometer has been
described [201]. Differences in the formation process and in the properties of the re-
action product of aniline electropolymerization and aniline/o-aminophenol copoly-
merization could be identified.
Two modes of operation of the spectroelectrochemical setup (including both the
infrared spectrometer and the devices for electrode potential control) are possible in
order to obtain the requested surface sensitivity and to remove unwanted absorption
contributions from solution, gas phase in sample chamber, etc.:
1. Modulation of the electrode potential
2. Modulation of the plane of polarization of the infrared light
In the first case, the electrode potential is switched between two values previously
identified as being suitable with cyclic voltammetry. By calculating the difference
between measured surface reflectivities (i.e. spectral intensities recorded at the se-
lected electrode potential as a function of wavenumber) as observed at both po-
tentials, the change of infrared absorption by species being adsorbed is detected
because absorption by all other species in the path of light will be the same at both
electrode potentials and they will cancel out each other. Depending on the behav-
ior of the adsorbate at the respective electrode potential, various combinations and
results are conceivable; the most likely major cases are:
1. The adsorbed species is present only at one of the electrode potentials and it is
completely desorbed (absent from the surface) at the other. Assignment of the
electrode potentials is arbitrary. In this example the former potential may rea-
sonably be called measurement potential (E m ) and the latter potential may be
called reference potential (E r ). Infrared absorption by the adsorbate will thus
be observed only at the former potential. In the case of the latter potential no
absorption will be effective. In the case of a FTIR spectrometer, measurement
of the reflected intensity R as a function of the wavenumber at these electrode
potentials is equivalent to recording a single beam spectra. Beyond the infrared
absorption by the adsorbate, both single beam spectra contain all the other ab-
sorptions of infrared active species in the optical beam path. Since these absorp-

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 5.2 Optical Spectroscopy in the Infrared Range 81

Fig. 5.50. Schematic infrared reflection absorption spectra, —·—·— reflectance at E r ; –·–·
at E m ; —– resulting spectrum; for details, see text

tions should in no way be influenced by the change in electrode potential, they

should be equal in both cases. Spectral calculation will thus cancel out these
contributions and, as a result, only the absorption spectrum of the adsorbate
will be obtained:
ΔR Rm Rr
= − .
R Rr Rr
In resulting spectra, ΔR/R without any indices is displayed. When the spec-
trometer software is run in a mode resulting in transmission spectra (with a
percent abscissa), calculation of the simple intensity ratio will result in a spec-
trum around the 100% line. Subtraction of the second term causes a shift with
the spectrum now displayed around a 0% line. Schematically this is shown in
Fig. 5.50 (a); for an experimental example, see Fig. 5.51.
2. Adsorbate coverage and band position are independent of electrode potential.
When the adsorbate is present at both electrode potentials and neither the degree
of coverage (i.e. the number of infrared radiation absorbing species) nor the
band position of observable infrared modes changes as a function of electrode
potential, the absorptions at both electrode potentials in the respective single
beam spectra will completely cancel out. Although this is not impossible, it is
at least highly unlikely.
3. Band position and/or coverage depend on electrode potential. In a more com-
mon situation, at least one property will change. If the band position changes
because the strength of metal-adsorbate interaction changes as a function of
electrode potential, the position of the absorption in the single beam spec-
tra will be different, spectral calculation will result in an s-shaped spectrum
(which looks like a differential spectrum14 ) when the change is small. In cases
of larger changes, two bands pointing in opposite directions will be observed
(see Fig. 5.50). If the band position does not change as a function of electrode
14 This similarity is indeed justified, because the band position is measured as a function of
electrode potential: dν̄/dE.
82 5 Spectroscopy at Electrochemical Interfaces

potential, but the coverage does, the resulting spectrum is somewhat ambigu-
ous, as shown in Fig. 5.50. In most cases both properties will change and the
observed spectra will be somewhere between the two extreme possibilities out-
lined above.
In Fig. 5.50, selected examples are illustrated schematically. For more varia-
tions, see [160, 202]. In case a, the absorption at the measurement potential E m is
smaller than at E r (because of a lower degree of coverage), the result is an upward
pointing band in the display of ΔR/R. Generally, the infrared reflection absorption
spectra (not single beam spectra, as available with some methods) obtained with
any of the methods described here are displayed in a way that results in bands above
the baseline that indicate higher absorption of any infrared-active species at E r and
downward pointing bands that indicate higher absorption at E m . In case b, the sit-
uation is just reversed, resulting in a downward pointing spectrum. In both cases,
determination of the band position is easy. Case c shows the major problem of the
experimental approach: The obtained band shows the typical “differential shape”,
making determination of the band position almost impossible. A rather rare case
with a considerably narrower band at E r is displayed in case d.
Obviously the absolute band position can only be extracted easily from the ob-
tained spectra in cases a and b. In most investigations, one electrode potential is kept
constant and subsequently called E r , whereas the other potential is changed and des-
ignated E m . The applied spectral calculation amounts to a division of the measured
infrared intensities arriving at the detector, which correspond directly to the reflec-
tivities of the electrode surface. For traditional reasons, this procedure has been
called spectral subtraction and the method outlined above is thus called SNIFTIRS:
subtractively normalized interfacial Fourier transform infrared spectroscopy. Be-
cause the electrode potential is switched (modulated), albeit very slow (after several
interferograms have been acquired), this method has also been called square wave
Fourier transform infrared reflection spectroscopy (SW-FTIRS) [203]. At this point,
the Connes advantage typical of FTIR spectroscopy can be usefully employed. At
both potentials E r and E m interferograms are collected and stored separately. Sub-
sequently, the electrode potential is switched repeatedly between both values; fast
Fourier transformation is applied only at the end of the sequence. Any fluctua-
tions will thus be eliminated and a significantly improved signal-to-noise ratio re-
sults. This procedure is unfortunately only applicable when the changes at the elec-
trochemical interface that occur as a function of the switched electrode potential
are entirely reversible, i.e. no chemical reaction interferes. In cases of irreversible
processes (e.g. dissociative chemisorption), only a single potential switch is possi-
ble. This methodology has been called single potential alternation infrared reflection
spectroscopy (SPAIRS). When single beam spectra are recorded during a very slow
electrode potentials scan with only one reference spectrum recorded initially or fi-
nally at E r , the single beam spectra recorded at slowly changing electrode potentials
are assigned to the average value of E m during the time interval of interferogram ac-
quisition. The method is called linear potential scan infrared reflection spectroscopy
(LPSIRS). The spectroelectrochemical setup always includes an FTIR spectrome-

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 5.2 Optical Spectroscopy in the Infrared Range 83

Fig. 5.51. IRRA spectra of COad on polycrystalline copper in contact with an aqueous solu-
tion of 0.1 M KClO4 , E r,RHE = −0.1 V, E m,RHE as indicated

ter, an external reflection accessory, a polarizer and the spectroelectrochemical cell

as depicted above in Figs. 5.47–5.49.
The first case (a) discussed above is nicely demonstrated in a study of car-
bon monoxide adsorption on copper in contact with an aqueous solution of 0.1 M
KClO4 [204]; only a single-sided band of the CO-stretching vibration is observed at
2110 cm−1 (Fig. 5.51).
The absence of an electrode potential induced shift of the band position has
been attributed to a relatively weak metal–CO interaction. Carbon monoxide is com-
pletely desorbed at E ref , thus none of the typical problematic features of differential
bands appear.
Electrode potential modulation15 can also be applied with dispersive infrared
spectrometers (EMIRS). In this case, potential modulation is done by using a square
wave potential function, switching the electrode potential between E r and E m . The
frequency is in the range of a few Hertz up to about 20 Hertz. The infrared intensity
arriving at the detector changes as a function of the changing electrode potential
provided that the adsorbed species show any of the potential dependent changes
discussed above. The absorption of all other components in the infrared beam does
not change and results only in a constant intensity at the detector. Assignment of the
observed intensity (i.e. reflectivity) to the respective electrode potential is achieved
by using a lock-in amplifier controlled from the potential modulation device. The
use of this technique results in an improved signal-to-noise ratio. However, this
advantage can only be practically employed if the studied range of wavenumbers is
limited to a few hundred wavenumbers. A comparison of EMIRS with other infrared
techniques, particularly SNIFTIRS, has been reported [205]. The infrared intensity
measured at the detector is recorded as a function of the slowly changed wavenum-
ber of the infrared radiation passing through the employed monochromator. As there
is no commercially available dispersive standard infrared spectrometer suitable for
this purpose, the required optical components are arranged as needed. The basic
optical layout has been described frequently (see [199, 208]). The need for a rather
15 The acronym EMIRS somewhat misleadingly refers to electrochemically modulated in-
frared reflectance spectroscopy.
84 5 Spectroscopy at Electrochemical Interfaces

fast potential modulation to operate the lock-in amplifier combined with the electro-
chemical thin layer cell arrangement causes some specific problems. Thin layer cell
arrangements—as pointed out repeatedly already—are prone to sluggish response
to potential changes. This is mostly caused by the large potential (iR) drop along the
poorly conducting thin electrolyte solution film that is trapped between the cell win-
dow and the electrode surface. Thus electrode potential values can only be approxi-
mate because the tip of the Luggin capillary is at the edge of the electrode (whereas
the infrared beam probes mostly the central part of the circular electrode surface).
The use of EMIRS in investigations of electrocatalysts has been reviewed [208].
In the fundamentally different second approach, the surface selection rules as
discussed above [181] are employed in a different manner. A species adsorbed on
the electronically conducting surface of the electrode with a change of its dipole mo-
ment perpendicular to the surface during a vibrational mode will interact only with
infrared radiation with its plane of polarization oriented parallel to the plane of re-
flection (p-polarized, for further details see above). With s-polarized light no absorp-
tion will occur. Absorption by anything else in the optical path of light will affect
light of both planes of polarization in exactly the same way. Provided that the light in
both planes shows exactly equal intensity, spectral subtraction should yield a spec-
trum with ΔR as a function of wavenumber showing only the absorption by species
at the interface; all other absorptions should cancel each other out. Various exper-
imental approaches to obtain and process the spectra have been described [206–
208]. In the most frequently employed spectroelectrochemical arrangement (based
on the initial setup described in [209]), the light from the infrared radiation source is
intensity-modulated by a mechanical chopper at a frequency ωc and passed through
a polarizer. Using a photoelastic modulator (PEM) (for the mode of operation of
a PEM, see [209]) the plane of polarization with respect to the plane of reflection
at the electrode surface is modulated between s- and p-polarization at a frequency
ωm = 2ωc . The modulated infrared intensity R arriving at the detector is demodu-
lated with lock-in amplifiers at these frequencies. As a result of further data treat-
ment
Rp − Rs
R=
Rp + Rs
is obtained. The modulation scheme also cancels out sample emission effects and
thus can also be applied with heated samples. Measurements are performed at a
fixed electrode potential, i.e. the obtained spectrum pertains to a single electrode
potential because no electrode potential modulation is involved. This in turn results
in spectra that are considerably more easy to interpret as compared to those ob-
tained by potential modulation: Sometimes these spectra are also called “absolute
spectra” (as compared to “differential spectra”). The method has been reviewed in
detail [210] and its limitations have been pointed out [211]. Detailed considerations
of the optimization of a low-noise spectrometer have been discussed [212].
Because of the advantages of FTIR spectrometers and their broad availability,
attempts have also been made to perform polarization measurements on such spec-
trometers. An experimental setup for polarization modulated Fourier transform in-

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 5.2 Optical Spectroscopy in the Infrared Range 85

Fig. 5.52. IRRA spectra of COad on polycrystalline platinum in 0.5 M K2 SO4 electrolyte
solution, E m,SCE = −0.35 V; based on data in [222]

frared reflection absorption spectrometry (PMFTIRRAS) has been described [213,

214] based on a spectrometer of the Genzel–Happ design [215, 216]. This type of
interferometer shows an almost perpendicular incidence of infrared radiation on the
beamsplitter and has rather equal transparency for all planes of polarization of the
incoming light. Beyond the addition of a polarizer and a photoelastic modulator,
extensive additions to the electronic data processing hardware and software of the
spectrometer are required. Results reported so far pertain to numerous different ad-
sorbates, interphases and species of interest, including dye films [217]; for selected
examples (see p. 85 ff.). The described modified PMFTIRRAS methodology results
in imperfect suppression of contributions from solution phase species [218].
Results of a typical application that nicely demonstrate the advantage of polar-
ization modulation pertaining to CO adsorption on a platinum electrode as a function
of the degree of CO coverage are shown in Fig. 5.52 [219].
The shift of the CO absorption band appearing 1978 cm−1 at the lower coverage
limit of 0.94 · 1014 molecules·cm−2 to 2063 cm−1 at the upper coverage limit of
0.5.6 · 1014 molecules·cm−2 has been attributed to electronic coupling between the
adsorbed molecules, which is obviously more effective at higher coverages [220,
221]. The mode around 1800 cm−2 assigned to CO adsorbed in “bridging” positions
(i.e. interacting with two platinum atoms instead of one as in the “on-top” position)
appears only when the “on-top” adsorption sites are filled; in addition, these species
have a lower infrared absorption cross section [222]. Carbon monoxide adsorbed
onto palladium layers growing on a Pt(111) electrode surface was used as a probe
to monitor the mode of layer growth and palladium deposition [223]. Further details
of CO adsorption on metal surfaces as studied ex situ have been reviewed else-
where [224]. The use of theoretical methods, particularly density functional theory
(DFT), to the understanding of the metal–CO bonds (including some other related
adsorbates) has been reviewed [225].
86 5 Spectroscopy at Electrochemical Interfaces

A Michelson interferometer (the type most frequently employed in commer-

cial FTIR spectrometers) has largely different transparencies for s- and p-polarized
light and is actually an effective polarizer. Attempts to use this type of spectrometer
and the spectral mathematics outlined above, which would be simple even without
extensive modification of the spectrometer, have failed. Applying various normal-
ization procedures as initially suggested by Golden et al. [217], the single beam
spectra (i.e. spectra obtained at a selected plane of polarization and electrode poten-
tial) were also normalized and ratioed without success. In a procedure described by
Westerhoff et al. [226–230], a somewhat different approach was tried. In the sam-
ple chamber of the spectrometer, a polarizer mounted on a motor-driven holder was
added to the electrochemical cell fixed on the external reflection accessory. By an
electrical signal synchronized with the interferogram acquisition, the motor could
move the polarizer into positions that resulted in only p- or s-polarized light reach-
ing the electrode surface. Because of the significant differences in signal intensity
reaching the detector (mostly due to the polarizing effect of the interferometer, but
also due to the polarizing effect of the flat ZnSe cell window), normalization of the
spectra was required. It was performed by measuring single beam spectra for s- and
p-polarized light both in the absence and the presence of the adsorbate to be stud-
ied. The former state can be achieved by exchange of electrolyte solution, oxidative
desorption or other means. The measured reflectivities are called R p with and R p0
without adsorbate for p-polarized light and R s with and R s0 for s-polarized light,
respectively. The final spectrum is calculated according to16

ΔR Rp − Rp0 Rs − Rs0
= −
R Rp + Rp0 Rs + Rs0

A typical set of results of a study of the adsorption of CO on oxide-free nickel

that employs this methodology is displayed in Fig. 5.53.
The positions of both the end-on and the bridged adsorbate can be easily iden-
tified as a function of electrode potential. For comparison, SNIFTIR spectra were
recorded in the same spectroelectrochemical setup as shown in Fig. 5.54.
The shift of both bands to higher values with increasingly positive electrode
potential is obvious, but because of the bipolar nature of the recorded bands less
obvious and well defined when studied with SNIFTIRS. Recording the spectra of
the electrode free of any adsorbate sometimes causes difficulties. In the worst case
the electrode has to be pulled back from the electrode and, after solution exchange,
purge, etc., it has to be pushed against the window again. In most cases, this will
result in slightly changed optical adjustments and, consequently, spectral artifacts.
A modification of the method combining potential and polarization modulation has
thus been proposed [231]. As a reference state, the electrode at a potential E r is
taken. The measured reflectivities are called R pm and R pr for p-polarized light and
16 Choice of signs and sequence are important when assigning observed bands, which point
upwards and downwards with respect to the baseline, to adsorbates being present at the two
electrode potentials E m and E r .

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 5.2 Optical Spectroscopy in the Infrared Range 87

Fig. 5.53. PMFTIRRA spectra of COad on a polycrystalline nickel electrode in contact with
an aqueous 0.1 M KClO4 electrolyte solution, E RHE as indicated

Fig. 5.54. SNIFTIR spectra of COad on a polycrystalline nickel electrode in contact with an
aqueous 0.1 M KClO4 electrolyte solution, E m,RHE as indicated; = 0.1 V (top spectrum),
0.2 V lower spectra; 8*100 or 16*100 interferograms

R sm and R sr for s-polarized light, respectively. The final spectrum is calculated ac-
cording to
ΔR Rpr − Rpm Rsr − Rsm
= − .
R Rpr + Rpm Rsr + Rsm
Assuming again that reversible changes occur between both electrode potentials,
repeated switching is possible, which results again in considerably improved signal-
to-noise ratios after data treatment.
In the following overview of further typical examples, no attempt is made to
distinguish between results obtained via potential and polarization modulation tech-
niques. An early overview of investigated systems is available [199].
88 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.55. Model of citrate anion adsorption on a Au(111) surface (based on data in [235])

In a typical study of the adsorption of an organic molecule, the interaction be-

tween the anion of citric acid and a Au(111) surface has been investigated with
SNIFTIRS [232]. Evaluation of the observed bands together with spectral simula-
tion resulted in a model of the adsorbate structure, as depicted in Fig. 5.55, where
the carboxylic groups fully deprotonated and interacted with the metal surface. The
carboxylate groups are slightly tilted.
Water orientation as a function of electrode potential at the solution/platinum
electrode interface has been studied with SNIFTIRS [233]. A change of the wa-
ter dipole as implied by electrostatic considerations was deduced. Differences in
the behavior of H2 O and D2 O were interpreted in terms of differences in hydrogen
bonding. A flat orientation of the water molecule around the E pzc and with the elec-
trode potential shifting gradually in anodic direction an orientation with only the
oxygen atoms directed to the surface at electrode potentials shifted gradually in an-
odic direction was derived. The adsorption of phosphoric and trifluoromethanesul-
fonic acid on platinum surfaces has been studied with SNIFTIRS and the radiotracer
method [234]. Coverage data obtained with both methods agree and deviations at
very positive potentials were attributed to chemical reactions. Structural models of
the anions in the electrochemical double layer were proposed. Sulfate adsorption on
Au(111) from solutions of various pH-values as a function of electrode potential has
been studied; results were compared with those obtained with STM [235]. Results
imply no marked influence of the adlayer ordering observed with the scanning probe
microscopy on the vibrational spectroscopy features. Adsorption of 2-halo-benzoic
acids on a Au(100) surface has been investigated with SNIFTIRS [236]. Results in-
dicate a change of orientation from flat at negative potentials to vertical with both
oxygen atoms oriented towards the gold surface at positive potentials. In the case
of 2-fluorobenzoate, evidence of the formation of an ordered adsorption layer was
found.
Beyond adsorption/desorption studies, including both the dynamics of the proc-
ess and the structure at the interface/of the interphase, measurements of various
deposits showing infrared active moieties have been reported. They include redox
processes at lead electrodes proceeding during charging/discharging processes in
lead acid batteries [237]. A quantitative determination of the amount of lead sul-
phate formed at the lead/solution interface was made by integrating the area under
the absorption band assigned to the asymmetric vibrational ν4 mode of the sul-
phate mode. Contributions from the solution were removed by spectral subtraction

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 5.2 Optical Spectroscopy in the Infrared Range 89

of a solution spectrum recorded under suitable conditions. Numerous other mole-

cular adsorbates have been investigated. In a typical study [238], the angle of the
C2-axis and the direction normal to the surface could be calculated (64 ± 4◦ ) for
2-mercaptobenzimidazole adsorbed on a Au(111) electrode. Deposition of gold and
silver and their alloys on glassy carbon and silicon substrates has been monitored
by measuring the infrared bands of cyanide ions present in the electrolyte solution.
Two different silver complexes [Ag(CN)2 ]− and [Ag(CN)3 ]2− and one gold com-
plex [Au(CN)2 ]− were identified with SPAIRS [239]. In electrocatalytic studies,
the oxidation of ammonia at various platinum single crystal surfaces in contact with
an alkaline electrolyte solution was investigated [240]. NH2 was found as an in-
termediate. Atmospheric corrosion of zinc caused by organic constituents in thin
water films on the metal surface has been studied using SNIFTIRS, with time as
the variable instead of the modulated electrode potential [241]. In the presence of
formic acid in the water film, zinc formate was observed as the dominant corrosion
product.
The use of an infrared microscope enables the investigation of the surface of
rather small electrodes. The resulting miniaturization of the necessary electrochem-
ical cell allows its operation as a flow cell in thin layer arrangement [242]. Com-
bined with a rapid-scan FTIR spectrometer, acquisition of infrared spectra dur-
ing electrode potential scans at a rate of dE/dt = 200 mV·s−1 are possible. The
time resolution is equivalent to one complete spectrum recorded every 2.6 mV.
The formation of various reaction intermediates of methanol oxidation in alkaline
solution at a platinum electrode could be assigned to specific electrode potential
ranges.
A drawback of polarization modulated IR spectroscopy using a FTIR spectrom-
eter is the slow scan rate of the moving mirror in the interferometer, which is nec-
essary to allow separation of the signals using a lock-in amplifier, and the increase
of noise by this amplifier [243]. Digitally sampling the interferogram at positions
corresponding to the two positions of the polarizer (i.e. to the two planes of polar-
ization of the incident light) has been reported as a significant improvement [244,
245]. Applications of this improved system in investigations of imidazole films de-
posited on copper electrodes [246] and of dye films on polycrystalline electrodes
have been described [247].
Infrared reflection absorption spectroscopy 17 (polarization modulated spectros-
copy with a dispersive spectrometer) has been used in studies of the kinetics of
the formation of CuSCN multilayer films [248]. An advantage of this method—
absolute spectra showing no differential bands, which are difficult to interpret—
became obvious in a study of CO adsorption on platinum [222]. With the various
neutral electrolyte solutions that are used, significant differences were observed in
the results obtained with acidic solutions. The mode of CO adsorbed in the bridged
position grows considerably in intensity and the position of the “on-top” COad is
slightly shifted (see Fig. 5.56).
17 The terms PM-IRRAS, IRRAS and even RAIRS seem to be used in the literature with the
same meaning.
90 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.56. IRRA spectra of COad on polycrystalline platinum in 0.5 M electrolyte solutions
(as indicated), E m,SCE = 0.15 V for H2 SO4 solution; E m,SCE = −0.35 V for K2 SO4
solution; (based on data in [222])

Structural changes in Langmuir–Blodgett bilayers of DMPC18 that are caused

by electrode potential changes have been studied with PMIRRAS [249]. Physical
state and molecular arrangement formed at the air/water interface are mostly pre-
served when bilayers are formed according to the Langmuir–Blodgett and Lang-
muir–Schaefer method.
In a simplified experimental approach, no selection of a plane of polarization is
attempted; thus solution phase species dominate the spectrum. Setups suitable in a
broad range of temperatures (−55 to 80°C) with an external reflectance attachment
(i.e. without fiber optics) have been described [250–252]. In a standard accessory
for liquid samples with two CaF2 windows, one window is replaced by a Teflon
disc of the dimensions of a window. A brass rod with a platinum foil welded on
top as the working electrode is pressed into a hole in this disc and a silver wire
is pressed into a groove around the circular working electrode as a reference elec-
trode. In one of the filler tubes attached to the back of the Teflon disc, a platinum
wire is inserted as counter electrode. The setup is mounted in a standard external
reflection accessory. Reported examples of applications include iron carbonyl com-
plexes [253] and bridged ruthenium cluster complexes [254] showing evidence of
intramolecular electronic coupling between the ruthenium ions in the infrared range.
In a study of a trinuclear ruthenium cluster with isocyanide ligands, unusually broad
infrared bands were observed in a selected combination of redox states of the par-
ticipating ruthenium atoms [255]. As an explanation, Fermi resonance between var-
ious modes of the ligand system was suggested. Based on the low wavenumber
transitions observed with the Creutz–Traube ion in aqueous solution, a complete
delocalization of the odd electron between the two Ru centers on the vibrational
time scale has been suggested in good agreement with the results of other spectro-
scopies [256]. In a series of trinuclear nickel complexes, the bridging behavior of
the capping isocyanide or carbonyl ligand upon single electron reduction was de-
18 1,2-dimyristoyl-sn-glycero-3-phosphocholine.

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 5.2 Optical Spectroscopy in the Infrared Range 91

rived from the infrared measurements [257]. The electrocatalytic reduction of CO2
with binuclear copper complexes enabled the identification of CO as a reduction
intermediate [258]. In a similar setup, one plate in a thin layer flow cell was a quartz
disc coated with a platinum layer as the working electrode. The other plate was
a CaF2 disc with platinum counter and pseudo-reference electrode deposited onto
acting as cell window [259]. The setup was mounted in an external reflectance ac-
cessory. In a study of arylisocyanide chromium complexes using this cell, changes
in internal bonding inside the ligand and between the ligand and the metal ion were
deduced from changes in band position and intensity. Structural features of electro-
chemically generated products of iron cyclopentadienyl carbonyl complexes have
been elucidated [260]. In a study of a selection of complexes containing various
metal ions (besides tin iron, molybdenum, manganese) and phenyl as well as carbon
monoxide ligands, structural changes upon electrochemical conversion were iden-
tified [261]. Carbon dioxide reduction products formed in the presence of iridium
1,8-diisocyanomethane complexes as catalysts have been identified [262].
The structure of the interphase between a salt melted at room temperature and a
gold surface has been studied with SNIFTIRS [263].

5.2.4 Attenuated Total Reflection Spectroscopy19

Fundamentals. If an infrared beam passing through a medium is reflected at an

interface, it impinges back into the medium provided the angle of incidence is larger
than an angle of incidence typical of the medium (Brewster angle, angle of total
reflection) [264]. The electric field extends a very small distance beyond the phase
boundary (evanescent wave). For a given wavelength λ1 this depth of penetration d p
can be calculated according to
λ1
dp =  ,
2π(sin2 a − (np /nc )2

assuming refractive indices np and nc for sample and crystal material, respectively,
at an angle of incidence α. Any species present within this distance (about 200 to
300 nm or even higher with materials showing extremely large values of nK ; the
actual value of this decay length depends upon the mentioned parameters20 ) may
absorb infrared radiation provided it has infrared active modes of vibration with
a change of the dipole moment perpendicular to the interface. The reflected beam
shows these corresponding absorptions. With a suitable optical arrangement, as out-
lined below, the reflected beam can be directed once more (or even more often)
towards the interface. Consequently the absorption bands will increase in intensity.
Another way of enhancing absorption (surface enhanced infrared absorption) is dis-
cussed on p. 94.
19 This method is infrequently called internal reflection spectroscopy.
20 The actual depth of information also depends on the modulation technique employed; the
reported value refers to electrode potential modulation.
92 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.57. Schematic design of an ATR element coated with a metal grid as conducting sup-
port for a polyaniline layer (top); three-electrode cell arrangement for FTIR-ATR spectro-
electrochemistry [268] (bottom)

Instrumentation. An attenuated reflection element (ATR element), i.e. a crystal

of a material like zinc selenide or silicon with suitable transparency in the infrared
range cut into a shape as depicted below (Fig. 5.57) is coated on one side with the
electrode material to be investigated (gold, silver, platinum, iron, etc.) or with a
metal grid, which in turn is coated with the material to be studied (e.g. a gold grid
coated with a layer of polyaniline [265]). The coated side is attached to a vessel
of glass that is used as electrochemical cell. The coating is used as the working
electrode. A reference electrode and a metal wire that is used as counterelectrode
are immersed in the electrolyte solution inside this cell. The fundamental advantage
of this method as compared to external reflection approaches is obvious. The elec-
trolyte solution in contact with the working electrode provides an almost unlimited
supply of reactands and there are no limitations caused by thin layer arrangements.
The construction of a cell permitting both FTIR measurements and electro-
chemical impedance measurements at buried polymer/metal interfaces has been de-
scribed [266]. Ingress of water and electrolyte, oxidation (corrosion) of the alu-
minum metal layer, swelling of the polymer and delamination of the polymer were
observed. A cell suitable for ATR measurements up to 80°C has been described
[267]. The combination of a cell for ATR measurements with DEMS (see Sect. 5.8.1)
has been developed [268]. It permits simultaneous detection of stable adsorbed
species and relatively stable adsorbed reaction intermediates (via FTIR spectros-
copy), quantitative determination of volatile species with DEMS and elucidation of
overall reaction kinetics. An arrangement with a gas-fed electrode attached to the
ATR element and operated at T = 60◦ C has been reported [269]. In this study,
the establishment of mixed potentials at an oxygen consuming direct methanol fuel
cell in the presence of methanol at the cathode was investigated. With infrared spec-

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 5.2 Optical Spectroscopy in the Infrared Range 93

troscopy, carbonate-containing species formed at the cathode as a result of methanol

crossover were detected. Complete methanol oxidation prevailed at elevated temper-
atures.
Fourier transform infrared spectrometers were used almost exclusively in re-
ported applications. Thus a single beam spectrum designated as a “reference spec-
trum” is initially recorded. Subsequent single beam spectra recorded at different
electrode potentials or as functions of time are ratioed versus this “reference spec-
trum”. Bands appearing in these differential spectra reveal changes in the coating
or in the adsorbate or surface layers on the coating that are affected by the changed
electrode potential or that occur as a function of time. Accordingly, this method
has been designated as a potential dependent attenuated total reflectance Fourier
transform infrared spectroscopy (PDATRFTIRS). The agreement of results obtained
with this method and with external reflection spectroscopy PDFTIRRAS has been
pointed out [270]. Time resolved measurements for kinetic studies are possible with
a sufficiently fast instrument [271]. Deposition of the metal film on a hemispherical
silicon (or any other suitable material for an ATR element) allows wide variations of
the angle of incidence, although obviously only a single reflection is possible. With
a platinum film working electrode the refractive index of the metal was found to
be different from the bulk value [296]. This was ascribed to the surface corrugation
of the evaporated film with only nanometric thickness as observed with scanning
tunneling microscopy. Considerable changes in reflection intensity as a function of
angle of incidence were observed when resonant absorption in the solution medium
occurred. The angle dependent infrared absorption band intensity (not to be con-
fused with the reflection intensity) showed considerable changes in magnitude up to
inversion for CO adsorbed on platinum. The excitation of resonant surface plasmon
waves at the interface was assumed to be the cause; a modelling of the three-layer
system, silicon/platinum/solution, supported the experimental observations and their
explanation.
A cell design employing attenuated total reflection without depositing the work-
ing electrode as a thin film on top of the ATR element has been described by Visser
et al. [272]. In this setup the three-electrode cell with a platinum wire mesh working
electrode is mounted on top of an ATR element made of KRS-5 that has a sensing
window made of diamond. Consequently the composition of the electrolyte solution
in front of this element is probed. A wide spectral window ranging from 250 cm−1
to 16700 cm−1 is accessible. This arrangement obviously provides no surface sen-
sitivity. Moon et al. [273] have reported on an optical arrangement, where the ATR-
crystal is pressed against the electrode surface and the arrangement is surrounded
by the electrolyte solution, which also contains counter and reference electrode.
This circumvents the need to deposit a metal film as a working electrode and allows
measurements on carbon surfaces or finely dispersed metal particles that otherwise
cannot be studied with ATR spectroscopy. Although the surface selection rules are
not completely maintained, there is nevertheless a large difference between spectra
collected with p- and s-polarized light, enabling deduction of adsorbate orientation.
94 5 Spectroscopy at Electrochemical Interfaces

Attenuated total reflection spectroscopy can also be employed in solid state

electrochemistry, i.e. in electrochemical systems without a liquid electrolyte solu-
tion/melt. These systems usually contain mixed-valence sites (e.g. Fe(III) and Fe(II)
sites in hexacyanoferrate systems) between which electron exchange is possible. In
addition, mobile counterions may be present. Changes in the spectroscopic proper-
ties of the material in the infrared range can be monitored with an ATR setup as
described by Kulesza et al. [274]. The material to be investigated is sandwiched be-
tween a germanium ATR element, which also acts as a working electrode, and an
additional germanium disc used to fix the material to be investigated on the ATR-
element; in addition it serves as both counter and reference electrode. The probed
thickness of the material was about 1 μm.

5.2.5 Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS)

Fundamentals. Hartstein et al. [275] observed for the first time that infrared ab-
sorption of organic films evaporated onto a silicon substrate was significantly strong-
er when a thin layer of silver was evaporated onto the adsorbate layer (metal over-
layer geometry). A similar enhancement was observed when the organic adsorbate
was deposited onto silver-coated substrates like CaF2 . Enhancement of infrared
absorption of species in close proximity to thin metal layers caused by surface
plasmon polaritons (transverse collective electron resonance) causing a locally in-
creased electromagnetic field has been observed frequently thereafter [276–278]
and has been treated theoretically [279, 280]. The abnormally high absorption of
IR active modes has been found mostly on structured surfaces that show surface
features of a nanometric size (e.g. metal islands of about 30-nm diameter and 10-
nm height). Obviously, similarities to surface enhancement as observed with Ra-
man spectroscopy can be found (although SEIRAS is not limited to certain met-
als, particularly coinage metals). This includes the importance of electromagnetic
contributions [281]. Other contributions similar to the charge transfer or chemi-
cal enhancement mechanism proposed for SERS are discussed [282–284]; for an
overview, see [285–287]. Chemisorbed molecules tend to show larger enhancements
than physisorbed ones. Chemisorption based on a stronger surface-adsorbate inter-
action tends to align molecules at the interface. Thus more molecules will interact
with the infrared light provided that the vibrational modes under investigation have
a significant component perpendicular to the metal surface. In cases of randomly
oriented adsorbate molecules, this will be less pronounced. Further contributions
by donor-acceptor interactions that result in large enhancement for modes involving
strongly polarizable groups are conceivable [285]. Theoretical calculations predict
SEIRA if the size and shape of particles as well as their proximity meet certain
criteria [285]; for further fundamental considerations, see [288, 289]. Enhancement
applies for all polarization states of the employed radiation [290]. Typical enhance-
ment values for CO adsorbed on gold film electrodes prepared by vapour deposition
are about 20; flame annealing results in a preferential 111 orientation of the gold
surface and an increase of the enhancement factor to about 40 [291]. Surface selec-
tion rules apply, as discussed for unenhanced reflection spectroscopy. At first glance,

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 5.2 Optical Spectroscopy in the Infrared Range 95

Fig. 5.58. Spectroelectrochemical cells and optical arrangements for SEIRAS in external
reflection (top) and attenuated total reflection (bottom)

this might look surprising because of the many different surface orientations of ran-
domly deposited metal island films. Assuming that the electric field exciting the
adsorbate vibrations is always perpendicular to the local metal surface, it seems rea-
sonable. The range of the enhancement (i.e. the distance wherein surface enhance-
ment is effective) is about 5 nm [285]. Observed band intensities depend on the
angle of incidence and the plane of polarization of the employed light. An alterna-
tive explanation of the enhancement that assigns the enhanced radiation absorption
not to the adsorbed molecules themselves but to a change in the effective dielectric
function of the metal island film at the frequencies of the molecular vibrations has
been proposed elsewhere [292]. The excitation of resonant surface plasmon waves
at the metal/solution interface has been invoked as an explanation of the angle-
dependency of the magnitude and—as observed under certain circumstances—the
inversion of infrared absorption bands [293]. Further unusual features of infrared
absorption bands generally called AIRE (abnormal infrared effects) like inversion
of absorption bands, change from single-side to pseudo-differential bands and in-
creased band width have been discussed elsewhere [294].
Instrumentation. In order to employ local enhancement of infrared absorption
by surface plasmon polaritons that cause locally enhanced surface electromagnetic
fields, a suitable optical arrangement is needed [295]. Surface enhanced infrared
absorption spectroscopy can also be observed in the transmission mode [285, 296].
However, since no application of this approach in spectroelectrochemistry has been
reported so far, it is not discussed further.
The Kretschmann design (see also Sect. 5.9) employs a hemicylindrical or trian-
gular prism of germanium coated with a thin layer (≈10 nm) of the metal to be inves-
tigated (e.g. silver). In this ATR arrangement, the slight enhancement of the incom-
ing light intensity as described elsewhere is also operative [267]. The preparation of
96 5 Spectroscopy at Electrochemical Interfaces

suitable electrode layers fulfilling the morphological requirements mentioned above

by deposition of various metals on ATR crystals has been described [297]. Chemical
deposition and sputtering of silver layer electrodes for SEIRAS in the Kretschmann
mode have been studied extensively [298]. Optimum deposition conditions with
respect to maximum intensity could be identified. This coated surface is brought
into contact with the electrolyte solution. A standard three-electrode arrangement
can be used. The infrared beam enters and leaves the crystal from the backside.
The polarization-modulation technique can be used. As a background spectrum, the
polarization-modulated spectrum obtained with the empty cell is used as a check for
the shape of the baseline [299]. Absorption bands caused by adsorbed species are
obtained as a function of electrode potential.
In several studies, adsorption phenomena of both solvents and dissolved species
have been investigated. The potential dependent orientation of water molecules at
the Au(111) interface in the presence of sulfuric acid has been reported [300];
for more recent results, see [301]. Suggested spatial arrangements of both water
molecules and electrolyte anions at the electrochemical interface are depicted in
Fig. 5.59.
At low sulfate ion coverage the ice-like structure is not disturbed by the sulfate
anions (they occupy water molecule positions) and, at higher degrees of coverage
and more positive electrode potentials, water molecules bridge adjacent sulfate an-
ions in various conceivable positions, resulting in slightly different spacings. Struc-
tural details of the water layer adjacent to a silver electrode have been reported in
a study of acetate anion adsorption [302]. Interaction of the acetate ion via its two
oxygen atoms was concluded.
The high sensitivity of SEIRAS (see above) allows measurements in real time
during a slow electrode potential scan [303–305]; for particularly fast acquisition,
step-scan interferometers may be used [306]. A series of time-resolved SEIRA spec-
tra recorded during reduction of heptyl viologen HV2+ to HV•+ at a silver electrode
in an aqueous solution of 0.3 M KBr is displayed in Fig. 5.60 [274].
Spectra were recorded at 100 μs intervals and were displayed in 1 ms intervals.
Bands caused by the formed radical developed as a function of time. It precipitated
onto the electrode as a film by association with supporting electrolyte anions accord-
ing to HV•+ Br− . Band intensities correlated well with coulometrically determined
charge consumption and they were proportional to t 3/2 for t < 12 ms and to t 1/2 for
t > 12 ms. These time dependencies imply a film formation via initial nucleation
and subsequent diffusion-controlled growth.
A significantly improved time resolution on the picosecond scale has been re-
ported [307, 308]. The method has been applied to study the potential jump at the
electrochemical interface platinum/aqueous solution of 0.1 M HClO4 saturated with
carbon monoxide induced by pulse irradiation with visible light. Position and inten-
sity of the infrared absorption caused by the CO stretching mode were measured as
a function of time after the 532 nm pump pulse.
The red shift of the stretch mode observed with a delay of about 200 ps is at-
tributed to a negative shift of the electrode potential and the heating of the in-plane

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 5.2 Optical Spectroscopy in the Infrared Range 97

Fig. 5.59. Orientations of water molecules on the Au(111) surface at electrode potentials
negative to the E pcz (top left), around the E pcz (top right), icelike water structure with small
coverage of coadsorbed sulfate ions (middle) and interfacial structure with large sulphate ion
coverage (bottom) with water molecules in various conceivable positions (based on [303])

frustrated translational mode of the adsorbed CO (see Fig. 5.61). The established
potential jump is caused by the heating of water layers near the metal surface. Mea-
surements of the change of metal reflectivity as a function of time enabled calcu-
lation of changes of both surface and solution temperature. The laser light of the
pump pulse does not interact with adsorbed CO or water and is only absorbed by
the electrode metal. Thus thermal energy transferred will diffuse into metal and so-
lution and any change of the respective temperatures will be delayed with respect to
the pulse. Calculations indicate an almost instantaneous temperature change at the
metal surface by about 70 K, whereas the temperature change in water layers several
nanometers away from the metal amount to a few tens of Kelvins with a delay of
about 200 ps. Thus the temperature jump in the water layers adjacent to the metal
contributes to the infrared band shift. Separation of the band shift into contributions
attributed to the temperature jump of the metal surface and to the potential change
in solution caused by the temperature change in the water layers and the associated
orientational change of water molecules close to the interface was possible.
98 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.60. Time-resolved SEIRA spectra of the reduction of HV2+ to HV•+ at a silver elec-
trode in an aqueous solution of 0.3 M KBr (based on data in [274])

Fig. 5.61. Time-resolved SEIRAS. Pump pulse 532 nm, 35 ps duration, 3 mJ cm−2 , temporal
profile indicated by dotted line; position and infrared absorption intensity of CO stretch mode
plotted as a function of time, platinum electrode, aqueous solution of 0.1 M HClO4 (based
on data in [310])

The transition between physisorption of cytosine on a gold electrode at negative

and chemisorption at the positive electrode potential was deduced from changes in
SEIRAS spectra in agreement with the charge transfer observed in cyclic voltam-
mograms [309]. In the case of pyridine adsorbed on a Au(111) surface, spectral
changes observed as a function of electrode potential were attributed to a reorienta-
tion; band intensities were not found to correlate with surface coverage of the gold
electrode with pyridine [310]. In a comparative study of pyrazine adsorbed on poly-
crystalline gold with SEIRAS and SERS end-on adsorption on the gold surface was
deduced from SEIRAS data. Comparison with SERS data provided arguments re-

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 5.2 Optical Spectroscopy in the Infrared Range 99

lated to the surface enhancement mechanism in SERS [311]. Self-assembled mono-

layers of benzenethiol on a Au(111) surface have been studied [312]. A symmetry
of the well-ordered adlayer commensurate with the supporting gold surface was ob-
served and differences between the amount of adsorbed molecules determined from
SEIRAS and cyclic voltammetry were tentatively attributed to coadsorbed sulfur
atoms and vacancies.
Further reported examples include electrocatalytic processes and their interme-
diates [313, 314]. Formate could be identified as an active intermediate of methanol
electrooxidation at a polycrystalline platinum electrode [315]. Water molecules co-
adsorbed during methanol adsorption on platinum were identified as those species
that react subsequently with COad that was formed as a result of methanol chemi-
sorption [316]. The high sensitivity of SEIRAS allows mapping of two-dimensional
spectra (for selected examples, see [285]). Finally, two-dimensional correlation
analysis of electrochemical reactions becomes possible [317].
The applicability of SEIRAS to metals other than coinage metals was shown
in a study of CO adsorption on platinum deposited chemically as an electrode on
an ATR crystal [318]. The extraordinary sensitivity also allowed time- and elec-
trode potential-resolved studies of the oxidation of methanol. Carbon monoxide ad-
sorption on platinum particles that were finely dispersed by electrodeposition into
a NAFION® film coated onto a gold electrode was studied [319]. The calculated
particle size was approx. 10 nm, thus it is likely that the obtained spectra were
surface enhanced. They indicated the presence of COad in two chemically differ-
ent environments. In a comparative study, the adsorption of pyridine at platinum
group metal electrodes was studied with SEIRAS [320]. Results revealed electrode-
potential dependent adsorbate orientation that was also dependent on the identity of
the electrode material. The structure and orientation of water molecules adsorbed
on a Au(111) surface [321] was investigated and elsewhere a potential dependent
reorientation [322] showing a weakly hydrogen-bonded water below the E pzc and
a strongly hydrogen-bonded ice-like structure at electrode potentials slightly above
the E pzc was reported. At even more positive electrode potentials the ice-like struc-
ture was broken up by specific adsorption of perchlorate anions from the supporting
electrolyte. Band shapes and intensities could be correlated to the deduced structural
changes. A study of first- and second-layer adsorbates employing the improved sen-
sitivity and spatial resolution has been reported [323]. The distinction between first-
and second-layer adsorbed anions could be based on the potential dependency of
vibrational modes of anions in the former layer; this dependency was absent in the
latter case.
Mechanism and reaction intermediates of the hydrogen oxidation reaction on
platinum have been studied with SEIRAS [324]. A band observed around 2090 cm−1
was assigned to adsorbed hydrogen species and the band height dependency on elec-
trode potential and hydrogen overpressure was found to match values predicted on
the basis of the Volmer–Tafel mechanism.
The interface platinum/NAFION® monomer in the presence of perchloric acid
was investigated with SEIRAS [325]. A band showing electrode potential depen-
100 5 Spectroscopy at Electrochemical Interfaces

dence was assigned to the symmetric vibration of the sulfonic acid substituent of the
polymer. Changes of band position and intensity suggested an electric field-driven
orientation and adsorption.
To prevent denaturation of redox proteins and enzymes upon immobilization on
an electrode surface that is necessary for electrochemical investigations, electrodes
may have to be modified with suitable biocompatible membranes. Studies of redox
processes and associated non-electrochemical processes of bound species with both
SEIRAS and SERS have been reviewed [326].
Although in all reported examples spectra were obtained by spectral subtraction
of a reference or background spectrum from a sample spectrum, the method has
been simply called SEIRAS. An attempt to designate this approach by a different
term, SEIDAS (surface enhanced infrared difference absorption spectroscopy), has
been reported. In it, the influence of the electrode potential on the spectroscopically
relevant changes in cytochrome c adsorbed on a chemically modified granular gold
surface was asserted [327]. Changes of the internal conformation induced by redox
reactions of the adsorbate were observed; they were not disturbed by the interaction
between cytochrome c and the various sulfur-containing layers used or chemical
modification.

5.2.6 Diffuse Reflectance Infrared Spectroscopy (DRIFT)

Fundamentals. Infrared radiation interacting with a surface can be absorbed or re-

flected. At a more or less ideally reflecting (smooth and planar, mirror-like) surface,
most of the reflected light will be observed at an angle identical with the angle of
incidence. With rough and corrugated surfaces, a considerable portion of light will
be reflected in various directions—basically all positions on a hemisphere on top
of the investigated surface will receive some reflected light. This is called diffuse
reflection [151]. The spectral information carried by the reflected light is basically
the same as with specularly reflected light.
Instrumentation. The interface within a suitably constructed electrochemical cell
to be investigated is placed in the sample position of a standard DRIFT accessory
for an infrared spectrometer; for a typical design, see [328, 329]. Examples reported
so far deal with solid polymer electrolyte fuel cells where the surface of the anode
layer exposed to a mixed gas atmosphere containing both water and methanol is
separated from the environment via a CaF2 window [331, 332]. Various oxidized
species and penetrating methanol were observed.

5.2.7 Photothermal Deflection Spectroscopy (PDS)

Fundamentals. Absorption of electromagnetic radiation illuminating an electrode

surface, particularly the surface layer, or by adsorbates on the electrode surface, can
result in thermal effects.21 These can be detected by various means, as described
21 The closely related photoacoustic method (wherein no wavelength dependency is taken
into consideration) is described in Sect. 5.9.4.

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 5.2 Optical Spectroscopy in the Infrared Range 101

Fig. 5.62. Spectroelectrochemical cell for IRPDS measurements according to [330]

below. Illumination of an interphase in the infrared range causes absorption by vi-

brational modes of species both in the interphase (e.g. polymer or passivation lay-
ers, adsorbed species) and in the solution in front of the electrode surface. The latter
absorption is of no interest in most cases and the associated loss of intensity arriv-
ing at the electrode surface is an inherent drawback. The actual IR absorption by
the species under investigation is rather small compared to this unwanted absorp-
tion, causing further experimental difficulties. Ways to overcome these problems in
various infrared reflection spectroscopies have been described above. An approach
proposed by Deng et al. [330] employing PDS addresses both drawbacks. Illumi-
nation of the interphase is performed with a tunable infrared diode laser of much
higher intensity as compared to conventional infrared sources. As no reflection is
involved, rough and non-reflective surfaces can be studied. Wavelength-dependent
infrared absorption in the interphase causes local heating, which in turn generates
thermal gradients in the adjacent electrolyte solution. These gradients are measured
by passing a laser beam in close proximity to the interphase through this gradient.
Instrumentation. The surface/interphase under investigation is illuminated with a
tunable infrared laser. The setup reported by Deng et al. [330] is adapted to inves-
tigations of surface layers on lithium metal in contact with thin solid electrolyte
films. Thus the thermal gradient has to be detected on the backside of the lithium
electrode. As depicted in Fig. 5.62, this is done by attaching the lithium foil elec-
trode to a piece of acrylic coated with a thin evaporated copper layer. The curved
electrode surface makes alignment of the laser beam easier; the thermal diffusivity
of acrylic is small, resulting in short thermal diffusion length.
The availability of tunable infrared diodes limits the accessible spectral range; in
the study by Deng et al. [330], data for the range 600–1000 cm−1 could be obtained.
LiOH was identified as the dominant species in the lithium/solid polymer electrolyte
interphase.

5.2.8 Infrared Emission Spectroscopy

Fundamentals. Emission of radiation by a body at T > O K is described by the

laws of Kirchhoff, Stefan–Boltzmann, Planck and Wien with the sum of emission,
reflection and transmission being unity [151]. In the mid-infrared range good emis-
sion spectra are already obtained with a sample at a temperature around T = 300 K
102 5 Spectroscopy at Electrochemical Interfaces

provided that the detector is cooled to a lower temperature. Otherwise sample and
detector might be in thermal equilibrium without a detectable signal; because liq-
uid nitrogen detectors are used, this requirement is easy to fulfill. According to
Planck’s law, nitrogen cooled emission decreases sharply at higher wavelengths,
thus emission spectra in the CH-region are weak. Emission spectra are equivalent
with transmission spectra with respect to band position; with respect to intensity,
they are considerably different. Because of the reabsorption of emitted radiation,
only species on the surface or very close to it will cause emission bands.
Instrumentation. Measurements are possible with an infrared spectrometer where
the emitting sample is placed instead of the radiation source. In FTIR-instruments
without an emission port (where the emitting sample is mounted in order to intro-
duce the emitted radiation properly) the sample can also be placed in the sample
chamber. Back reflection of the Michelson interferometer (about 50%) provides
the needed spectral separation. Reference (background) single beam spectra are
obtained with a standard black body; further spectral correction might be neces-
sary [151]. Investigations reported so far are limited to solid electrolytes of solid
oxide fuels (SOFC) operating at elevated temperatures (e.g. 550°C), as is typical for
SOFCs. The surface of the electrolyte to be investigated, which is coated with the
electrocatalyst as used for the electrode reaction, is located in the sample chamber of
the FTIR spectrometer under a suitably designed KBr-dome in the sample position
of a diffuse reflectance accessory. Emitted radiation is collected, spectrally sepa-
rated and guided to a liquid nitrogen cooled MCT detector.22 Single beam spectra
(actually, spectral intensity vs. wavenumber relationships) are collected at selected
electrode potentials and ratioed vs. a spectrum collected at open circuit electrode
potential. Spectral differences showing increased or decreased emittance as a func-
tion of wavenumber are indicative of changes in the concentration of the emitting
species. Using this technique, various dioxygen species could be identified on a
working cathode surface in a solid oxide fuel cell [331].

5.2.9 Far Infrared Spectroscopy

Fundamentals. Absorption of infrared radiation in the range between a few wave-

numbers (approx. 10 cm−1 ) and about 600 cm−1 can provide valuable information
about interactions between adsorbed species and the electrode surface. In addition,
internal molecular modes of metal complexes or inorganic films on the electrode
may become observable. The low intensity of most laboratory light sources and the
strong absorption by water and numerous gases in this spectral region has hindered
investigations considerably. Only one study of lithium deposition on a mercury sur-
face with a nonaqueous electrolyte solution using a conventional light source has
been reported [332]. The advent of synchrotron radiation as an intense light source
in this region has somewhat changed this situation [333, 334], consequently the
corresponding spectroscopy has been named SFIRS (synchrotron far infrared spec-
troscopy).
22 MCT: Mercury cadmium telluride.

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 5.2 Optical Spectroscopy in the Infrared Range 103

Instrumentation. An experimental setup with a thin layer electrochemical cell us-

ing a reflecting electrode surface in the external reflection mode as described above
is used in a standard infrared spectrometer with a detector particularly sensitive
in the FIR region [335]. The sample chamber is purged with dry nitrogen in or-
der to minimize light absorption by water vapour. Because of radiation absorption
by lattice modes, particularly those involving heavy atoms, most crystalline win-
dow materials are not suitable. Instead polyethylene film may be used. Systems that
have been investigated so far are adsorbed hydroxyl species on a platinum elec-
trode [336], surface films on a copper electrode [337, 338], oxoanions on gold sur-
faces [339] and pseudohalide ions on a silver electrode [340].
Alternatively, SFIRS can be done in the attenuated total reflection mode [341].
A gold film is evaporated onto a silicon hemicylinder. Vibrational modes of ad-
sorbed halide ions have been detected [344].

5.2.10 Raman Spectroscopy

Although Raman spectroscopy does not employ absorption of infrared radiation as

its fundamental principle of operation, it is combined with other infrared spectro-
scopies into a joint section. Results obtained with various Raman spectroscopies as
described below cover vibrational properties of molecules at interfaces complement-
ing infrared spectroscopy in many cases. A general overview of applications of laser
Raman spectroscopy (LRS) as applied to electrochemical interfaces has been pro-
vided [342]. Spatially offset Raman spectroscopy (SORS) enables spatially resolved
Raman spectroscopic investigations of multilayered systems based on the collection
of scattered light from spatial regions of the samples offset from the point of illu-
mination [343]. So far this technique has only been applied in various fields outside
electrochemistry [344]. Fourth-order coherent Raman spectroscopy has been devel-
oped and applied to solid/liquid interfaces [345]; applications in electrochemical
systems have not been reported so far.
Fundamentals. Provided enough substance is present at the electrochemical inter-
face in a fairly thick film of corrosion products or in a modifying layer, identification
of the constituent matter is possible with (normal) Raman spectroscopy (NRS). Al-
though this approach is not exactly surface specific, it is included because it has been
applied frequently. The same argument applies to Raman spectroscopy applied with
the help of a microscopy (Raman microscope).
Instrumentation. An experimental setup suitable for studies of corrosion films
formed at the metal/solution interface that employs a microscope has been described
[346] and an overview pertaining to corrosion and passivation of metals is avail-
able [345]. Measurements at elevated temperatures (up to 200°C) and pressures of
6.9 MPa, resembling the conditions in operating plants, are possible with specifi-
cally designed cells described in [345]. Studies of layer formation, particularly on
lead and mercury, are favored by the combination of these high atomic number el-
ements, forming large molecules (e.g. Hg2 Br2 ) with highly polarizable electronic
104 5 Spectroscopy at Electrochemical Interfaces

structures and showing large cross sections for Raman scattering. Green rust cor-
rosion compounds were formed when 1024 mild steel was exposed to phosphate
and bicarbonate solutions containing chloride and sulfate ions. A number of further
corrosion products was observed during carbon steel corrosion [347]. Stress cor-
rosion cracking of iron in the presence of carbonate-containing solutions has been
investigated [348]. Various iron-containing corrosion products were identified. Sur-
face Raman spectra of magnetic nanoparticles composed of maghemite (γ -Fe2 O3 ),
a surface layer of FeOOH and a positively charged non-stoichiometric Fe(III) oxy-
hydroxide layer have been reported with a smooth silver electrode [349]. Presum-
ably the claimed surface enhancement (if any) is caused by the large area of the
nanoparticles and their surfaces, which are rich in active sites (micro-roughness).
Raman microscopy has been employed in a study of electrochemical intercalation
of tetraethylammonium (Et4 N+ ) and tetrafluoroborate ([BF4 ]− ) ions into micro-
crystalline graphite [350]; a suitable cell setup is described. From changes of the
G-band (around 1578 and 1600 cm−1 [351]) upon intercalation of tetrafluoroborate
into the positive electrode, the formation of staged compounds was deduced; after
deintercalation the single G-band (1600 cm−1 ) was reversibly returned. Upon inter-
calation the D-band (1329 cm−1 ) disappears; after deintercalation it reappears with
greater intensity, indicating possible lattice damage during the process.

5.2.11 Surface Raman Spectroscopy

At first glance, Raman spectroscopy seems to be a rather unsuitable tool for inter-
facial investigations. The photon yield (scattered intensity) in the Raman process
is notoriously low—values around 10−6 going down to 10−8 to 10−10 have been
frequently quoted. Considering the rather limited numbers of potential Raman scat-
terers at an electrochemical interface, the measurement of a Raman spectrum of
an adsorbed species seems to be a pointless undertaking. Surface enhanced Raman
spectroscopy will be treated first because of both its overwhelming importance and
its popularity. Subsequently other methods, including those wherein presumably
no surface enhancement as claimed with the initially described approach is opera-
tive, will be discussed. Because a well-defined distinction is lacking and most likely
even in the latter some enhancement (because of surface roughness and associated
electromagnetic enhancement) is operative, this arrangement seems to be plausible.
Conceivable overlap with normal Raman spectroscopy as described above should
also be kept in mind.

5.2.12 Surface Enhanced Raman Spectroscopy

The discovery of a particular enhancement effect (up to 106 ) that affects only species
in close contact with the metal electrode surface (i.e. adsorbed species) by
Fleischmann et al. [352] and slightly later by Jeanmaire et al. [353] and a report
on the utilization of resonance enhancement in surface Raman spectroscopy [354]
demonstrated surprisingly the feasibility of vibrational studies of electrochemical

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 5.2 Optical Spectroscopy in the Infrared Range 105

interfaces with Raman spectroscopy (for a recent introductory overview, see [355]).
Although the applicability was initially limited to electrodes prepared from coinage
metals (i.e. copper, silver and gold) or species showing electronic transitions close
to the wavelength of the illuminating light in resonance Raman studies, these initial
reports opened a floodgate to the application of Raman spectroscopy in interfacial
electrochemistry. The wide range of accessible wavelengths (100–4000 cm−1 ), the
possible resolution (1 cm−1 or better), the fast response of the detection setup (ns)
and the lack of interference by water (the most frequently employed electrolyte
solvent in electrochemistry) because of its weak Raman scattering have propelled
this development. The number of review papers is considerable; however, they are
mostly of a general type. Thus information pertaining to a specific adsorbate system
is hard to find. Early overviews of investigated adsorbates are helpful [356, 357];
unfortunately they have not been updated. The terminology is also rather complex.
Simple surface Raman spectroscopy of non-coinage metals like platinum, the use
of illuminating wavelengths that are known not to support surface enhancement
(e.g. λ0 = 514.5 nm for a gold electrode) or the use of smooth surfaces might be
called surface Raman spectroscopy (SRS) because of the absence of the surface en-
hancement features, particularly typical of the d-metals. This methodology has also
been called surface unenhanced surface Raman spectroscopy (SUERS) [358]. Spec-
troscopy employing this particular enhancement feature is generally called SERS.
Spectroscopy performed with surfaces where enhancement has been quenched by
deposition/adsorption of foreign metal atoms [359, 360] has been designated deen-
hanced SERS (DESERS) [362] (see p. 104). Raman spectroscopy of molecules,
adsorbates, films, etc. that is resonantly enhanced because of the optical absorp-
tion properties of the species on the electrode surface is called surface resonance
Raman spectroscopy SRRS (see p. 125). When rough, surface enhancement active
coinage metals are used as support, the method is termed SERRS. The possibility
of using focused laser beams for illumination, particularly when combined with a
microscope, provides considerable spatial resolution in surface studies. Since light
from sites providing particularly effective surface enhancement will dominate, the
scattered signal assignment of observed modes to specific surface features (kinks,
edges, local adsorbates, etc.) is possible.
Fundamentals. A polyatomic molecule exposed to a monochromatic light scat-
ters electromagnetic radiation. The radiation scattered exactly (elastically) at the
illuminating frequency is called Rayleigh scattering and is of minor interest in sur-
face studies; mostly it is a nuisance because of its large intensity, which extends
up to a frequency (wavenumber) region where sometimes low-energy vibrational
modes of adsorbate-surface interactions occur. In addition, scattered light at higher
wavenumbers (anti-Stokes) and lower wavenumbers (Stokes) can be observed. The
former results from species being initially in an excited vibrational state and relax-
ing into a vibrational ground state, the latter is caused by species starting in the
vibrational ground state and ending in an excited vibrational state. In this model,
assuming excitation into a virtual electronic state, resonance enhancement can be
explained by invoking excitation into a higher real electronic state of the molecule.
106 5 Spectroscopy at Electrochemical Interfaces

Scattered light is observed in all cases only when the polarizability of the illumi-
nated species changes during the involved vibrational mode (Raman selection rule)
[165, 205].
In a quantitative study of some representative adsorbates, Weaver et al. [361]
have determined surface enhancement factors for numerous internal modes of spe-
cies that are considered to be specifically adsorbed (“inner-sphere”, chemisorbed)
or non-specifically adsorbed (“outer-sphere”, physisorbed). Factors were found to
always be between 1 and 10 · 105 provided that no resonance effect interfered.
This implies that a particularly strong adsorptive interaction is no prerequisite for
effective enhancement. Numerous reviews that cover fundamental aspects of en-
hancement mechanisms [289, 362, 363, 369] and various applications have been
published [370–380]. Under near field conditions, enhancement factors up to 1010
can be rationalized [381]. Surface enhancement as observed with rhodamine 6G de-
posited on a self-affine silver surface is localized down to less than 200 nm portions
of the surface [382]. These “hot spots” are not necessarily topographic elements like
interstices or gaps between nanoparticles. This localized enhancement is assumed
to be 103 larger than the enhancement observed with conventional far-field mea-
surements. Despite the still ongoing discussion of the various enhancement mecha-
nisms and their contribution to the observed overall enhancement, there seems to be
general agreement that an electromagnetic effect (EM) associated with microscopic
roughness features and the correspondingly increased local electric field strength
of both the incident radiation and the inelastically scattered Raman radiation and a
chemical effect (CT,23 this contribution is sometimes also called chemical mecha-
nism [383]) associated with adsorbate-metal interactions (but not necessarily with
strong chemisorption) are operative. Their actual contributions depend on the type
of metal, adsorbate, metal surface roughness and, conceivably, further influences.
The EM contribution can be associated with surface plasmons, which can be ex-
cited with visible light in the case of the coinage or “free-electron” metals copper,
silver and gold [384]. In an early overview, optical resonances were used as a more
general term [385]. Using this concept, the dependency on the illuminating light
wavelength, the variation between metals (in this case between Cu, Ag, Au and Li)
and the distance between scattering molecule and surface as well as surface rough-
ness effects could be explained. It is closely related to the particle size and shape
(“lightning rod effect”) [386] and it scales with the distance d between the involved
scattering species and the radius r of a spherical particle according to [r/(r + d)]12
[387]. The actual dependence on d at distances beyond 2–3 nm shows a slight de-
cay only by a factor of 1/10 [388, 389]. An additional image dipole enhancement
effect has been proposed [389]. Support for this model (also called the image field
model) has been gained from measurements of pyridine adsorbed on copper with
various illuminating wavelengths [390]. Interactions between size features of illu-
minated particles and plasmon bands have been investigated with nanorods of silver
23 CT refers to charge transfer because some explanations of the chemical enhancement
effect assume a charge transfer between the metal and the adsorbate, resulting in the observed
enhancement of scattered Raman radiation.

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 5.2 Optical Spectroscopy in the Infrared Range 107

Fig. 5.63. Scheme of the four steps involved in the CT mechanism according to [398]

and gold [391]. Nanorods of suitable size (aspect ratio) that show an overlap of
plasmon band and excitation source show an enhancement 10 to 102 greater than
without this match. The relationship found between the size of nanostructures com-
posed of different numbers of gold nanoparticles and the enhancement factors im-
plies distinct excitation of various structural features by different wavelengths of the
illuminating light [392]. Surface enhanced Raman spectra of pyridine adsorbed on
gold nanorods have been reported [393]. Silver island films prepared by pulsed laser
deposition showed increased enhancement only after annealing [394]. According to
AFM images, the initially oblate islands coalesce into larger, less oblate and longer
particles. The SERS activity of the silver islands depends on a complex interplay of
several structural features beyond merely the nanometer scale. The dependency of
surface enhancement on active sites has been illuminated in a comparative study of
cyanide adsorption on gold with SERS and SFG [395].
The CT effect seems to be related to molecular resonance effects or, more pre-
cisely, to resonant electron transfer effects between the metal and the adsorbate that
involve electronic states created by the adsorptive interaction [396, 397]. A sche-
matic diagram depicting the conceivably participating electron transfers is shown in
Fig. 5.63.
An incident photon induces an intraband transition. An electron is transferred
from the metal to an excited state of the adsorbate. For physisorbed species, this
may occur via tunneling; for chemisorbed species, hybridization has been proposed.
Subsequently an electron is transferred back to the metal, leaving the adsorbate in an
excited vibrational state. Finally this electron recombines with the hole in the metal
below the Fermi level, resulting in photon emission (Stokes scattering). The elec-
tron transfer across the interface may occur under resonant conditions; for further
details, see [401]. The energy of the Fermi level E F is connected to the electrode
potential when the metal is immersed in an electrolyte solution. Consequently the
whole scheme as displayed might show some dependency on electrode potential.
This might affect the scattered intensity in particular, because shifts in energies in
this scheme will most likely affect transition probabilities. Correlations between
SERS intensities, electron affinities of various organic adsorbates and the applied
electrode potential have been studied [399] and the results support the described as-
sumption and the model of a resonant CT mechanism in SERS. A detailed review
of this model is available [400]. The contributions from both enhancement effects
108 5 Spectroscopy at Electrochemical Interfaces

have been summed up in

1
μ = αElocal + β∇E,
3
with the induced dipole μ, the molecular polarizability α (which is increased be-
cause of the suggested formation of a CT metal-molecule complex with a vibrational
transition in resonance with both the incidence and the scattered light) and the local
field E local increased by surface roughness and excitation of SPPs by both incoming
and scattered light. The second term describes the field gradient contribution to the
induced molecular dipole.
The additional enhancement provided by coadsorbed halide ions on a colloidal
silver surface has been pointed out [401]. As an explanation, morphological changes
effected by the strongly adsorbed anions have been invoked. The photo-driven CT
that is assumed to proceed from filled metal states near the Fermi level of the metal
to the first and second excited state in the case of pyrazine adsorbed on polycrys-
talline gold has been invoked as the cause for the breakdown of Raman selection
rules upon adsorption (i.e. the activation of originally Raman-forbidden vibrational
modes) [314].
This effect is not inherently dependent on surface roughness but, as in most
studies where rough surfaces are investigated, it is hard to separate the influence
of roughness on the enhancement from CT enhancement. Nevertheless, there have
been studies of smooth (up to low indexed single crystal) coinage metal surfaces
reported [402–404]. They are of particular interest because the use of a well-defined
smooth surface provides a fixed geometrical reference with respect to orientation of
molecular adsorbates. The deduction of molecular orientation of an adsorbate is one
of the most frequently investigated topics with in situ vibrational spectroscopies.
Whereas in case of infrared spectroscopy the surface selection rules as discussed
above provide a well-defined frame of reference with Raman spectroscopy, a less
clear-cut situation is present here. Basically, selection rules that are considerably
more complicated than those for an ideally reflecting metal surface in infrared spec-
troscopy can be derived [405–407]; for an overview, see also [408]. In practical
applications the easy use of these rules is prevented by the mostly rough or other-
wise imperfect surfaces and the rather complicated formalism of the rules. Instead,
in numerous investigations (e.g. [409]) of adsorbates with well-defined adsorption
geometries that have been verified with other methods (e.g. infrared spectroscopies),
features of SER spectra that are useful for the identification of adsorbate orientation
have been derived. In general, molecular modes perpendicular to the electrode sur-
face will be particularly intense [410].
The conceivable effect of laser-induced local damage and the possible effect of
carbonaceous deposits on surface enhancement have been reviewed by Cooney and
Mernagh [411].
Beyond the enhancement provided by metals exhibiting surface plasmon res-
onances (i.e. copper, silver and gold in particular) with suitably rough surfaces,
other means of enhancement have become available. The use of tip-enhancement
is particularly promising. The tip of a scanning tunneling microscope that is in close

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 5.2 Optical Spectroscopy in the Infrared Range 109

proximity to the surface under investigation is illuminated. Its sharp apex provides
the required enhancement of the electric field locally [412–414]. So far, adsorption
of cyanide ions on a gold surface has been studied with a silver tip. With the tip
in a distance enabling tunneling a Raman band of the adsorbed cyanide ion at the
position previously observed with roughened gold electrodes was found. An addi-
tionally observed band at the position where cyanide had previously been adsorbed
on a rough silver electrode was seen and taken as evidence that some cyanide ions
are also adsorbed on the silver tip. The scattering of the adsorbed cyanide ions on
the smooth gold surface is tip-enhanced and the scattering of the ions on the silver
tip is surface enhanced. The use of fiber tips as localized probes wherein the fiber
both guides laser illumination to the surface under investigation and guides the scat-
tered light to the spectrometer has been reported [415]. An additional enhancement
caused by the use of the fiber tip and depending on the tip preparation, in particular
its coating, has been found. Use in electrochemical systems seems to be feasible,
but has not yet been reported.
Ab initio calculations of vibrational frequencies of adsorbates on metal (sur-
faces) have been reported. In the case of pyridine adsorbed on silver, all calculations
imply an edge-on interaction with an Ag+ species as part of the active site [416]. As-
suming this particular adsorbate-metal model, the mode ν Ag–N could be predicted
satisfactorily. The potential dependence of the position of this mode can thus be
modeled assuming a chemical bond with a strength influenced by charge distrib-
ution and donation instead of assuming a vibrational Stark effect [417–420]. The
use of other theoretical approaches, e.g. density functional theory (DFT), has been
reviewed—in particular with respect to adsorbed CO; for details, see p. 85. The
position of vibrational bands of adsorbates as observed with all vibrational spectro-
scopies depends on various factors. Besides the already mentioned electric field,
which can show extremely large values inside the electrochemical double layer,
the electrical charge on the electrode, the local crystallographic arrangement of
those metal atoms interacting with the adsorbate and the presence of particular con-
stituents in the electrolyte solution are only some of many conceivable influences.
Because of the strong dependency of band positions of simple adsorbates like CO or
CN− on the electrode potentials, this relationship has attracted particular attention.
An electric dipole, i.e. the infrared active part of an adsorbate, that is exposed to
an external electric field will show a change of its observed vibrational frequency
as a function of the effective electric field; this is called Stark tuning (see p. 109).
The direction of the change of the vibrational frequency as a function of the elec-
trode potential depends on the type of molecular orbitals involved; both positive and
negative Stark tuning have been observed. Any adsorbate showing strong interac-
tion with the electrode surface (indicated by free enthalpies of adsorption in excess
of 20 kJ·mol−1 ) is bound implicitly with a considerable covalent contribution to the
adsorptive interaction (in contrast with the purely electrostatic interaction during the
weaker physisorption). This interaction implies electronic charge donation/back do-
nation between molecular and atom orbitals of the adsorbate and suitable electronic
states of the metal. Consequently a change of the charge density on the metal—
110 5 Spectroscopy at Electrochemical Interfaces

closely connected with a change of the electrode potential—will also affect this
electronic interaction. In turn, bond orders and/or bond strength inside the adsor-
bate may be affected. Changes of the vibrational frequency will result, which are
not an effect of Stark tuning.
Instrumentation. Because water is a weak Raman scatterer (for a review of vibra-
tions of water molecules adsorbed on a SERS-active metal surface, see [421]) and
most other electrolyte solution constituents are present only in small concentrations,
standard cells with the working electrode surface close to a flat window are suitable;
no thin layer arrangement is required. This results in good electrode potential con-
trol and current distribution. A typical design is depicted in Fig. 5.64; for further
examples and details of both the electrochemical and the spectrometric setup, see
also [372].
The cell is mounted in the sample chamber of the Raman spectrometer. The il-
luminating light is guided towards the electrode surface with an angle of incidence
of about 60◦ ; this angle has been identified as being suitable for maximum scatter-
ing intensity [422–425]. Further details of the cell setup are depicted in Fig. 5.65.
A similar design has been described elsewhere [426]. In investigations of sensitive
systems (e.g. systems that are prone to photochemical conversion or to photother-
mal degradation effects), a moving cell with continuously changing sections of the
electrode surface exposed to the laser beam may be helpful [427].
Illumination is provided most frequently from laser systems. The light is filtered
in order to remove plasma emission lines (in case of gas ion lasers) and preferably
shaped to a rectangular cross section. Thus the illuminated surface can match the
entrance slit of the spectrometer in an almost perfect way. Various types of spec-
trometers and detectors have been used and there are no special requirements with
respect to their application in surface studies. With respect to the metal (or other

Fig. 5.64. Spectroelectrochemical setup and cell for in situ surface Raman studies; AE: work-
ing electrode; BE: reference electrode; GE: counter electrode; N2 : nitrogen purge inlet;
S: mirror; Z: cylindrical lens; K: camera lens; E: entrance slit of spectrometer; OA: optical
axis of spectrometer

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 5.2 Optical Spectroscopy in the Infrared Range 111

Fig. 5.65. Schematic vertical cross section of a spectroelectrochemical cell for in situ Raman
measurements

substrate) to be investigated, the choice of illuminating light wavelength has to be

made. Whereas for silver surfaces laser light of λ0 = 488 nm, 514.5 nm or shorter
as emitted from rather popular Ar+ -gas ion laser systems is suitable, d-metals like
gold or copper require longer wavelengths above 600 nm as provided by Kr+ -gas ion
laser systems because of the interband transitions of the latter metals. This in turn
might have consequences with respect to the choice of detector, particularly when
photomultipliers are used. The use of solid state lasers with emitted wavelengths in
the near-infrared (e.g. 1064 nm emitted by Nd:YAG lasers) combined with Fourier
transform spectrometers is possible in most cases. The advantage of excitation far
away from any electronic absorption of the illuminated species can result in reduced
fluorescence [404, 428]. The additional advantages of Fourier transform spectrom-
eters for infrared spectroscopy, as discussed above (p. 73), are also helpful [429].
The dependency of Raman scattered light intensity on the illuminating wavelength
(the intensity increases with the fourth power of the frequency of the illuminating
light) might nevertheless result in poor spectra, which can in part be compensated
by coaddition of spectra (employing the Connes advantage) [430]. With ultravio-
let illumination (λ0 = 325 nm), no surface enhancement was observed [431]; for
details (see p. 121).
Preparation of the electrode surface is a central step in any SERS study. Al-
though surface Raman spectra from smooth surfaces can be obtained with a consid-
erably more demanding experimental setup, in most studies reported so far surfaces
were roughened to provide the desired electromagnetic enhancement and to pro-
vide an artificially increased surface area with a correspondingly higher number
of Raman scatterers illuminated by the exciting light. Roughening of the electrode
surface is most conveniently done by applying oxidation-reduction electrode poten-
tial cycling (ORC) in a suitable electrolyte solution. In the case of coinage met-
als, chloride-containing solutions have frequently been used. Although chloride is
known to adsorb strongly on these metal surfaces, numerous studies have demon-
112 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.66. Cyclic voltammogram of a gold electrode in contact with an aqueous solution of
0.1 M KCl, dE/dt = 0.1 V s−1 , nitrogen saturated

strated that adsorbed chloride can be washed off completely, leaving no spectro-
scopical evidence in subsequently recorded spectra. In the case of silver, only a few
electrode potential excursions into the range of anodic silver dissolution are needed.
Electrode potentials that are too negative should be avoided due to irreversible loss
(quenching) of surface enhancement that presumably occurs because of surface re-
ordering. In the case of gold, potential cycling beyond the first peak in the cyclic
voltammogram as depicted in Fig. 5.66 is required.
Keeping the electrode potential at the upper limit for some time (a few sec-
onds), as proposed by Gao et al. [432] and studied later in more detail [433], re-
sults in particularly stable surfaces. Nevertheless it could be shown elsewhere that
even without this delay period highly active surfaces could be obtained [434]. The
electrode potential program proposed by Gao et al. can nevertheless be obtained
with an inexpensive trapezoidal voltage function generator [436]. Surface roughen-
ing should be done preferably in a solution that does not contain the species to be
adsorbed later. As has been reported, adsorbate species already present during the
roughening might be trapped in the modified surface, causing considerable spectral
artifacts [435–437]. Trapping can also be observed when electrochemical processes
(reduction, oxidation) occur that involve species that adhere to the surface, partic-
ularly in combination with electrode metals like copper or silver, which are easy
to oxidize and subsequently to reduce [438]. A review of electrochemical surface
treatment (most commonly called activation) procedures is available [372].
The roughness and thus the surface enhancement are stable even at very nega-
tive electrode potentials in the case of a gold electrode. With a silver electrode, the
potential window extends only to less negative values. In Fig. 5.67, the scattered
intensity of the silver–chloride stretching mode is shown as function of the slowly
scanned electrode potential.
In the negative-going scan, a maximum of scattered intensity is reached, which
can be assigned to an electrode potential dependent degree of coverage and to a
change of the enhancement conditions for the CT contribution. These contributions
have to be kept in mind generally when evaluating potential dependent SERS in-

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 5.2 Optical Spectroscopy in the Infrared Range 113

Fig. 5.67. Raman intensity of the silver–chloride stretching mode at 240 cm−1 ; aqueous
solution of 0.1 M KCl, λ0 = 488 nm, P = 400 mW, resolution ∼ = 10 cm−1 , dE/dt =
−1
2.5 mV s , nitrogen saturated

tensities. Beyond this maximum the intensity decreases. The maximum is located
at an electrode potential E SCE = 0.2 V positive to the electrode potential of zero
charge for a silver electrode in this solution [439]. Assuming a considerable contri-
bution of the potential dependent coverage to the scattered intensity, this was to be
expected because of the negative charge of the adsorbate. When the electrode po-
tential is scanned back from the negative limit, this mode is not observed anymore
and the surface enhancement property of the silver electrode is irreversibly lost. The
influence of the electrode potential on the adsorbate orientation has been studied
frequently; in a typical example, the orientation of interfacial methanol on a silver
electrode has been reported [440]. Whereas the C–O bond is parallel to the metal
surface at all investigated electrode potentials, at potentials positive to the E pzc only
one oxygen p-orbital seems to interact with the silver surface. Near the E pzc , two
methanol orientations appear to be present.
The surface roughness induced by electrochemical roughening as well as by
other means (e.g. metal deposition, evaporation under vacuum, etc.) has been char-
acterized with various techniques (for early reviews, see [441, 442]). Although sim-
ple double layer capacitance measurements did not show a significant increase and
thus no considerable increase of electrochemically active surface area [437], inves-
tigations of scattered intensity as a function of size of nanometer-scale roughness
features imply a relationship. In a study of the polycrystalline gold surface, fea-
tures with a size of about 100 nm showed a maximum scattered intensity [407].
The availability of polystyrene and silica nanospheres of narrow and well-defined
diameters has opened another access route to nanoscale surface features. A solution
containing these nanospheres (typical diameter: 50 nm) is spin-coated on an inert
substrate (e.g. gold-coated glass). After drying, a further layer of gold is deposited.
These layers show large enhancement factors [443]. This procedure has been devel-
oped further [444] and applied to selected systems [445]. Use in surface enhanced
resonance Raman spectroscopy (SERRS) has been reported [446].
114 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.68. SER spectra of a gold electrode in contact with various halide solutions (0.1 M),
electrode potentials as indicated, λ0 = 647 nm, P0 = 400 mW, resolution 7 cm−1

Even very simple adsorbates without internal vibrational modes, like halide ions,
show well-defined spectra (Fig. 5.68).
The position of the vibrational band depends primarily on the mass of the ad-
sorbed halide ion, which could be approximately explained based on a harmonic
oscillator model [437]. Whereas the mass of the adsorbed ion used in this calcula-
tion poses no problem, the metal surface was assumed to be of infinite mass. This
assumption has been questioned before [447]. Because of the notion of “SERS ac-
tive sites”, which are presumably adatoms or nanoscale metal clusters, various more
complicated models were used. The adsorbed atom was assumed to interact with a
single atom, which in turn was interacting with a very large mass (i.e. the metal
surface). In a second model, the adsorbate molecules were assumed to be interact-
ing with a metal cluster of four metal atoms in a square array. Correlations between
band positions and masses of the assumed species were slightly better for the first
model, thus a distinct identification of the actual mode of interaction is not reliable.
The dependence of the band position on the electrode potential implies chemisorp-
tion with a considerable degree of covalence of the halide–gold interaction [448,
449]. An unusually high wavenumber of 865 cm−1 for terminal oxygen atoms in
paramolybdate anions ([Mo7 O24 ]6− ) that interact with a copper surface has been
reported [450]. The assignment was based on the appearance of a band downshifted
from the position at 940 cm−1 . This band has been assigned to the stretching mode
of terminal oxygens of the Mo-O moiety.24 The adsorption of both organic and inor-
24 This assignment leaves open the possibility that the downshifted mode is actually not an
O-Cu mode, but a shifted Mo-O mode. Such shifts of internal modes upon interaction with
an electrode surface are conceivable and have been observed frequently (mostly with organic

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 5.2 Optical Spectroscopy in the Infrared Range 115

Fig. 5.69. SER spectra of a gold electrode with a self-assembled monolayer of 4-mercap-
topyridine in a solution of 0.15 M KF at EAg/AgCl = −700; −300; 100; 500 mV (from
bottom to top, traces offset by 300 s−1 ), λLaser = 647 nm, P0 = 30 mW, resolution 2 cm−1

ganic molecules acting as corrosion inhibitors is of great practical importance. Ac-

cordingly, the understanding of their action requires considerable attention. Raman
spectroscopy has been frequently employed, particularly with copper metal (widely
used in boilers, heat exchangers, etc.). Because copper shows a surface enhance-
ment typical of a coinage metal (i.e. both EM and CT enhancement, particularly
when even only slightly roughened), most studies should be considered applications
of SERS; a review is available [345].
Self-assembled monolayers (SAM) are another class of systems investigated
with SERS [451]. Figure 5.69 shows a set of SER spectra obtained with a roughened
gold electrode modified with a SAM of 4-mercaptopyridine:

The observed bands can be assigned to modes of the adsorbate that is pre-
dominantly present in its thiole form. Particularly noteworthy is the band around
adsorbates, because inorganic adsorbates like small oxyanions show rather strong internal
binding that is hardly affected by such adsorptive interaction). The observed direction of the
shift supports this suggestion.
116 5 Spectroscopy at Electrochemical Interfaces

264 cm−1 . It is caused by the gold–sulfur stretching mode; this implies that the
adsorbate is bound via the sulfur substituent, which has lost its attached hydrogen
atom. Taking into consideration the free enthalpy of this bond, this mode of inter-
action is highly likely; it is supported by the fact that a complete assignment of
observed bands supports a perpendicular adsorbate orientation [452]. Mapping of
surface gradients of gold (metal film over nanosphere surfaces) covered with self-
assembled various aromatic thiols using SERS has been described [446]. The effect
of the electrode potential on the acid–base behavior of a SAM of ω-functionalized
2-aminoethanethiol has been studied with SERS [453]. The explanation invokes the
effect of the electrochemical double layer on the surface pK a . For a review of fur-
ther studies of SERS applied to SAMs, see [454]; studies of surfactant adsorption
have been reviewed by Matejka [455]. In a study of self-assembled monolayers of
4-mercaptobenzoic acid on a silver electrode, the feasibility of SERS at a silver elec-
trode prepared by electrodeposition of silver from a room-temperature ionic liquid
(RTIL) and studied in the presence of an RTIL was demonstrated [456].
The use of rough surfaces for SERS has been considered a drawback. The elec-
trochemical roughening employed most frequently is suspected of introducing sur-
face sites that have properties different from the rest of the surface. In the case
of cold-deposited copper, the vibrational spectrum of adsorbed ethylene enabled the
identification of Cu(110), Cu(111) and other surface defect sites of unknown config-
uration. When the latter disappear upon annealing, the resulting scattered intensity
followed a simple electromagnetic enhancement model. Consequently these sites
were called “SERS active” (this implies a somewhat more narrow sense of surface
enhancement by limiting the term to the “charge transfer enhancement”) [457]. The
surface changes introduced by roughening are the formation of metal clusters, de-
fects and other irregularities. They may show different adsorption properties and
geometrical environments. In addition, the roughening excludes studies of single
crystal surfaces, which are fairly popular with various other spectroelectrochem-
ical and surface analytical techniques. Thus attempts have been reported to use
both atomically smooth (polished, not roughened) and single crystal surfaces. With
smooth polycrystalline gold, the scattered intensity of adsorbed pyrazine tracked the
molecular coverage up to about 2/3 of a monolayer; beyond this value the intensity
decreased, presumably because of interactions between the induced dipoles of the
adsorbed molecules [407]. With a Au(210) electrode, spectra of adsorbed pyrazine
could be detected. No simple relationship between molecular coverage and scat-
tered intensity was observed [406]. The relationship between the intensity of Ra-
man bands was not observed with pyrazine itself (forbidden bands) but was seen
for adsorbed pyrazine (indicative of changed, presumably lowered, symmetry); the
orientation of the adsorbed molecule on a silver electrode and the two mechanisms
of surface enhancement have been discussed [458].
The limitation of SERS studies to electrodes made from coinage metals has se-
riously hampered a widespread application to other metals and further substrates of
interest. Deposition of the metal of interest as a thin (a few nm), pinhole-free layer
on electrochemically roughened gold [459–461] or smooth [462] or again electro-

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 5.2 Optical Spectroscopy in the Infrared Range 117

Fig. 5.70. SER spectra of a gold electrode coated with a rhodium overlayer in an aqueous
solution of 0.5 M H2 SO4 + ca. 10 mM benzene at E RHE = −0.2 V (based on data in [465])

Fig. 5.71. SER spectra of a gold electrode coated with palladium overlayer in an aqueous
solution of 0.5 M H2 SO4 + ca. 10 mM benzene at E RHE = −0.2 V (based on data in [465])

chemically roughened [463] silver electrode surfaces yields SER spectra showing
features typical of the deposited metal instead of the supporting substrate. Surface
enhanced Raman spectra of numerous adsorbates that show spectral features typ-
ical of the overlayer metal have been reported. The use of this method has met
some criticism as the applied methods show some limits in generalization; in some
cases, the deposited thin transition metal films may have crystallinities different
from those encountered with bulk metal samples [464]. Typical examples are shown
in Figs. 5.70–5.73.
The vibrational bands observed with both metal overlayers are clearly different
from those observed with uncoated gold electrodes. The band positions show no
appreciable dependence on electrode potential and their intensity decreases towards
more positive electrode potentials. Evaluation of band position, band intensity and
symmetry reveals a flat orientation of the adsorbed benzene molecule with both
rhodium and palladium.
Toluene is also adsorbed on the palladium surface in a flat orientation, whereas
benzonitrile is adsorbed pendant with the nitrile group interacting with the sur-
118 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.72. SER spectra of a gold electrode coated with a palladium overlayer in an aqueous
solution of 0.1 M HClO4 + ca. 20 mM benzonitrile at E RHE = 0 V (based on data in [465])

Fig. 5.73. SER spectra of a gold electrode coated with a palladium overlayer in an aqueous
solution of 0.1 M HClO4 + ca. 5 mM toluene at E RHE = −0.2 V (based on data in [465])

face [465]; this is in agreement with similar studies with gold [466] and silver elec-
trodes [467, 468].
In a study of the adsorption of ionic species on gold and upd-modified sur-
faces (not perfect, pinhole-free overlayers), the displacement of adsorbed sulfate
by oxalate anions can be shown by comparing SER spectra obtained without and
with oxalate anions present (Fig. 5.74) [469]. The gold-sulphate stretching mode at
177 cm−1 dominates the spectrum in the absence of oxalate; in the presence of the
latter anion only one band assigned to the oxalate-gold interaction at 259 cm−1 is
observed; this implies a complete displacement.
Upon upd-modification with tin (Fig. 5.75) and nickel (Fig. 5.76), the band as-
signed to the oxalate-metal stretching mode is shifted only very slightly to 256 cm−1
and to 257 cm−1 , respectively. The band position is almost independent of the nature
of the upd-metal, implying rather unspecific and weak interactions (physisorption).
Based on the evaluation of further internal modes of the adsorbed oxalato anion,
small changes in band position indicative of the presence of the upd-metal could be
identified.

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 5.2 Optical Spectroscopy in the Infrared Range 119

Fig. 5.74. SER spectra of a polycrystalline gold electrode in contact with an aqueous solution
of 1 M Na2 SO4 (top) and with added 0.01 M Fe(II)/Fe(III)oxalate (bottom), EHgSO4 =
613 mV (based on data in [469])

Fig. 5.75. SER spectra of the upd-tin modified gold electrode in an aqueous solution of 1 M
Na2 SO4 + M 0.01 Fe(II)/Fe(III)oxalate at EHgSO4 = 613 mV (based on data in [469])

As an alternative approach, gold particles have been deposited on iron electrodes

in studies of passive films on iron [470]. A layered structure was found. The inner
layer is composed mostly of Fe3 O4 ; the outer layer contains Fe(III) species and may
also contain γ -Fe2 O3 .
Surface Raman spectra of non-coinage metals have been reported repeatedly
[471]. In practically all cases the surface under investigation was roughened (prefer-
ably by applying electrode potential cycling) and thus the electromagnetic contri-
bution was certainly effective. An alternative approach employs an aluminum foil
etched with aqueous alkaline solution as a substrate [472]. When brought into con-
tact with aqueous solutions of both coinage and non-coinage metals, the dissolved
metal ions are reduced and deposited onto the aluminum foils, which are presum-
ably somewhat roughened by the preceding etching; the foils nevertheless show no
120 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.76. SER spectra of the upd-nickel modified gold electrode in an aqueous solution of
1 M Na2 SO4 + 0.01 M Fe(II)/Fe(III)oxalate at EHgSO4 = 613 mV (based on data in [469])

Fig. 5.77. SR spectra of an electrochemically roughened polycrystalline platinum electrode

in contact with an aqueous solution of 0.5 M sulfuric acid and 0.244 mM Sn(SO4 )2 , E RHE =
1.191 V, nitrogen saturated, λ0 = 488 nm, P = 40 mW, resolution ∼ = 10 cm−1 (based on
data in [472])

surface enhanced Raman spectrum of adsorbed pyridine. The deposited metals ad-
sorb pyridine. The vibrational spectra of the adsorbate show typical features already
observed before implying the formation of α-pyridyl species and end-on adsorbed
pyridine as well as side-on adsorbed α-pyridyl species. The metal deposits (e.g. de-
posits of nickel, cobalt) have also been prepared with this template technique in the
form of nanorod arrays [473] showing significant surface enhancement with pyri-
dine as a probe molecule.
In a typical application the oxidation state of upd-tin on a platinum surface
electrochemically roughened by fast electrode potential cycling (roughness fac-

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 5.2 Optical Spectroscopy in the Infrared Range 121

tor approx. 2.7) was studied using adsorbed hydrogensulfate or sulfate ions as a
probe [474].
Based on a comparison with Raman spectra obtained with tin electrodes and
with solutions of various tin salts, the observed bands and their potential dependence
support an oxidation state of 2+ or 4+ for the tin that is underpotentially adsorbed on
the platinum electrode [472]. In a study of the adsorption of thiourea TU on a rough-
ened platinum electrode, interaction via the sulfur atom with tilted, potential depen-
dent orientation was found [475]. Dissociation and formation of surface sulfide was
observed at open circuit potential (i.e. in the absence of potential control). This sug-
gests the need for proper potential control during immersion of the electrode in the
case of particularly reactive adsorbate species. Further examples refer to pyridine
adsorbed on platinum and nickel electrodes [476] or the adsorption of saccharin on
a nickel electrode [477]. In a study of the adsorption of p-hydroxybenzoic acid on a
roughened gold surface with ultraviolet laser light illumination (λ0 = 325 nm), the
obvious mismatch of the excitation light with the electronic transitions in the metal
resulted in extremely poor spectra despite the fact that scattered Raman intensity
basically scales with υ 4 [434]. Considerable instrumental improvements that enable
acquisition of surface Raman spectra from non-coinage metals have been possible
by applying confocal optics (see p. 128 for details).
Modification (i.e. decoration) of graphite surfaces also results in considerable
enhancement of vibrational bands of the carbon substrate; in addition, modes of
electrolyte solution constituents may be observed. In the case of a glassy carbon
surface that is electrochemically activated by repeated electrode potential, cycling
deposition of silver micro- and nanocrystals results in SER spectra, as shown in
Fig. 5.78.

Fig. 5.78. SR spectra of a glassy carbon electrode activated electrochemically before (—) and
after decoration with silver in contact with an aqueous solution of 0.1 M K2 SO4 , open circuit
electrode potential, λLaser = 514.5 nm, P0 = 100 mW, resolution 2 cm−1 (based on data
in [354])
122 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.79. Scanning electron microscope picture of the electrode surface as employed for the
measurement illustrated in Fig. 5.78

The major bands of the carbon substrate around 1607 cm−1 (E2g mode) and
1360 cm−1 (A1g mode) are already visible with the activated surface. After decora-
tion with silver particles, the scattered intensity of these bands is significantly en-
hanced. An additional band assigned to the silver–oxygen stretching mode caused
by adsorbed sulfate ions is observed; the value of about 230 cm−1 is typical of this
anion when it is adsorbed on a silver surface.
Although no average particle size of the silver deposits has been reported, the
visible particles show dimensions in the range of about 100 nm; this size has been
observed to be particularly effective for surface enhancement (see p. 106).
The E2g mode has been monitored in a study of lithium intercalation into graphite
[478]. A shift of about 7 cm−1 from the initial to the final state of intercalation
was found. Initially intercalation occurs statistically and, upon formation of the
phase LiC27 , two different types of graphite layers are observed, resulting in a split-
ting of the observed Raman band. The bands are assigned to the LiC27 structure
and to a structure caused by statistical intercalation. Upon reaching the composition
corresponding to LiC12 , no further bands are observed.
A spectroelectrochemical flow cell suitable for kinetic investigations has been
described by Luo and Weaver [479]. A cell for time-resolved SERS that is used for
the investigation of electron transfer dynamics based on a cylindrical rotating silver
disc has been reported [480, 481]. Surface enhanced Raman spectroscopy measure-
ments taken at a high temperature in molten salts have been reported for the identi-
fication of oxygen species that appear at gold electrodes during electroreduction of
dioxygen [482]. The problem of black body radiation was solved by spectrally sub-
tracting a spectrum obtained without laser illumination. The combination of Raman
spectroscopy and optical microscopy that results in micro-Raman spectroscopy,25
enabling surface studies with high local resolution, has been reviewed [483]; so far
in numerous studies only localized measurements have been performed, whereas a
25 The term “microsurface-enhanced Raman spectroscopy” is misleading and should not
be used. Terms like “microprobe Raman spectroscopy” or “Raman microscopy” are more
appropriate.

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 5.2 Optical Spectroscopy in the Infrared Range 123

useful spatial resolution resulting in information about differences in surface prop-

erties has been employed only infrequently and, in most cases, in combination with
other microscopic techniques (see Sect. 5.2.15 for confocal spectroscopy; see p. 128
for near field Raman spectroscopy). In a typical study wherein spatial resolution
was of no particular importance, the oxidation of mercury at the mercury/aqueous
solution of 0.1 M KClO4 has been investigated [484]. Based on the appearance of
the Hg–Hg band around 175 cm−1 , the solvated dimeric Hg(I) cation was the only
oxidation product. At very anodic electrode potentials, a mercury-perchlorate pre-
cipitate was formed. In the presence of pyridine it yielded soluble Hg(II)-pyridine
complexes. Azide anions were identified as participants in electrooxidation of am-
monia in alkaline solution at nanostructured platinum electrodes with SRS26 [485].
The high sensitivity of SERS has attracted analytical applications [486] and further
interest from various fields, including medicine and biophysics [487–489] as well
as the chemical industry [490].
Photochemical reactivity of adsorbed species is a topic that is easily overlooked.
Although there have been only infrequent reports, photoinduced reduction of p-
nitrothiophenol incorporated in SAMs [491] and photoinduced reduction of polyani-
line [492] are illustrative examples.

5.2.13 Surface Enhanced Hyper-Raman Spectroscopy (SEHRS)

Fundamentals. In hyper-Raman scattering, two photons of the illuminating light at

ω0 and the scattered photon with ω participate. The scattered light corresponding to
a vibrational mode of the scattering species is observed at a Raman shift of 2ω0 –ω.
Selection rules are relaxed in comparison to both Raman and infrared spectroscopy,
which affects centrosymmetric molecules in particular. The theory of hyper-Raman
scattering has been treated extensively elsewhere [493]. The scattering cross section
is extremely weak—scattering intensities are about 10−7 to 10−5 for a laser field of
1010 W·cm2 . For an introductory overview of SEHRS in electrochemistry, see [494,
495]. Surface enhancements of 1013 have been reported [496].
Instrumentation. Instrumentation in the reported investigations is similar to that
employed in SERS [497]. A powerful laser system is employed. In a study of
pyrazine and pyridine adsorbed on a roughened silver electrode, it was observed,
that spectra measured with adsorbed centrosymmetric pyrazine showed additional
bands that were not observed with SERS [497]. With the non-centrosymmetric pyri-
dine, the SEHR spectra were very similar to the respective SER spectra; no new
bands were found. Surface enhanced hyper-Raman spectra were found to be more
sensitive (than SERS) towards interaction between the adsorbate and the surface.
This is illustrated in vibrational spectra of bis(4-pyridine)acetylene (BPA) adsorbed
on a silver electrode [497].
26 Because of the floating boundaries between SRS and SERS (e.g. simply roughening an
electrode may already yield the shift from the former to the latter), numerous authors simply
claim to have performed SERS without providing any supporting arguments. In the present
case, the nanostructuring most likely provided EM enhancement.
124 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.80. Spectra of bis(4-pyridine)acetylene adsorbed on a silver electrode; top: SEHR spec-
trum, aqueous solution of 0.1 M KCl, EAg/AgCl = −0.5 V, λ0 = 1064 nm, P0 = 2 W;
bottom: SER spectrum, aqueous solution of 0.1 M KCl, EAg/AgCl = −0.6 V, λ0 = 532 nm,
P0 = 10 mW; data taken from [500]

In bulk state, BPA belonging to the symmetry group D 2h is centrosymmetric,

thus it is particularly sensitive towards hyper-Raman scattering. The SEHR spec-
trum is considerably different from the corresponding SER spectrum (the small
difference in electrode potential is of minor importance). A particularly striking
feature is the absence of the acetylene stretching mode that is observed in SERS
at 2226 cm−1 in the SEHR spectrum. In SEHR spectra obtained at less negative
potentials, this mode appears weakly. These observations imply a significantly low-
ered adsorption symmetry at the latter electrode potential. A combination of infrared
spectroscopy, normal Raman spectroscopy, SERS and SEHRS was used in a study
of trans-1,2-bis(4-pyridyl)ethylene adsorbed on a silver electrode [498]. The cen-
trosymmetric molecule should not have common Raman and hyper-Raman lines
provided that its symmetry is not strongly disturbed upon adsorption. Besides a
well-defined C=C stretch mode seen only in SERS, many other bands overlap in
both spectroscopies. In addition, by using ab initio calculated spectra, observed
bands could be assigned and good agreement between the results of all employed
methods could be found. The results finally suggest that SEHRS spectra are consis-
tent with the expected three-photon selection rules; they are not caused by surface
second harmonic generation followed by surface enhanced Raman scattering that is
excited at the second harmonic frequency, as proposed elsewhere.
In a study of phenazine adsorbed on a silver electrode that employed both SERS
and SEHRS, the electroreduction product of phenazine and the reduction interme-
diates could be identified [499]. In a comparative study with SERRS and resonantly
enhanced hyper-Raman spectroscopy SERHRS, several dyes adsorbed on a rough-
ened silver electrode were investigated [500]. According to the results, the efficiency

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 5.2 Optical Spectroscopy in the Infrared Range 125

Fig. 5.81. Molecular formula of investigated transition metal complexes (R = phenyl, p-

methoxyphenyl, 4-pyridyl, p-chlorophenyl; M = Fe, Co, Ni; L = Cl− , Br− for M = Fe)

of SEHRS depends not only on the type of surface employed (roughened silver as
compared with silver colloid) but also on the type of dye.

5.2.14 Surface Resonance Raman Spectroscopy (SRRS)

Fundamentals. Illumination of a sample with light of a frequency matching the en-

ergy of an optical transition in the sample might result in vastly enhanced scattered
Raman light intensity (104 to 106 ). Because of the closeness of the energy values
involved, this is called resonance enhancement and the spectroscopy is termed res-
onance Raman spectroscopy (RRS). When applied to a surface it is called surface
resonance Raman spectroscopy (SRRS). In cases where the species under investi-
gation is present both as an adsorbate or adlayer and a dissolved species, resonance
enhancement will be effective for all of them; thus Raman scattering from dissolved
species might interfere.
Instrumentation. The experimental setup is basically the same as the one em-
ployed in SERS. For obvious reasons—the wavelength of the used light should
match electronic transitions (i.e. optical absorptions) of the species at the investi-
gated interface or in the interphase—sources with several tunable wavelengths are
preferred. Dye lasers or gas ion lasers showing several laser lines are the source of
choice.
Studied examples include dye molecules or other strongly colored molecules
adsorbed on metal surfaces or other materials suitable to be used as electrodes (e.g.
glassy carbon). In several studies transition metal complexes like porphyrines and
tetraazaannulenes have been investigated [501–505]. An earlier, unfortunately rather
incomplete and inconclusive report27 is available [345].
Raman spectra recorded under resonant or pre-resonant (i.e. the laser line is
somewhat away from the optical absorption maximum) conditions were obtained
for the bulk complex cobalt tetra-p-methoxyphenylporphyrine Co(TMPP).
27 Somewhat surprisingly, the authors fail to notice that resonance enhancement is operative
despite the fact that they elaborate in detail on the UV-Vis spectroscopy of some transition
metal complexes.
126 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.82. Raman spectra of Co(TMPP) in KBr and on carbon supports: I: blank pyrolytic
graphite (PG) surface; II: PG with Co(TMPP) film; III: identical to II but magnified by a
factor 5; IV: Co(TMPP) in KBr. λ0 = 457.9 nm, P0 = 200 mW

Bands could be assigned to vibrations of the complex. In addition, two bands

of the carbon surface were assigned. Changes upon exposure of the CoTMPP-
coated PG-electrode to an acidic electrolyte solution could be explained by assum-
ing solvent-complex interactions. When dioxygen is coordinated to the central metal
ion in an axial position, depending on the electrode potential, a stretching mode of
end-on coordinated dioxygen at 1204 cm−1 can be identified (see Fig. 5.83). To-
gether with further results, this implies a reduction mechanism for dioxygen pro-
ceeding via the superoxide stage.
These spectra were obtained with a smooth, polished surface. Thus no surface
enhancement was effective. The molecules under investigation can alternatively be
deposited onto roughened surfaces and the obtained spectra show a combination of
surface and resonance enhancement. The method is called surface enhanced reso-
nance Raman spectroscopy (SERRS).
Because of the strong coloration, depending on their state of oxidation, intrin-
sically conducting polymers have frequently been studied with SRRS [507, 508].
Molecular vibrations could be assigned based on various approaches. Most fre-
quently band positions of the monomers and of already known oligomers were
compared with those of the polymers. Alternatively, band positions were calculated
based on an effective conjugation coordinate [509–516]. In a typical example shown
in Fig. 5.84, SRR spectra of polyaniline are displayed as a function of electrode po-
tential.

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 5.2 Optical Spectroscopy in the Infrared Range 127

Fig. 5.83. Raman spectra of Co(TMPP) in situ Raman spectra of (FeTMPP)2 O in dioxygen-
saturated (upper trace) and dioxygen-free (lower trace) aqueous solution of 0.1 M HClO4 ,
λ0 = 457.9 nm, P0 = 200 mW, E RHE = 400 mV (based on data in [506])

Fig. 5.84. SRR spectra of a polyaniline film deposited on a platinum electrode, in contact
with an aqueous solution of 1 M HClO4 , electrode potentials as indicated, the band around
932 cm−1 is caused by the perchlorate ions

The observed bands can be assigned to internal modes of the aniline repeat
units that are present in their benzoid form at lower electrode potentials and in their
quinoid form at higher electrode potentials. In addition, modes assigned to molecu-
lar vibrations of the bonds connecting these repeat units predominantly in the para
position can be identified. The resonant enhancement of a band may depend sig-
nificantly on the illuminating wavelength. In the case of polyaniline, the pH-value
of the electrolyte solution has a strong influence on the actual molecular structure
(by protonation/deprotonation equilibria). This has been employed in an attempt to
monitor the pH-value of a solution by registering the scattered light intensity of
particularly sensitive bands [517].
The bands observed with a polypyrrole film under resonant and off-resonant
conditions can again be explained in terms of inter- and intramolecular vibrational
128 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.85. SRR spectra of a polypyrrole film deposited onto a platinum electrode galvanosta-
tically, in contact with an aqueous solution of 1 M HClO4 , electrode potentials as indicated

modes. The frequency dispersion of the band around 1580 cm−1 has been identified
as an indicator of chain length. Alternatively, the effective conjugation coordinate
approach has been employed.

5.2.15 Confocal Raman Spectroscopy

Fundamentals. In a confocal optical arrangement, a pinhole inserted in front of the

optical detection system (photomultiplier, spectrometer, etc.) allows only light from
the focal point to pass. Depending on the size of the pinhole and other properties of
the optical setup, this can result in considerably high spatial resolution. In the case
of confocal Raman spectroscopy, the sample under investigation is illuminated with
laser light using a microscope objective. The scattered light is collected and guided
using the same objective, i.e. a backscattering geometry is employed. For further
details, see [518–521]. Single molecule surface enhanced Raman spectroscopy (sm-
SERS or SMSERS) becomes possible when surface enhancement conditions are
met (suitable metal, finely dispersed) [522, 523]. The structural basis of this giant
enhancement has been discussed [524].
Instrumentation. The optical setup is depicted schematically in Fig. 5.86. By op-
timizing the optical geometry, a high collection efficiency can be achieved [467].
In the z-direction, a spatial resolution of about 20 μm is feasible. This might be
of interest in attempts to separate scattered light from the interface from contribu-
tions originating from solution phase species. The laser beam is focused to a spot
size of 1 to 2 μm, which allows measurement with corresponding lateral resolution.
In the case of substrates showing no particular surface enhancement effect (e.g. in
the case of non-coinage metals), suitable roughening procedures can be employed
to enhance scattered light intensity. Details of procedures employed with various
transition metals have been reviewed [467]. Despite the seductive gains achieved by

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 5.2 Optical Spectroscopy in the Infrared Range 129

Fig. 5.86. Schematic setup for confocal Raman microscopy

Fig. 5.87. Surface Raman spectra of an iron electrode in contact with an aqueous solution
of 0.1 M KCl + 0.01 M pyridine with various surface treatments applied: (a) mechanically
polished; (b) chemically etched in 2 M H2 SO4 solution; (c) ex situ activation; (d) in situ
activation (based on data in [467])

activating the metal surface under investigation in the presence of the species to be
adsorbed [467], this procedure should be avoided because of the danger of exper-
imental artifacts caused by trapping the adsorbate in the roughened surface [438,
439]. Reported investigations deal mainly with adsorption of various molecules on
transition metal surfaces. The influence of the roughening procedure on the scat-
tered light intensity is obvious in Fig. 5.87. The in situ roughening procedure based
on a double step oxidation reduction cycling (for details, see [467]) yields a con-
siderably stronger signal without any evidence of “trapping”. Oxide films on nickel
exposed to strongly alkaline electrolyte solutions that were composed of various
nickel oxides were identified [525].
Because the use of colloidal silver or gold as a substrate for single molecule
SERS, as observed with confocal microscopy, has met with some criticism (the
chemically prepared colloids are exposed to the molecules to be adsorbed and are
subsequently deposited onto a substrate, e.g. an ITO-coated glass slide; during this
130 5 Spectroscopy at Electrochemical Interfaces

procedure, agglomerization may occur resulting in poor definition of size and shape
of the particles that are finally studied), an electrochemical procedure for deposi-
tion of silver clusters of variable size and density has been developed [525]. The
lower detection limits for selected dyes are still not as low as those observed with
silver colloids. Silver and gold nanoparticles of 10 to 500 nm size that are pre-
pared with this electrochemical double pulse procedure have been characterized
with confocal and surface enhanced Raman spectroscopy [526]. The maximum en-
hancement factors observed were 1010 for silver and 108 for gold particles. Surface
enhanced Raman spectroscopy was described as a localized phenomenon. Only a
few particles were “Raman active”. The strongest enhancement was observed with
agglomerates; irregular structures like necks in agglomerates are preferential scat-
tering sites.

5.2.16 Near Field Raman Microscopy (Micro-Spectroscopy)

Fundamentals. In near field microscopy (see also Sect. 7.3.1), close range interac-
tions between sample and probe are utilized as with scanning probe microscopies
(see Sect. 5.3: AFM, STM, etc.). Because of the miniaturization of the probe, spa-
tial resolution beyond the Abbé limit (see Chap. 7) is possible. Since the probe is
scanned across the investigated surface, the method is termed scanning near field
optical microscopy (SNOM). A scanning near field optical probe for Raman spec-
troscopy has been described [527]. Localized evanescent fields associated with elec-
tromagnetic waves as also encountered with attenuated total reflectance (ATR) are
of central importance. Probes are metal-coated sharpened glass fiber tips with a hole
of the coating at the tip (about 50 to 100 nm in size, i.e. below the wavelength of vis-
ible light). At a short range (e.g. 10 nm) from the sampled surface, the optical near
field is distorted by the sample surface. Light thus emitted by the surface can be de-
tected in reflection or transmission.28 Interaction between the light emitted from the
fiber and the scanned surface may result in inelastic (Raman) light scattering. Opti-
cal setups with and without aperture (aSNOM) are possible. In the former case, light
is guided to the surface as described above. The resolution is controlled by the size
of the aperture. Limitations of this size are mostly given by the optical properties of
the coating material (for an introduction and further details, see [528]). Calculations
have indicated a resolution limit of 12 nm [529]. Because of the extremely low in-
tensity of the normal Raman scattering effect, apertures of 50 to 100 nm are used. In
addition, enhancement of scattered light intensity by resonance of the applied light
and the species observed on the sample surface or surface enhancement by suitably
prepared (roughened coinage metals surfaces, see SERS) [530] are utilized. With-
out an aperture, the surface under investigation is illuminated. The required near
field interaction is caused by a tiny tip smaller than the wavelength of the employed
light. Nanometer-sized metal particles (of metals employed in SERS) or the tip of
28 In conventional microscopy, the evanescent field is not utilized; instead, far field effects
are employed, which results in the diffraction limit of resolution.

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 5.3 Spectroscopy in the X-ray Range 131

a scanning probe microscope may be used. In the latter case, the method is termed
tip-enhanced Raman spectroscopy (TERS) (see p. 79 ff.).
Instrumentation. In both cases, a near field probe is employed—either a metal-
coated fiber (aperture-based) or a metal tip (apertureless). Distance regulation, as
used with scanning probe methods (see Sect. 7.2), controls the probe–surface gap; it
may also be used to obtain a topographic mapping of the studied surface. Scattered
light is collected and guided to a Raman spectrometer. In a (non-electrochemical)
study, dye-labeled DNA that had adsorbed onto evaporated silver layers on PTFE
nanospheres was observed [531]. Special surface sites with particularly high en-
hancement could be identified.

5.3 Spectroscopy in the X-ray Range

Absorption of electromagnetic radiation in the X-ray range (gamma ray range) of
the electromagnetic spectrum can occur in various ways that involve different parts
of an atom, a molecule or an interface and can result in various effects. Photoelec-
tron spectroscopy can be done using X-rays to generate photoelectrons. Absorption
of gamma radiation close to the K-edge of a given atom can result in an absorp-
tion spectrum showing a fine structure (EXAFS, XANES). Recoilless emission and
absorption of gamma radiation can also be used in Mössbauer spectroscopy. The
various spectroscopies and their in situ applications in electrochemistry will be de-
scribed here. An X-ray light source frequently used is a synchrotron; radiation pro-
vided by this source has been treated in Chap. 4 and elsewhere [532–534].

5.3.1 Mössbauer Spectroscopy29

Fundamentals. The energy of a gamma quantum emitted or absorbed by an atomic

nucleus usually differs somewhat from the actual energy difference between the nu-
clear states because of recoil and Doppler-broadening induced by thermal move-
ment. At room temperature, the value differs by about 10−2 to 10 eV from the true
energy value hν0 of the nuclear transition. The recoil energy E R and the correspond-
ing momentum p are

E R = p 2 /(2M) = (hν0 )2 /(2Mc2 ),

with M as the nuclear mass. An emitted nuclear quantum has the energy

hν = hν0 − E R ,

whereas for absorption the quantum needs to have the energy

hν = hν0 + E R .
29 Although the proper name is Mößbauer, the preferred spelling in the Anglo-American
literature is Mössbauer, as employed here.
132 5 Spectroscopy at Electrochemical Interfaces

Emission and absorption lines consequently differ by 2 E R (≈ 1 eV as a typical

value). Since nuclear transition energies are very narrow (10−10 to 10−4 eV), res-
onant absorption is only possible if the lacking energy is supplied somehow. With
freely moving species, this can be achieved by the Doppler effect, e.g. in an ultra-
centrifuge. When the involved atom is part of a rigid crystalline structure, the recoil
is transferred to the crystal instead of to the single atom. Because the mass of the
crystal is much larger than the mass of the atom, the recoil energy and the Doppler
shift practically disappear to about 10 meV, which is in the same order of magnitude
as the phonons in the crystal lattice (Mössbauer effect). The corresponding gamma
line (sometimes also called the Mössbauer line) shows only the natural linewidth
(5 × 10−13 eV for 57 Fe; 5 × 10−16 eV for 67 Zn), which is reduced by about five
orders of magnitude. Because of the extremely narrow linewidth resonance, the con-
ditions might already be lost if the source or absorber crystal are moving even at low
speed (fractions of mm/s). This provides a simple possibility to measure shifts of the
line induced by other influences. Measuring such a shift requires simply to move the
source or the absorber at a well-defined acceleration and look for resonant absorp-
tion. Consequently, the resulting Mössbauer spectra are usually displayed with the
gamma transmission of the sample vs. the velocity of the source. In the emission
mode, the intensity is displayed as a function of the speed.
Shifts of the absorption line can be induced by changes in the electron density
around the atomic nucleus. These changes can be effected by filled inner-core or-
bitals and partially filled valence orbitals; they are called isomer shifts. The change
influences both the ground state and the excited state; in sum, a change of the ab-
sorption energy is observed as depicted in Fig. 5.88.
This shift is indicative of the nature of the chemical bond between the investi-
gated atom and its neighbors or the state of oxidation. Figure 5.89 provides a rough
correlation between the state of oxidation of iron and the isomer shift.
The deviation of the nuclear charge distribution from an ideal spherical one
is described with the nuclear quadrupole moment. This moment can interact with
the gradient of the electric field generated by charged species (ions and electrons)
around this nucleus and thus the degeneracy of the nuclear states may be lifted,
resulting in a splitting of the single absorption line into several lines. This may oc-

Fig. 5.88. Effects of isomer shift (A) and quadrupole splitting (B) upon allowed nuclear tran-
sitions

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 5.3 Spectroscopy in the X-ray Range 133

Fig. 5.89. Correlation between state of oxidation of iron ions and the observed isomer shift
(based on literature data [535])

Fig. 5.90. Effects of magnetic splitting upon allowed nuclear transitions (Dependencies of
energies of states upon mi are slightly complicated, resulting in arrangements contrary to
simple expectations)

cur only when the nuclear quadrupole moment is different from zero and when the
nuclear state spin quantum number is larger than 1/2. This effect is called quadru-
pole splitting, where Δ describes the actual line splitting. A similar splitting can
be caused by an external magnetic field that results from magnetic species present
in the sample (magnetic hyperfine interaction). It causes splitting of the nuclear
state with spin quantum number I into 2I + 1 equally spaced states, as shown in
Fig. 5.90.
Further details and tabulated values can be found elsewhere [536, 537]. The
various parameters, observables and properties are collected in the table below.

Mössbauer parameter Observed quantity Obtained information

Isomer shift Charge density at nucleus Valence/oxidation state
Quadrupole splitting Electric field gradient at Symmetry of charge
nucleus environment
Magnetic splitting Magnetic field at nucleus Magnetic ordering,
particle size
134 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.91. Schematic experimental setup for Mössbauer spectroscopy in the transmission
mode

Instrumentation. In order to record a Mössbauer spectrum, an emitter producing

the requested monochromatic gamma radiation is needed. The minute modulation
of the energy of the emitted radiation is accomplished by moving the emitter at a
low speed in the range of mm/s. To probe the whole range of resonance conditions,
the speed is varied slowly from slow approaching to slow departing. The absorbing
sample is kept in a fixed position. Absorption is detected by positioning a gamma
counter behind the sample. Upon resonance, the amount of passing radiation arriv-
ing at the detector will be diminished. A simple setup is shown schematically in
Fig. 5.91.
Besides this transmission mode, an emission mode is possible. In this mode the
gamma emission of the sample containing suitable isotopes of the atom to be in-
vestigated is passed through an absorber of known properties to detect the desired
transition energies. Finally measurements of signals formed during the deexcitation
of nuclei after absorption of gamma rays is possible. Gamma rays, X-rays or con-
version electrons can be formed during this process. This technique is particularly
useful with samples that are too thick for transmission measurements. In addition,
the technique can be made particularly surface selective when the emitted electrons
(conversion electrons) are measured, because these electrons have only a very short
mean free path length in solids.
The source most commonly employed with 57 Fe Mössbauer spectroscopy is
elemental 57 Co, which is incorporated into rhodium or copper metal. During the
radioactive decay of the cobalt isotope into 57 Fe, the needed gamma radiation is
emitted. For measurements with tin (119 Sn), sources of CaSnO3 or BaSnO3 en-
riched with 119m Sn are used, which again release the proper radiation during their
radioactive decay. The source is moved at constant positive and subsequently nega-
tive accelerations (i.e. linearly varying speed) to probe the resonant absorption.
The sample, i.e. the electrode material to be investigated, is mounted in an
electrochemical cell particularly suited for the employed mode of Mössbauer spec-
troscopy. A cell designed for measurements in the transmission mode is shown in
Fig. 5.92. In order to achieve a maximum surface sensitivity, the electrode should be
made as thin as feasible because Mössbauer-active species deep inside the electrode
that are not affected by the electrochemical processes occurring at the solution/solid

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 5.3 Spectroscopy in the X-ray Range 135

Fig. 5.92. Electrochemical cell for in situ Mössbauer spectroscopy in the transmission
mode [538]

interface will also absorb gamma radiation. Besides making thin porous electrodes
wherein a maximum amount of the electrochemically active surface of the electrode
material is in contact with solution, thin film electrodes deposited onto insulating
carriers or electrochemically inert materials are used.
In this cell the iron is deposited as a thin film onto a gold substrate. Gold de-
posited onto a thin plastic film serves as a counter electrode.
Because of the very limited escape depths of conversion electrons (about 1.8 μm
in water, 0.25 μm in metallic iron), their detection is somewhat difficult. This seem-
ing drawback provides a unique surface sensitivity. In a rotating disc electrode
arrangement Kordesch et al. [539] have used a disc-shaped electrode that slowly ro-
tates with part of the disc immersed in the electrolyte solution. As a thin electrolyte
film thin enough to permit escape of conversion electrons adheres to the metal sur-
face, potential control is always maintained. Conversion electrons were detected
using a suitable gas-filled detector mounted close to the upper emersed part of the
disc. In a study of passive oxide films on iron, the advantage of this approach was
demonstrated; beyond an unmatched surface sensitivity, the measurement time was
reduced to a small fraction of that needed for transmission measurements [543]. An
inherent drawback of the setup is the poor current distribution inside the very thin
electrolyte film (its thickness is around 4 nm as reported by Gordon [540]).
Mössbauer spectra are mostly displayed as gamma transmission/absorption vs.
velocity of the source. Investigations deal preferentially with metal surfaces con-
taining suitable Mössbauer-active species. They include studies of corroding iron
surfaces, electrode surfaces modified with iron-containing complexes (e.g. hexa-
cyanoferrates, transition metal macrocyclic complexes), tin electrodes and cobalt-
electrodes. In a typical experiment, Vertes et al. [541, 542] have recorded Mössbauer
spectra of a 119 Sn enriched tin electrode deposited on an aluminum substrate in con-
tact with a borate buffer solution (pH = 8.4) at various electrode potentials in order
to elucidate the passive film (Fig. 5.93). At E SCE = −0.9 V β-Sn (δ = 2.5 mm s−1 )
and SnO2 or Sn(OH)4 (δ = 0.03 mm s−1 ) can be identified. The weak absorption
shoulder at δ = 4.3 mm s−1 was attributed to Sn(II) species being present in amor-
phous form. This feature could not be observed at more positive electrode potentials.
Thus the authors concluded that at electrode potentials negative to E SCE = −0.78 V,
the passive films contain highly amorphous Sn(OH)2 besides SnO2 and/or Sn(OH)4 .
136 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.93. In situ Mössbauer spectra of a tin electrode at various electrode potentials in a
borate buffer solution (pH = 8.4) (based on data in [546])

Fig. 5.94. In situ Mössbauer spectra of a film of Prussian blue deposited on a glassy carbon
electrode in an aqueous solution of 1 M KCl (pH = 4) at E SCE = 0.6 V (top) and E SCE =
−0.2 V (bottom) (based on data by [549])

Prussian blue that is formed as a highly colored colloidal precipitate by adding

Fe(III) ions to a solution of Fe(II) hexacyanide [543] has been identified as being
electrochromic [544]. Redox processes occurring during the reversible change of
colour have been studied with Mössbauer spectroscopy [545]. At E SCE = 0.6 V, the
Prussian blue film formed from Fe(II) hexacyanide and highly enriched 57 Fe(III)Cl3
shows two absorptions with δ = 0.37 mm s−1 and Δ = 0.41 mm s−1 typical of
an Fe(III) in its high spin state (Fig. 5.94). The Mössbauer spectrum at E SCE =
−0.2 V shows two lines typical of high spin Fe(II) ions (δ = 1.14 mm s−1 and
Δ = 1.31 mm s−1 ). The electrochromic redox reaction obviously involves the un-
coordinated iron species; no iron exchange seems to take place.

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 5.3 Spectroscopy in the X-ray Range 137

Mössbauer spectroscopy has been used frequently in in situ studies of electrode-

posits [546, 547], passivation phenomena [548–551], battery materials [552] and
transition metal complexes [553–555]. Co2 SnO4 has been studied with respect to its
use in lithium ion batteries ex situ with 119 Sn Mössbauer spectroscopy [556]; results
indicate a consumption of Sn(IV) species accompanied by formation of a cobalt–tin
intermetallic compound. Finally, a tin-rich lithium phase is found. Upon charging
the initial state is finally restored. CoSn2 as an electrode material has been investi-
gated with in situ 119 Sn Mössbauer spectroscopy [557]. Upon discharge a lithium-
rich phase of approximate composition Li3.5 Sn and cobalt nanoparticles are formed.
Upon charging, the more complex processes include conversion of the lithium-rich
phase into a modified CoSn2 nanocompound (i.e. a matrix of Liz Coy Sn2 ), which is
the active fraction in subsequent cycling.

5.3.2 X-Ray Absorption Spectroscopy30 (XAS)

Fundamentals. Electromagnetic radiation in the X-ray range of the spectrum may
be scattered (as employed in diffraction methods, see below) or absorbed. The rela-
tionship between the incident radiation intensity, I0 , and the transmitted one, I , is
given by Lambert’s law
I = I0 e(−μm m),
with the mass absorption coefficient μm and the mass per unit area m. The value of
μm increases with wavelength and there is no simple relationship. When the energy
of the incident radiation is sufficient to eject a core level electron, the μm shows
a sharp increase (edge) and the respective energy is typical of the absorbing ele-
ment. The actual value depends slightly on the state of oxidation of the element,
e.g. with increasing positive valency the energy shifts to higher values. For an in-
troduction, see [558]. A general overview of recent technological advances is avail-
able [559]. The element specificity of the absorption is employed in microradiology
(microradiography)—see Sect. 7.6.
Instrumentation. An overview of experimental approaches and results has been
provided elsewhere [560]. A cell suitable for time-resolved studies with XAS has
been described [561]. Ex situ studies of battery materials have been reported [562,
563].

5.3.3 X-Ray Absorption Fine Structure Spectroscopy

Fundamentals. The absorption of X-rays at high resolution close to the absorp-
tion edge of atoms under investigation can be measured in order to obtain informa-
tion about the structural and chemical environment of these atoms [564–566]. Mea-
surements at energies (wavelengths) slightly below the absorption edge are called
XANES31 (X-ray absorption near edge structure/spectroscopy) or NEXAFS (Near
30 Somewhat confusingly studies employing investigations of the absorption fine structure
(see p. 137) are sometimes also labeled simply XAS studies.
31 The final letter S in XANES, EXAFS, etc. refers both to structure and spectroscopy, thus
causing confusion in proper designation of results.
138 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.95. Characteristic SEXAFS spectra of atomic oxygen adsorbed on Cu(110) in a

Cu(110)-(2 × 1)-O arrangement, smooth line shows absorption of free atoms (based on data
in [571])

Fig. 5.96. Principle of photon interference in X-ray absorption

edge X-ray absorption fine structure/spectroscopy), whereas measurements around

the absorption edge and slightly above it are called EXAFS32 (extended X-ray ab-
sorption fine structure/spectroscopy). Because of the penetration depth of X-rays,
these methods are not intrinsically surface sensitive. Depending on the experimen-
tal setup and/or the selection of the X-ray energy, and in turn the atoms to be probed,
species at the interface can be studied specifically.
The absorption coefficient μ of an atom in a molecule or a solid has a fine struc-
ture33 amounting to about 15% of the absorption jump at the edge and extending
up to several hundred electron volts above the absorption edge, whereas a free atom
only shows a smooth absorption as seen in Fig. 5.95 [567].
The oscillations of the observed absorption are caused by interference between
the photon emitted from the absorbing atom and photon waves emitted from neigh-
bor atoms, as depicted in Fig. 5.96.
32 In its surface sensitive adaptation, the method is called SEXAFS (surface extended X-ray
absorption fine structure spectroscopy).
33 This absorption is sometimes called AXAFS (atomic X-ray absorption fine structure).

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 5.3 Spectroscopy in the X-ray Range 139

Fig. 5.97. Characteristic SEXAFS spectra of O adsorbed on Ni(111) in a Ni(111)-c(4×1)-NO

arrangement (based on data by [571])

When the neighbor atoms are surface atoms the distance between the atoms of
interest and the surface atoms r AS can be determined. This distance determines the
frequency of the absorption oscillation, whereas the amplitude is influenced by the
number and identity of the neighbors and their distance. The polarization of the in-
cident X-rays strongly influences the observed oscillations. Bonds with interatomic
vectors in the plane of polarization contribute significantly, whereas bonds perpen-
dicular to this plane do not (for further details, see [568]).
With atomic species, the near edge structure is of no further interest. With molec-
ular adsorbates, the near edge X-ray absorption is dominated by intramolecular tran-
sitions (μ- and σ -resonances). Their dependency on the polarization provides infor-
mation on the orientation of the molecule. From the energy of the σ -resonance in-
tramolecular bond lengths, r AB can be estimated for simple molecules. Figure 5.97
shows an X-ray absorption spectrum of NO adsorbed on a nickel surface.
These arguments are of course also valid for species on top of a surface. Fig-
ure 5.98 shows the structural information available from both spectroscopies. Dis-
tances can be determined with a precision of about ±1 pm and the number of atoms
can be determined with a precision of about 15%. Since no diffraction is involved,
samples without any long range ordering can be studied.
As already indicated, X-ray absorption spectroscopy is inherently not surface
sensitive. By adjusting the photon energy to a value matching the absorption edge
of species sitting on a surface, this sensitivity can be easily obtained. With photons
impinging at a grazing angle below the angle of total reflection, contributions from
the substrate are suppressed to a large extent [569] and the depth of information is
reduced to only a few nanometers. The method is called grazing incidence EXAFS
(GIXAFS).
Instrumentation. X-ray absorption spectroscopy is done mostly with synchrotron
radiation (see Chap. 4); for an introductory overview, see [570, 571]. The linearly
140 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.98. Structural features determined with X-ray absorption spectroscopy

Fig. 5.99. Setup for an X-ray absorption experiment in the fluorescence mode

polarized light is monochromatized (resolution down to 100 meV or better) and

guided to the sample as outlined in Fig. 5.99.
The electrochemical cell is mounted on a moveable holder, allowing measure-
ments at different angles and polarizations of the incident light. Unfortunately, the
number of atoms absorbing radiation is very small (a monolayer of atoms or even
less), thus simple absorption measurements like the ones that can be achieved with
bulk samples are impossible. Instead, the measurement of Auger electrons (possible
only under UHV conditions) or of fluorescence intensity is possible.
Alternatively, measurement in the transmission mode is possible. A simple cell
design has been described [572]; see Fig. 5.100.
The solution level is kept at the upper limit during electrochemical experiments,
providing complete participation of the working electrode surface in any electro-
chemical process. In order to minimize solution absorption of the X-rays, the level
is lowered before X-ray absorption measurements. As the lower edge of the working
electrode is still immersed in the electrolyte solution, electrode potential control is
maintained.
Evaluation of the measured absorption starts with subtraction of the smooth un-
derground and normalization. The oscillating absorption in SEXAFS contains infor-

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 5.3 Spectroscopy in the X-ray Range 141

Fig. 5.100. Electrochemical cell for XANES/SEXAFS measurements in the transmission

mode (based on a design in [576])

mation on distance, number and identity of neighbor atoms. Same atoms are sum-
marized in shells. Evaluation of polarization dependencies and further spectroscopic
data in XANES provide information about intramolecular bond length and the rela-
tive arrangement of adsorbate species with respect to the surface (for further details,
see [571]).
Depending on the type of measurement (absorption or emission), different types
of cells and samples have been employed. A slightly modified working fuel cell
using an ion exchange polymer membrane as solid electrolyte coated with vari-
ous catalyst layers has been described [573] that enables investigations of the plat-
inum and ruthenium atoms incorporated in the catalyst layers. In order to avoid
convolution of signals of both electrode layers (which are penetrated by the X-ray
beam), one catalyst layer (the cathode) was removed (cut out) in the area of the
beam path.
Time-resolved measurements can be made at storage rings with high flux in-
sertion devices that use a quick-scanning mode of operation of the monochroma-
tor [574]. In a reported study, products of Mo corrosion in KOH solution could be
identified and quantified [578]. Application of time-resolved dispersive high-energy
X-ray absorption fine structure (DXAFS) measurements on platinum nanoparticles
in a fuel electrode have been described [575]. Results indicate severe surface re-
construction of the nanoparticle surface, showing at least three types of Pt–O bonds
(adsorbed OH, adsorbed atomic O and amorphous PtOx ) under oxidative conditions.
Numerous studies pertaining to upd-adsorbates have been reported that contain
data on the bond distance between substrate atoms and deposits and the relative po-
sitions of the involved atoms [572–579]. Beyond these data the valence state of the
adsorbed atoms and modifications of the electronic structure of the support upon
adsorption of the upd-layer could be determined. In an approach where only the
absorption modulation intensity is evaluated, changed electronic properties of plat-
inum particles deposited on a carbon support could be explained by invoking chang-
ing charge on the metal as a function of the electrode potential [580]. In a compar-
ison of carbon-supported platinum modified with upd-Sn and a carbon-supported
142 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.101. Normalized XANES of copper foil (—–), Cu2 O (- - -) and upd-Cu on Pt/C (· · · · ·)
(based on data in [576])

platinum–tin alloy, the significantly higher electrocatalytic activity of the former

system was attributed to electronic effects. In the alloy, tin causes partial filling of
the d-band vacancies of platinum and an increase in Pt–Pt bond length. Upd-Sn
does not perturb platinum, either electronically or structurally. In both systems, tin
is associated with oxygen containing species at all electrode potentials [581]. In a
similar investigation of upd-Cu on platinum deposited on a carbon support, a result
as depicted in Fig. 5.101 was obtained.
A copper coverage of 0.57 was deduced. The position of the absorption edge
of upd-Cu is close to that of Cu+ . Further differences between the traces for upd-
Cu and Cu2 O were explained by invoking crystal symmetry; in this case upd-Cu
is present in a tetrahedral environment [576]. Stimulated by the considerable and
still growing interest in binary and ternary electrocatalysts, XANES and SEXAFS
(mostly combined) have frequently been used. The coverage of a single crystal plat-
inum surface with iodine was monitored [575] and results were found to be in good
agreement with those of AES at an emersed electrode at electrode potentials below
the estimated potential of zero charge E pzc [582]. The composition of a Pt–Ru alloy
with 25% of Ru in the actual alloy and an excess of 90% of Ru not alloyed at all was
reported [583]. Further details of the electronic band structure and changes in Pt–Pt
bond distances could be elucidated. The structure of small two-dimensional clusters
and linear nanostructures of copper and cadmium deposits on Pt(533) at character-
istic electrode potentials in the upd-range has been studied with GIXAFS combined
with GIXD [584]. Catalytic mechanisms at binary platinum–metal (metal = Co, Cr,
Ni, Fe) alloys deposited on carbon for water activation and dioxygen reduction in
perchloric acid have been elucidated with XANES and EXAFS [585]. A cell suit-
able for in situ investigations of catalysts in operating PEM34 fuel cells has been
described and applied for determination of coverage of PtRu catalysts with CO and
other species (O[H]) involved in the electrocatalytic processes as a function of cur-
34 PEM = polymer electrolyte membrane.

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 5.4 Magnetic Resonance Spectroscopy 143

rent [586]. Both a bifunctional mechanism and an electronic ligand effect are op-
erative in CO oxidation at PtRu surfaces. Changes of the electronic properties of a
cobalt porphyrin as a function of electrode potential and of interaction with solution
phase species has been monitored with XANES [587]. An overview of applications
in fuel cell studies is available [588].
Studies of passivation layers and corrosion phenomena, particularly with iron
and magnesium using EXAFS, NEXAFS and related X-ray absorption spectro-
scopies have been reviewed elsewhere [589]. Using GIXAFS, depth profiling has
become possible and spatially resolved studies of silver dissolution and lithium in-
tercalation have been reported.
The formation and dissociation of S–S bonds in poly(tricyanuric acid), which is
proposed as electrode material for lithium batteries, has been studied [590, 591]. The
reversibility of the process essential for the use of this material in a secondary battery
could be established. Further studies of battery materials have been reported [592,
593]. X-ray absorption near edge structure spectroscopy has been successfully em-
ployed in studies of inhibiting species in passive films and the adjacent electrolyte
solutions.

5.4 Magnetic Resonance Spectroscopy

Magnetic resonance spectroscopies are methods capable of detecting transitions of
spin orientations of electrons or atomic nuclei between states separated energeti-
cally under the influence of an external magnetic field. Transitions involving the
spin of the nucleus of an atom with a nonzero magnetic moment are studied with
nuclear magnetic resonance spectroscopy (NMR), whereas transitions involving the
spin of unpaired electrons in paramagnetic samples are investigated with electron
spin resonance spectroscopy (ESR).35 Both methods are widely employed in ana-
lytical chemistry. Nuclear magnetic resonance spectroscopy, preferably of protons,
13 C-atoms and further selected atoms, is presumably the most important method

in analytical organic chemistry. Electron spin resonance spectroscopy is used less

frequently in studies of free radicals (chemical species with unpaired electrons) ob-
served typically in organic reactions and in investigations of transition metal ions
and paramagnetic substances.
Because in many electrochemical reactions, particularly in electroorganic ones,
radicals are formed as reactive intermediates, ESR has been applied frequently to
studies of the mechanism and the kinetics of these reactions [594–596]. Although
possible, NMR spectroscopy has been used infrequently and only in very recent
experiments, mainly because of the considerably larger experimental effort [597].
With NMR spectroscopy, information about surface structure, surface diffusion and
electron spillover from the metal electrode onto an adsorbate can be obtained. So
35 This method has frequently been called electron paramagnetic resonance spectroscopy
(EPR) because the presence of one or several unpaired electrons, being a precondition for
this spectroscopy, is also closely related to the phenomenon of paramagnetism.
144 5 Spectroscopy at Electrochemical Interfaces

far, an application as broad as that of ESR has not materialized. Both methods have
been employed infrequently to monitor the concentration of species involved in elec-
trochemical reactions in order to established reaction kinetic parameters, activation
energies, etc. These applications do not fall within the scope of this book, so they
are not considered here.
Fundamentals. Atoms are composed of nucleons: electrons, protons and neutrons
(except the hydrogen atom, which has no neutron). These elementary particles have
a spin—a property described in classical physics as a rotational movement of the
particle around its own axis. It is a quantum property showing only certain quan-
tisized values; for the electron, the spin is s with the corresponding spin quantum
number s = 1/2. The spin of an atomic nucleus, I , is composed √ of contributions
of the nucleons. The corresponding angular momentum is |s| = h̄/ s(s + 1). This
momentum is a vector, and its component parallel to a magnetic field H oriented
in the z-direction can be +h̄/2 or −h̄/2. Because the proton and the electron are
charged particles, their rotation corresponds to a flow of electricity. This results in a
magnetic momentum for the electron:

ms = g e γ s = γ e s,

with g e = electron g-factor, γ = magnetogyric ratio and γ e = electron magneto-

gyric ratio.
When considering an atom containing these nucleons in numbers characteristic
for a given element, the resulting properties of the atom are slightly more complex.
The resulting spin of the atomic nucleus depends upon the number of protons and
neutrons and the relationship between both as listed in Table 5.1.
The value of the magnetic momentum ml for the atomic nucleus is

ml = g N γ I = γ N I ,

with g N = nuclear g-factor and γ N = nuclear magnetogyric ratio.

In atoms or molecules containing several electrons, only unpaired electrons
present in singly occupied atomic or molecular orbitals show an effective magnetic
momentum.
The vectors representing the nuclear or the electron angular momentum and
the associated magnetic momentum of particles in a given sample are randomly
orientated. This is changed drastically when the sample is exposed to an external

Table 5.1. Resulting nuclear spins as a function of protons and neutrons

np nn Resulting nuclear spin I Example
odd odd integer number 2 H, 14 N, 10 B
odd even half-number value H, 13 C, 15 N, 19 F, 31 P, 11 B, 29 Si
even odd half-number value see above
even even zero 12 C,16 O, 28 Si, 30 Si

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 5.4 Magnetic Resonance Spectroscopy 145

magnetic field. Because of the interaction between the magnetic field and the mag-
netic momentum of the electron or the atomic nucleus, the momentum is oriented in
one of two possible directions relative to the external field vector. The momentum
is not oriented exactly parallel to the field vector; consequently the vector shows a
precession movement with a characteristic Larmor frequency. A calculation of the
potential energy of the species in the magnetic field is based on the size of the vec-
torial component of the magnetic moment in the z-direction. This is given for an
electron by
|msz | = |−g e μB ms |,
with μB = Bohr magneton.
The corresponding value for a nucleus is

|mlz | = |g N μN mN |,

with μN = nuclear Bohr magneton.

The potential magnetic energy E for a dipole mz in a magnetic field is

E = −mz B.

With the electron, the result is

E = g e μB ms B,

for the nucleus it is

E = −g N μN ml B.
For a proton with mN = 1/2 only two orientations corresponding to ml = 1/2 and
ml = −1/2 are possible; this case will subsequently be considered as an example
for NMR. Of course, other nuclei with mN > 1/2 possess more than only two
nondegenerate energy levels. They are spaced equally, which implies that only one
resonant transition is observed.
For both the electron and the nuclear momentum the calculated energy depends
upon the actual orientation of the momentum vector. The values that are energeti-
cally lower are those corresponding to ms = −1/2 and ml = +1/2. Energies for
the electron are larger by three orders of magnitude. The actual energies and the dif-
ferences between various orientations depend upon the magnitude of the magnetic
field. A calculation of the difference is possible by assuming a temperature of 300 K
and a magnetic flux density of B = 0.3 T for investigations of the electron spin and
B = 1.409 T for those of the nuclear (in this example, the proton) spin. Results are:

ΔE s = g e μB B = 5.57 · 10−24 J

and
ΔE N = g N μN B = 3.97 · 10−26 J.
The differences in population between the corresponding states can be calcu-
lated by assuming a Boltzmann distribution. For the electron spin, the ratio ns,high /
146 5 Spectroscopy at Electrochemical Interfaces

ns,low = 0.99866; for the proton, nN,high /nN,low = 0.99999039. A transition of the
orientational state of the spins from the lower into the higher state is possible only if
the necessary energy is supplied under resonant conditions to the system. Continu-
ous absorption of this specific energy occurs only when there is a smaller population
of the higher energy level. This in turn depends upon relaxation of the spins from the
higher state into the lower one, which is possible only when effective ways of dissi-
pating the energy exist. Spontaneous emission, which provides an effective path of
depopulating higher levels in optical spectroscopies, is extremely low and can be ne-
glected. Consequently, stimulated emission initiated by the incoming radiation and
interactions with other particles (spin–spin relaxation) and the surrounding matter
(spin–lattice relaxation) provide the required energy dissipation. Since the differ-
ence in energies between both states of orientation depends upon the strength of the
magnetic field B, the resonance condition is described properly by stating both B
and the frequency of the electromagnetic radiation. For a proton in a magnetic field
with a flux density of B = 1.409 T, the frequency is 60 · 109 s−1 ; at a stronger mag-
netic flux density of B = 11.74 T, which is employed in advanced spectrometers,
resonance occurs at 500 · 106 s−1 . For an electron in a field of B = 0.34 T the value
is 9.5 · 109 s−1 .
The previous discussion assumes that both the unpaired electron(s) and the
atomic nuclei interact solely with the magnetic field. Correspondingly, the reso-
nance condition should be fixed as described. In reality, both are surrounded by
other species that influence the effective magnetic field at the location of the elec-
tron or nucleus by means of their own electric and magnetic properties. Based on
the type of chemical bond and the electronegativity of the participating elements, the
electron density at the atom under investigation can change considerably. In the case
of the nucleus, the resulting effect is particularly pronounced. The actual resonance
condition is changed accordingly. Appropriately, this is called a chemical shift; be-
cause of its high specificity, it can be used as a tool in identification of the molecular
structure. The influence upon the unpaired electrons is much smaller and of only
very limited analytical value. Besides this effect, which is related to the local elec-
tron density, the magnetic spins of neighboring atoms can influence the local field.
Depending upon the relative orientation, the field is increased or decreased and the
resonance condition is changed again. Because of the number of combinations of
orientations of magnetic spins in a multi-atom system, several additional resonant
transitions may occur. The effect is termed hyperfine splitting with ESR; in NMR, it
is called spin–spin splitting because it is the result of an interaction of nuclear spins.
In solid samples anisotropic effects of electrostatic or magnetic fields caused by the
atomic or molecular constituents of the sample and their particular arrangement can
also change the effective magnetic field, resulting in both shifts and splitting. This
effect is not present in liquid and gaseous samples. With both spectroscopies the
number of additional lines, their relative intensities and energetic difference provide
valuable information for the elucidation of the molecular structure. In the electro-
chemical applications discussed below in more detail, ESR is used more often, thus
some example will illustrate the brief outline of magnetic resonance spectroscopies.

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 5.4 Magnetic Resonance Spectroscopy 147

Fig. 5.102. Calculated ESR absorption spectrum of the methyl radical

The number N of lines created by n nuclei labelled k of spin I k is


N= (2nk I k + 1).
k

The distance of the lines corresponding to the energetic difference is stated by

giving a splitting constant a (sometimes also called the coupling constant). The
relative intensity of the lines depends upon the probability of transitions between the
states involved; this in turn depends on the probability of the various combinations
of orientations. In Fig. 5.102, the calculated ESR spectrum of the methyl radical is
depicted.
As in ESR spectra, because of the mode of detection of the absorption signal
(see p. 149) the first derivative is always measured and the simulated spectra shown
here are plotted accordingly. With a spin I H = 1/2 and n = 3, the number N of
lines is four. A surprisingly simple spectrum (as shown in Fig. 5.103) results with
a considerably more complex molecule: di-tert-butyl nitroxide in its radical form.
We can understood it easily when taking into account that the unpaired electron is
located at the nitrogen atom (I = 1), whereas both oxygen and carbon have I = 0
(see p. 144).
A check for the correctness of a simulated spectrum is provided by comparing
calculated and measured spectra. In Fig. 5.104, the measured and the calculated
spectra of the electrochemically generated nitropropane radical are shown.
Upon the rather wide splitting caused by the nitrogen atom, a further splitting
caused by the two methylene hydrogen atoms at the carbon atom next to the nitrogen
is superimposed. The hydrogen atoms at the vicinal methyl group are too far away
and do not cause any further splitting. Further details are discussed in textbooks of
magnetic resonance spectroscopy (see suggested reading).
Instrumentation. From the description of the fundamentals of magnetic resonance
spectroscopy, basic building blocks and functional elements of the experiment can
148 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.103. Calculated ESR absorption spectrum of the di-tert-butyl nitroxide radical

Fig. 5.104. ESR absorption spectrum of the electrochemically generated nitropropane radical
anion; E NHE = −1740 mV; top: measured spectrum, bottom: calculated spectrum; hyperfine
splitting constants a N = 2.48 mT, a H = 0.998 mT

be derived easily: The sample has to be brought into a magnetic field of appro-
priate strength. The energy corresponding to the difference between the two states
of the nuclear or electron spin is supplied as electromagnetic radiation of suitable
frequency—generally in the radio frequency range or, more precisely, in the micro-
wave range for ESR and in the UHF range for NMR.36 Because of the modes of
propagation of radiation in the micro-wave range waveguides have to be used in-
stead of cables. The sample is inserted into a cavity at the end of a waveguide in
between the poles of the magnet. Since the actual resonance conditions are shifted
from the reference values stated above, either the strength of the magnetic field (i.e.
the magnetic flux) or the radiation frequency has to be tuned in order to detect the
actual resonance. A modulation of the frequency of the radiation supplied at con-
36 UHF: ultra high frequency.

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 5.4 Magnetic Resonance Spectroscopy 149

stant intensity (cw: continuous wave) with the necessary precision and stability is
somewhat difficult to obtain for reasons related to high frequency electronics. A di-
rect modulation of the magnetic field by simply changing the current flowing across
the coils of the electromagnets, which are employed frequently in NMR and prac-
tically exclusively in ESR, is cumbersome because of the need to control pretty
large electric currents. This is impossible in the case of very strong magnets that
use superconducting coils, anyway. A more effective approach is the addition of
small coils attached to the poles of the main magnet. The additional magnetic flux
provided by these modulation coils can be easily controlled. Consequently, the res-
onance conditions are probed by slowly changing the magnetic field. Absorption of
electromagnetic radiation can be detected by various means. The actual absorption,
particularly with ESR, is rather small because of the small difference in occupa-
tion of both states. An increase of sensitivity can be obtained by applying sophis-
ticated amplification and detection methods (phase sensitive detection with lock-in
amplifiers). In the case of ESR, this results in spectra that are equivalent to the first
derivative of the actual absorption spectrum. More recently, the Fourier transform
(FT) technique already described in Sect. 5.2 as applied to vibrational spectroscopy
has been adapted for ESR and NMR. The electromagnetic radiation is supplied as a
pulse. Detection and data manipulation is more complex, the advantage is a greatly
enhanced sensitivity. This is described in more detail in textbooks of spectroscopy.
Basically, an NMR or ESR spectrometer is composed of a magnet; a radio fre-
quency generator; an additional generator driving the field modulation coils; and
the necessary detector, data manipulation, and storage electronics. The sample is
inserted into the magnet between its poles. Some preparation of the sample is gen-
erally necessary; materials containing ESR- or NMR-active substances have to be
avoided as sample holders. Various types of cuvets for solid, liquid and gaseous
samples are in use. In NMR spectroscopy, quartz tubes of various diameters that are
free of paramagnetic impurities are used almost exclusively. In ESR spectroscopy,
different shapes (tubes, flat cells) of cuvets are used, depending upon the type of
cavity (cylindrical ones for the former, rectangular ones for the latter cuvets).
For electrochemical applications, the experimental arrangement is rather sim-
ple. Because of the broad application of ESR, this method is treated first. Some
additional information on NMR in electrochemistry can be found at the end of this
section. In ESR experiments the spectrum can be recorded when the species un-
der investigation is created either just inside the spectrometer (intra muros genera-
tion, subsequently treated as the in situ method) or outside the spectrometer (extra
muros). In the latter case the sample has to be transferred by means of a flow appa-
ratus or by removal of a small sample from the electrochemical cell, which is put
into a standard ESR cuvet. For reasons already outlined in Chap. 4, the latter pro-
cedure, which is similar to an ex situ experiment, carries some inherent sources of
error because of the limited lifetime or subsequent chemical reactions of the species
initially created by the electrochemical reaction. Since no particular design of the
cuvet is necessary with respect to the ESR spectrometer, the latter procedure will
not be discussed in detail.
150 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.105. ESR spectrum of the hydrogen adduct of NtB generated electrochemically at
E SCE = 0.2 V in an aqueous solution of 0.5 M LiClO4 [598]

The experimental requirements of the spectrometer and an appropriate electro-

chemical cell design need to be considered in the generation of species and their
detection inside the cavity of the ESR spectrometer. Since most electrochemical re-
actions proceed at metal electrodes, a very fundamental problem is encountered in
any attempt to obtain ESR spectra of radicals that are still adsorbed, i.e. interact-
ing strongly, on the electrode surface. This interaction between the unpaired elec-
tron of the radical and the electrons in the metallic conductor will quench the free
spin and no ESR spectrum will be observed. This is different with semiconductor
or insulator electrode surfaces. The quenching can be suppressed by coating the
electrode with a layer of nonmetallic material (chemically modified electrode), but
obviously this may change the interesting properties of the electrode considerably.
Nevertheless ESR-active species can be detected as soon as they leave the elec-
trode surface and stay in the electrolyte solution at a sufficiently large concentration
for a time long enough to allow the measurement of a spectrum. The first require-
ment seems somewhat odd at first glance because ESR is a rather sensitive spec-
troscopy. Paramagnetic species at a concentration as low as 10−10 mol dm−3 can be
detected easily. Unfortunately the high reactivity of organic radicals tends to keep
the stationary concentration low. In addition, the components of the electrochemi-
cal cell (electrolyte, solvent, electrodes) reduce the sensitivity of the spectrometer
considerably—particularly by increasing dielectric losses. Detection of radicals that
are present in only very small concentrations or have a short lifetime can be facil-
itated by using “spin traps”. These are mostly organic compounds that form stable
radicals by reaction with the radicals formed during the investigated process. In
many cases, these spin traps contain a nitroso group. The observed ESR spectra are
more or less complicated depending on the type of spin trap and the trapped radical.
A fairly simple spectrum is obtained by using t-nitroso-butane (NtB) as a spin trap
(for further details, see pp. 150, 158). The adduct formed with hydrogen radicals
causes the spectrum depicted in Fig. 5.105; for further details, see pp. 150, 158.

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 5.4 Magnetic Resonance Spectroscopy 151

Fig. 5.106. Cell design for ECESR spectroscopy according to Maki and Geske [599]

Fig. 5.107. Cell design for ECESR spectroscopy according to Piette et al. [606]

A first cell design with two electrodes was reported by Maki and Geske [599–
603] (Fig. 5.106). A platinum wire used as a working electrode was mounted in the
center of a quartz tube that served as a cell vessel, which is placed in the middle of
the ESR cavity at the position of highest sensitivity. A platinum wire as the counter
electrode was mounted in the tube at a position outside the cavity of the spectrom-
eter. Any species created at this counter electrode were not detected; in addition,
the distance between both electrodes reduced the risk of unwanted electrochemical
reactions at the working electrode of species created at the counter electrode. The
small actual surface area of the working electrode limited the rate of formation of
species to be studied; very precise positioning was required. Despite its simplicity,
this cell design has nevertheless been used continuously even with its obvious draw-
backs and limitations [604]. Using a vanadium wire as working electrode, VO2+
ions could be identified as electrooxidation products [605].
An increase of the surface area was realized by Piette et al. [606] (Fig. 5.107).
A platinum gauze electrode was put inside a flat cuvet used as the electrochemical
cell. The counter electrode was mounted inside a glass tube attached to the flat cell
below the working electrode and outside the ESR cavity.
A cell of this design was employed in studies of microcrystal solids attached
to a platinum flag electrode [608]. The measured ESR spectrum of electrochem-
ically reduced 7,7
,8,8
-tetracyanoquinodimethane was in perfect agreement with
the respective spectrum of the chemically prepared compound and the simulated
spectrum.
152 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.108. Cell design for ECESR spectroscopy according to Möbius [609]

Fig. 5.109. Cell design for ECESR spectroscopy according to Piette et al. [611]

A cell design suitable for investigations with a mercury electrode was described
by Möbius [609, 610] (Fig. 5.108).
Unfortunately these two-electrode cell designs did not allow for proper control
of the electrode potential of the working electrode. In a modified design, Piette et
al. [611, 612] added a reference electrode connected to the electrolyte volume via
the glass tube on top of the flat cell (Fig. 5.109).
This design has been employed to study the electrochemistry of microdroplets
attached to an electrode in contact with an electrolyte solution [613]. A micro-
droplet of N ,N ,N
,N
-tetrahexylphenylene diamine deposited onto a gold electrode
immersed into an aqueous electrolyte solution showed only a symmetric single
line ESR signal similar to those observed with intrinsically conducting polymers.
A well-resolved spectrum showing the expected hyperfine structure was observed
in a dilute solution of the same molecule in a suitable organic solvent. Using a
commercially available cell of this design, the electrochemical properties of some
naturally occurring α-hydroxyquinones have been studied [614].
A design similar to that of Piette et al. was reported by Koopman and Gerischer
[615] (see Fig. 5.110).
A significantly simpler cell design with a smaller working electrode surface and
consequently smaller currents flowing through the cell in the case of potentiostati-
cally controlled measurements has been reported by Bagchi et al. (Fig. 5.111) [616].

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 5.4 Magnetic Resonance Spectroscopy 153

Fig. 5.110. Cell design for ECESR spectroscopy according to Koopman and Gerischer [615]

Fig. 5.111. Design of an ECESR cell proposed by Bagchi et al. [616]

A capillary tube housing a platinum wire that acts as a reference electrode fits into
a modified cuvet that is placed in the microwave cavity of the ESR spectrometer,
thus displacing most of the electrolyte solution in the lower part of the cell that is
exposed to the microwave. Accordingly solvents with high dielectric constants can
be used with a satisfactory ESR response. The platinum wire sealed into the bottom
of the Pyrex cuvet that acts as the working electrode can be coated easily with a
drop of mercury for experiments where this type of electrode is required. The Pyrex
glass may cause unwanted ESR signals; unfortunately, platinum cannot be sealed
directly to quartz glass.
Mu and Kadish have described an ECESR cell with a thin layer design suitable
for measurements at both ambient and low temperatures [617]. The thin layer of
electrolyte solution is enclosed by the quartz tube inserted into the microwave cav-
ity of the ESR spectrometer and a solid quartz rod fixed in the center of the tube. An
expanded platinum mesh in the gap is used as the working electrode. At low elec-
trode potential scan rates, the cell shows an acceptable electrochemical response.
A mechanically robust ECESR cell that is suitable for measurements even at
very low temperatures with all kinds of electrolyte solvents and that employs a plat-
inum wire loop as the working electrode located at the bottom of a 4 mm ESR cuvet
has been developed by Fiedler et al. [618]. The reference and counter electrodes
are placed above the working electrode outside of the sensitive region of the ESR
cavity.
154 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.112. Cell design for ECESR spectroscopy according to Dohrmann and Vetter [619–
622]

Fig. 5.113. Cell design for ECESR spectroscopy according to Goldberg and Bard [623]

The very small electrolyte volume present inside the flat cell poses a serious
problem, because the concentration of the reacting species is rapidly diminished
upon continuous flow of a Faradaic current. In the latter design, this was corrected
by a slow upward flow of electrolyte solution through the cell. A very similar setup
was described by Dohrmann and Vetter (Fig. 5.112) [619–622].
The fairly long solution pathways in the three-electrode cell designs caused a
poor dynamic response of the cell under instationary conditions; the electrode poten-
tial control was imperfect. A flat cell design by Goldberg and Bard [623] provided
considerable improvement (Fig. 5.113). The limited amount of electrolyte solution
resulted in fast depletion of reactand.
A considerable improvement in terms of electrode potential distribution inside
the ECESR cell, available electrolyte solution volume and ease of manufacturing
was provided with the cell design of Allendoerfer et al. [624, 625], which was sub-
sequently improved by Heinzel et al. [606, 626]. A metal wire coil of the working
electrode material is inserted into a quartz glass tube. Because of the limited pen-
etration depth of the microwaves, only the solution volume enclosed by the wire
surface and the inner glass wall was probed. The insertion of the counter and the
reference electrode centrally inside the working electrode coil can be made without
major constraints caused by cell or working electrode design. Because of the size

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 5.4 Magnetic Resonance Spectroscopy 155

Fig. 5.114. The components of an ECESR cell according to Heinzel et al. [606]

Fig. 5.115. Cyclic voltammogram of a platinum wire working electrode inside an ECESR
cell according to Heinzel et al.; electrolyte solution 0.5 M H2 SO4 , dE/dt = 50 mV s−1 ;
nitrogen purged [627]

of the cell, a less common large cylindrical microwave resonator cavity is required.
The cell components and their placement inside the resonator between the magnet
poles are shown in detail in Fig. 5.114.
The superior electrochemical performance of this design is demonstrated with a
cyclic voltammogram, as shown Fig. 5.115.
The cell has been employed in studies of the electrooxidation of organic fu-
els [606, 608–628] and of the nitrogen-containing monomers for the generation of
intrinsically conducting polymers [629–631]. In numerous studies, films of intrin-
156 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.116. ESR spectra of a film of polyaniline in a solution of 0.1 M LiClO4 in acetonitrile

sically conducting polymers deposited onto the working electrode have been inves-
tigated [632–634]. Because of the high degree of delocalization, the radical cations
created by the oxidation (p-doping) of the film show only a single line. The ampli-
tude of the signal corresponds to the concentration of free spins and thus presumably
to the number of mobile charge carriers. In a plot of ESR spectra obtained as a func-
tion of electrode potential, this can be illustrated (Fig. 5.116). The striking similarity,
which in some cases even extends to small asymmetries in line shape, has caused
early erroneous assignments of the line to mobile electrons as observed with ESR
in case of metals by Dyson (Dysonian line, [635]).
The major drawbacks of cells with stationary solutions or very low solution flow,
as described above, are the limited supply of reactand and consequent limited max-
imum concentration of species to be studied. Various designs of flow-through cells
have been proposed. A review by Bagchi et al. [636] describes selected examples.
Since it has been shown that the stationary concentration of the species to be de-
tected decreases with an increasing flow rate [637], the actual operating conditions
have to be optimized individually. A cell design as proposed by Bagchi et al. [623]
is shown in Fig. 5.117.
An optimized design employing a tubular electrode in a cylindrical cavity has
been described [638]. The mechanism and kinetics of the electrooxidation of several
para-haloanilines and the follow-up reactions in acetonitrile have been investigated
with this cell [639]. A similar design that is suitable for low temperature measure-
ments (233 K) has been reported [640]. It has been employed in a study of the
temperature dependence of the reduction of bromonitrobenzene in acetonitrile solu-
tion. The electroreduction of perinaphthenone in a single electron process has been
investigated with this cell [641]. The lifetime of the neutral radical formed by de-
protonation of the radical anion has been estimated to be around 1 min. A similar
electrochemical behavior of benzanthrone was observed.
Free radicals formed by the electroreduction of several different nitroso phenyl
1,4-dihydropyridines at a mercury electrode were studied with a flat ECESR cell

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 5.4 Magnetic Resonance Spectroscopy 157

Fig. 5.117. Design of a flow-through ECESR cell proposed by Bagchi et al. [623]

(not further specified) in an aprotic medium [642]. Increasing stabilization of the

free radical with increasing bulkiness of the alkyl substituents from methyl to iso-
propyl in 3- and 5-position was found.
A combination of ECESR and in situ UV-Vis spectroscopy has been proposed by
Petr et al. [643]. In the case of a cell that was designed to be similar to the ECESR
cell proposed by Piette [613], a UV-Vis spectrometer is coupled with the cell via
fiber optics. The working electrode is of a minigrid type. A cell design with an
electrochemical cell directly coupled with a cuvet fitting into the ESR spectrometer
has been described by Friedrich and Baumgarten [644].
Although the detection limit for ESR spectroscopy per se is extremely low, the
use of electrochemical cells filled with solvents that have high dielectric constants
results in considerable losses in the cavity of the ESR spectrometer. This in turn
increases the limit of detection. In the case of electrode reactions that have only
very small stationary concentrations of radicalic intermediates, detection may be
impossible. The use of spin traps may help. These compounds are rather simple or-
ganic molecules that react easily with radicals forming adducts (see Fig. 5.118). The
molecular structure of the intermediate may be deduced from the known structure
of the spin trap and the observed ECESR spectrum. Unfortunately, this technique
doesn’t necessarily trap the major reaction intermediate; rather, it only traps those
which react easily with the spin trap. Consequently, misinterpretations are possible.
Cell designs for in situ NMR spectroscopy with electrochemical cells are scant.
Because of the low sensitivity, designs with working electrodes that have large active
surface areas (powder electrodes, metal-coated inert supports like silica or alumina)
have been described [645, 646]. This is a result of the fact that, in a typical NMR
experiment, about 1019 spins are required. Assuming 1015 surface atoms on 1 cm2
metal surface area at complete coverage of all adsorption sites, a 1 m2 working
electrode surface area is required. A typical design is shown in a schematic drawing
in Fig. 5.119. If continuous electrode potential control during the acquisition of the
NMR spectrum is desired, particular attention has to be paid to proper shielding and
decoupling of the electrical wiring between the potentiostat and NMR probe head.
158 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.118. Examples of organic compounds used as spin traps in ECESR spectroscopy

Fig. 5.119. Schematic drawing of an electrochemical cell for in situ NMR spectroscopy [649].
A: counter electrode connection; B: reference electrode joint; C: counter electrode; D: plat-
inum black working electrode; E: working electrode connection; F: purge connection

Results reported so far pertain in particular to 13 C NMR spectroscopy of ad-

sorbed CO and CN− ions on platinum [649, 647, 648]. Besides information about
surface diffusion and electronic adsorbate–surface interaction, data on the effect
of the strong electric field at the electrochemical interface (typically 107 V cm−1 )
have been reported. With both adsorbates the 13 C resonance becomes more shielded
at more positive electrode potentials as expected when assuming an adsorbate at-
tachment via the carbon atom. These results were supported with data from 195 Pt

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 5.5 Magnetooptic and Magnetic Methods 159

NMR spectroscopy [649]. Differences in the electrooxidation of methanol and CO

on carbon-supported platinum have been associated with different linewidths of the
13 C signal [650].

The use of NMR spectroscopies with various species, e.g. H, F, Na, Al or Li, in
studies of solid electrolytes has been reviewed elsewhere [651].

Further Reading
On ESR spectroscopy:
R. Kirmse, J. Stach, ESR-Spektroskopie (Akademie-Verlag, Berlin, 1985)
J.E. Wertz, J.R. Bolton, Electron Spin Resonance (Chapman & Hall, New York, 1986)
N.M. Atherton, Principles of Electron Spin Resonance (Ellis Horwood/Prentice Hall, Chich-
ester, 1993)
K. Scheffler, H.B. Stegmann, Elektronenspinresonanz (Springer, Berlin, 1970)
C.P. Poole, Jr., Electron Spin Resonance (Dover, Mineola, 1996)
C.P. Poole, H.A. Farach, Handbook of Electron Spin Resonance, vol. 1 (AIP, 1997)
C.P. Poole, H.A. Farach, Handbook of Electron Spin Resonance, vol. 2 (Springer, 1999)
J.A. Weil, J.R. Bolton, Electron Paramagnetic Resonance (Wiley, Hoboken, 2007)
On NMR spectroscopy:
J.W. Akitt, NMR and Chemistry (Chapman & Hall, New York, 1983)
E.D. Becker, High Resolution NMR (Academic Press, New York, 1980)
F.A. Bovey, Nuclear Magnetic Resonance Spectroscopy (Academic Press, New York, 1988)
R.K. Harris, Nuclear Magnetic Resonance Spectroscopy (Longman Scientific & Technical,
Essex, 1986)

5.5 Magnetooptic and Magnetic Methods

5.5.1 Magnetic Circular Dichroism
Fundamentals. Linearly polarized light passing an optically transparent material
in a magnetic field will show a rotation of the plane of polarization (Faraday effect).
This phenomenon is also called magnetooptical rotation (magnetooptical rotatory
dispersion) and is closely related to the Zeeman effect. Electronic transitions are
affected by the external magnetic field in various ways. The ground or the excited
state may split or a mixing of states may occur. Further details and accompany-
ing changes in the observed spectra are described in detail elsewhere [652]. As a
result, information pertaining to the electronic structure of the investigated mole-
cules may be obtained. Spectroelectrochemical studies reported so far have only
employed light in the UV-Vis range; basically, extension into the NIR range seems
to be possible [653].
Instrumentation. The spectroelectrochemical cell described by Kobayashi and Ni-
shiyama includes a minigrid working electrode in a glass cuvet (approx. 3 mm op-
tical pathlength) attached to the bottom of a cylindrical cell body with counter elec-
trode and reference electrode mounted therein. The cuvet is exposed to the magnetic
160 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.120. MCD (top) and conventional UV-Vis spectra of an aqueous solution of 10−4 M
tetrasulfonated cobalt(III)phthalocyanine in 0.05 M H2 SO4 , H = 7.7 T, based on data
in [660]

field [654]. An experimental setup suitable for measurements with solid electrodes
(e.g. polycrystalline gold) has been described by Zhao et al. [655, 656]. The loss in
active surface area as compared to the previously described design is compensated
in part by a modified beam path arrangement. The light of a tungsten halogen lamp
passes a monochromator, a fixed polarizer and a photoelastic modulator. It is col-
limated and directed into the bore of a superconducting magnet. The cell mounted
inside the magnet is of a thin layer design. The beam is reflected off the working
electrode at near normal incidence. The reflected beam is guided with an additional
mirror towards the photomultiplier detector. A conventional UV-Vis spectrum and
an MCD spectrum obtained with this experimental setup are shown in Fig. 5.120.
The UV-Vis spectrum shows a prominent Q-band around 668 nm. The MCD
spectrum implies an axially coordinated complex with at least a threefold symmetry
axis. The degenerate excited state thus possible is non-degenerate in the magnetic
field, resulting in further optical transitions at different energies selectively excited
by right and left circularly polarized light. Further systems that have been investi-
gated include additional transition metal complexes (tetracarboxylated phthalocya-
nines) [658].

5.5.2 Magneto-Optical Kerr Effect (MOKE)37

Fundamentals. The plane of polarization and the ellipticity of light of a fixed

wavelength are changed upon reflection at the surface of a magnetic material ex-
37 When applied in surface investigations, this effect is also called surface magneto-optical
Kerr effect (SMOKE) [661].

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 5.5 Magnetooptic and Magnetic Methods 161

Fig. 5.121. Possible geometries in SMOKE experiments: (top) longitudinal; (middle) trans-
verse; (bottom) polar

posed to an external magnetic field38 (magneto-optical Kerr effect39 ) [657]. When

the light is linearly polarized, it becomes elliptically polarized in the reflected beam.
When only p- or s-polarized light is employed, the state of polarization is main-
tained and the plane of polarization is only rotated. In the polar Kerr effect, the
plane of reflection of the employed beam of light and the magnetization are per-
pendicular with respect to the surface; in the longitudinal effect, the beam impinges
non-perpendicularly and the magnetization is oriented in the plane of reflection.
In the transverse (equatorial) Kerr effect, the magnetization is perpendicular to the
plane of reflection. These different geometries (see also Fig. 5.121) enable detection
of the orientation of the magnetization of the sample under investigation.
The amount of change is directly proportional to the magnetization of the re-
flecting surface layer. The probing depth is about 10–20 nm, thus the method is not
particularly surface sensitive [658–660]. If surface specificity is required, magne-
tization induced second harmonic generation might be useful; applications of this
method under in situ conditions in electrochemical studies have not been reported
so far.
Instrumentation. The surface under investigation is exposed to an external mag-
netic field with adjustable strength. Illumination of the surface is accomplished by a
laser beam. Although laser light from most sources is already polarized, a polarizer
is employed between source and cell and an additional polarizer adjusted to maxi-
mum extinction at 90° rotation is mounted between cell and detector. Any change in
the position of the plane of polarization causes a rise in the detector signal. A me-
chanical chopper at the source is added for better signal processing. A typical cell
38 This effect is related to the Cotton–Mouton effect of magnetic birefringence.
39 The Kerr effect is observed upon reflection, whereas the Faraday effect is observed in
transmission [as employed in optical components for ellipsometry (Sect. 5.9.5)]. The Kerr
effect itself relates to the change of the refractive index of a medium exposed to an electric
field.
162 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.122. Longitudinal MOKE results of a nickel film (thickness as indicated) on a Ag(111)
supporting electrode; film deposited from aqueous solution of 1 mM NiSO4 + 10 mM
H3 BO3 , corrected for diamagnetic contributions from cell window and solution, based on
data in [662]

Fig. 5.123. Polar MOKE results of a nickel film (thickness as indicated) on a Ag(111) sup-
porting electrode; film deposited from aqueous solution of 1 mM NiSO4 + 10 mM H3 BO3 ,
corrected for diamagnetic contributions from cell window and solution, based on data in [662]

and optical setup have been described [662, 664]. A representative set of results is
displayed in Figs. 5.122 and 5.123.
Applications in studies of magnetic layers and monolayers have been reported
frequently [663, 664]. Ultrathin cobalt film that is deposited under particularly clean
conditions has been studied [665]. In ex situ studies of electrochemically deposited
mono- and multilayers, SMOKE has been employed [666, 664]. The capability of
MOKE to study buried interfaces has been demonstrated [667].

5.5.3 Alternating Gradient Field Magnetometry (AGFM)

Fundamentals. A ferromagnetic sample at the end of a glass rod is suspended in

an alternating magnetic field gradient ∇H generated by an AC current into the two

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 5.5 Magnetooptic and Magnetic Methods 163

Fig. 5.124. AGFM results (parallel configuration) of a nickel film (thickness as indicated) on
a Au(111) supporting electrode; film deposited from aqueous solution of 1 mM NiSO4 +
10 mM K2 SO4 + 0.1 mM KCl + 1 mM H2 SO4 , based on data in [668]

coils on both sides of the sample. The frequency of the AC current is tuned to the
resonance frequency of the sample assembly. The force thus generated at the sample
is measured by registering the electrical voltage across a bimorph piezo element at
the lower end of the sample assembly. It is of particular interest when the plane of
the sample is either parallel or perpendicular to the external magnetic field lines.
Instrumentation. The sample is mounted inside an electrochemical cell between
the poles of a magnet. Details of the cell and the additional experimental setup have
been described [668, 669]. In a typical result (see Fig. 5.124) obtained with nickel
films, the similarity with MOKE results (see above) is obvious.

5.5.4 SQUID Magnetometry

Fundamentals. Movement of charged particles (e.g. an electronic current) causes

a magnetic field. Very small fields can be detected with a SQUID.40 The small size
of the sensitive elements in a SQUID allows spatially resolved measurements of
magnetic fields down to a resolution of about 1 mm.
Instrumentation. The sample under investigation is placed in an electrochemical
cell mounted close to the pickup coils of the SQUID, generally inside a magnetic
shield providing low magnetic gradients. Data processing provides images of local
magnetic flux density, which in turn is related to local electric current density. Re-
ported examples deal mostly with corroding metals like aluminum alloys and other
metallic materials [670–684]. In particular, hidden corrosion in aircraft aluminum
alloys has been studied.
40 Supraconducting quantum interference device.
164 5 Spectroscopy at Electrochemical Interfaces

5.6 Photoelectrochemical Methods

In photoelectrochemical methods, the electrochemical response as a function of il-
lumination either with white light or with light of a selected wavelength is stud-
ied by measuring photocurrents, photovoltages, etc. In most applications, this is
done without spatial resolution. Attempts to provide photoelectrochemical images
by recording these responses as a function of localization with a focused light spot
have been described [685]; for an exemplary study of passivating oxide films on
iron, see [686]. The function of a random array of gold disc microelectrodes has
been evaluated using the photothermal effect at a local resolution of 1 μm [687].
The approach has been termed photoelectrochemical microscopy [688]. When using
a scanning laser light source, the name is modified to scanning laser photoelectro-
chemical microscopy (SLAPEM); its application in a study of hexacyanoferrate(II)
oxidation at a gold electrode has been reported [692].

5.6.1 Photoemission Spectroscopy

Fundamentals. A photon of sufficiently high energy (i.e. short wavelength) can be

absorbed by a metal or a semiconductor, overcome the binding energy of an electron
and thus generate an excited electron (“hot electron”) with enough energy to pene-
trate the potential barrier at the metal/solution interface. This electron is emitted into
solution. Because a free electron is not stable in aqueous media, it passes various
relaxation steps to end in a capturing reaction with a suitable solution phase species
(scavenger), which is left in its reduced form. The whole process corresponds to
a photon induced electron transfer across the interface. Experimentally it can be
watched by measuring the photoemission current. The yield of photon induced gen-
eration of emitted electrons is low because of the fast thermal recombination of
photogenerated charge carriers in the metal and the high probability of the electrode
itself recapturing the emitted electron without generating a measurable current. The
photoemission current depends on the photon energy according to the following
equation,41 which is slightly different from the relationship for photoemission into
the vacuum:
I PE = A · (h · ν − h · ν0 − eE)5/2 ,
with the photocurrent I PE ; a constant A; the energy of the photon h·ν; the threshold
energy h·ν0 for photoemission at zero charge electrode potential E pzc ; e as the elec-
tron charge and E as the electrode potential [689–696]. The low yield has limited
studies to metals like gold or mercury, which show limited electrocatalytic activity
and, in turn, may not cause additional Faradaic processes that add electrical current
to the photocurrent. If the photocurrent itself is studied as a function of illuminating
wavelength, suitable scavengers are nitrous oxide, nitrate ions or protons in acidic
solutions. The solvated electron reacts according to
41 This equation is also known as “five-halves law”; other authors have observed relation-
ships similar to “Fowler’s square law”.

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 5.6 Photoelectrochemical Methods 165

N 2 O + e−
aq → N2 O
−

N2 O− + H2 O → N2 + OH− + OH∗ .

The formed hydroxyl radical can be reduced at the electrode

OH∗ + e− → OH− ,

resulting in a measurable electrical current. The factors influencing the photocur-

rents produced by UV irradiation of a mercury electrode have been discussed ex-
tensively [697]. Fundamentals and theoretical aspects of processes occurring at so-
lution/semiconductor interfaces have been reviewed [693].
Instrumentation. The experimental setup is composed basically of an electrochem-
ical cell suitable for in situ studies under illumination of the electrode surface with
visible light. Because of the low yield of the photoemission process (10−2 to 10−5
electrons per incoming photon), careful design of the cell with respect to light de-
tection, powerful sources of light (laser light or high-pressure xenon or mercury
lamps) and sophisticated detection (lock-in amplification combined with chopped
or otherwise modulated light intensity) are required. Because some common sub-
stances are powerful scavengers, the cell has to be perfectly air-tight (oxygen and
carbon dioxide are electron scavengers). Electrolyte solutions have to be purified
carefully.
Reported studies deal with measurements of the electrode potential of zero
charge E pzc [698, 699], double layer investigations [700–702] and studies of elec-
trode reaction mechanisms [703, 704]; for an overview, see also [693, 697]. Nu-
merous studies (beyond many conducted ex situ) deal with intrinsically conducting
polymers, particularly photogenerated mobile charge carriers [705–707].

5.6.2 Photocurrent Spectroscopy (PCS)

Fundamentals. Illumination of a surface, especially of semiconducting materials,

can result in the generation of electron-hole pairs, which in turn may be the cause
of electrochemical charge transfers across the electrode/solution interface [708–
714]. Both cathodic (i.e. electron emission) and anodic (hole recombination with
oxidizable solution species) currents can be observed. Measurements with a single
wavelength (monochrome) or with white light (polychrome) are termed photocur-
rent measurements, whereas studies of the photocurrent as a function of the illumi-
nating wavelength are called photocurrent spectroscopy (PCS).42 The dependence
of the observed photocurrents on wavelength, electrode potential and solution com-
position may provide information about the nature of the ongoing photoprocess and
its energetics and kinetics (e.g. the behavior of oxalic acid in an aqueous solution in
contact with a polycrystalline anatase electrode and the associated kinetics) [715].
42 Although the difference between both methods is substantial, in most published reports
measurements of both types are frequently employed in a single study, thus no distinction is
made here between these methods.
166 5 Spectroscopy at Electrochemical Interfaces

In addition, the characteristics of various materials of the semiconductor can be de-

rived from the observed relationships. Photocurrents can also be observed because
of photochemical (essentially photolytic or photothermal) processes in the solution
that are close to the surface under investigation.
Instrumentation. The electrode under investigation is mounted in an electrochem-
ical cell and illuminated with light of a single wavelength (tunable laser, light from
a lamp passed through a monochromator) or with light from a white light source
(tungsten or xenon lamp). A combination of a chopper and a lock-in amplifier al-
lows measurements of the photocurrent–voltage relationship of the electrode, which
has to be corrected for the spectral intensity of the used lamp. This way currents
caused by competing Faradaic processes can be separated [718]. Conversion effi-
ciencies can be calculated, indicating the yield of electrons per incident photon.
Typical examples include measurements at inorganic and organic semiconductors
and other semiconducting materials, like heavy or transition metal halides, chalco-
genides and pnictides [716]. Reviews of the photoelectrochemistry of diamond have
been provided [717–719]; for a broader overview, see [720]. The thickness of very
thin semiconductor films that are otherwise hard to measure could be determined;
in the case of PbO, layers down to 100 nm thickness were studied [718]. Changes
in polarity of the measured photocurrent as a function of applied electrode poten-
tial at fixed wavelength provide information about semiconductor properties of the
investigated films.
The determination of threshold energies as shown in the inset is based on a
modified display of the obtained photocurrent spectrum (see Fig. 5.125). The two
linear sections yield two threshold energies, for a detailed treatment, see [722]. Mea-
surements of photocurrents at p-type synthetic diamond electrodes that have wave-
lengths ranging from λ0 = 193 to 351 nm yielded results implying that only illu-
mination with the short wavelength (supra-bandgap illumination) was able to excite
electrons into the conduction band [723].

Fig. 5.125. Photocurrent spectrum of a polycrystalline diamond electrode in contact with an

aqueous solution of 0.5 M H2 SO4 at an electrode potential of E NHE = 0.05 V (based on
data in [721])

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 5.6 Photoelectrochemical Methods 167

Beyond photocurrent measurements at constant light intensity, experiments with

modulated light intensity have been proposed. A generalized theory for the use
of intensity modulated photocurrent spectroscopy (IMPS) to determine the rate of
charge transfer and recombination at the semiconductor/solution interface has been
described by Ponomarev and Peters [724] and extended to the treatment of multi-
step electron transfer mechanisms involving surface-bound intermediates [725]; for
an overview, see also [726]. In this method, an AC perturbation (modulation) of
the impinging light causes periodic changes of the photocurrent. This response is
measured as a function of the perturbation frequency. Because of the competition
between transfer of interfacial minority carriers and electron–hole recombination in
a complex plane plot of the real and the imaginary part of the conversion efficiency
(or an equivalent experimental signal), a semicircle in the first quadrant is observed.
Using IMPS, transient photocurrents at a passivated iron electrode that is in contact
with an alkaline solution have been studied [727]. Upon addition of [Fe(CN)6 ]4− ,
a change of the frequency response is observed and interpreted in terms of com-
petitive multistep and single step reactions of photoexcited carriers generated in the
passive film. Figure 5.126 shows the complex plane plot of the real and imaginary
parts of the AC component of the electrode’s photocurrent response.
A comparison of this method with photoelectrochemical impedance spectros-
copy43 as applied to photoelectrochemical hydrogen evolution at p-InP has been
reported [728]. Intensity modulated photocurrent spectroscopy has been compared
with intensity-modulated photovoltage spectroscopy (IMVS) [729]. Intensity modu-
lated photocurrent spectroscopy has been applied in a study of the silicon dissolution
in aqueous solutions of NH4 F [730] and n-GaAs electrodes [731]; a general review
is available [732]. Photocorrosion of CdS has been investigated with IMPS and pho-
toelectrochemical impedance spectroscopy (PEIS) [733]; a mechanism could be de-

Fig. 5.126. IMPS plot for an iron electrode in an aqueous solution of 0.1 M KOH with ad-
dition of 1.7 mM K4 Fe(CN)6 , illumination with laser light of λ0 = 442 nm (based on data
in [731])
43 The use of spectroscopy in connection with impedance measurements is not reasonable,
thus it is frequently discouraged.
168 5 Spectroscopy at Electrochemical Interfaces

rived. Polythiophene has been studied as a material for photovoltaics devices with
IMPS [734].
Semiconductors formed on various metals have been studied with PCS. In an
investigation of passivated iron electrodes [735], the potential dependence of the
photocurrent observed at a fixed wavelength is displayed in Fig. 5.127.
The oxidation of lead in various electrolyte solutions has been studied [736–
738]. In a tetraborate solution, the photocurrent spectrum measured with white light
showed a marked dependence on the positive (anodic) potential limit of the po-
tential scans. With the most positive limit, the photocurrent–potential relationship
displayed in Fig. 5.128 was obtained. The formation of tetragonal PbO by reduction
of α-PbO2 was monitored. The onset of the photocurrent indicates the appearance
of the formation of PbO and the electrode potential coincides with the sudden onset
of the photocurrent in the anodic scan. In the positive-going scan, the photocur-

Fig. 5.127. Potential dependence of the peak photocurrent of an iron electrode in an aqueous
buffer solution (pH = 4.8) (based on data in [735])

Fig. 5.128. Potential dependence of the photocurrent of a lead electrode in an aqueous solu-
tion of 0.1 M Na2 B4 O7 , λ = 340 nm (based on data in [736])

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 5.6 Photoelectrochemical Methods 169

rent collapses rapidly when formation of α-PbO2 proceeds. The disappearance of

the cathodic photocurrent coincides with the complete reduction of PbO to lead as
observed in cyclic voltammograms. The changes between anodic and cathodic pho-
tocurrents have been associated with intrinsic semiconductor properties of the oxide
film.
In a sulfuric acid solution, the formation of PbO during the corrosion of lead
without any other phase of PbOx (1 < x < 2) has been observed; the sensitivity of
the method approached the monolayer level [742]. Passive films on nickel and iron
surfaces have been studied both with polychromatic and monochromatic light [739].
Characteristic data of the semiconducting surface layers (flatband potentials, charge
carrier densities, bandgap energies) could be obtained. The limitations of the tra-
ditional band model that is used in solid state physics for ideal crystalline solids
with practically unlimited periodicity have been pointed out and the additional dif-
ficulties caused by the polycrystalline or even amorphous nature of these films were
stressed.
In a study of anodic oxide films grown on titanium [740], photocurrent spectra
were converted, yielding photocurrent conversion efficiencies Φ as a function of
electrode potential (see Fig. 5.129).
The smooth increase of Φ with photon energy and the implicit absence of any re-
duction in efficiency at short wavelengths suggest negligible surface recombination
under the employed experimental conditions. Composite oxide films on a nickel sur-
face exposed to an alkaline electrolyte solution have been studied with PCS [741].
Measurements of the photocurrent as a function of the electrode potential at
various fixed wavelengths of the illuminating light have been employed in a study
of rhodium iodide photoconductors [742]. The quantum yield of a photosensitive
film of Bi2 S3 in contact with an aqueous solution of Na2 S measured as a function of
the wavelength of incident monochromatic light has been found to approach unity

Fig. 5.129. Potential dependence of the photocurrent conversion efficiencies Φ at various

electrode potentials (vs. E SCE , as indicated) for a titanium electrode in contact with an aque-
ous electrolyte solution of 1 M H2 SO4 (based on data in [740])
170 5 Spectroscopy at Electrochemical Interfaces

at light energies above 2 eV [743]. The absorption spectrum of the semiconductor

was constructed from the results. It shows an indirect transition at 1.25 eV and
possibly a direct transition around 1.7 eV. Films of CdS that were electrochemically
grown from aqueous solutions of Na2 S have been characterized with PCS [744].
The corrosion of CdS films has been studied with intensity-modulated PCS [745].
A multilayer film assembled from highly sulfonated polyaniline and diazoresin
has been studied with PCS [746]. The PCS response agrees with the optical ab-
sorption spectrum, implying that the multilayer film is responsible for photocurrent
generation.
Photocurrent spectroscopy and a time-resolved variant of this method have been
used to characterize hybrid thin films of crystalline ZnO modified by 5,10,15,20-
tetrakis(4-sulfonatophenyl)porphyrinato zinc (TSTPPZn) and 2,9,16,23-tetrasulfo-
phthalocyaninatozinc(II) (TSPcZn), which were prepared by electrochemical depo-
sition [747]. In films containing both sensitizers, panchromatic sensitization was
observed. Details of the modification procedure had considerable influence on the
photoelectrochemical efficiency of the films.
The mechanism of photoreduction of CO2 and water at the p-type GaP in con-
tact with aqueous solutions has been studied with PCS under chopped light illumi-
nation [748]. Results show a photo-anodic sub-bandgap response and, as a conse-
quence, a photo-cathodic current.
The bandgap of an intrinsically conducting polymer (polypyrrole) has been de-
termined with photocurrent spectra [749].

5.6.3 Photovoltage Spectroscopy44 (PVS)

Fundamentals. Illumination of a semiconductor with monochromatic light might

result in a transfer of charge carriers between the surface and the bulk [750, 751].
Separation of the charge is caused by a surface barrier. The magnitude of the surface
photovoltage dU s depends on the net change of the electronic charge dQss on the
surface, which is caused by surface states lying within the energy gap of the semi-
conductor. Thus dU s is proportional to dQss . The type of photoionization transition
determines the sign of the photovoltage. Photoionization of an electron from a sur-
face state to the conduction band in a p-type semiconducor decreases the amount of
negative charge and results in an increase of the surface barrier heights. An electron
promoted from the valence band into a surface state increases the negative charge
and consequently the height of the surface barrier. In this case, a negative photo-
voltage signal is observed. Measurements of electrode potentials under illumination
have been called photopotential measurements; for an example, see [752]. Intensity-
modulated photovoltage spectroscopy (IMVS) has been described [733].
Instrumentation. The electrode is illuminated with monochromatic light. The elec-
trode potential is registered as a function of the wavelength of the incident light ver-
sus a reference electrode. Investigated systems include p-type indium phosphide in
44 Because the central process occurs at the solution interface, the method is also named
surface photovoltage spectroscopy (SPS).

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 5.6 Photoelectrochemical Methods 171

contact with alkaline electrolyte solutions [754] modified by etching, foreign metal
deposition or extended cathodic hydrogen evolution. Obtained spectra enabled the
identification of surface states at the semiconductor electrode. In measurements at
p-type InP in contact with aqueous solutions of sulphuric acid band-bending un-
der illumination was found [753–755]. In a study of CVD-generated diamond elec-
trodes with nanosecond laser flashes (λ0 = 337.7 nm), photopotential transients
were recorded. The decay behavior could be explained by invoking an equivalent
circuit deduced from electrochemical transient measurements.
Heterojunctions formed by electrodepositing polypyrrole or polyaniline on n-
type silicon were studied with PVS [756]. Experimental observations were explained
invoking photosensitization by electrochemically generated polarons in the polymer
film. The effects of nano-sized particles of Fe2 O3 that were incorporated into films
of polypyrrole were investigated with PVS [757].
In IMVS, the light intensity applied to the electrode under investigation is mod-
ulated by adding light from an additional source, which can be modulated easily
(e.g. with the use of a light emitting diode). The observed photovoltage U photo is
composed of a steady state value U0 and a varying component according to

U photo = U0 + ΔU ei(ωt−ϕ) ,

with frequency of modulation ω and phase shift ϕ; for further details, see [758].
Results of electrochemical impedance measurements obtained with dye solar cells
could be explained based on IMVS data [762]. Intensity-modulated photovoltage
spectroscopy has been applied in a study of dye-sensitized photo electrodes [733];
for a description of the experimental setup, see [762].

5.6.4 Photoluminescence (PL)

Fundamentals. Luminescence, i.e. the emission of light from a substance not based
on its (high) temperature can be caused in numerous ways. In the case of photolu-
minescence (PL), the emission of light is caused by illumination with light. The
wavelengths of the illuminating and emitted light may differ. Photoluminescence
of the semiconductor/solution interface is very sensitive to the generation of new
phases as caused by metal deposition and potential distribution across the interface
and to the surface charge carrier recombination velocity. Changes in the PL signal
allow detection of the formation of a fraction of a metal monolayer [759].
Instrumentation. The electrode (e.g. a GaAs disc) is mounted in an electrochem-
ical cell behind a suitable window (quartz glass) in a three-electrode arrangement.
Illumination can be provided by a laser operating at a rather low power (a few mW).
In order to facilitate detection of the PL light, the laser light is interrupted periodi-
cally with a mechanical chopper. Photoluminescence light is measured with collec-
tion optics, a monochromator, a photomultiplier and a lock-in amplifier connected
with the mechanical chopper. Photoluminescence intensities are plotted as a func-
tion of the electrode potential. Typical results as observed during deposition on a
GaAs surface are shown in Fig. 5.130.
172 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.130. Photoluminescence intensity of a p-doped (100)-oriented GaAs electrode as

a function of electrode potential and concentration of CuSO4 : a: 10−4 M; b: 10−3 M;
c: 3 × 10−3 M; supporting aqueous electrolyte solution 1 N H2 SO4 ; dE/dt = 20 mV·s−1 ,
arrows indicating scan direction; based on data in [763]

In an optical arrangement used for surface plasmon resonance spectroscopy (see

Sect. 5.9.6), PL light locally enhanced by the surface plasmon field can be de-
tected as is done in surface plasmon field-enhanced light scattering (surface plas-
mon field-enhanced photoluminescence (SPPL) spectroscopy). A photomultiplier is
mounted on the bottom side of the electrochemical cell opposite the prism arranged
in the Kretschmann setup [760]. In a study of poly(3,4-ethylenedioxythiophene)
(PEDOT), a change in SPPL intensity was observed. In the dedoped state the signal
increased considerably under open circuit conditions. Obviously, in the absence of
an applied electrode potential, ionic charge carriers migrate into the polymer layer,
thus quenching the photoluminescence.

5.6.5 Micro-Optical Ring Electrode (MORE)

Fundamentals. The insulating material inside a microring electrode can be man-

ufactured from an optically transparent material as employed in fiber optics. Light
piped into the electrolyte solution inside an electrochemical cell close to the ring
electrode may be used to cause photochemical processes, which in turn can result
in species that can be detected at the ring electrode [761, 762]. Compared with
the photoelectrochemical microscope (PECM) only low levels of light intensity are
employed, resulting in a significantly reduced risk of thermal perturbation or other
undesirable side effects.
Instrumentation. An electrode design has been reported [765, 766] together with
applications pertaining to the quenching of photoexcited Ru(bipy)3 ]2+ by Fe3+ and
the photoelectrochemistry of methylene blue [765].

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 5.7 Nonlinear Optical Methods 173

5.7 Nonlinear Optical Methods

Illumination of a surface or interface with poly- or monochromatic light of very high
intensity can result in non-linear optical phenomena like the generation of light with
the second (SHG) or third harmonic generation (THG) of the incoming frequency
or in sum (SFG) or difference frequency generation (DFG). For general reviews, in-
cluding theoretical considerations, see [763, 764]. Surface second harmonic gener-
ation is more simple and versatile, whereas SFG is more powerful because it allows
identification of adsorbed species at the interface via their vibrational resonances.

5.7.1 Second Harmonic Generation

Fundamentals. The optical response of certain media upon illumination with light
of sufficiently high intensity can become nonlinear, i.e. in the reflected or trans-
mitted light second, third or higher harmonics of the fundamental frequency of the
illuminating light can be observed. This example of nonlinear optics is particularly
fascinating and helpful in interfacial studies because the SHG is governed by selec-
tion rules that localize the origin to regions (or more generally media) lacking inver-
sion symmetry. The interface region between two centrosymmetric media provides
this particular asymmetry quite naturally, thus the method is by itself surface spe-
cific. The generated harmonic provides information about electronic and structural
properties of the interface, but only to a limited extent of adsorbed species on the
surface. Depth of penetration of the incoming probe and depth of information of the
obtained signal are about 2 to 3 atomic layers of the solid. In single crystal surfaces
and systems where the surface nonlinear susceptibility is dominated by molecular
contributions from the adsorbate, dependencies on the angle of rotation of the sur-
face may be observed. Theoretical treatments have been provided elsewhere [765,
766]. The theory of the generation of second harmonics via plasmon surface polari-
tons has been described [767]. A theoretical treatment of the combined effects of
wavelength of illuminating light and rotational anisotropy useful in investigations
of single crystal/solution interfaces has been given [768].
Instrumentation. An experimental setup is depicted in Fig. 5.131. Laser light of
sufficiently high intensity is filtered to remove light at harmonic frequencies and re-
flected off the surface under investigation. From the reflected light that appears at an
angle45 determined by the Fresnel factors at the given wavelength, the fundamental
and the third harmonic are filtered out and the second harmonic intensity is detected
with a CCD camera.
Numerous studies employing both polycrystalline and single crystal metal elec-
trodes and semiconductor surfaces have been reported; for an overview, see [772].
The possible advantages of a simultaneous (double beam) application of electrore-
flectance spectroscopy and second harmonic generation have been pointed out [769].
45 This angle is generally close to the angle of specular reflection, e.g. 60° in and 58° out at
578-nm incident light wavelength and 289-nm SHG. The difference in the index of refraction
of water between these wavelengths causes the change of the angle.
174 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.131. Schematic setup for SHG experiments

Fig. 5.132. SHG signal of a polycrystalline platinum electrode in contact with a solution of
0.5 M H2 SO4 , based on data in [770]

In a typical study of a polycrystalline platinum surface in contact with a solution of

0.5 M H2 SO4 , an electrode potential dependent intensity as shown in Fig. 5.132 was
recorded [770].
The intensity increase in the positive-going potential scan starting at minimum
intensity around the potential of zero charge E pzc (around approx. E SCE = −0.1 V)
was assigned to bisulfate adsorption in the double layer region. The subsequent drop
at more positive potentials was attributed to surface oxide formation. The increase
of SHG intensity at potentials negative to the E pzc was explained by invoking hy-
drogen adsorption [776]. The nonlinear surface susceptibility was found to correlate
linearly with the surface coverage with hydrogen species. With single crystal elec-
trodes, further structural information about the interface can be obtained from mea-
surements of the SHG intensity on the angle of rotation of the surface; for a theoret-
ical treatment and an overview, see [771, 772]. The combined effect of a wavelength
ranging from the UV into the infrared region and the rotational anisotropy observed
at the Ag(111)/solution interface has been explained by invoking the electronic band
structure of the metal [774]. Extension of the study to single crystal silver electrode
surfaces during charging and adsorption as well as modification by upd-layers of
lead and thallium has been reported [773]; for a review, see [774].
During a slow electrode potential scan, a change in the SHG has been observed
with a Au(111) electrode (Fig. 5.133) [775, 776].

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 5.7 Nonlinear Optical Methods 175

Fig. 5.133. SHG signal as a function of electrode potential for a Au(111) surface in contact
with a solution of 0.01 M HClO4 , dE/dt = 0.1 mV s−1 , based on data in [775]

It has been explained by invoking a slow reconstruction of the gold surface from
the (1 × 23) surface structure into the unreconstructed (1 × 1) surface. The observed
hysteresis implies a slow surface reconstruction, which is complete on a minute
time scale. Rotation of the samples revealed a threefold symmetry pattern for the
unreconstructed Au(111)-(1 × 1) surface, whereas the Au(100)–(1 × 1) surface did
not show rotational anisotropy of SHG intensity as expected for C4v symmetry.
Second harmonic generation has also been used to study the semiconductor/
solution interface during the deposition of gold on Si(111) [777]. In a setup com-
bining SHG and the electrochemical quartz crystal microbalance (EQCM), the un-
derpotential deposition of copper on a polycrystalline gold surface has been stud-
ied; a decrease of the SHG signal by 60% upon formation of the upd-layer was
found [778]. A study of the electrochemical liquid/liquid interface between two im-
miscible solutions where adsorption of surfactants occurred has been reported [779].

5.7.2 Sum and Difference Frequency Generation

Fundamentals. Sum frequency generation (SFG)46 and the closely related differ-
ence frequency generation (DFG) are second-order non-linear optical processes.
Light of a fixed frequency ω1 interacts with light of a frequency ω2 in space and
time at an interface where the local susceptibility χ (2) is non-zero, thereby generat-
ing a coherent beam with the frequency ωs = ω1 + ω2 in SFG and ω = ω1 − ω2 in
DFG, which is superimposed on a non-resonant background signal. This is basically
the result of the non-linear susceptibility of the interface and the non-linear polariz-
ability of adsorbed species. The rather complicated mathematics for the interaction
occurring at a metal/solution interface have been treated elsewhere [780–783]. The
46 Because mostly vibrational modes at interfaces are investigated, the method has also been
called vibrational sum frequency generation (VSFG).
176 5 Spectroscopy at Electrochemical Interfaces

interface region between two centrosymmetric media provides this particular asym-
metry quite naturally, thus the method is by itself surface-specific [784]. With one
light frequency that is tunable, the resulting sum frequency can be tuned accord-
ingly. According to theory, the SFG intensity is enhanced when either ωs , ω1 or ω2
are in resonance with a vibrational transition in an adsorbate that is present at the
interface or an electronic transition in the metal of the electrode. In addition the vi-
brational mode of the adsorbate has to be both infrared and Raman-active. Because
of the large reduction in molecular symmetry upon adsorption on a surface, this
condition is met in most cases. With a light source of tunable frequency emitting in
the infrared (e.g. a tunable infrared laser diode, a tunable infrared laser (CO laser,
dye laser) or a free-electron laser), the vibrational properties of the interface (i.e. of
adsorbates and their bonding to the metal surface) can be probed. Besides their con-
ceptual similarity, DFG differs from SFG in two details. The more stringent phase
matching requirements for the two light beams pose narrower limits for the exper-
imental design. A more effective filtering of the light emitted from the interface
is necessary because of the competition between the desired DFG signal and the
undesired fluorescence that is sometimes induced by the visible light beam [785].
For selected adsorbates, the observed SFG data have been modeled using multi-
configurational self-consistent field calculations [786]. Sum frequency generation
at metal/solution and other interfaces has been reviewed extensively [787–791].
Instrumentation. For electrochemical studies two laser light beams—one operat-
ing in the visible and one that is tunable operating in the infrared—are required.
The advent of tunable Ti:sapphire-based lasers might provide an additional source
of infrared radiation [792]. The sum frequency intensity coming from the electro-
chemical interface at an angle of emission somewhere between the respective angles
for the reflected beams of frequencies ω1 and ω2 is detected with a photomultiplier.
The electrochemical cell is equipped with a prismatic window (e.g. CaF2 ) to avoid
refraction and unwanted reflection of the laser beams. Single crystal and polycrys-
talline electrodes can be investigated. In a broad study the structure of water at the
silver/water interface has been investigated with SFG [793]. Peaks correlated with
low-order water, water interacting with electrolyte ions, water specifically adsorbed
on the silver surface and hydronium species were observed.
COad formed by chemisorption of methanol on a platinum electrode has been
studied with SFG (see Fig. 5.134) [786].
The spectra show two resonances located around 2065 cm−1 and 1965 cm−1 .
The first corresponds to linearly bound CO, the latter was assigned to CO in a
bridge-bound position [786]. The conversion of CO in a bridging location into
species atop has been identified with SFG [794]. The combination of the high
light intensity (e.g. free-electron lasers) and the possibility to obtain absolute spec-
tra without any modulation technique has allowed the detection of generally weak
bands like those of over- and underpotential deposited hydrogen on a platinum elec-
trode [795, 796]. Studies of coadsorption of cyanide anions and cetylpyridinium
cations on Au(111) and Au(210) revealed marked differences [797]. CN− is bound

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 5.7 Nonlinear Optical Methods 177

Fig. 5.134. SFG spectra of adsorbed CO on a polycrystalline platinum electrode in an aqueous

solution of 0.1 M HClO4 and 0.5 M methanol at various electrode potentials as indicated;
data taken from [786]

more strongly on the more open Au(210) surface; the presence of cetylpyridinium47
shows no significant effect. On the denser Au(111) surface, CN− is less strongly
adsorbed; the observed features, including surface ion pair formation, imply coad-
sorption of cetylpyridinium. Vibrational lifetimes of CN− adsorbed on Pt(111) and
on polycrystalline gold and silver electrode surfaces have been measured with SFG
[798]. Lifetimes on platinum and gold ranging from 3 to 8 ps and 10 to 19 ps, re-
spectively, are electrode potential dependent; at more positive electrode potentials,
longer lifetimes were observed. Significantly longer lifetimes were observed with a
silver electrode. In a solution of 0.1 M NaClO4 in H2 O a value of 28 ps was found
and, in D2 O, a lifetime of 60 ps was found. These values are close to those found for
the free, solvated cyanide anions. The values are surprisingly large since lifetimes in
the range of 1.5 to 3 ps are observed for the isoelectronic CO. Time-resolved SFG
has been applied in studies of various species, including CO at the metal/solution
interface [799].
In a study of thiocyanate adsorption on a polycrystalline gold surface and on
electrodeposited cobalt and nickel films, changes in band frequencies were observed
when moving from the naked gold to the electroplated surface. In the case of cobalt
electrodeposition, an anion-induced underpotential deposition was proposed. Fur-
ther changes of spectral feature were interpreted assuming differences in strength
of interaction related to d-band filling of the substrate and in different adsorbate
geometries [800]. Measurements of vibrational dynamics, i.e. vibrational lifetimes,
are possible [801]. Vibrational sum frequency generation (VSFG) has been em-
ployed in a study of the atmospheric corrosion of zinc by various organic com-
47 Cetylpyridinium is a popular electrolyte solution additive in electroplating baths.
178 5 Spectroscopy at Electrochemical Interfaces

pounds [802]. In the case of acetic acid, various species formed by hydrogen bond-
ing were identified; acetaldehyde underwent a hydration process resulting in the
presence of a gem-diol at the interface. Rapid acquisition of spectra (5 s−1 ) is possi-
ble using a femtosecond broad-band multiplex SFG apparatus; SFG spectra can be
recorded during a slow electrode potential scan [803, 804]. Studies reported so far
with this setup deal with CO-adsorption on platinum and Pt/Ru electrode surfaces.
The strictly interfacial sensitivity of SFG as compared to the dependency of surface
enhancement on active sites has been illuminated in a comparative study of cyanide
adsorption on gold with SERS and SFG [805].
Approaches to interpretation of results based on quantum mechanical calcula-
tions have been described [806]. The interface between a platinum electrode surface
and a room temperature ionic liquid (1-butyl-3-methylimidazolium tetrafluorobo-
rate) in the presence of adsorbed CO has been probed with SFG [807]. The position
of the electrode potential of zero charge E pzc could be estimated and reorientation
of adsorbed ions as a function of applied electrode potential could be deduced.

5.8 Mass Spectrometry48

Mass spectrometry has been applied in electrochemical investigations predominantly

as an ex situ method because of the obvious incompatibility of the high vacuum
needed for all types of mass spectrometry and the presence of a liquid electrolyte
solution. Because of the amount of information provided in a mass spectrum, there
have been various attempts to couple mass spectrometers with electrochemical cells
as described below.

5.8.1 Differential Electrochemical Mass Spectrometry (DEMS)

Fundamentals. Mass spectrometry (MS) is an extremely powerful spectroscopy

suitable not only for determination of molar masses, but also for identification of
chemical species and molecular structures. It works only under ultrahigh vacuum
conditions. Combining mass spectrometry with electrochemistry directly requires
a special experimental setup matching the seemingly incompatible requirements.
A first attempt was reported by Bruckenstein and Gadde [808, 809]. Using a hy-
drophobic porous membrane of polytetrafluoroethylene (PTFE), an electrochemical
cell was coupled to a mass spectrometer. Gaseous reaction products dissolved in
the electrolyte solution were sucked into the inlet system of the mass spectrome-
ter. The mass intensity recorded with a time delay (rise time) of about 20 seconds
was found to be proportional to the charge consumed during the electrochemical
reaction. A similar setup using a silicone rubber membrane has been described by
Brockman and Anderson [810]. In a further development of the experimental setup,
48 The terms mass spectrometry and mass spectroscopy are used synonymously; because
of the usage in another major field of application, the mass spectrometers used in the
applications reviewed here are sometimes called residual gas analysers (RGA).

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 5.8 Mass Spectrometry 179

Fig. 5.135. Hydrophobic porous electrode and inlet system for DEMS [811]

Wolter and Heitbaum shortened the delay time significantly. In addition, they ap-
plied a different and more effective method of evacuation [811, 812]. The porous
electrode and the inlet system connecting the electrochemical cell and the mass
spectrometer are shown schematically in Fig. 5.135.
The hydrophobic porous membrane made frequently from PTFE serves as a
mechanical separator between the liquid (aqueous and nonaqueous electrolyte solu-
tions) inside the electrochemical cell and the vacuum in the ionization chamber of
the mass spectrometer. Because of the nonwetting surface properties of the polymer
and the small pore size, no liquid will penetrate the membrane. Water vapour (or the
vapour of any other liquid used in the electrolyte solution) will pass the pores and
establish a fairly high partial pressure in the inlet system. Powerful turbomolecular
pumps keep the pressure at sufficiently low levels in this chamber. A narrow slit is
inserted between the inlet system and analyser section. This pumping technique is
generally called differential pumping. The working electrode is also porous in or-
der to enable passage of any species to be analysed through the electrode towards
the porous membrane. Any other volatile constituent of the electrolyte solution (e.g.
dissolved alcohol) will show up in the ionization chamber. During interpretation of
mass spectra, the high vapour pressure of these species has to be kept in mind as it
may interfere with signals from other species in the search.
As a result, Wolter and Heitbaum obtained a mass signal proportional to the
rate of the electrochemical reaction, i.e. to the current flowing through the porous
electrode. Because of the applied pumping technique and because of the propor-
tionality between electrochemical current (i.e. derivative of consumed charge) and
mass signal, the method was called differential electrochemical mass spectrometry
(DEMS).49
Instrumentation. The experimental setup includes a mass spectrometer (initially
this was a standard type using magnetic mass separation; in subsequent versions and
49 The name PERMS (permeable membrane mass spectrometry) suggested by Brockman
and Anderson [810] has not entered the standard terminology.
180 5 Spectroscopy at Electrochemical Interfaces

in setups reviewed elsewhere [813], quadrupole mass spectrometers have frequently

been used), at least two turbomolecular pumps and an electrochemical cell incorpo-
rating a porous working electrode, a counterelectrode and a reference electrode. The
use of a porous electrode limits the scope of electrode materials to noble metals and
other materials that can be prepared to be painted lacquer-like on the PTFE mem-
brane or on other suitably porous materials [814, 815]. Modifications of the inlet
system have enabled the use of compact electrode materials (including single crys-
tals [816]) with the porous PTFE membrane mounted in close distance [817, 820]
to the solid bulk electrode under investigation or with the material to be investigated
mounted as a rotating electrode close to the inlet system [818–820]. An improved
setup with significantly shorter response time, enabling the application of potential
scan rates up to 1 V·s−1 , has been described by Wasmus et al. [821]. The combina-
tion of DEMS with an electrochemical quartz microbalance (EQMB), allowing si-
multaneous detection of volatile products via DEMS and solid deposits via EQMB,
has been described by Jusys et al. [822]. Systems investigated include fuel oxidation
reactions (identification of volatile intermediates and reaction products) [824, 823],
carbon dioxide reduction [826, 824, 825], electrolyte solution decomposition (i.e.
of organic solvent as used in lithium batteries yielding CO2 , which is presumably
involved in the formation of a solid electrolyte interface (SEI) [826, 827]), gas evo-
lution reactions (oxygen evolution during water electrolysis, gassing of lead acid
batteries) [820, 828] and systems of general technological interest, like hydroxy-
lamine [829] or the electrooxidation of N ,N -dimethyl-p-phenylenediamine [830].
Gas diffusion electrode-employing materials and processes as used for the fabri-
cation of fuel cell electrodes have been studied in a comparative investigation of
alcohol oxidation [831]. In the case of the C2 alcohols (ethanol and ethylene gly-
col), a strong dependency of carbon dioxide yield on the electrode potential was
found. Formation of further oxidation products showing different capabilities of be-
ing further oxidized depending on the composition of the gas diffusion electrode was
reported. The electrooxidation of ammonia at the three basal planes of monocrys-
talline platinum in contact with an alkaline solution has been studied with a thin
layer flow cell [832]. Ammonia is oxidized almost exclusively at the Pt(100) sur-
face towards N2 , NO and N2 O; prior to surface oxidation, a poison is formed that
inhibits N2 formation specifically. Electrochemical reduction of CO2 and water at
TiO2 electrodes has been studied with DEMS [833].
A scanning type of DEMS (named SDEMS) has been described [834, 835].
A capillary with a porous membrane separating the inner vacuum line to the quadru-
pole mass spectrometer from the surrounding electrolyte solution is scanned over
the electrode surface under investigation. Local electrocatalytical activities can be
resolved on a mm scale.

5.8.2 Electrospray Mass Spectrometry

Fundamentals. Mass spectroscopy of species showing only low vapour pressures

has been made possible using electrospray ionization coupled with a mass selector
and detector [836, 837]. The liquid to be analysed is pumped through a capillary

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 5.8 Mass Spectrometry 181

placed at a high electric potential of a few keV. The resulting large electric field
results in rapid dispersion of the liquid, which is electrically charged. After evap-
oration of the solvent, the sample molecules are present as charged species, which
are extracted into the UHV system of the mass spectrometer.
Instrumentation. Basically, a small-volume (preferably thin layer) electrochemi-
cal cell is coupled to a mass spectrometer (most frequently a quadrupole or a time-
of-flight instrument) with an electrospray ionization source as the interfacing de-
vice (ESI–MS). A typical setup has been described elsewhere [838, 839] and a
critical review of various combinations of different electrochemical cells with an
ES-MS is available [840]. The influence of the design of the TLC on the mass
spectra has been discussed [841]. In particular, interfering contributions from the
processes at the counter electrode and incomplete conversion of the species un-
der investigation can result in artifacts, which may change intensities and distribu-
tions of observed peaks and, in the worst case, these effects may result in a com-
plete loss of the mass spectrum of the species formed at the working electrode.
Suggestions for suitable cell design and adaptations of already available cells are
described. Electrolyte solution is continuously pumped through the electrochemi-
cal cell into the ionization source. Reported studies deal with the electroreduction
of 7,7
,8,8
-tetracyanoquinodimethane (TCNQ) and the electrooxidation of triph-
enylamine (TPA) [846]. In the former case, the initial radical anion, single- and
double-charged charge transfer complexes and the double-charged anion were ob-
served. Nearly complete transformation of the initial radical anion into an adduct
[(TCNQ2 )2− + Li+ ] was deduced from the experimental results. This adduct was
also found as the result of the second electron transfer via a different route. In the
case of the oxidation of TPA, monomer and dimer radical cations as well as neu-
tral dimers were found. Formation of molecular dications (nickel and cobalt oc-
taethylporphyrin) in the gas phase from neutral organics was assigned to the in-
herent electrolytic process occurring during electrospray ionization [842]. Cyanide
ion oxidation from a nonaqueous acetonitrile-based electrolyte solution has been
investigated and [C5 N5 ]− , [C12 N12 ]2− and [C6 N6 ]∗ − have been identified as inter-
mediates [843]. Cesium ion uptake into and release from hexacyanoferrate films has
been studied [844]. Electrooxidation of ruthenium cyclopentadienyl complexes at
a platinum electrode was investigated with ESI-MS coupled to an electrochemical
cell [845]. The use of ESI-FTMS (electrospray ionization Fourier transform mass
spectrometry) in investigations of conducting polymers has been proposed [846]. In
a study of oxidation of substituted polyamides at a glassy carbon electrode ESI-MS
was used [847].
The combination of ESI–MS with electrochemically modulated liquid chromato-
graphy (EMLC) has been described [848]. In EMLC, an electrically conductive
phase (e.g. porous carbon) is used as the stationary phase in an LC instrument.
By modulating the electrode potential of this phase the retention of analytes is al-
tered. Reported applications mainly involved separation of complex mixtures of
organic compounds, including aromatic sulfonates, carboxylic acids, dansylated
amino acids, corticosteroids, benzodiazepines and inorganic and metal ions.
182 5 Spectroscopy at Electrochemical Interfaces

5.8.3 Thermospray Mass Spectrometry

Fundamentals. In order to identify nonvolatile species in the effluent of a liquid

chromatography (LC) setup with mass spectroscopy, the thermospray interface has
been developed [849]. The effluent of the LC is pumped through a heated capillary
into the ionization chamber of a mass spectrometer (typically a quadrupole mass
spectrometer). With adequate pumping, a pressure low enough for chemical ioniza-
tion could be maintained therein. The mechanism of thermospray ionization starts
with almost complete evaporation of the solvent upon entrance into the ionization
chamber, resulting in a supersonic jet of a superheated mist [850]. The nonvolatile
components, including the ions of the electrolyte that is required for further ion-
ization in the liquid phase, are kept in the droplets, which are charged positively
or negatively corresponding to their composition of anions and cations. Assisted
by the large local electric field around the droplets, molecular ions of nonvolatile
components with a few solvent molecules evaporate from the droplets. After ther-
mal equilibration with the solvent vapor in the ionization chamber, the ions diffuse
towards the sampling aperture into the mass spectrometer.
Instrumentation. Hambitzer and Heitbaum described a coupling of the thermo-
spray inlet system with an electrochemical cell [851, 852]. The electrolyte solution
is pumped into the cell. The working electrode was initially mounted as a coil of
platinum wire around the exit bore connecting the cell to the interface. Thus the liq-
uid in which the reaction products are present was transferred directly to the thermo-
spray interface. An advanced version that could be used with flat electrodes instead
of a wire is depicted in Fig. 5.136.
This setup has been used in studies of electrooxidation of aniline [853–855].
Higher aniline oligomers were identified. In an improved version described by Volk
et al. [856] the dead time between electrochemical generation of a species (i.e. cur-
rent signal) and the appearance of the corresponding mass signal was reduced to
0.5 s. Results obtained during the electroreduction of uric acid at a graphite elec-
trode are displayed in Fig. 5.137.

Fig. 5.136. Electrochemical cell for thermospray mass spectrometry [851]

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 5.8 Mass Spectrometry 183

Fig. 5.137. Cyclic voltammogram and selected mass intensity vs. electrode potential curves
measured during electrooxidation of uric acid at pyrolytic graphite; m/e 157 ≡ allantoine,
m/e 167 ≡ (uric acid - H)− , m/e 183 ≡ imine alcohol, based on data in [856]

5.8.4 Inductively Coupled Plasma Mass Spectrometry (ICPMS)

Fundamentals. Mass spectroscopy of species released from a suitable electrode

by anodic stripping voltammetry (ASV) can be detected online by moving the elec-
trolyte solution from the electrode into the ionization chamber of an inductively
coupled plasma mass spectrometry. In the electrically generated plasma with a tem-
perature of several thousand Kelvin, both metals and nonmetals are simply ionized.
Using ASV, both preconcentration of the species to be measured (mostly heavy ions
like Cd2+ or Cu2+ ) and removal over other interfering cations can be afforded [857].
Instrumentation. Application in determination of As(III) and Se(IV) species with
ICPMS coupled directly with a porous gold-plated carbon electrode (reticulated vit-
reous carbon) that is operated in the anodic stripping mode has been reported [858];
similar studies of Cr(IV) and V(V) [859] and Cu and Cd [860] determination are
available.

5.8.5 Thermodesorption Mass Spectrometry (TDMS)

Fundamentals. Besides introduction of gaseous species into the ionization cham-

ber, other techniques have been employed to transfer species to be analysed [861].
For analysis of materials adsorbed or deposited as solids on an inert support, ther-
mally induced desorption is a possible approach. The flow of particles desorbing
from the surface, which is heated with the temperature increasing linearly with time,
is analysed with respect to intensity and particle mass. Results yield information
about the strength of bonding and/or adsorptive interaction and about the chemical
composition of the species. An alternative approach is the use of secondary ion mass
spectrometry (SIMS) [862, 863]. Obviously both approaches are feasible only under
184 5 Spectroscopy at Electrochemical Interfaces

UHV conditions. As has been demonstrated in selected cases, the electrochemical

double layer may adhere to an electrode surface upon emersion of the electrode from
an aqueous electrolyte solution [864] making this method a valid approach.
Instrumentation. A mass spectrometer equipped for thermal desorption is inter-
faced with an electrochemical cell [865]. The working electrode, which is made of
metal foil, is mounted on a manipulator. It can be immersed into the electrolyte so-
lution for electrochemical measurements. After emersion, it is transferred into the
ultrahigh vacuum part (ionization chamber) of the mass spectrometer. Care must be
taken to exclude contact of the electrode with ambient air. Because any solvent ad-
hering to the electrode and the manipulator will be removed by vigorous pumping,
the loss of species only weakly bound to the electrode surface must be taken into
account during interpretation of the measured mass spectra. Heating of the electrode
can be done with a high intensity halogen lamp. The small number of reports deals
mostly with investigations of fuel cell reactions, particularly with strongly adsorbed
reaction intermediates and reaction products [820, 872, 866].

5.9 Miscellaneous Spectroscopies and Methods

5.9.1 Probe beam deflection (PBD)50

Fundamentals. When a narrow beam of light (e.g. a laser) passes a condensed

phase of inhomogeneous density (gradients of density caused by local changes in
concentration) it is deflected (mirage effect, see Fig. 5.138). The actual deflection
Ψ of the beam depends for small angles and considering geometric optics only
on the path length w of the light beam in the inhomogeneous medium and on the
dependence of the refractive index n on the concentration c according to
w ∂n ∂c
Ψ = .
n ∂c ∂z

Fig. 5.138. Principle of probe beam deflection

50 The term “photothermal deflection” is used as an equivalent to “probe beam deflection”;
the term “optical beam deflection” has been used only infrequently.

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For most binary electrolyte solutions ∂n/∂c is constant. Since both the length
of the pathway where the laser beam is influenced by the concentration gradient
and the refractive index n of the solution are constant, the deflection Ψ depends
practically only on ∂c/∂z [867].
In general, the beam is deflected towards a region of higher concentration. A pos-
itive deflection (away from the electrode surface) thus indicates a lower concentra-
tion at the interface and a higher concentration inside the bulk of the solution. Ac-
cordingly, the concentration gradient is caused by an ion flux towards the interface.
An ion flux in the opposite direction causes a negative beam deflection. Strictly
speaking, this assignment is correct only for simple binary electrolytes and positive
values of ∂c/∂z. This beam deflection effect has been applied to study the mecha-
nism and kinetics of electrode processes accompanied by significant changes in the
concentration of species in the solution phase involved in this electrochemical re-
action. Measurements of the probe beam deflection as a function of the wavelength
of light illuminating the electrochemical interface are also possible; they are called
photothermal deflection spectroscopy and are treated elsewhere (Sect. 5.2.7) [868].
(Actually this effect is used when aligning the setup: A choppered beam of light is
directed perpendicularly towards the surface and the signal at the position-sensitive
detector is subsequently maximized by adjustment of the cell and the measuring
beam.) A combination of both methods has been treated in [869]. Theoretical mod-
elling has been described [870] and a comprehensive overview has been provided
[871]. Changes of mass, composition and other properties of the interphase that are
closely connected to the flux of the ion are conveniently studied with ellipsome-
try (see p. 192) or the electrochemical quartz microbalance. Laser interferometry
as a somewhat related technique has been applied infrequently in studies yielding
information similar to that obtained with PBD [872, 873].
Instrumentation. The experimental setup is simple and straightforward. The elec-
trochemical interphase to be investigated is mounted inside an electrochemical cell
that allows a beam of light (usually laser light, which is provided most commonly
by HeNe gas ion lasers adjusted to a typical diameter of 80 μm) to enter the cell and
pass the solution phase parallel and as close to the electrode surface as possible. The
exciting beam arrives at a position sensitive detector that indicates any deflection of
the beam as a function of electrode potential. The setup is shown in Fig. 5.139.
A scanning refractometer that is basically very similar to the setup described in
detail above has been reported by Tamor and Zanini [874]. The laser beam scans the
electrolyte solution volume close to the electrode surface. Data on beam position
and refracted beam incidence were used to calculate local refractive indices as a
function of distance from the electrode, current density, etc.
Probe beam deflection can be observed during metal deposition and dissolu-
tion. The method is sensitive towards changes in the concentration gradient orig-
inating from dissolution or deposition of submonolayer amounts of material on
the electrode surface [875]. A typical result of PBD measurements is displayed in
Fig. 5.140. The negative PBD response observed during anodic stripping of the
silver indicates concentration decay into the solution phase. The positive response
186 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.139. Experimental setup for probe beam deflection studies

Fig. 5.140. Cyclic voltammogram (top) and PBD response (bottom) observed with a silver
electrode exposed to an electrolyte solution of 2 M HClO4 + 0.0015 M AgClO4 , dE/dt =
20 mV s−1 [875]

during cathodic silver deposition is caused by the concentration decrease close to

the electrode surface.
In a study of silver dissolution into an aqueous perchlorate solution, (Ag+ )solv
ions were identified as oxidation products [876]. Probe beam deflection studies of
underpotential deposition have been described [877]. Probe beam deflection has
frequently been employed in investigations of doping and dedoping phenomena of
intrinsically conducting polymers [878–905]. During the former process, a consid-
erable number of anions are incorporated into the polymer for charge compensa-
tion; alternatively, protons may leave the polymer for charge compensation. During
dedoping, the reverse processes may take place. Considerable changes in concen-
tration of the species involved in the solution are observed. In a study of the effect
of the concentration of HCl on the exchange of protons and anions during oxidative
doping/reductive dedoping of polyaniline, PBD responses that varied significantly
from acid concentration were found (see Fig. 5.141).

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 5.9 Miscellaneous Spectroscopies and Methods 187

Fig. 5.141. Cyclic voltammogram (top) and PBD responses (bottom) at various concentra-
tions of HCl observed with a polyaniline film on a gold electrode exposed to an aqueous
electrolyte solution of x M HCl, dE/dt = 50 mV s−1 (based on data in [906])

Both protons and chloride ions are exchanged. At low electrode potentials, pro-
ton exchange dominates the charge compensation equilibria. At higher potentials
the type of anion (sulfate ions were used in addition to chloride) determines the
relative contribution of protons and anions.
The influence of the molecular structure of the intrinsically conductive polymer
and, consequently, the chemical identity of the redox reaction center has a dominant
influence on the PBD response, indicating again different contributions of cations
and anions in the charge compensation (compare Figs. 5.142 and 5.143).
Poly(N-methylaniline) shows a considerably closer spacing between the two re-
dox processes associated with the transition from the fully reduced leucoemeraldine
state into the semioxidized emeraldine and finally into the fully oxidized pernigrani-
line state. Both electrode potential shifts can be explained by invoking structural
changes effected by the introduction of the methyl group. Further assignment of the
movement of ionic species that are associated with the redox processes and neces-
sary for charge compensation are possible based on the PBD response. A positive
sign of the beam deflection indicates ion insertion. A negative sign implies ion ex-
pulsion. During the first oxidation peak both polymers show a similar positive re-
sponse indicating anion insertion; the zero deflection range has been explained by
assuming protonation of the reduced state of the polymer. During the second peak,
the response differs considerably. Insertion is followed by ion (proton) expulsion
with the polyaniline ion (anion), whereas in case of poly(N-methylaniline) the re-
sponse indicates ion (anion) insertion at all potentials in the peak range. This qualita-
tive difference in ion exchange mechanisms is related to the structural modification
at the nitrogen atom, which is effected by methyl substitution. The flat response at
low potentials might be caused by a compensating effect of simultaneous proton
egress and anion ingress.
188 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.142. Cyclic voltammogram and PBD response observed with a polyaniline film on
a gold electrode exposed to an aqueous electrolyte solution of 1 M HClO4 , dE/dt =
50 mV s−1 (based on data in [907])

Fig. 5.143. Cyclic voltammogram (top, dE/dt = 100 mV s−1 ) and PBD response (bottom,
dE/dt = 50 mV s−1 ) observed with a poly(N-methylaniline) film on a gold electrode ex-
posed to an aqueous electrolyte solution of 1 M HClO4 , dE/dt = 100 mV s−1 (based on
data in [907])

Reported studies include various deposition and dissolution processes [876, 908]
and mechanistic studies of electrode processes at redox-active polymer-coated sur-
faces [909–912]. In a typical study of a polymer film containing ruthenium ions as
redox-active centers, a cyclic voltammogram indicative of the one electron transfer
at this center is observed as depicted in Fig. 5.144. The movement of ions needed
for charge compensation in the film after a change of the redox state can be detected
with PBD. The positive-going response during oxidation of the ruthenium center

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 5.9 Miscellaneous Spectroscopies and Methods 189

Fig. 5.144. Cyclic voltammogram (top) and PBD response (bottom) of a redox-active film
of [Ru(pby)2 ClPVP]Cl exposed to an aqueous electrolyte solution of 1 M HCl, dE/dt =
50 mV·s−1 (based on data in [909])

and the corresponding negative response upon reduction imply anion movement.
The slight delay between the signals is mainly caused by the fact that the laser beam
probes changes in refractive index, i.e. in local changes of concentration gradient,
which are about 50 to 100 μm away from the electrode. The concentration changes
effected by anion ingress at the film/solution interface need some time to extend so
far into the solution.
Although the mechanism of the electron transfer itself is on a time-scale that is
not accessible with PBD-associated processes, the movement of ionic and solvent
species can be detected. Separation of thermal and ionic effects is possible [913]
and the Peltier effects of redox couples could be measured [920].

5.9.2 Light Reflection Method

Fundamentals. Reflection of light (monochromatic or white) at an electrode sur-

face will depend basically on two influences: Absorption of light by colored surface
layers and scattering in case of rough or otherwise not ideally reflecting surfaces.
Both influences may depend on electrode potential.
Instrumentation. A beam of light from a suitable source (e.g. a laser or white light
source) is directed at the surface under investigation after passage through a chopper.
The reflected light is analysed with respect to its intensity. An application in studies
of the kinetics of redox transformations of intrinsically conducting polymers (uti-
lizing the rather fast response time of the employed optical components) has been
reported and rate constants in the range of 0.05 . . . 8 s−1 were deduced [914].
190 5 Spectroscopy at Electrochemical Interfaces

5.9.3 Phase-Shift Interferometry

Fundamentals. A beam of monochromatic light is polarized and split into two

beams. One beam passes an optical medium, e.g. the electrolyte solution in an elec-
trochemical cell close to the solution/electrode interface. After passage it interferes
with the other beam; for a review of two-beam interferometry; see [915, 916]. This
technique was limited both with respect to spatial resolution and sensitivity; for fur-
ther details, see [917]. Temporal or spatial modulation of the reference beam enabled
the use of very thin cells (i.e. the sensitivity was increased) and the two-dimensional
reconstruction of concentration maps.
Instrumentation. A thin layer cell consisting of two high-quality glass windows
and two wires acting as electrodes and spacers in a galvanostatic two-electrode
arrangement is inserted into the sample beam of a two-beam interferometer. The
laser light is polarized and adjusted in intensity by a half-wave retardation plate and
split by a polarizing cube beamsplitter. The sample beam passes the electrochemical
cell close to the solution/electrode interface to be investigated. The reference beam
passes an additional half-wave retardation plate, the phase modulation mirror op-
erated by a piezo actuator and a mechanical chopper enabling the measurement of
temporal changes in concentration distribution. With a beamsplitter, both beams are
mixed and the resulting interference patterns are recorded with a camera. From the
obtained fringe pattern, the concentration map is calculated [924]. Reported results
dealing with metal deposition processes, deposition of conducting polymers and
magnetic field effects during electrodeposition have been reviewed elsewhere [924].

5.9.4 Photoacoustic Methods

Fundamentals. Illumination of a surface or interface both with monochromatic or

with white light can result in considerable temperature fluctuations because of the
photothermal effect. As a consequence of heating the illuminated surface and its
support or the adjacent phase (solution), pressure changes can be induced. These
pressure changes can be detected using a piezoelectric element or a microphone
brought into mechanical contact with the substrate that supports the illuminated
surface. Changes in the piezoelectric signal (the photoacoustic signal) can be cor-
related with processes taking place at the electrode surface or with structural or
further features of the interface/interphase [918]. Measurements taken as a function
of wavelength of the illuminating light are called photoacoustic spectroscopy (see
Sect. 5.1.9, see also Sect. 5.1.10).
Instrumentation. Metal sheets are used as working electrodes. Piezoelectric el-
ements were coupled mechanically with this electrode by using a thin layer of
grease [919–921]. Figure 5.145 shows the experimental setup. For increased sen-
sitivity, the incident light beam was modulated by means of a mechanical chopper
and the photoacoustic signal was detected via a lock-in amplifier.
Detection of heat generated by absorbed radiation converted nonradiatively has
also been done using pyroelectric materials like β-poly(vinylidene) fluoride onto

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 5.9 Miscellaneous Spectroscopies and Methods 191

Fig. 5.145. Experimental setup for photoacoustic measurements [921]

Fig. 5.146. Cyclic voltammogram (bottom) and potential dependent photoacoustic re-
sponse (top) of a silver electrode in a solution of 0.1 M NaClO4 + 0.01 M Pb(ClO4 )2 +
0.005 M HClO4 , scan rate 1 mV·s−1 , modulation frequency 125 Hz (based on data in [921])

which the material under investigation is deposited [922]. This principle has not
been applied to electrochemical in situ studies.
A typical set of results as observed during the underpotential deposition and dis-
solution of lead onto a silver electrode is shown in Fig. 5.146. The increased absorp-
tivity of the silver electrode covered with lead results in an increased photoacoustic
signal. As the electrode potential is scanned only in the underpotential deposition
region, the deposited amount of lead should correspond to a monolayer of atoms
or a fraction thereof. Measurements of the photoacoustic signal as a function of
time at various electrode potentials illustrate this point. At electrode potentials in
the underpotential region the signal rises rapidly to a constant value.
At more negative potentials, the signal rises continuously as a function of time,
indicating bulk deposition. Accordingly, this method is capable of indicating depo-
192 5 Spectroscopy at Electrochemical Interfaces

sition of metal monolayers or similar deposits provided that their light absorption
is different from the absorptivity of the substrate. A review of applications is avail-
able [925]. A variation of this method is known as photoacoustic spectroscopy (see
p. 60). The incident light beam is composed not of white light as described above
(p. 190), but is of a well-defined wavelength. Recording the photoacoustic signal as
a function of the applied wavelength provides the desired absorption spectrum.

5.9.5 Ellipsometry

Fundamentals. Light emitted from a glowing wire (an incandescent or tungsten

halogen lamp), or from most other natural and artificial sources, shows no preferred
polarization, i.e. the electric and the magnetic vector (both are coupled, their planes
of oscillation enclose an angle of 90°) of emitted electromagnetic waves are ran-
domly oriented. When such a beam of light is reflected at a surface, the actual ori-
entation of the electric vector with respect to the plane of reflection (defined by the
incoming and the outgoing beams) has considerable influence on the properties of
the outgoing wave. This influence can be studied more precisely with polarized light.
The latter type of electromagnetic radiation is generated by certain types of lasers
(gas ion) employing windows mounted at the Brewster angle51 (so-called Brewster
windows) at the ends of the plasma tube. Polarized light can be obtained from other
sources by means of a polarizer52 [923].
Upon reflection of polarized light, both the amplitude (i.e. the magnitude of the
electric field vector) and the phase might undergo changes. This depends on the
complex refractive index N of the material designated 1 according to

N1 = n1 − ik1 ,

with the refractive index n1 and the extinction coefficient k1 . The refractive index
n1 can be measured using an Abbé refractometer; the extinction coefficient k1 is
related to the absorption coefficient α1 according to

α1 = 4πk1 /λ.

Further understanding of the interaction is most straightforward when only incident

light with its electromagnetic vector parallel with the plane of reflection (E p ) and
with its vector perpendicular (E s 53 ) are treated. After superposition of the electric
field vectors of these two waves the resulting vector describes a circle, provided they
were in phase and of the same amplitude. After reflection the mentioned changes
51 The Brewster angle is the angle at which reflected light is completely linearly polarized;
the reflected and the diffracted beams are perpendicular to each other.
52 There are numerous polarizing optical components available. Their operation is based
on birefringence, polarization at mirrors at the Brewster angle, optical dichroism, etc. Preci-
sion achieved with sheet polarizers is inadequate, thus devices like Glan–Thompson, Glan–
Foucault or Rochon prisms have to be used.
53 The symbol s derives from the German term for perpendicular, “senkrecht”.

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 5.9 Miscellaneous Spectroscopies and Methods 193

result in a superposition wherein the resulting electric field vector describes an el-
lipse, hence the name of the method. The changes caused by the reflection can be
expressed in various ways. A very convenient and popular description using the
physical parameters gives the amplitude ratio as
|Ep |
tan Ψ = .
|Es |
The difference Δ of the time-independent phases ε of the two components is

Δ = εp − εs .

Both parameters are combined in the basic equation of ellipsometry

ρ = (tan Ψ )eiΔ .

These parameters are related to the optical properties of the investigated films.
Textbooks on ellipsometry are available [924–926]. Thorough reviews of the fun-
damentals, including selected applications related to electrochemistry, have been
published [927–930].
Instrumentation. An ellipsometer is used to determine the change of the polar-
ization of light effected by reflection at a surface, as expressed with ρ. The prin-
cipal optical elements are polarizer and compensators. The former device has been
introduced on p. 192. The latter devices (also known as retarders) introduce a de-
fined phase difference between two orthogonal components of a passing wave. The
difference may be fixed (e.g. 90° or quarter-wave) or variable. Compensators are
manufactured from crystalline birefringent materials like mica, calcite or quartz;
their operation has been treated in detail elsewhere [931]. Measurements can be
performed at a fixed angle of incidence or at variable angles; the wavelength used
can be a fixed one or can be variable. In the latter case, the instrument is called a
spectroscopic ellipsometer. Instruments can be grouped into two types: compensat-
ing and photometric (noncompensating). The basic components of a commercially
designed spectroscopic ellipsometer of the former type are depicted in Fig. 5.147.
In the compensating instrument the phase change caused by the reflection is
counteracted by a compensator yielding, in effect, linearly polarized light. The re-
quired information is extracted from the position of the fixed polarizer, the compen-
sator in the incoming beam and the polarizer in the reflected beam. Further details
of the instrumental setup and measurement procedure have been described in detail
elsewhere [934]. This setup is also called a nulling ellipsometer because the correct
adjustment of the three optical components resulting in an intensity minimum at
the detector is searched. The sensitivity of the photomultipliers frequently used as
detectors has to be taken into account. Obviously this approach is too slow for prac-
tical application. By adding Faraday modulators54 in incoming and reflected beams,
54 A Faraday modulator is a glass or fused silica cylinder mounted axially in an electrical
coil powered by an electrical (AC or DC) current.
194 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.147. Components of a spectrometric rotating polarizer ellipsometer

Fig. 5.148. Components of an automatic nulling ellipsometer

an oscillation of the plane of polarization is possible. Phase-sensitive detection of

the signal at the detector with respect to the modulation allows faster determina-
tion of the minimum and the relevant position of the corresponding settings of the
three optical devices. Further compensation of mechanical adjustment errors is pos-
sible by adding two further Faraday modulators that are operated with a constant
current. The technical status of this type of instrument has been reviewed together
with further types of instruments [932] and the setup of the former type is shown
schematically in Fig. 5.148.
A further type of fast automatic ellipsometer for electrochemical investigations
has been described [933] and an experimental approach to observe fast transients
with ellipsometry was reported [934]. In the photometric mode, the intensity of the
reflected light is measured as a function of the position of polarizer and sometimes
compensator in the incoming beam; for further details and an overview, see [934].
A general overview of instrumental developments has been provided [935].
The process of an ellipsometric experiment can be separated into five steps [935]:
1. Providing an incident beam of a known state of polarization
2. Allowing this beam to interact with the interface/interphase under investigation
3. Measuring the state of the emerging light
4. Determination of parameters, like Ψ and Δ or their equivalents
5. Inferring properties and changes from these parameters

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 5.9 Miscellaneous Spectroscopies and Methods 195

The final step almost always involves formulation of a model that describes
the system under investigation. The parameters of this model are compared with
those measured. By successive approximation, the parameters of the model are op-
timized until agreement is reached. In the most simple case, a clean, homogeneous
and isotropic surface with N2 is covered with a medium of a known value of N1
and a two-layer model can be applied. From a single ellipsometric measurement the
value of N2 can already be determined [937]. When the surface is covered with a
layer of a foreign material, a three-layer model must be used. Although the values
of N1 and N3 can be determined in many cases, the number of parameters is consid-
erably larger in a separate experiment where the intermediate layer is absent, which
indicates a need for multiple experiments [937]. Numerous models combining in-
formation about optical parameters of ideal films with their real morphology and
composition have been used to evaluate ellipsometric data [934]; nevertheless, in
many studies, ellipsometry is used mostly to determine film thickness. A modifica-
tion of an ellipsometer enabling microscopically resolved measurements (ellipsomi-
croscopy EMSI) has been described [936] and applied to studies of the spreading of
corrosion on stainless steel.
Ellipsometry at noble metal electrode/solution interfaces has been used to test
theoretically predicted microscopic parameters of the interface [937]. Investigated
systems include numerous oxide layer systems [934–943], metal deposition proc-
esses [934], adsorption processes [934, 944] and polymer films on electrodes [945–
947]. Submonolayer sensitivity has been claimed. Expansion and contraction of
polyaniline films was monitored with ellipsometry by Kim et al. [948]. Film thick-
ness as a function of the state of oxidation of redox active polyelectrolyte layers
has been measured with ellipsometry [949]. The deposition and electroreduction of
MnO2 films has been studied [950]; below a thickness of 150 nm, the anodically
formed film behaved like an isotropic single layer with optical constants indepen-
dent of thickness. Beyond this limit, anisotropic film properties had to be assumed.
Reduction was accompanied by an increase in thickness, which started at the ox-
ide/solution interface.

5.9.6 Surface Plasmon Resonance Spectroscopy55

Fundamentals. Surface plasmon polaritons (SPP)56 are electromagnetic charge

density waves57 (plasma oscillations) that collectively propagate along the metal/
solution (or any other dielectric medium) interface [951–953]. They can be gener-
ated by electromagnetic radiation (e.g. light in the visible range of the electromag-
55 The method is sometimes called surface plasmon spectroscopy (SPS); the term
“resonance” refers to the peculiarities of the reflectivity vs. angle of incidence plots obtained
with the method (minimum of reflectivity).
56 SPPs are sometimes also called PSPs (plasmon surface polaritons).
57 The transversal electromagnetic modes are either photon-like or similar to optical
phonons, if their nature is a mix between these forms, the modes are sometimes called polari-
tons.
196 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.149. Otto (left) and Kretschmann (right) configuration for SPP excitation

netic spectrum) coupling with oscillating modes of the electron density at this in-
terface. Surface plasmon polaritons are generated only with p-polarized light waves
with electric field vectors that are oriented parallel to the plane of incidence. Their
propagation or wave vector lies in the plane of the metal surface. The field ampli-
tudes associated with SPPR have a maximum at the interface and decay exponen-
tially into both adjacent phases, making their investigation an extremely surface sen-
sitive technique. Because of the electrooptical peculiarities SPPs cannot be caused
by simple external reflection of a light beam at a smooth metal surface. Instead,
prism coupling is needed, which uses either the Otto or the Kretschmann configura-
tion depicted in Fig. 5.149. In the former configuration an electrolyte solution layer
with the thickness of about the wavelength of the used light is inserted between the
prism and the solid metal. In the latter configuration, the metal layer of about this
thickness is deposited directly onto the prism. Details are discussed in the following
section.
Surface plasmon polaritons have been used to enhance the surface sensitivity
of various spectroscopic techniques like surface enhanced Raman spectroscopy and
second harmonic generation. The generation of SPPs at an interface causes a lower
intensity of the reflected light beam. This intensity reaches a minimum at a typical
angle of incidence. This angle is called a surface plasmon resonance angle (θ sp ).
Because the shape of the reflectivity vs. the angle of incidence curve depends on
the electrooptical properties of the involved materials on both sides of the interface
and can be calculated using Fresnel calculations, measurements of these curves pro-
vide a possibility to investigate the interface and any changes occurring therein by
adsorption on the metal surface. Further details are provided elsewhere [954]. An
overview of SPS in electrochemistry has been provided [955].
Instrumentation. For the measurement of the surface plasmon resonance, a suit-
able electrochemical cell incorporating the crucial elements needed for SPP excita-
tion is required. A simple design based on the Kretschmann configuration is shown
in Fig. 5.150. Because the metal under investigation has to be deposited by vapor
deposition, only polycrystalline surfaces can be studied. The Otto configuration re-
quires a well-defined, narrow gap between the base of the prism and the metal film.
Depending on the employed wavelength, this distance ranges from 500 to 1000 nm.
Invoking a typical distance of about 200 nm, dust particles have been noted as possi-
ble disturbances, making this arrangement practically meaningless [952]. Neverthe-
less, successful applications were previously reported, wherein the proper distance

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 5.9 Miscellaneous Spectroscopies and Methods 197

Fig. 5.150. Electrochemical cell for SPR measurements based on the Kretschmann configu-
ration

Fig. 5.151. Experimental setup for detection of SPR

was adjusted with a micrometer screw [956]. The Otto arrangement allows investi-
gations of single crystal surfaces or of polymer coats on metal substrates.
The obvious advantage of the Kretschmann design is a simple setup without
any specific problems related to the arrangement of the electrodes. A drawback is
the need to have the working electrode under investigation deposited as a thin film
on the prism. As already discussed in relation to various other internal reflection
mode techniques, this might cause problems because of the poor electronic conduc-
tivity of thin metal films. This may result in uneven electrode potential distribution
within the film and a poor response to fast changes of the electrode potential. In ad-
dition, the preparation of the metal layer itself might be a problem because of poor
adhesion or uneven thickness. With the Otto configuration, this problem is readily
avoided. Instead, the usual problems encountered with thin electrolyte films (TLC)
have to be expected. The SPR is detected as a minimum in the reflected light inten-
sity. The setup needed for this measurement includes a monochromatic light source
(usually a laser), a polarizer for selection of the p-polarized light and a detector (e.g.
photodiode matched to the wavelength of the incident light). Cell and detector are
mounted on a θ-2θ -stage, as shown schematically in Fig. 5.151. Additional lenses
are needed for focusing the incident beam and a chopper is used to simplify and
improve light intensity measurements. Instead of a simple prism, a hemispherical
prism is used, this results in a constant position of the incident beam on the elec-
trode surface.
Surface plasmon resonance has been used to study condensed films at metal/
solution interfaces [957, 958]. A typical result is displayed in Fig. 5.152.
The SPR is found around ϕ0 = 46◦ . From data taken at various electrode poten-
tials, the number of organic species in the condensed thymine film could be calcu-
lated [957]. With a combination of SPR and EQCMB, the adsorption of a perfluo-
198 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.152. Reflectivity of the interface mercury/aqueous solution of 1 M NaCl + 1 mM

thymine as a function of the angle of incidence ϕ0 and of the electrode potential as indicated,
pH = 6; λ = 600 nm; data taken from [957]

ropolyether surfactant on a gold electrode has been investigated [959]. In studies of

the potential dependency of the SPR as a function of electrode potential for a silver
electrode in contact with aqueous solutions containing various anions, strong effects
of specifically adsorbed halide ions were found [960]. Time-dependent measure-
ments of SPR enabled separation of various stages of adsorption and surface oxide
film formation on a gold electrode [961]. Oxidation and reduction of mercury and
its ions at an ultrathin gold electrode was monitored with SPR [962]. Results imply
a partially reversible formation of a gold amalgam with optical properties between
those of gold and mercury; the mercury content was estimated to be about 12%.
Surface plasmon resonance studies of a gold surface coated for corrosion protection
with a thin layer of silica indicate that silica provides effective protection without
completely inhibiting electrochemical processes [963]. These multilayer systems
are under development with respect to analytical applications.
Surface plasmon resonance has been applied to studies of intrinsically con-
ducting polymers. Electrochromic properties and optical conductivity were mea-
sured [964]. Ion ingress and egress processes could be related to doping/dedoping
processes of polypyrrole; accumulation of neutral salt and solvent in the film were
observed with a combination of SPR and the quartz crystal microbalance [965]. The
mechanism of copolymerization of terthiophene with a carbazole and the properties
of the obtained product were studied with a combination of various electrochemical
methods, including the quartz crystal microbalance and SPR [966]. The advanta-
geous effects of a micellar solution of a monomer (3,4-ethylene dioxythiophene
EDOT, aqueous micellar solution) could be verified [967]. Self-assembled layer-
by-layer films of polyaniline and sulfonated polyaniline (self-doped PANI) were
investigated with a combination of SPR and surface plasmon field-enhanced light

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 5.9 Miscellaneous Spectroscopies and Methods 199

scattering (see below) [968]. Morphological changes and changes of the dielectric
properties could be observed during electrochemical cycling of the ultrathin films.
Kinetic studies of various adsorption processes have been reviewed [64].

5.9.7 Surface Plasmon Excitation and Related Methods

Fundamentals. Surface plasmons (SP) can be used to monitor optical properties of

metal and semiconductor surfaces. For introductory overviews, see [969, 970]. Sur-
face plasmon field-enhanced light scattering (SPFELS) is observed when an inter-
face is illuminated by light under conditions stimulating surface plasmon excitation
as reported [971].
Applications in electrochemistry similar to surface plasmon (resonance) spec-
troscopy are treated in the previous sections. Photoluminescence associated with
surface plasmons is treated in Sect. 5.6.4.
Instrumentation. The experimental setup is similar to the one used in SPR. An
additional photomultiplier mounted at fixed angle with respect to the base of the
prism at the solution side of the electrode films is used to detect light scattered from
the rough electrode surface and/or the polymer film deposited on the metal film (see
Fig. 5.153).
With a combination of SPR and SPFELS, changes of optical (dielectric con-
stant) and electrochemical properties during doping/dedoping of layer-by-layer self-
assembled conducting films of polyaniline and sulfonated polyaniline were mea-
sured; results are displayed in Figs. 5.154 and 5.155 [968]. In a study of polyaniline
deposition by electropolymerization, changes of both reflectivity and scattered light
intensity were observed [971].
The observed change in reflectivity can be explained when taking into account
ion movement (both cation egress and anion ingress) during oxidative doping.
Changes in the dielectric constant of the film associated with doping/dedoping are
evident in the SPFELS curves below.

Fig. 5.153. Experimental setup for detection of SPFELS

200 5 Spectroscopy at Electrochemical Interfaces

Fig. 5.154. Cyclic voltammogram of polyaniline and surface plasmon resonance reflectivity
with a solution of 0.5 M H2 SO4 , second scan, dE/dt = 20 mV·s−1 , based on data in [971]

Fig. 5.155. Cyclic voltammogram of polyaniline and surface plasmon field-enhanced light
scattering with a solution of 0.5 M H2 SO4 , second scan, dE/dt = 20 mV·s−1 , based on data
in [971]

5.9.8 Inductively Coupled Plasma Atomic Emission Spectroelectrochemistry

Fundamentals. The composition of liquids with respect to both identity and con-
centration of dissolved species can be determined with inductively coupled plasma
atomic emission spectrometry (ICP-AES) [972]. The employed spectrometer can
be coupled directly with an electrochemical cell wherein processes like corrosion
or anodic dissolution occur. Continuous aspiration of very small liquid volumes
transferred into the spectrometer allows determination of rates of dissolution as a
function of various experimental parameters like electrode potential [973].
Instrumentation. An electrochemical flow cell (flow rate approx. 2–3 mL·min−1 )
is connected to an electrolyte solution reservoir. The solution is supplied via a peri-
staltic pump. The outlet is connected to the ICP-AES. Depending on the type and

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 5.9 Miscellaneous Spectroscopies and Methods 201

setup of the spectrometer, several metal ions can be monitored. In a study of the
anodic dissolution of 304 stainless steel, the dissolution rates of numerous metallic
components could be determined [980].

5.9.9 Positron Annihilation Spectroscopy (PAS)58

Fundamentals. Vacancies, vacancy clusters, nanometer-sized voids, dislocations

and other open volume defects of atomic size can be detected and studied with
positron annihilation spectroscopy [974, 975]. Positrons (p+ or e+ ) are nuclear
species with the same mass and spin, but the opposite charge and magnetic mo-
mentum of the electron. The positron is the antiparticle of the electron as postulated
by Dirac (1930) and finally detected by Anderson (1932). Positrons are formed dur-
ing nuclear decay reactions of various isotopes (e.g. 58 Co, 22 Na, 64 Cu) or in lin-
ear accelerators. Monochromatic positrons of desired energy are obtained by using
moderators (e.g. mono- or polycrystalline nickel or tungsten crystals). The positron
is implanted in the solid under investigation. Its annihilation with an electron in the
solid produces gamma radiation (about 511 keV) according to:

p+ (e+ ) + e− → positronium → 2h · ν(511 keV).

The gamma radiation is Doppler shifted because of the momentum that is trans-
ferred to the photon during annihilation. This momentum is in turn controlled by
the momentum of the annihilating electron, which is related to the nature of the an-
nihilation site. In voids, valence electrons dominate with a narrow distribution of
momentum, whereas in the bulk of a crystal a much broader distribution of elec-
tron momenta is observed. The Doppler broadening is wider in the latter case. The
presence of defects can thus be detected by measuring the line shape of the annihila-
tion photopeak. Positrons of variable energy and correspondingly different depth of
penetration can be used for depth profiling. Thus this method can be used to study
defects close to a surface, i.e. the metal/solution interface, as formed during open
circuit dissolution of aluminum in caustic solutions [976].
Instrumentation. The experimental setup includes a positron source with a suit-
able converter (e.g. Cu(111)+S crystal) that is used for moderation of decay posi-
trons from the radioactive source (e.g. 200–300 mCi 58 Co) into thermal positrons
[977]. A NaI(Tl) or Ge(Li) crystal is used to detect the annihilation photons pro-
duced during interaction of positrons with the material under investigation. Light
from these crystals is guided via a light pipe to a photomultiplier. Samples to be
investigated have to be transferred from the electrochemical cell into the PASCA
setup. Investigations reported so far have dealt mainly with metal dissolution and
oxide layer formation processes [983], metal swelling upon hydrogen sorption [978]
and intrinsically conducting polymers [979, 980].
58 This method has also been called PASCA (Positron annihilation spectroscopy for
chemical analysis).
202 5 Spectroscopy at Electrochemical Interfaces

5.9.10 Neutron Reflectivity

Fundamentals. A collimated beam of neutrons generated in a nuclear reactor or a

spallation source with wavelength λ impinges onto an interface at an angle θ (close
to glancing angle). The reflected intensity R is measured as a function of momentum
transfer Q
4π
Q= sin θ.
λ
The recorded reflectivity R(Q) depends on the neutron refractive index perpendic-
ular to the interface. This index depends on the scattering length density Nb, which
is composed of the number density N of nuclei per cm3 and the sum of the neutron
scattering lengths b of the various nuclei. Because values of b vary for different nu-
clei, isotopic exchange causes variation of the neutron reflectivity without changing
the electrochemical properties to a significant extent.59 The reflectivity of an inter-
face with a film attached is described by the Fresnel coefficients. Even in the ap-
proximate form [981], the recorded reflectivity profile cannot be deconvoluted into
a scattering length density profile because of the lack of phase information. Instead,
a calculated reflectivity profile based on a model of the Nb profile is fitted to the
measured profile. Thus the desired structural information along the z-axis (perpen-
dicular to the solution/electrode interface) is obtained. Using isotope exchange, the
scattering length density gradients in the system can be varied systematically. Fur-
ther details of the fundamentals and of the data interpretation have been reviewed
elsewhere [982, 988]. A major advantage of the method is the high spatial (depth)
resolution down to nanometers.
Instrumentation. Films to be investigated are deposited on a material (e.g. single
crystal quartz) that is transparent for thermal neutrons (0.1 nm < λ < 0.6 nm).
A typical cell is displayed in Fig. 5.156. The electrochemically inert metal used as

Fig. 5.156. Spectroelectrochemical cell for in situ neutron reflectivity measurements [989]
59 This may be different in kinetic studies, where the kinetic isotope effect might come into
play.

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 5.9 Miscellaneous Spectroscopies and Methods 203

a conductive layer between the quartz plate and the film under investigation has to
be selected with respect to matching the scattering density of quartz and metal (for
an example, see [988]).
Investigated examples include the determination of the spatial distribution of a
polymer, solvent and mobile species in poly(o-toluidine) [983, 984] and polybithio-
phene [989] films, film swelling and solvent content in electroactive films containing
transition metal complexes [988, 985], postdeposition modified electroactive poly-
mers [986] and organic adsorbate layers [987]. The method allows also the investi-
gation of buried interfaces in bilayer systems of various polymers [988].

5.9.11 Neutron Scattering

Fundamentals. Neutrons can interact with matter in several ways. Depending on

the neutron–nucleus interaction, they can be scattered coherently or incoherently
and both processes can occur elastically or inelastically. For structural studies in
electrochemical systems, diffraction, i.e. elastic coherent scattering, is of particu-
lar interest. Fundamentals of these modes of interaction, including spectroscopic
aspects relevant for mobility studies, have been reviewed [989].
Instrumentation. The basic setup of a neutron scattering experiment is depicted in
Fig. 5.157.
In experiments reported so far, which mostly pertain to electrode materials show-
ing intercalation processes like those of transition metal chalcogenides or graphite
(for a review, see [989]), an angular dispersive setup with position-sensitive detec-
tors has been used. In this arrangement, the position of the detector is moved from
angles corresponding to 2θ1 to 2θ2 . Further studies of processes in molten elec-
trolytes and during surface oxidation of various metals have been reported [989]. In
inelastic scattering experiments, the energy change of the neutron is determined by
moving the crystal serving as a monochromator. The resulting Doppler effect causes
a modulation of the beam energy (in a typical case, by about ±30 μeV).

Fig. 5.157. Simplified setup for neutron scattering measurements

204 5 Spectroscopy at Electrochemical Interfaces

References
1. N. Sheppard, H.A. Willis, J.C. Rigg, Pure Appl. Chem. 57, 105 (1985)
2. X.G. Zhang, Electrochemistry of Silicon and its Oxide (Kluwer/Plenum, New York,
2001)
3. J.B. Wagner Jr., in Techniques for Characterization of Electrodes and Electrochemical
Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 3
4. H. Ohno (ed.), Electrochemical Aspects of Ionic Liquids (Wiley, Hoboken, 2005)
5. C. Aliaga, C.S. Santos, S. Baldelli, Phys. Chem. Chem. Phys. 9, 3683 (2007)
6. K.E. Johnson, Interface 16, 38 (2007)
7. T. Tsuda, C.L. Hussey, Interface 16, 42 (2007)
8. V.E. Norvell, G. Mamantov, in Molten Salt Techniques, ed. by D.G. Lovering, R.J. Gale
(Plenum, New York, 1983), p. 151
9. I. Galasiu, R. Galasiu, J. Thonstad, in Nonaqueous Electrochemistry, ed. by D. Aurbach
(Dekker, New York, 1999), p. 461
10. F. Scholz, U. Schröder, R. Gulaboski, Electrochemistry of Immobilized Particles and
Droplets (Springer, Heidelberg, 2005)
11. C.K. Mann, in Electroanalytical Chemistry, vol. 3, ed. by A.J. Bard (Dekker, New York,
1969), p. 57
12. W.R. Heineman, F.M. Hawkridge, H.N. Blount, in Electroanalytical Chemistry, vol. 13,
ed. by A.J. Bard (Dekker, New York, 1984), p. 1
13. T. Kuwana, W.R. Heineman, Acc. Chem. Res. 9, 241 (1976)
14. W.R. Heinemann, Extended Abstracts of the 201st Meeting of the Electrochemical So-
ciety, Philadelphia, USA, 12–17.05.2002, Ext. Abstr. #1301
15. A. Yildiz, P.T. Kissinger, C.N. Reilley, Anal. Chem. 40, 1018 (1968)
16. J. Lippe, PhD Thesis. Universität Oldenburg, 1991
17. R. Holze, Collect. Czech. Chem. Comm. 65, 899 (2000)
18. P.D. Boyle, D.C. Boyd, A.M. Mueting, L.H. Pignolet, Inorg. Chem. 27, 4424 (1988)
19. R.A. Hatton, S.R. Day, M.A. Chesters, M.R. Willis, Thin Solid Films 394, 292 (2001)
20. E. Matveeva, J. Electrochem. Soc. 152, H138 (2005)
21. M. Hupert, A. Muck, R. Wang, J. Stotter, Z. Cvackova, S. Haymond, Y. Show, G.M.
Swain, Diam. Relat. Mater. 12, 1940 (2003)
22. H. Tian, A.J. Bergren, R.L. McCreery, Appl. Spectrosc. 61, 1246 (2007)
23. E. Steudel, J. Posdorfer, R.N. Schindler, Electrochim. Acta 40, 1587 (1995)
24. J.P. Bullock, K.R. Mann, Inorg. Chem. 28, 4006 (1989)
25. R. Holze, Spectroelectrochemistry of Conducting Polymers, in Handbook of Electronic
and Photonic Materials and Devices, vol. 8, ed. by H.S. Nalwa (Academic Press, San
Diego, 2000), p. 209
26. R. Holze, in Handbook of Advanced Electronic and Photonic Materials, vol. 2, ed. by
H.S. Nalwa (OPA N.V. and Gordon&Breach, Singapore, 2001), p. 171
27. A.M. Bond, F. Marken, E. Hill, R.G. Compton, H. Hügel, J. Chem. Soc. Perkin Trans. II
1997, 1735 (1997)
28. M.H. Barley, C.E. Anson, J. Lewis, B.F.G. Johnson, J. Organometal. Chem. 339, 151
(1988)
29. E.W. Becker, W. Ehrfeld, P. Hagmann, A. Maner, D. Münchmeyer, Microelec. Eng. 4,
35 (1986)
30. W. Ehrfeld, D. Münchmeyer, Nucl. Instr. Meth. Phys. Res. A303, 523 (1991)
31. L. Dunsch, A. Neudeck, P. Rapta, Fresenius J. Anal. Chem. 367, 314 (2000)
32. A. Neudeck, L. Dunsch, Ber. Bunsenges. Phys. Chem. 97, 407 (1993)

www.ebook3000.com
 References 205

33. A. Neudeck, L. Dunsch, J. Electroanal. Chem. 386, 135 (1995)

34. M.B.G. Pilkington, B.A. Coles, R.G. Compton, Anal. Chem. 61, 1787 (1989)
35. F. Hartl, H. Luyten, H.A. Nieuwenhuis, G.C. Schoemaker, Appl. Spectrosc. 48, 1522
(1994)
36. M. Kummer, J.R. Kirchhoff, Anal. Chem. 65, 3720 (1993)
37. M. Kummer, J.R. Kirchhoff, Electroanal. 8, 524 (1996)
38. S.C. Paulson, C.M. Elliott, Anal. Chem. 68, 1711 (1996)
39. T.B. Jarbawi, M.T. Stankovich, Anal. Chim. Acta 292, 71 (1994)
40. W.R. Heinemann, B.J. Norris, J.F. Goelz, Anal. Chem. 47, 79 (1975)
41. R.W. Murray, W.R. Heineman, G.W. O’Dom, Anal. Chem. 39, 1666 (1967)
42. J. Salbeck, Anal. Chem. 65, 2169 (1993)
43. J. Zak, M.D. Porter, T. Kuwana, Anal. Chem. 55, 2219 (1983)
44. M.J. Simon, W.R. Heineman, G.P. Kreishman, Anal. Chem. 54, 2382 (1982)
45. J.D. Brewster, J.L. Anderson, Anal. Chem. 54, 2560 (1982)
46. Y.F. Lee, J.R. Kirchhoff, Anal. Chem. 65, 3430 (1993)
47. G. Mamantov, C.L. Hussey, R. Marassi, in Techniques for Characterization of Elec-
trodes and Electrochemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York,
1991), p. 471
48. C.Y. Chung, T.C. Wen, A. Gopalan, Electrochim. Acta 47, 423 (2001)
49. A.A. Nekrasov, V.F. Ivanov, A.V. Vannikov, Electrochim. Acta 46, 3301 (2001)
50. F. Alakhras, R. Holze, Synth. Met. 157, 109 (2007)
51. P. Marque, J. Roncali, J. Phys. Chem. 94, 8614 (1990)
52. W.T. Yap, G. Marbury, E.A. Blubaugh, R.A. Durst, J. Electroanal. Chem. 271 325
(1989)
53. J. Salbeck, J. Electroanal. Chem. 340, 169 (1992)
54. S. Mho, S.N. Hoier, B.-S. Kim, S.-M. Park, Bull. Kor. Chem. Soc. 15, 739 (1994)
55. F. Gaillard, E. Levillain, J. Electroanal. Chem. 398, 77 (1995)
56. D.-H. Han, B.-S. Kim, S.-J. Choi, Y. Jung, J. Kwak, S.-M. Park, J. Electrochem. Soc.
151, E283 (2004)
57. I.S. Zavarine, C.P. Kubiak, J. Electroanal. Chem. 495, 106 (2001)
58. R.S. Robinson, C.W. McCurdy, R.L. McCreery, Anal. Chem. 54, 2356 (1982)
59. R.S. Robinson, R.L. McCreery, Anal. Chem. 53, 997 (1981)
60. C.D. Batich, H.A. Laitinen, H.C. Zhou, J. Electrochem. Soc. 137, 883 (1990)
61. J. López-Palacios, A. Colina, A. Heras, V. Ruiz, L. Fuente, Anal. Chem. 73, 2883
(2001)
62. O. Orcajo, E. Ventosa, A. Martinez, A. Colina, A. Heras, V. Ruiz, J. Lopez-Palacios, J.
Electroanal. Chem. 596, 95 (2006)
63. W. Knoll, Ann. Rev. Phys. Chem. 49, 569 (1998)
64. W.J. Doherty III, C.L. Donley, N.R. Armstrong, S.S. Saavedra, Appl. Spectrosc. 56,
920 (2002)
65. J.N. Richardson, Z. Aguilar, N. Kaval, S.E. Andria, T. Shtoyko, C.J. Seliskar, W.R.
Heineman, Electrochim. Acta 48, 4291 (2003)
66. A.J. Bard, L.R. Faulkner, Electrochemical Methods, 2nd edn. (Wiley, New York, 2001),
p. 736
67. H.G.O. Becker, H. Böttcher, F. Dietz, D. Rehorek, G. Roewer, K. Schiller, H.-J. Timpe,
in Einführung in die Photochemie, ed. by H.G.O. Becker (Wissenschaften, Berlin,
1991)
68. A.B. Ellis, in Chemistry and Structure at Interfaces, ed. by R.B. Hall, A.B. Ellis (VCH,
Deerfield Beach, 1986), p. 245
206 5 Spectroscopy at Electrochemical Interfaces

69. R.G. Compton, A.C. Fisher, R.G. Wellington, Electroanalysis 3, 27 (1991)

70. R.G. Compton, A.C. Fisher, R.G. Wellington, J. Winkler, J. Phys. Chem. 96, 8153
(1992)
71. R.G. Compton, A.C. Fisher, R.G. Wellington, J. Winkler, J. Chem. Soc. Perkin Trans.
1992, 1359 (1992)
72. J.S. Littig, T.A. Nieman, Anal. Chem. 64, 1140 (1992)
73. L. Sun, R.M. Crooks, J. Electrochem. Soc. 152, E371 (2005)
74. B. Valeur, J.-C. Brochon (eds.), New Trends in Fluorescence: Application to Chemical
and Life Sciences (Springer, Berlin–Heidelberg, 2001)
75. M. Dias, P. Hudhomme, E. Levillain, L. Perrin, Y. Sahin, F.-X. Sauvage, C. Wartelle,
Electrochem. Commun. 6, 325 (2004)
76. J. Salbeck, J. Electroanal. Chem. 340, 169 (1992)
77. P. Jennings, A.C. Jones, A.R. Mount, Phys. Chem. Chem. Phys. 2, 1241 (2000)
78. H. Nagatani, R.A. Iglesias, D.J. Fermin, P.-F. Brevet, H.H. Girault, J. Phys. Chem. B
104, 6869 (2000)
79. H. Nagatani, T. Ozeki, T. Osakai, J. Electroanal. Chem. 588, 99 (2006)
80. N. Nishi, K. Izawa, M. Yamamoto, T. Kakiuchi, J. Phys. Chem. B 105, 8162 (2001)
81. J.D.E. McIntyre, in Advances in Electrochemistry and Electrochemical Engineering,
vol. 9, ed. by P. Delahay, C.W. Tobias (Wiley, New York, 1973), p. 61
82. D.M. Kolb, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New York, 1988),
p. 87
83. W. Plieth, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 223
84. D.E. Aspnes, Surf. Sci. 37, 418 (1973)
85. L.M. Abrantes, R. Peat, L.M. Peter, A. Hamnett, Ber. Bunsenges. Phys. Chem. 91, 369
(1987)
86. A. Tadjeddine, D.M. Kolb, R. Kötz, Surf. Sci. 101, 277 (1980)
87. C. Gutierrez, in Spectroscopic and Diffraction Techniques in Interfacial Electrochem-
istry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Acad-
emic, Dordrecht, 1990), p. 261
88. R.A. Castelli, P.D. Persans, W. Strohmayer, V. Parkinson, Corr. Sci. 49, 4369 (2007)
89. M. Zhao, H. Huang, B.D. Cahan, I.T. Bae, S. Klippenstein, D.A. Scherson, Extended
Abstracts of the 179th Meeting of the Electrochemical Society, Washington DC, USA,
05.05–10.05.1991, Ext. Abstr. #654
90. T.E. Furtak, D.W. Lynch, Phys. Rev. Lett. 35, 960 (1975)
91. T.E. Furtak, D.W. Lynch, J. Electroanal. Chem. 79, 1 (1977)
92. K.L. Shaklee, F.M. Pollak, M. Cardona, Phys. Rev. Lett. 15, 883 (1965)
93. L.M. Abrantes, R. Peat, L.M. Peter, A. Hamnett, Ber. Bunsenges. Phys. Chem. 91, 369
(1987)
94. I. Fromondi, D.A. Scherson, Electrochemical Society Spring Meeting 209th, Denver,
Colorado, USA, May 7–11, 2006, Ext. Abstr. #1098
95. D.M. Kolb, J. Schneider, Surf. Sci. 162, 764 (1985)
96. S.H. Liu, C. Hinnen, C. Nguyen Van Huong, N.R. de Tacconi, K.M. Ho, J. Electroanal.
Chem. 176, 325 (1984)
97. D.M. Kolb, J. Schneider, Electrochim. Acta 31, 929 (1986)
98. B. Pettinger, U. Wenning, D.M. Kolb, Ber. Bunsenges. Phys. Chem. 82, 1326 (1978)
99. B.G. McMillan, E.A. Berlouis, F.R. Cruickshank, P.F. Brevet, Electrochim. Acta 53,
1157 (2007)

www.ebook3000.com
 References 207

100. P.H. Schmidt, W.J. Plieth, J. Electroanal. Chem. 201, 163 (1986)
101. F. Henglein, J. Lipkowski, D.M. Kolb, J. Electroanal. Chem. 303, 245 (1991)
102. F. Henglein, D.M. Kolb, L. Stolberg, J. Lipkowski, Surf. Sci. 291, 325 (1993)
103. T. Sagara, H. Kawamura, N. Nakashima, Langmuir 12, 4253 (1996)
104. F. Bedioui, C. Bied-Charreton, C. Bongars, J. Devynck, C. Hinnen, J. Electroanal.
Chem. 207, 87 (1986)
105. B.G. McMillan, L.E.A. Berlouis, F.R. Cruickshank, P.F. Brevet, J. Electroanal. Chem.
599, 177 (2007)
106. K. Nogami, H. Ueno, K. Yoshino, J. Appl. Phys. 64, 6460 (1988)
107. W. Plieth, W. Kozlowski, T. Twomey, in Adsorption of Molecules at Metal Electrodes,
ed. by J. Lipkowski, P.N. Ross (VCH, New York, 1992), p. 239
108. F. Scholz, B. Meyer, in Electroanalytical Chemistry, vol. 20, ed. by A.J. Bard (Dekker,
New York, 1998), p. 1
109. U. Schröder, F. Scholz, J. Solid State Electrochem. 1, 62 (1997)
110. Y. Borensztein, W.L. Mochan, J. Tarriba, R. Barrera, A. Tadjeddine, Phys. Rev. Lett.
71, 2334 (1993)
111. A. Tadjeddine, D.M. Kolb, R. Kötz, Surf. Sci. 101, 277 (1980)
112. J. Tarriba, W.L. Mochan, Phys. Rev. B 46, 12902 (1992)
113. W.L. Mochan, R. Barrera, Y. Borensztein, A. Tadjeddine, Physica A 207, 334 (1994)
114. O. Acher, B. Drevillon, Rev. Sci. Instr. 63, 5332 (1992)
115. D.E. Aspnes, J.P. Harbison, A.A. Stunda, L.T. Florez, J. Vac. Sci. Technol. A 6, 1327
(1988)
116. D.E. Aspnes, J.P. Harbison, A.A. Studna, L.T. Florez, Phys. Rev. Lett. 59, 1687 (1987)
117. P. Harrison, T. Farrell, A. Maunder, C.I. Smith, P. Weightman, Meas. Sci. Technol. 12,
2185 (2001)
118. V. Mazine, Y. Borensztein, L. Cagnon, P. Allongue, Phys. Status Solidi A 175, 311
(1999)
119. B. Sheridan, D.S. Martin, J.R. Power, S.D. Barrett, C.I. Smith, P. Weightman, C.A.
Lucas, R.J. Nichols, Phys. Rev. Lett. 85, 4618 (2000)
120. A.J. Motheo, E.R. Gonzalez, G. Tremilliosi, A. Rakotondrainibe, J.M. Leger, B. Beden,
C. Lamy, J. Brazil. Chem. Soc. 9, 31 (1998)
121. C.I. Smith, A.J. Maunders, C.A. Lucas, R.J. Nichols, P. Weightman, J. Electrochem.
Soc. 150, E233 (2003)
122. C.I. Smith, N.J. Almond, P. Weightman, J. Electrochem. Soc. 154, F90 (2007)
123. C.E. Vallet, S. Berns, J.J. Hendrickson, C.W. White, J. Electrochem. Soc. 135, 387
(1988)
124. R.E. Malpas, A.J. Bard, Anal. Chem. 52, 109 (1980)
125. C.E. Vallet, in Spectroscopic and Diffraction Techniques in Interfacial Electrochem-
istry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Acad-
emic, Dordrecht, 1990), p. 133
126. G.H. Brilmyer, A.J. Bard, Anal. Chem. 52, 685 (1980)
127. A.C. Boccara, D. Fournier, J. Badoz, Appl. Phys. Lett. 36, 130 (1980)
128. J.D. Rudnick, F.R. McLarnon, E.J. Cairns, in Techniques for Characterization of Elec-
trodes and Electrochemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York,
1991), p. 127
129. R.E. Russo, F.R. McLarnon, J.D. Spaer, E.J. Cairns, J. Electrochem. Soc. 134, 2783
(1987)
130. B.S.H. Royce, D. Voss, A. Bocarsley, J. Phys. (Orsay, Fr.) 44, C6-325 (1983)
131. C. Barbero, R. Kötz, O. Haas, Synth. Met. 101, 170 (1999)
208 5 Spectroscopy at Electrochemical Interfaces

132. J.E. de Albuquerque, W.L.B. Melo, R.M. Faria, Rev. Sci. Instr. 74, 306 (2003)
133. K. Nakanashi, N. Berova, R.W. Woody (eds.), Circular Dichroism – Fundamentals and
Applications (VCH, New York, 1994)
134. for an introduction to the related linear dichroism effect (LD) see: J. Michl, E.W. Thul-
strup, Acc. Chem. Res. 20 (1987) 192 and references therein
135. E. Charney, The Molecular Basis of Optical Activity: Optical Rotatory Dispersion and
Circular Dichroism (Wiley, New York, 1979)
136. J. Bindl, P. Seitz, U. Seitz, E. Salbeck, J. Salbeck, J. Daub, Chem. Ber. 120, 1747 (1987)
137. J. Salbeck, I. Aurbach, J. Daub, in DECHEMA-Monographie, vol. 112, ed. by J. Russow
(VCH Verlagsgesellschaft, Weinheim, 1988), p. 177
138. J. Daub, J. Salbeck, I. Aurbach, Angew. Chem. 100, 278 (1988)
139. X. Liu, K. Liu, G. Cheng, S. Dong, J. Electroanal. Chem. 510, 103 (2001)
140. H. Goto, J. Electrochem. Soc. 154, E63 (2007)
141. A. Abd-Elwahed, R. Holze, Curr. Top. Electrochem. 9, 93 (2003)
142. R. Holze, J. Solid State Electrochem. 8, 982 (2004)
143. C.M. Duff, G.A. Heath, Inorg. Chem. 30, 2528 (1991)
144. J. Salbeck, J. Electroanal. Chem. 340, 169 (1992)
145. L. Yu, J.-I. Lee, K.-W. Shin, C.-E. Park, R. Holze, J. Appl. Polym. Sci. 88, 1550 (2003)
146. A. Abd-Elwahed, R. Holze, Elektrokhimiya 39, 431 (2003)
147. W. Suëtaka, in Surface Infrared and Raman Spectroscopy, ed. by C.J. Powell, A.W.
Czanderna, D.M. Hercules, T.E. Madey, J.T. Yates Jr. Methods of Surface Characteri-
zation, vol. 3 (Plenum, New York, 1995)
148. A.M. Bradshaw, N.V. Richardson, Pure Appl. Chem. 68, 457 (1996)
149. J.C. Lindon, G.E. Tranter, J.L. Holmes (eds.), Encyclopedia of Spectroscopy and Spec-
trometry (Academic Press, New York, 2000)
150. H. Günzler, H.M. Heise, IR-Spektroskopie (VCH, Weinheim, 1996)
151. H. Günzler, H.-U. Gremlich, IR Spectroscopy (VCH-Wiley, Weinheim, 2002)
152. R.A. Nyquist, C.L. Putzig, M.A. Leugers, Infrared and Raman Spectral Atlas of In-
organic Compounds and Organic Salts: Text and Explanations (Academic Press, San
Diego, 1996)
153. I.R. Lewis, Handbook of Raman Spectroscopy (Dekker, New York, 2001)
154. W. Suëtaka, J.T. Yates, Surface Infrared and Raman Spectroscopy – Methods and Ap-
plications (Plenum, New York, 1995)
155. M. Pemble, in Surface Analysis – The Principal Techniques, ed. by J.C. Vickerman
(Wiley, Chichester, 1997), p. 267
156. M.W. Urban, Vibrational Spectroscopy of Molecules and Macromolecules on Surfaces
(Wiley, New York, 1993)
157. R.L. McCreery, in Raman Spectroscopy for Chemical Analysis, ed. by J.D. Wineford-
ner. Chemical Analysis, vol. 157 (Wiley, New York, 2000)
158. H. Baumgärtel, H.-W. Jochims, B. Brutschy, Z. Phys. Chem. NF 154, 1 (1987)
159. A. Bewick, K. Kunimatsu, B.S. Pons, J.W. Russell, J. Electroanal. Chem. 160, 47
(1984)
160. P.R. Griffiths, Chemical Infrared Fourier Transform Spectroscopy (Wiley, New York,
1974)
161. B.C. Smith, Fourier Transform Infrared Spectroscopy (CRC, Boca Raton, 1996)
162. D.A. Long, The Raman Effect (Wiley, Chichester, 2002)
163. for an introductory overview including analytical applications see: R. Kellner, B.
Mizaikoff, M. Jakusch, H.D. Wanzenböck, N. Weissenbacher, Appl. Spectrosc. 51, 495
(1997)

www.ebook3000.com
 References 209

164. see also: N. Weissenbacher, B. Lendl, J. Frank, H.D. Wanzenböck, B. Mizaikoff, R.

Kellner, J. Mol. Struct. 410, 539 (1997)
165. H. Ibach, Electron Energy Loss Spectroscopy and Surface Vibrations (Academic Press,
New York, 1982)
166. M. Krejcik, M. Danek, F. Hartl, J. Electroanal. Chem. 317, 179 (1991)
167. S.P. Best, Coord. Chem. Rev. 249, 1536 (2005)
168. H.R. Sun, S.Y. Zhang, J.Q. Xu, G.Y. Yang, T.S. Shi, J. Electroanal. Chem. 455, 57
(1998)
169. J.P. Bullock, D.C. Boyd, K.R. Mann, Inorg. Chem. 26, 3084 (1987)
170. C.A. Blaine, J.E. Ellis, K.R. Mann, Inorg. Chem. 34, 1552 (1995)
171. K.S. Yun, S. Joo, H.J. Kim, J. Kwak, E. Yoon, Electroanalysis 17, 959 (2005)
172. C.M. Burba, R. Frech, 209th Electrochemical Society Spring Meeting, Denver, Col-
orado, USA, May 7–11, 2006, Ext. Abstr. #248
173. C.M. Burba, R. Frech, Electrochim. Acta 52, 780 (2006)
174. G.J. Hansen, W.N. Hansen, Ber. Bunsenges. Phys. Chem. 91, 317 (1987)
175. K.P. Pang, J.B. Benziger, M.P. Soriaga, A.T. Hubbard, J. Phys. Chem. 88, 4583 (1984)
176. V.K.F. Chia, J.L. Stickney, M.P. Soriaga, S.D. Rosasco, G.N. Salaita, A.T. Hubbard,
J.B. Benziger, K.W.P. Pang, J. Electroanal. Chem. 163, 407 (1984)
177. O. Hofmann, K. Doblhofer, H. Gerischer, J. Electroanal. Chem. 161, 337 (1984)
178. R.G. Greenler, J. Chem. Phys. 44, 310 (1966)
179. W.G. Golden, D.D. Saperstein, M.W. Severson, J. Overend, J. Phys. Chem. 88, 574
(1984)
180. J.B.L. Harkness, PhD. Dissertation. Massachusets Institute of Technology, Cambridge,
1970
181. J.I. Apse, PhD. Dissertation. Massachusets Institute of Technology, Cambridge, 1973
182. S.A. Francis, A.A. Ellison, J. Opt. Soc. Am. 49, 131 (1959)
183. N.J. Harrick, Internal Reflection Spectroscopy (Interscience, London, 1967)
184. K. Molt, Fresenius Z. Anal. Chem. 319, 743 (1984)
185. Y. Nishikawa, K. Fujiwara, K. Ataka, M. Osawa, Anal. Chem. 65, 556 (1993)
186. J.-T. Li, Q.-S. Chen, S.-G. Sun, Electrochim. Acta 52, 5725 (2007)
187. J.-T. Li, S.-R. Chen, X.-Y. Fan, L. Huang, S.-G. Sun, Langmuir 23, 13174 (2007)
188. S. Schomaker, Dissertation. Universität Oldenburg, 1992
189. D.B. Parry, J.M. Harris, K. Ashley, Langmuir 6, 209 (1990)
190. I.T. Bae, X. Xing, C.C. Liu, E. Yeager, J. Electroanal. Chem. 284, 335 (1990)
191. M.G. Samant, K. Kunimatsu, H. Seki, Anal. Chem. 66, 1781 (1994)
192. R.G. Greenler, J. Chem. Phys. 44, 310 (1966)
193. W.R. Fawcett, A.A. Kloss, J.J. Calvente, N. Marinkovic, Electrochim. Acta 44, 881
(1998)
194. J.D. Mozo, M. Dominguez, E. Roldan, J.M.R. Mellado, Electroanal. 12, 767 (2000)
195. R.J. Nichols, in Adsorption of Molecules at Metal Electrodes, ed. by J. Lipkowski, P.N.
Ross (VCH, New York, 1992), p. 347
196. B. Beden, C. Lamy, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New York,
1988), p. 189
197. D.S. Bethune, A.C. Luntz, J.K. Sass, D.K. Roe, Surf. Sci. 197, 44 (1988)
198. P. Liu, B. Jin, F. Cheng, J. Electroanal. Chem. 603, 269 (2007)
199. S.J. Borg, S.P. Best, J. Electroanal. Chem. 535, 57 (2002)
200. F. Joho, P. Novak, Electrochim. Acta 45, 3589 (2000)
201. M. Liu, M. Ye, Q. Yang, Y. Zhang, Q. Xie, S. Yao, Electrochim. Acta 52, 342 (2006)
202. R. Holze, Habilitationsschrift. Universität Oldenburg, 1988
210 5 Spectroscopy at Electrochemical Interfaces

203. G. Orozco, C. Gutierrez, J. Electroanal. Chem. 484, 64 (2000)

204. B. Westerhoff, R. Holze, Ber. Bunsenges. Phys. Chem. 97, 418 (1993)
205. B. Beden, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 103
206. W.G. Golden, D.S. Dunn, J. Overend, J. Catal. 71, 395 (1981)
207. F. Hoffman, Surf. Sci. Rep. 3, 107 (1983)
208. J.B. Benziger, R.E. Preston, G.R. Schoofs, Appl. Opt. 26, 343 (1987)
209. I. Chabay, G. Holzwarth, Appl. Opt. 14, 454 (1975)
210. A. Bewick, S. Pons, in Advances in Infrared and Raman Spectroscopy, vol. 12, ed. by
R.J.H. Clark, R.E. Hester (Wiley/Heyden, London, 1985)
211. H. Seki, K. Kunimatsu, W.G. Golden, Appl. Spectrosc. 39, 437 (1985)
212. J.B. Benziger, R.E. Preston, G.R. Schoofs, Appl. Opt. 26, 343 (1987)
213. W.G. Golden, D.D. Saperstein, M.W. Severson, J. Overend, J. Phys. Chem. 88, 574
(1984)
214. W.G. Golden, D.D. Saperstein, J. Electron Spectrosc. Relat. Phenom. 30, 43 (1983)
215. Opt. Commun. 8, 26 (1973)
216. J. Gast, L. Genzel, U. Zwick, IEEE Trans. Microwave Theory Tech. 22(12), 1026
(1974)
217. E.I. Sáez, R.M. Corn, Electrochim. Acta 38, 1619 (1993)
218. T. Iwasita, F.C. Nart, in Advances in Electrochemical Science and Engineering, vol. 4,
ed. by H. Gerischer, C.W. Tobias (VCH, Weinheim, 1995), p. 123
219. W. Tornquist, F. Guilleaume, G.L. Griffin, Langmuir 3, 477 (1987)
220. R.M. Hammaker, S.A. Francis, R.P. Eischens, Spectrochim. Acta 21, 1295 (1965)
221. A. Crossley, D.A. King, Surf. Sci. 68, 528 (1977)
222. B.E. Hayden, A.M. Bradshaw, Surf. Sci. 125, 787 (1983)
223. B. Alvarez, A. Rodes, J.M. Perez, J.M. Feliu, J. Phys. Chem. B 107, 2018 (2003)
224. F. Hoffman, Surf. Sci. Rep. 3, 107 (1983)
225. S.A. Wasileski, M.J. Weaver, Faraday Discuss. 121, 285 (2002)
226. B. Westerhoff, PhD. thesis. Universität Oldenbrug, 1994
227. B. Westerhoff, R. Holze, Bull. Electrochem. 12, 560 (1996)
228. M. Bron, R. Holze, J. Electroanal. Chem. 385, 105 (1995)
229. M. Bron, R. Holze, Fresenius J. Anal. Chem. 361, 694 (1998)
230. M. Bron, R. Holze, Electrochim. Acta 45, 1121 (1999)
231. J. Poppe, PhD thesis. Technische Universität Chemnitz, 2002. http://archiv.tu-
chemnitz.de/pub/2002/0002
232. R.J. Nichols, I. Burgess, K.L. Young, V. Zamlynny, J. Lipkwoski, J. Electroanal. Chem.
563, 33 (2004)
233. M.A. Habib, J.O’M. Bockris, Langmuir 2, 388 (1986)
234. P. Zelenay, M.A. Habib, J.O’M. Bockris, Langmuir 2, 393 (1986)
235. G.J. Edens, X.P. Gao, M.J. Weaver, J. Electroanal. Chem. 375, 357 (1994)
236. Y. Ikezawa, A. Yoshida, T. Ariga, Electrochim. Acta 51, 3752 (2006)
237. G.L.J. Trettenhahn, G.E. Nauer, A. Neckel, Electrochim. Acta 41, 1435 (1996)
238. T. Doneux, C. Buess-Herman, M.G. Hosseini, R.J. Nichols, J. Lipkowski, Electrochim.
Acta 50, 4275 (2005)
239. K. Marquez, R. Ortiz, J.W. Schultze, O.P. Marquez, J. Marquez, G. Staikov, Elec-
trochim. Acta 48, 711 (2003)
240. V. Rosca, M.T.M. Koper, Phys. Chem. Chem. Phys. 8, 2513 (2006)
241. C.M. Johnson, C. Leygraf, J. Electrochem. Soc. 153, B547 (2006)

www.ebook3000.com
 References 211

242. Z.-Y. Zhou, N. Tian, Y.-J. Chen, S.-P. Chen, S.-G. Sun, J. Electroanal. Chem. 573, 111
(2004)
243. P.W. Faguy, W.N. Richmond, R.S. Jackson, S.C. Weibel, G. Ball, J.H. Payer, Appl.
Spectrosc. 52, 557 (1998)
244. B.J. Barner, M.J. Green, E.I. Saez, R.M. Corn, Anal. Chem. 63, 55 (1991)
245. M.J. Green, B.J. Barner, R.M. Corn, Rev. Sci. Instr. 62, 1426 (1991)
246. W.N. Richmond, P.W. Faguy, S.C. Weibel, J. Electroanal. Chem. 448, 237 (1998)
247. E.I. Saez, R.M. Corn, Electrochim. Acta 38, 1619 (1993)
248. F. Guillaume, G.L. Griffin, Langmuir 5, 783 (1989)
249. I. Zawisza, X. Bin, J. Lipkowski, Langmuir 23, 5180 (2007)
250. R.E. Wittrig, C.P. Kubiak, J. Electroanal. Chem. 393, 75 (1995)
251. I.S. Zavarine, C.P. Kubiak, J. Electroanal. Chem. 495, 106 (2001)
252. S.P. Best, R.J.H. Clark, R.P. Cooney, R.C.S. McQueen, Rev. Sci. Instr. 58, 2071 (1987)
253. I.S. Zavarine, T. Richmond, C.P. Kubiak, Inorg. Chem. Commun. 2, 519 (1999)
254. T. Ito, T. Hamaguchi, H. Nagino, T. Yamaguchi, H. Kido, I.S. Zavarine, T. Richmond,
J. Washington, C.P. Kubiak, J. Am. Chem. Soc. 121, 4625 (1999)
255. I.S. Zavarine, C.P. Kubiak, T. Yamaguchi, K. Ota, T. Matsui, T. Ito, Inorg. Chem. 39,
2696 (2000)
256. S.P. Best, R.J.H. Clark, R.C.S. McQueen, S. Joss, J. Am. Chem. Soc. 111, 548 (1989)
257. J. Washington, C.P. Kubiak, Can. J. Chem. 74, 2503 (1996)
258. R.J. Haines, R.E. Wittrig, C.P. Kubiak, Inorg. Chem. 33, 4723 (1994)
259. J.P. Bullock, K.R. Mann, Inorg. Chem. 28, 4006 (1989)
260. J.P. Bullock, M.C. Palazotto, K.R. Mann, Inorg. Chem. 30, 1284 (1991)
261. J.P. Bullock, M.C. Palazzotto, K.R. Mann, Inorg. Chem. 29, 4413 (1990)
262. S.C. Cheng, C.A. Blaine, M.G. Hill, K.R. Mann, Inorg. Chem. 35, 7704 (1996)
263. N. Nanbu, Y. Sasaki, F. Kitamura, Electrochem. Commun. 5, 383 (2003)
264. for an introduction and overview see e.g.: W. Knoll, Ann. Rev. Phys. Chem. 49, 569
(1998)
265. Z. Ping, H. Neugebauer, A. Neckel, Electrochim. Acta 41, 767 (1996)
266. M. Öhman, D. Persson, Electrochim. Acta 52, 5159 (2007)
267. Y.X. Chen, M. Heinen, Z. Juysy, R.J. Behm, Poster at 3rd Gerischer-Symposium,
Berlin, 06–08.07.2005
268. M. Heinen, Y.X. Chen, Z. Jusys, R.J. Behm, Electrochim. Acta 52, 5634 (2007)
269. I.T. Bae, J. Electrochem. Soc. 153, A2091 (2006)
270. I.T. Bae, M. Sandifer, Y.W. Lee, D.A. Tryk, C.N. Sukenik, D.A. Scherson, Anal. Chem.
67, 4508 (1995)
271. M. Osawa, K. Yoshii, K. Ataka, T. Yotsuyanagi, Langmuir 10, 640 (1994)
272. H. Visser, A.E. Curtright, J.K. McCusker, K. Sauer, Anal. Chem. 73, 4374 (2001)
273. S.-M. Moon, C. Bock, B. MacDougall, J. Electroanal. Chem. 568, 225 (2004)
274. P.J. Kulesza, M.A. Malik, A. Denca, J. Strojek, Anal. Chem. 68, 2442 (1996)
275. A. Hartstein, J.R. Kirtley, J.C. Tsang, Phys. Rev. Lett. 45, 201 (1980)
276. A. Hatta, Y. Chiba, W. Suetaka, Appl. Surf. Sci. 25, 327 (1986)
277. M. Osawa, M. Ikeda, J. Phys. Chem. 95, 9914 (1991)
278. M. Osawa, K. Ataka, K. Yoshii, T. Yotsuyanagi, J. Electron Spectrosc. Relat. Phenom.
64–65, 371 (1993)
279. M. Osawa, A. Hatta, M. Kuramitsu, W. Suetaka, Surf. Sci. 175, L787 (1986)
280. M. Osawa, K. Ataka, K. Yoshii, Y. Nishikawa, Appl. Spectrosc. 47, 1497 (1993)
281. M. Osawa, W. Suetaka, Surf. Sci. 186, 583 (1987)
282. M. Osawa, Bull. Chem. Soc. Jpn. 70, 2861 (1997)
212 5 Spectroscopy at Electrochemical Interfaces

283. R.F. Aroca, D.J. Ross, Appl. Spectrosc. 58, 324 (2004) A
284. M. Osawa, in Handbook of Vibrational Spectroscopy, ed. by J.M. Chalmers, P.R. Grif-
fiths (Wiley, Chichester, 2002), p. 785
285. R. Aroca, S. Rodriguez-Llorente, J. Mol. Struct. 408/409, 17 (1997)
286. R. Aroca, J. Mol. Struct. 292, 17 (1993)
287. R. Aroca, Surface-Enhanced Vibrational Spectroscopy (Wiley, Chichester, 2006)
288. M. Osawa, Near-Field Opt. Surf. Plasmon Polaritons 81, 163 (2001)
289. M. Osawa, K. Ataka, K. Yoshii, Y. Nishikawa, Appl. Spectrosc. 47, 1497 (1993)
290. A. Hatta, Y. Chiba, W. Suetaka, Surf. Sci. 158, 616 (1985)
291. S.G. Sun, W.B. Cai, L.J. Wan, M. Osawa, J. Phys. Chem. B 103, 2460 (1999)
292. M. Osawa, K. Ataka, Surf. Sci. 262, L118 (1992)
293. M. Loster, K.A. Friedrich, Surf. Sci. 523, 287 (2003)
294. S.-G. Sun, in Catalysis and Electrocatalysis at Nanoparticle Surfaces, ed. by A. Wieck-
owski, E.R. Savinova, C.G. Vayenas (CRC, Boca Raton, 2003), p. 785
295. M. Osawa, K. Ataka, K. Yoshii, T. Yotsuyanagi, J. Electron. Spectrosc. Relat. Phenom.
64–65, 371 (1993)
296. A. Pucci, Phys. Stat. Solid. B 242, 2704 (2005)
297. H. Miyake, S. Ye, M. Osawa, Electrochem. Commun. 4, 973 (2002)
298. J.M. Delgado, J.M. Orts, A. Rodes, Electrochim. Acta 52, 4605 (2007)
299. A. Hatta, Y. Sasaki, W. Suetaka, J. Electroanal. Chem. 215, 93 (1986)
300. K. Ataka, M. Osawa, Langmuir 14, 951 (1998)
301. Th. Wandlowski, K. Ataka, S. Pronkin, D. Diesing, Electrochim. Acta 49, 1233 (2004)
302. J.M. Delgado, J.M. Orts, A. Rodes, Langmuir 21, 8809 (2005)
303. M. Osawa, K. Yoshii, K. Ataka, T. Yotsuyanagi, Langmuir 10, 640 (1994)
304. M. Osawa, K. Yoshii, Appl. Spectrosc. 51, 512 (1997)
305. M. Osawa, Denki Kagaku 64, 957 (1996)
306. W. Uhmann, A. Becker, C. Taran, F. Siebert, Appl. Spectrosc. 45, 390 (1991)
307. A. Yamakata, T. Uchida, J. Kubota, M. Osawa, J. Phys. Chem. B 110, 6423 (2006)
308. A. Yamakata, J. Kubota, M. Osawa, 210th Electrochemical Society Meeting, Cancun,
Mexico, 29.10–03.11.2006, Ext. Abstr. #1915
309. K. Ataka, M. Osawa, J. Electroanal. Chem. 460, 188 (1999)
310. S.G. Sun, W.B. Cai, L.J. Wan, M. Osawa, J. Phys. Chem. B 103, 2460 (1999)
311. W.-B. Cai, T. Amano, M. Osawa, J. Electroanal. Chem. 500, 147 (2001)
312. L.J. Wan, M. Terashima, H. Noda, M. Osawa, J. Phys. Chem. B 104, 3563 (2000)
313. A. Miki, S. Ye, T. Senzaki, M. Osawa, J. Electroanal. Chem. 563, 23 (2004)
314. M.H. Shao, R.R. Adzic, Electrochim. Acta 50, 2415 (2005)
315. Y.X. Chen, A. Miki, S. Ye, H. Sakai, M. Osawa, J. Am. Chem. Soc. 125, 3680 (2003)
316. H. Shiroishi, Y. Ayato, K. Kunimatsu, T. Okada, J. Electroanal. Chem. 581, 132 (2005)
317. M. Osawa, K. Yoshii, Y. Hibino, T. Nakano, I. Noda, J. Electroanal. Chem. 426, 11
(1997)
318. A. Miki, S. Ye, M. Osawa, Chem. Commun. 2002, 1500 (2002)
319. M. Osawa, K. Ito, W. Suetaka, T. Nakane, J. Electroanal. Chem. 270, 459 (1989)
320. Q.-X. Li, X.-K. Xue, Q.-J. Xu, W.-B. Cai, Appl. Spectrosc. 61, 1328 (2007)
321. Th. Wandlowski, K. Ataka, S. Pronkin, D. Diesing, Electrochim. Acta 49, 1233 (2004)
322. K. Ataka, T. Yotsuyanagi, M. Osawa, J. Phys. Chem. 100, 10664 (1996)
323. M. Futamata, J. Electroanal. Chem. 550-551, 93 (2003)
324. K. Kunimatsu, H. Uchida, M. Osawa, M. Watanabe, J. Electroanal. Chem. 587, 299
(2006)
325. Y. Ayato, K. Kunimatsu, M. Osawa, T. Okada, J. Electrochem. Soc. 153, A203 (2006)

www.ebook3000.com
 References 213

326. D.H. Murgida, P. Hildebrandt, Phys. Chem. Chem. Phys. 7, 3773 (2005)
327. K. Ataka, J. Heberle, J. Am. Chem. Soc. 126, 9445 (2004)
328. Q.B. Fan, C. Pu, K.L. Lay, E.S. Smotkin, J. Electrochem. Soc. 143, L21 (1996)
329. Q.B. Fan, C. Pu, E.S. Smotkin, J. Electrochem. Soc. 143, 3053 (1996)
330. Z.Y. Deng, J.D. Spear, J.D. Rudnicki, F.R. McLarnon, E.J. Cairns, J. Electrochem. Soc.
143, 1514 (1996)
331. X. Lu, P.W. Faguy, M. Liu, J. Electrochem. Soc. 149, A1293 (2002)
332. J.L.J. Daschbach, J.J. Smith, M.D. Morse, J. Electroanal. Chem. 209, 387 (1986)
333. G.P. Williams, C.J. Hirschmugl, E.M. Kneedler, E.A. Sullivan, D.P. Siddons, Y.J. Cha-
bal, F. Hoffman, K.D. Moeller, Rev. Sci. Instr. 60, 2176 (1989)
334. C.J. Hirschmugl, Surf. Sci. 500, 577 (2002)
335. Considerations of sensitivity, noise and other aspects pertaining to detectors in the far
infrared have been reported in: J. Piotrowski, Photonics Spectra, May 2004, p. 80
336. C.A. Melendres, B. Beden, G.A. Bowmaker, J. Electroanal. Chem. 383, 191 (1995)
337. C.A. Melendres, G.A. Bowmaker, J.M. Leger, B. Beden, Nucl. Instrum. Meth. Phys.
Res. B 133, 109 (1997)
338. C.A. Melendres, G.A. Bowmaker, J.M. Leger, B. Beden, J. Electroanal. Chem. 449,
215 (1998)
339. C.A. Melendres, F. Hahn, G.A. Bowmaker, Electrochim. Acta 46, 9 (2000)
340. G.A. Bowmaker, J.M. Leger, A. Lerille, C.A. Melendres, A. Tadjeddine, J. Chem. Soc.
Faraday Trans. 94, 1309 (1998)
341. C.A. Melendres, F. Hahn, J. Electroanal. Chem. 463, 258 (1999)
342. C.A. Melendres, in Spectroscopic and Diffraction Techniques in Interfacial Electro-
chemistry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer
Academic, Dordrecht, 1990), p. 181
343. P. Matousek, I.P. Clark, E.R.C. Draper, M.D. Morris, A.E. Goodship, N. Everall, M.
Towrie, W.F. Finney, A.W. Parker, Appl. Spectrosc. 59, 393 (2005)
344. N.A. Macleod, C. Eliasson, P. Matousek, Spectrosc. Eur. 19(5), 7 (2007)
345. T. Nomoto, H. Onishi, Phys. Chem. Chem. Phys. 9, 5515 (2007)
346. S. Simard, M.S. Odziemkowski, D.E. Irish, L. Brossard, H. Menard, J. Appl. Elec-
trochem. 31, 913 (2001)
347. C.T. Lee, M.S. Odziemkowski, D.W. Shoesmith, J. Electrochem. Soc. 153, B33 (2006)
348. M. Odziemkowski, J. Flis, D.E. Irish, Electrochim. Acta 39, 2225 (1994)
349. G.V.M. Jacintho, P. Corio, J.C. Rubim, J. Electroanal. Chem. 603, 27 (2007)
350. L.J. Hardwick, M. Hahn, P. Ruch, M. Holzapfel, W. Scheifele, H. Buqa, F. Krumeich,
P. Novak, R. Kötz, Electrochim. Acta 52, 675 (2006)
351. P. Mayer, R. Holze, Surf. Sci. 522, 55 (2003)
352. M. Fleischmann, P.J. Hendra, A.J. McQuillan, Chem. Phys. Lett. 26, 163 (1974)
353. D.L. Jeanmaire, R.P. van Duyne, J. Electroanal. Chem. 84, 1 (1977)
354. D.L. Jeanmaire, M.R. Suchanski, R.P. van Duyne, J. Am. Chem. Soc. 97, 1699 (1975)
355. C.L. Haynes, A.D. MacFarland, R.P. van Duyne, Anal. Chem. 77, 339A (2005)
356. H. Seki, J. Electron Spectrosc. Relat. Phenom. 30, 287 (1983)
357. H. Seki, J. Electron Spectrosc. Relat. Phenom. 39, 289 (1986)
358. M. Fleischmann, P. Graves, I. Hill, A. Oliver, J. Robinson, Electrochemical Society
Spring Meeting, Cincinnati, USA, 6–11 May 1984, Ext. Abstr. #427
359. for overviews see: P. Mayer, R. Holze, Surf. Sci. 522, 55 (2003)
360. for overviews see: S. Kania, R. Holze, Surf. Sci. 408, 252 (1998)
361. M.J. Weaver, S. Farquharson, M.A. Tadayyoni, J. Chem. Phys. 82, 4867 (1985)
214 5 Spectroscopy at Electrochemical Interfaces

362. R.K. Chang, T.E. Furtak (eds.), Surface Enhanced Raman Spectroscopy (Plenum, New
York, 1982)
363. R. Aroca, G.J. Kovacs, in Vibrational Spectra and Structure, vol. 19, ed. by H.R. During
(Elsevier, Amsterdam, 1991), p. 55
364. A. Otto, Coll. Surf. 38, 27 (1989)
365. A. Otto, Appl. Surf. Sci. 6, 309 (1980)
366. R.K. Chang, J. Phys. C 10(12), 283 (1983)
367. D.A. Weitz, M. Moskovits, J.A. Creighton, in Chemistry and Structure at Interfaces,
ed. by R.B. Hall, A.B. Ellis (VCH, Deerfield Beach, 1986), p. 197
368. A. Campion, P. Kambhampati, Chem. Soc. Rev. 27, 241 (1998)
369. R.K. Chang, in Spectroscopic and Diffraction Techniques in Interfacial Electrochem-
istry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Acad-
emic, Dordrecht, 1990), p. 155
370. D.A. Weitz, M. Moskovits, J.A. Creighton, in Chemistry and Structure at Interfaces,
ed. by R.B. Hall, A.B. Ellis (VCH, Deerfield Beach, 1986), p. 197
371. R.L. Birke, T. Lu, J.R. Lombardi, in Techniques for Characterization of Electrodes and
Electrochemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991),
p. 211
372. R. Holze, Bull. Electrochem. 10, 45 (1994)
373. R. Holze, Current Topics in Electrochemistry, vol. 2 (Council of Scientific Information,
Trivandrum, 1993), p. 293
374. A.G. Brolo, D.E. Irish, B.D. Smith, J. Mol. Struct. 405, 29 (1997)
375. E.S. Brandt, T.M. Cotton, in Physical Methods of Chemistry Series, vol. 9B, ed. by
B.W. Rossiter, R.C. Baetzold (Wiley, New York, 1993), ch. 8
376. J.E. Pemberton, in Electrochemical Interfaces: Modern Techniques for in-situ Interface
Characterization, ed. by H.D. Abruna (VCH, New York, 1991), p. 195
377. B. Pettinger, in Adsorption of Molecules at Metal Electrodes, ed. by J. Lipkowski, P.N.
Ross (VCH, New York, 1992), p. 285
378. M. Moskovits, Rev. Mod. Phys. 57, 783 (1985)
379. M.J. Weaver, S. Zou, in Advances in Spectroscopy, Spectroscopy of Surfaces, vol. 26,
ed. by R.J.H. Clark, R.E. Hester (Wiley, Chichester, 1998), Chap. 5
380. S.P. Mulvaney, C.D. Keating, Anal. Chem. 72, 145 (2000) R
381. V.A. Markel, V.M. Shalaev, P. Zhang, W. Huynh, L. Tay, T.L. Haslett, M. Moskovits,
Phys. Rev. B 59, 10903 (1999)
382. P. Zhang, S. Smith, G. Rumbles, M.E. Himmel, Langmuir 21, 520 (2005)
383. P. Kambhampati, C.M. Child, M.C. Foster, A. Campion, J. Chem. Phys. 108, 5013
(1998)
384. B. Pettinger, U. Wenning, H. Wetzel, Chem. Phys. Lett. 67, 192 (1979)
385. T.E. Furtak, J. Electroanal. Chem. 150, 375 (1983)
386. J. Gersten, A. Nitzan, J. Chem. Phys. 73, 3023 (1980)
387. M.J. Weaver, S. Zou, H.Y.H. Chan, Anal. Chem. 72, 39A (2000)
388. Q. Ye, J.X. Fang, L. Sun, J. Phys. Chem. B 101, 8221 (1997)
389. G. Compagnini, C. Galati, S. Pignataro, Phys. Chem. Chem. Phys. 1, 2351 (1999)
390. C.S. Allen, G.C. Schatz, R.P. van Duyne, Chem. Phys. Lett. 75, 201 (1980)
391. C.J. Orendorff, L. Gearheart, N.R. Jana, C.J. Murphy, Phys. Chem. Chem. Phys. 8, 165
(2006)
392. C.J. Addison, A.G. Brolo, Langmuir 22, 8696 (2006)
393. B.G. McMillan, E.A. Berlouis, F.R. Cruickshank, P.F. Brevet, Electrochim. Acta 53,
1157 (2007)

www.ebook3000.com
 References 215

394. E. Vogel, W. Kiefer, V. Deckert, D. Zeisel, J. Raman Spectrosc. 29, 693 (1998)
395. B. Bozzini, B. Busson, G.P. De Gaudenzi, L. D’Urzo, C. Mele, A. Tadjeddine, J. Elec-
troanal. Chem. 602, 61 (2007)
396. P. Kambhampati, C.M. Child, A. Campion, J. Chem. Soc. Faraday Trans. 92, 4775
(1996)
397. A. Campion, P. Kambhampati, Chem. Soc. Rev. 27, 241 (1998)
398. R.K. Chang, Ber. Bunsenges. Phys. Chem. 91, 296 (1987)
399. J.F. Arenas, D.J. Fernandez, J. Soto, I. Lopez-Tocon, J.C. Otero, J. Phys. Chem. B 107,
13143 (2003)
400. A.G. Brolo, D.E. Irish, B.D. Smith, J. Mol. Struct. 405, 29 (1997)
401. P. Hildebrandt, S. Keller, A. Hoffmann, F. Vanheckke, B. Schrader, J. Raman Spectrosc.
24, 791 (1993)
402. T. Sueoka, J. Inukai, M. Ito, Electron Spectrosc. Relat. Phenom. 64–65, 363 (1993)
403. A.G. Brolo, D.E. Irish, J. Lipkowski, J. Phys. Chem. B 101, 3906 (1997)
404. A.G. Brolo, D.E. Irish, G. Szymanski, J. Lipkowski, Langmuir 14, 517 (1998)
405. M. Moskovits, D.P. DiLella, K.J. Maynard, Langmuir 4, 67 (1988)
406. M. Moskovits, J. Chem. Phys. 77, 4408 (1982)
407. M. Moskovits, J.S. Suh, J. Phys. Chem. 88, 5526 (1984)
408. R.L. Birke, J.R. Lombardi, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New
York, 1988), p. 263
409. X.P. Gao, J.P. Davies, M.J. Weaver, J. Phys. Chem. 94, 6858 (1990)
410. R. Holze, Bull. Electrochem. 10, 45 (1994)
411. R.P. Cooney, T.P. Mernagh, J. Electroanal. Chem. 168, 67 (1984)
412. B. Pettinger, G. Picardi, R. Schuster, G. Ertl, J. Electroanal. Chem. 554-555, 293 (2003)
413. B. Pettinger, G. Picardi, R. Schuster, G. Ertl, Electrochemistry 68, 942 (2000)
414. B. Pettinger, B. Ren, G. Picardi, R. Schuster, G. Ertl, Phys. Rev. Lett. 92, 096101-1
(2004)
415. C. Viets, W. Hill, J. Mol. Struct. 563, 163 (2001)
416. A. Vivoni, R.L. Birke, R. Foucault, J.R. Lombardi, J. Phys. Chem. B 107, 5547 (2003)
417. D.K. Lambert, Sol. State Commun. 51, 297 (1984)
418. D.K. Lambert, Phys. Rev. Lett. 50, 2106 (1983)
419. D.K. Lambert, Electrochim. Acta 41, 623 (1996)
420. S. Venkatesan, G. Erdheim, J.R. Lombardi, R.L. Birke, Surf. Sci. 101, 387 (1980)
421. Y.X. Chen, S.Z. Zou, K.Q. Huang, Z.Q. Tian, J. Raman Spectrosc. 29, 749 (1998)
422. B. Pettinger, U. Wenning, H. Wetzel, Chem. Phys. Lett. 67, 192 (1979)
423. U. Wenning, B. Pettinger, H. Wetzel, Chem. Phys. Lett. 70, 49 (1980)
424. H. Wetzel, B. Pettinger, U. Wenning, Chem. Phys. Lett. 75, 173 (1980)
425. B. Pettinger, U. Wenning, H. Wetzel, Surf. Sci. 101, 409 (1980)
426. E.S. Brandt, Anal. Chem. 57, 1276 (1985)
427. G. Niaura, A.K. Gaigalas, V.L. Vilker, J. Raman Spectrosc. 28, 1009 (1997)
428. J.W.M. Nissink, J.H. van der Maas, Appl. Spectrosc. 53, 528 (1999)
429. P. Hendra, C. Jones, G. Warnes, Fourier Transform Raman Spectroscopy (Ellis Hor-
wood, New York, 1991)
430. A. Crookell, M. Fleischmann, P.J. Hendra, M. Hanniet, Chem. Phys. Lett. 149, 123
(1988)
431. R. Wen, Y. Fang, J. Electroanal. Chem. 576, 237 (2005)
432. P. Gao, M.L. Patterson, M.A. Tadayyoni, M.J. Weaver, Langmuir 1, 173 (1985)
433. R. Holze, Rev. Sci. Instr. 60, 3348 (1989)
434. R. Holze, Surf. Sci. 202, L612 (1988)
216 5 Spectroscopy at Electrochemical Interfaces

435. R.L. Garrell, K.D. Beer, W. Tanner, The 1987 Pittsburgh Conference, Atlantic City, NJ,
USA, March 9–13, 1987, Ext. Abstr. #1025
436. K.D. Beer, W. Tanner, R.L. Garrell, J. Electroanal. Chem. 258, 313 (1989)
437. see also for an example I.C.N. Diogenes, I.M.M. de Carvalho, E. Longhnotti, L.G.F.
Lopes, M.L.A. Temperini, G.F.S. Andrade, I.S. Moreira, J. Electroanal. Chem. 605, 1
(2007)
438. A.G. Brolo, D.E. Irish, J. Chem. Soc. Faraday Trans. 93, 419 (1997)
439. Landolt-Börnstein, Numerical data and functional relationships in science and tech-
nology, in New Series, Group IV: Physical Chemistry, vol. 9: Electrochemistry, Sub-
volume A: Electrochemical Thermodynamics and Kinetics, ed. by W. Martienssen,
M.D. Lechner (Springer, Berlin, 2007)
440. R.L. Sobocinski, J.E. Pemberton, Langmuir 6, 43 (1990)
441. J.E. Pemberton, D.D. Tuschel, R.L. Sobocinski, A.L. Guy, N.A. Cross, Appl. Surf. Sci.
32, 33 (1988)
442. D.D. Tuschel, J.E. Cook, J.E. Pemberton, Langmuir 2, 380 (1986)
443. K.M. Balss, T.C. Kuo, P.W. Bohn, J. Phys. Chem. B 107, 994 (2003)
444. S. Cintra, M.E. Abdelsalam, P.N. Bartlett, J.J. Baumberg, T.A. Kelf, Y. Sugawar, A.E.
Russell, Faraday Discuss. 132, 191 (2006)
445. M.E. Abdelsalam, P.N. Bartlett, J.J. Baumberg, S. Cintra, T.A. Kell, Electrochem. Com-
mun. 7, 740 (2005)
446. S. Mahajan, J.J. Baumberg, A.E. Russell, P.N. Bartlett, Phys. Chem. Chem. Phys. 9,
6016 (2007)
447. M. Moskovits, Chem. Phys. Lett. 98, 498 (1983)
448. S. Kania, R. Holze, in GDCh-Monographie, vol. 14, ed. by J. Russow, G. Sandstede, R.
Staab (GDCh, Frankfurt, 1998), p. 115
449. P. Gao, M.J. Weaver, J. Phys. Chem. 90, 4057 (1986)
450. M.L. Patterson, C.S. Allen, Appl. Surf. Sci. 18, 377 (1984)
451. C. Vericat, M.E. Vela, R.C. Salvarezza, Phys. Chem. Chem. Phys. 7, 3258 (2005) (for
an overview focussed on surface analytical techniques applied to SAMs)
452. M. Bron, R. Holze, J. Solid State Electrochem. (submitted)
453. X.-W. Cao, J. Raman Spectrosc. 36, 250 (2005)
454. Y. Maeda, H. Kitano, Kobunshi Ronbunshu 52, 737 (1995)
455. P. Matejka, Chem. Listy 86, 875 (1992)
456. P. He, H.T. Liu, Z.Y. Li, Y. Liu, X.D. Xu, J.H. Li, Langmuir 20, 10260 (2004)
457. C. Siemes, A. Bruckbauer, A. Goussev, A. Otto, M. Sinther, A. Pucci, J. Raman Spec-
trosc. 32, 231 (2001)
458. A.G. Brolo, D.E. Irish, J. Electroanal. Chem. 414, 183 (1996)
459. S. Zou, M.J. Weaver, Anal. Chem. 70, 2387 (1998)
460. S. Zou, C.T. Williams, E.K.Y. Chen, M.J. Weaver, J. Am. Chem. Soc. 120, 3811 (1998)
461. M.J. Weaver, S. Zou, H.Y. Chan, Anal. Chem. 72, 38 (2000) A
462. M. Fleischmann, Z.Q. Tian, J. Electroanal. Chem. 217, 411 (1987)
463. M. Fleischmann, Z.Q. Tian, L.J. Li, J. Electroanal. Chem. 217, 397 (1987)
464. B. Ren, X.F. Lin, Y.X. Jiang, P.G. Cao, Y. Xie, Q.J. Huang, Z.Q. Tian, Appl. Spectrosc.
57, 419 (2003)
465. S. Zou, C.T. Williams, E.K.Y. Chen, M.J. Weaver, J. Phys. Chem. B 102, 9039 (1998),
9743
466. P. Gao, M.J. Weaver, J. Phys. Chem. 89, 5040 (1985)
467. R. Holze, Electroanal. 5, 497 (1993)
468. R. Holze, Electrochim. Acta 36, 1523 (1991)

www.ebook3000.com
 References 217

469. S. Kania, R. Holze, Electrochim. Acta 48, 945 (2003)

470. V. Schroeder, T.M. Devine, J. Electrochem. Soc. 146, 4061 (1999)
471. Z.-Q. Tian, B. Ren, D.-Y. Wu, J. Phys. Chem. B 106, 9463 (2002)
472. C. Zuo, P.W. Jagodzinski, J. Phys. Chem. B 109(109) 1788
473. J.L. Yao, G.P. Pan, K.H. Xue, D.Y. Wu, B. Ren, D.M. Sun, J. Tang, X. Xu, Z.Q. Tian,
Pure Appl. Chem. 72, 221 (2000)
474. R. Holze, B. Bittins-Cattaneo, Electrochim. Acta 33, 353 (1988)
475. J.-Z. Zheng, B. Ren, D.-Y. Wu, Z.-Q. Tian, J. Electroanal. Chem. 574, 285 (2005)
476. P.G. Cao, R.A. Gu, B. Ren, Z.Q. Tian, Chem. Phys. Lett. 366, 440 (2002)
477. H. Kwon, A.A. Gewirth, J. Electrochem. Soc. 154, D577 (2007)
478. S. Migge, G. Sandmann, D. Rahner, H. Dietz, J. Solid State Electrochem. 9, 132 (2005)
479. H. Luo, M.J. Weaver, J. Electroanal. Chem. 502, 141 (2001)
480. S. Lecomte, H. Wackerbarth, T. Soulimane, G. Buse, P. Hildebrandt, J. Am. Chem. Soc.
120, 7381 (1998)
481. H. Wackerbarth, U. Klar, W. Günther, P. Hildebrandt, Appl. Spectrosc. 53, 283 (1999)
482. T. Itoh, K. Abe, K. Dokko, M. Mohamedi, I. Uchida, A. Kasuya, J. Electrochem. Soc.
151, A2042 (2004)
483. E. Koglin, M.J. Schwuger, Faraday Discuss. 1992, 213
484. A.G. Brolo, M. Odziemkowski, D.E. Irish, J. Raman Spectrosc. 29, 713 (1998)
485. F.J. Vidal-Iglesias, J. Solla-Gullón, J.M. Pérez, A. Aldaz, Electrochem. Commun. 8,
102 (2006)
486. P. Etchegoin, R.C. Maher, L.F. Cohen, H. Hartigan, R.J.C. Brown, M.J.T. Milton, J.C.
Gallop, Chem. Phys. Lett. 375, 84 (2003)
487. K. Kneipp, H. Kneipp, I. Itzkan, R.R. Dasari, M.S. Feld, Curr. Sci. 77, 915 (1999)
488. K. Kneipp, H. Kneipp, I. Itzkan, R.R. Dasari, M.S. Feld, J. Phys.-Condens. Matter. 14,
R597 (2002)
489. I. Nabiev, I. Chourpa, M. Manfait, J. Raman Spectrosc. 25, 13 (1994)
490. I. Nabiev, M. Manfait, Rev. Instr. Fr. Petrol. 48, 261 (1993)
491. N. Matsuda, T. Sawaguchi, M. Osawa, I. Uchida, Chem. Lett. 1995, 145
492. T. Fukuda, H. Takezoe, K. Ishikawa, A. Fukada, H.S. Woo, S.K. Jeong, E.J. Oh, J.S.
Suh, Synth. Met. 69, 175 (1995)
493. S.J. Cyvin, J.E. Rauch, J.C. Decius, J. Chem. Phys. 43, 4083 (1965)
494. W.H. Li, X.Y. Li, N.T. Yu, Chem. Phys. Lett. 305, 303 (1999)
495. S.M. Nie, L.A. Lipscomb, N.-T. Yu, Appl. Spectrosc. Rev. 26, 203 (1991)
496. J.T. Golab, J.R. Sprague, K.T. Carron, G.C. Schatz, R.P. van Duyne, J. Chem. Phys. 88,
7942 (1988)
497. S. Nie, PhD thesis. Northwestern University, Evanston, Illinois, 1989
498. W.H. Yang, J. Hulteen, G.C. Schatz, R.P. Van Duyne, J. Chem. Phys. 104, 4313 (1996)
499. W.H. Li, X.Y. Li, N.T. Yu, Chem. Phys. Lett. 327, 153 (2000)
500. W.H. Li, X.Y. Li, N.T. Yu, Chem. Phys. Lett. 312, 28 (1999)
501. R. Holze, Z. Phys. Chem. 185, 1 (1994)
502. R. Holze, Electrochim. Acta 36, 999 (1991)
503. R. Holze, Electrochim. Acta 33, 1619 (1988)
504. S. Popovici, W. Leyffer, R. Holze, J. Porphyrins Phthalocyanins 2, 249 (1998)
505. S. Popovici, W. Leyffer, R. Holze, J. Porphyrins Phthalocyanins 3, 265 (1999)
506. M. Stelter, PhD thesis. Universität Chemnitz, 2001. http://archiv.tu-chemnitz.de/pub/
2001/0065/index.html
507. R. Holze, in Handbook of Advanced Electronic and Photonic Materials and Devices,
vol. 8, ed. by H.S. Nalwa (Academic Press, San Diego, 2001), p. 209
218 5 Spectroscopy at Electrochemical Interfaces

508. R. Holze, in Advanced Functional Molecules and Polymers, vol. 2, ed. by H.S. Nalwa
(Gordon & Breach, Amsterdam, 2001), p. 171
509. B. Tian, G. Zerbi, J. Chem. Phys. 92, 3886 (1990)
510. B. Tian, G. Zerbi, J. Chem. Phys. 92, 3892 (1990)
511. G. Zerbi, C. Castiglioni, M. Gussoni, Synth. Met. 41–43, 3407 (1991)
512. G. Zerbi, C. Castiglioni, B. Tian, M. Gussoni, in Springer Series in Solid State Sci. Elec-
tronic Properties of Conjugated Polymers III, vol. 91, ed. by H. Kuzmany, M. Mehring,
S. Roth (Springer, Berlin, 1989), p. 106
513. G. Zerbi, M. Veronelli, S. Martina, A.D. Schlüter, G. Wegner, J. Chem. Phys. 100, 978
(1994)
514. G. Zerbi, M. Veronelli, S. Martina, A.-D. Schlüter, G. Wegner, Adv. Mater. 6, 385
(1994)
515. G. Zerbi, B. Chierichetti, O. Inganäs, J. Chem. Phys. 94, 4637 (1991)
516. B. Tian, G. Zerbi, in Springer Series in Solid State Sci. Electronic Properties of Conju-
gated Polymers III, vol. 91, ed. by H. Kuzmany, M. Mehring, S. Roth (Springer, Berlin,
1989), p. 113
517. T. Lindfors, A. Ivaska, J. Electroanal. Chem. 580, 320 (2005)
518. M. Minsky, Scanning 10, 128 (1988)
519. T. Wilson, C.J.R. Sheppard, Scanning Optical Microscopy (Academic Press, London,
1984)
520. M. Delhaye, J. Barbillat, J. Aubard, M. Bridoux, E. Da Silva, in Raman Microscopy:
Developments and Applications, ed. by G. Rurrell, J. Corset (Academic Press, San
Diego, 1996)
521. T.G. Corle, G.S. Kino, Confocal Scanning Optical Microscopy and Related Techniques
(Academic Press, New York, 1996)
522. T. Vosgröne, A.J. Meixner, A. Anders, H. Dietz, G. Sandmann, W. Plieth, Surf. Sci.
597, 102 (2005)
523. K. Kneipp, H. Kneipp, Appl. Spectrosc. 60, 322A (2006)
524. Z. Wang, S. Pan, T.D. Krauss, H. Du, L.J. Rothberg, Proc. Natl. Acad. Sci. U.S.A. 100,
8638 (2003)
525. J. Nan, Y. Yang, Z. Lin, Electrochim. Acta 51, 4873 (2006)
526. W. Plieth, H. Dietz, A. Anders, G. Sandmann, A. Meixner, M. Weber, H. Kneppe, Surf.
Sci. 597, 119 (2005)
527. D.A. Smith, S. Webster, M. Ayad, S.D. Evans, D. Fogherty, D. Batchelder, Ultrami-
croscopy 61, 1 (1995)
528. R. Zenobi, V. Deckert, Angew. Chem. Int. Ed. 39, 1747 (2000)
529. V. Deckert, C. Budich, E. Bailo-Mur, GIT Labor-Fachzeitschrift 50, 1014 (2006)
530. D. Zeisel, V. Deckert, R. Zenobi, T. Vo Dinh, Chem. Phys. Lett. 283, 381 (1998)
531. V. Deckert, D. Zeisel, R. Zenobi, T. Vo-Dinh, Anal. Chem. 70, 2646 (1998)
532. H. Baumgärtel, H.-W. Jochims, B. Brutschy, Z. Phys. Chem. NF 154, 1 (1987)
533. E.M. Rowe, Phys. Today 5/1981, 28 (1981)
534. C.J. Sparks Jr., Phys. Today 5/1981, 40 (1981)
535. P. Gütlich, R. Link, A. Trautwein, Mössbauer Spectroscopy and Transition Metal
Chemistry (Inorganic Chemistry Concepts 3) (Springer, Berlin, 1978)
536. D.A. Scherson, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New York, 1988),
p. 399
537. A.G. Maddock, Mössbauer Spectroscopy: Principles and Applications (Ellis Horwood,
Chichester, 1997)
538. J. Blomquist, U. Helgeson, L.C. Moberg, Electrochim. Acta 27, 1453 (1982)

www.ebook3000.com
 References 219

539. M.E. Kordesch, J. Eldridge, D. Scherson, J. Electroanal. Chem. 164, 393 (1984)
540. J.G. Gordon, J. Phys. 44, C10-171 (1983)
541. A. Vertes, H. Leidheiser Jr., M.L. Varsanyi, G.W. Simmons, L. Kiss, J. Electrochem.
Soc. 125, 1946 (1978)
542. M.L. Varsanyi, J. Jaen, A. Vertes, L. Kiss, Electrochim. Acta 30, 529 (1985)
543. K. Itaya, I. Uchida, V. Neff, Acc. Chem. Res. 19, 162 (1986)
544. N.R. de Tacconi, K. Rajeshwar, R.O. Lezna, Chem. Mater. 15, 3046 (2003)
545. K. Itaya, T. Ataka, S. Toshima, T. Shinohara, J. Phys. Chem. 86, 2415 (1982)
546. H. Leidheiser Jr., J. Electrochem. Soc. 135, 5C (1988)
547. C. Fierro, R.E. Carbonio, D. Scherson, E.B. Yeager, J. Phys. Chem. 91, 6579 (1987)
548. W.E. O’Grady, J.O’M. Bockris, Chem. Phys. Lett. 5, 116 (1970)
549. W.E. Grady, J.O’M. Bockris, Surf. Sci. 38, 249 (1973)
550. W.E. O’Grady, J. Electrochem. Soc. 127, 555 (1980)
551. D.A. Corrigan, R.S. Conell, C.A. Fierro, A. Scherson, J. Phys. Chem. 91, 5009 (1987)
552. W. Wen, S. Ghosh, R.C. Urian, C. Heath, W. Reiff, S. Mukerjee, V. Naschitz, S. Licht,
Extended Abstracts of the 203rd Meeting of the Electrochemical Society, Paris, France,
27.04–02.05.2003, Ext. Abstr. #67
553. D.A. Scherson, S.L. Gupta, C. Fierro, E.B. Yeager, M.E. Kordesch, J. Eldridge, R.W.
Hoffman, J. Blue, Electrochim. Acta 28, 1205 (1983)
554. D.A. Scherson, C. Fierro, D. Tryk, S.L. Gupta, E.B. Yeager, J. Eldridge, R.W. Hoffman,
J. Electroanal. Chem. 184, 419 (1985)
555. E. Yeager, D.A. Scherson, C.A. Fierro, ACS Symp. Ser. 288 (Catal. Charact. Ser.), 535
(1985)
556. R. Alcántara, G.F. Ortiz, P. Lavela, J.L. Tirado, Electrochem. Commun. 8, 731 (2006)
557. C.M. Ionica-Bousquet, P.E. Lippens, L. Aldon, J. Olivier-Fourcade, J.C. Jumas, Chem.
Mater. 18, 6442 (2006)
558. B.K. Agarwal, X-Ray Spectroscopy (Springer, Berlin, 1991)
559. K. Tsuji, J. Injuk, R. Van Grieken (eds.), X-Ray Spectrometry: Recent Technological
Advances (Wiley, Chichester, 2004)
560. Electrochim. Acta 47(Special issue) (2002) 3035 ff
561. R. O’Malley, T. Rayment, A. Vollmer, H. Headspith, I. Harvey, S. Fiddy, Extended
Abstracts of the 203rd Meeting of the Electrochemical Society, Paris, France, 27.04–
02.05.2003, Ext. Abstr. #2835
562. W.-S. Yoon, C.P. Grey, M. Balasubramanian, X.-Q. Yang, J. McBreen, Chem. Mater.
15, 3161 (2003)
563. W.-S. Yoon, M. Balasubramanian, X.-Q. Yang, Z. Fu, D.A. Fischer, J. McBreen, J.
Electrochem. Soc. 151, A246 (2004)
564. P.A. Lee, P.H. Citrin, P. Eisenberger, B.M. Kincaid, Rev. Mod. Phys. 53, 769 (1981)
565. M. Bauer, H. Bertagnolli, Bunsenmagazin 9, 216 (2007)
566. J.A. Horsley, F.W. Lytle, in Chemistry and Structure at Interfaces, ed. by R.B. Hall,
A.B. Ellis (VCH, Deerfield Beach, 1986), p. 1
567. J. Haase, Chem. unserer Zeit 26, 219 (1983)
568. G.M. Bommarito, D. Acevedo, J.F. Rodriguez, H.D. Abruna, J. Electroanal. Chem. 379,
135 (1994)
569. H.-H. Strehblow, Extended Abstracts of the 203rd Meeting of the Electrochemical So-
ciety, Paris, France, 27.04–02.05.2003, Ext. Abstr. #2833
570. L.R. Sharpe, W.R. Heinemann, R.C. Elder, Chem. Rev. 90, 705 (1990)
571. H.D. Abruna, J.H. White, M.J. Albarelli, G.M. Bommarito, M.J. Bedzyk, M. McMillan,
J. Phys. Chem. 92, 7045 (1988)
220 5 Spectroscopy at Electrochemical Interfaces

572. J. McBreen, W.E. O’Grady, G. Tourillon, E. Dartyge, A. Fontaine, J. Electroanal. Chem.

307, 229 (1991)
573. C. Roth, N. Martz, T. Buhrmester, J. Scherer, H. Fuess, Phys. Chem. Chem. Phys. 4,
3555 (2002)
574. D. Lützenkirchen-Hecht, R. Frahm, J. Phys. Chem. 105, 9988 (2001)
575. H. Imai, K. Izumi, Y. Kubo, K. Kato, Y. Imai, Extended Abstracts of the 209th Meeting
of the Electrochemical Society Spring Denver, Colorado, USA, 07.05–11.05.2006, Ext.
Abstr. #302
576. A. Tadjeddine, G. Tourillon, D. Guay, Electrochim. Acta 36, 1859 (1991)
577. T.E. Furtak, L. Wang, E.A. Creek, P. Samanta, T.M. Hayes, G. Kendall, W. Li, G. Liang,
C.-M. Lo, Electrochim. Acta 36, 1869 (1991)
578. M.F. Toney, J. McBreen, Interface 2, 22 (1993)
579. L.B. Lurio, J. Pant, T.M. Hayes, L. Wang, T.E. Furtak, Physica B 209, 413 (1995)
580. W.E. O’Grady, D.E. Ramaker, Electrochim. Acta 44, 1283 (1998)
581. S. Mukerjee, J. McBreen, J. Electrochem. Soc. 146, 600 (1999)
582. F. Lu, G.N. Salaita, H. Baltruschat, A.T. Hubbard, J. Electroanal. Chem. 222, 305
(1987)
583. J. McBreen, S. Mukerjee, J. Electrochem. Soc. 142, 3399 (1995)
584. H. Prinz, H. Strehblow, Electrochim. Acta 47, 3093 (2002)
585. M. Teliska, V.S. Murthi, S. Mukerjee, D.E. Ramaker, J. Electrochem. Soc. 152, A2159
(2005)
586. C. Roth, N. Benker, T. Buhrmester, M. Mazurek, M. Loster, H. Fuess, D.C. Konings-
berger, D.E. Ramaker, J. Am. Chem. Soc. 127, 14607 (2005)
587. I.T. Bae, W.-S. Yoon, 210. Electrochemical Society Meeting, Cancun, Mexico, 29.10–
03.11.2006, Ext. Abstr. #697
588. A.E. Russell, A. Rose, Chem. Rev. 104, 4613 (2004)
589. G.G. Long, J. Kruger, in Techniques for Characterization of Electrodes and Electro-
chemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 167
590. X.Q. Yang, K.H. Xue, H.S. Lee, Y.H. Guo, J. McBreen, T.A. Skotheim, Y. Okamoto, F.
Lu, J. Electrochem. Soc. 140, 943 (1993)
591. T.A. Skotheim, X.Q. Yang, K.H. Xue, H.S. Lee, J. McBreen, F. Lu, Electrochim. Acta
37, 1635 (1992)
592. W.-S. Yoon, C.P. Grey, M. Balasubramanian, X.-Q. Yang, J. McBreen, Chem. Mater.
15, 3161 (2003)
593. O. Haas, A. Deb, E.J. Cairns, A. Wokaun, J. Electrochem. Soc. 152, A191 (2005)
594. R.G. Compton, A.M. Waller, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum,
New York, 1988), p. 349
595. T.M. McKinney, in Electroanalytical Chemistry, vol. 19, ed. by A.J. Bard (Dekker, New
York, 1996), p. 109
596. R. Holze, Recent Res. Devel. Electrochem. 6, 111 (2003)
597. A. Wieckowski, Extended Abstracts of the 203rd Meeting of the Electrochemical Soci-
ety, Paris, France, 27.04–02.05.2003, Ext. Abstr. #1249
598. A. Heinzel, PhD Dissertation. Universität Oldenburg, 1985
599. A.H. Maki, D.H. Geske, Anal. Chem. 31, 1450 (1959)
600. A.H. Maki, D.H. Geske, J. Chem. Phys. 30, 1356 (1959)
601. A.H. Maki, D.H. Geske, J. Chem. Phys. 33, 825 (1960)
602. D.H. Geske, A.H. Maki, J. Am. Chem. Soc. 82, 2671 (1960)
603. D.H. Geske, A.H. Maki, J. Am. Chem. Soc. 83, 1852 (1961)
604. W. Kaim, S. Ernst, V. Kasack, J. Am. Chem. Soc. 112, 173 (1990)

www.ebook3000.com
 References 221

605. M.A.M. Ameer, A.A. Ghoneam, J. Electrochem. Soc. 142, 4082 (1995)
606. L.H. Piette, R. Ludwig, R.N. Adams, J. Am. Chem. Soc. 83, 3909 (1961)
607. L.H. Piette, R. Ludwig, R.N. Adams, J. Am. Chem. Soc. 84, 4212 (1962)
608. A.M. Bond, D.A. Fiedler, J. Electrochem. Soc. 144, 1566 (1997)
609. K. Möbius, Z. Naturf. 20A, 1093 (1965)
610. K. Möbius, Angew. Physik 17, 534 (1964)
611. L.H. Piette, R. Ludwig, R.N. Adams, Anal. Chem. 34, 916 (1962)
612. L.H. Piette, R. Ludwig, R.N. Adams, Anal. Chem. 34, 1587 (1962)
613. F. Marken, R.D. Webster, S.D. Bull, S.G. Davies, J. Electroanal. Chem. 437, 209 (1997)
614. C. Frontana, I. Gonzalez, J. Electroanal. Chem. 603, 155 (2007)
615. R. Koopman, H. Gerischer, Ber. Bunsenges. Phys. Chem. 70, 118 (1966)
616. R.N. Bagchi, A.M. Bond, F. Scholz, J. Electroanal. Chem. 252, 259 (1988)
617. X.H. Mu, K.M. Kadish, Electroanalysis 2, 15 (1990)
618. D.A. Fiedler, M. Koppenol, A.M. Bond, J. Electrochem. Soc. 142, 862 (1995)
619. J.K. Dohrmann, K.J. Vetter, J. Electroanal. Chem. 20, 23 (1969)
620. J.K. Dohrmann, Ber. Bunsenges. Phys. Chem. 74, 575 (1970)
621. J.K. Dohrmann, F. Galluser, Ber. Bunsenges. Phys. Chem. 75, 432 (1971)
622. J.K. Dohrmann, F. Galluser, H. Wittchen, Faraday Discuss. Chem. Soc. 56, 350 (1973)
623. I.B. Goldberg, A.J. Bard, J. Phys. Chem. 75, 3281 (1971)
624. R.D. Allendoerfer, G.A. Martincheck, S. Bruckenstein, Anal. Chem. 47, 890 (1975)
625. R.D. Allendoerfer, J. Am. Chem. Soc. 97, 218 (1975)
626. A. Heinzel, R. Holze, C.H. Hamann, J.K. Blum, Z. Phys. Chem. NF 160, 11 (1989)
627. R. Holze, Habilitation thesis. Universität Oldenburg, 1989
628. A. Heinzel, R. Holze, C.H. Hamann, J.K. Blum, Electrochim. Acta 34, 657 (1989)
629. C.H. Hamann, R. Holze, F. Köleli, DECHEMA-Monographie 121, 297 (1990)
630. R. Holze, F. Köleli, C.H. Hamann, DECHEMA-Monographie 117, 315 (1989)
631. R. Holze, C.H. Hamann, Tetrahedron 47, 737 (1991)
632. J. Lippe, PhD Dissertation. Universität Oldenburg, 1991
633. J. Lippe, R. Holze, Synth. Met. 41–43, 2927 (1991)
634. R. Holze, J. Lippe, Bull. Electrochem. 8, 516 (1992)
635. F.J. Dyson, Phys. Rev. 98, 349 (1955)
636. R.N. Bagchi, A.M. Bond, F. Scholz, Electroanalysis 1, 1 (1989)
637. W.J. Albery, R.G. Compton, C.C. Jones, J. Am. Chem. Soc. 106, 469 (1984)
638. A.J. Wain, M. Thompson, O.V. Klymenko, R.G. Compton, Phys. Chem. Chem. Phys.
6, 4018 (2004)
639. I. Streeter, A.J. Wain, M. Thompson, R.G. Compton, J. Phys. Chem. 109, 12636 (2005)
640. A.J. Wain, R.G. Compton, J. Electroanal. Chem. 587, 203 (2006)
641. A.J. Wain, L. Drouin, R.G. Compton, J. Electroanal. Chem. 589, 128 (2006)
642. L.J. Nunez-Vergara, P. Santander, P.A. Navarrete-Encina, J. Valenzuela, J.C. Sturm, J.A.
Squella, J. Electrochem. Soc. 153, E144 (2006)
643. A. Petr, L. Dunsch, A. Neudeck, J. Electroanal. Chem. 412, 153 (1996)
644. J. Friedrich, M. Baumgarten, Appl. Magn. Reson. 13, 393 (1997)
645. J. Wu, J.B. Day, K. Franaszczuk, B. Montez, E. Oldfield, A. Wieckowski, P.-A. Vuissoz,
J.-P. Ansermet, J. Chem. Soc., Faraday Trans. 93, 1017 (1997)
646. J.B. Day, J. Wu, E. Oldfield, A. Wieckowski, in Electrochemical Nanotechnology, ed.
by W.J. Lorenz, W. Plieth (Wiley-VCH, Weinheim, 1998), p. 291
647. Y.Y. Tong, H.S. Kim, P.K. Babu, A. Wieckowski, J. Am. Chem. Soc. 124, 468 (2002)
648. Y.Y. Tong, J.J. van der Klink, in Catalysis and Electrocatalysis at Nanoparticle Sur-
faces, ed. by A. Wieckowski, E.R. Savinova, C.G. Vayenas (CRC, Boca Raton, 2003),
p. 455
222 5 Spectroscopy at Electrochemical Interfaces

649. P.K. Babu, Y.Y. Tong, H.S. Kim, A. Wieckowski, J. Electroanal. Chem. 524–525, 157
(2001)
650. P. McGrath, A.M. Fojas, B. Rush, J.A. Reimer, E.J. Cairns, Electrochemical Society
Spring Meeting 209th, Denver, Colorad, USA, May 7–11, 2006, Ext. Abstr. #1097
651. J.B. Wagner Jr., in Techniques for Characterization of Electrodes and Electrochemical
Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 3
652. S.B. Piepho, P.N. Schatz, Group Theory in Spectroscopy with Applications to MCD
(Wiley, New York, 1983)
653. for a representative study see: P.M.A. Gadsby, A.J. Thomson, J. Am. Chem. Soc. 112,
5003 (1990)
654. N. Kobayashi, Y. Nishiyama, J. Phys. Chem. 89, 1167 (1985)
655. M. Zhao, S. Kim, I.T. Bae, C. Rosenblatt, D.A. Scherson, J. Electroanal. Chem. 297,
507 (1991)
656. M. Zhao, S. Kim, I.T. Bae, C. Rosenblatt, D.A. Scherson, Anal. Chem. 63, 2990 (1991)
657. S.D. Bader, J. Magn. Magn. Mater. 100, 440 (1991)
658. E.R. Moog, C. Liu, S.D. Bader, J. Zak, Phys. Rev. B 39, 6949 (1989)
659. H.A. Wierenga, W. de Jong, M.W.J. Prins, Th. Rasing, R. Vollmer, A. Kirilyuk, H.
Schwabe, J. Kirschner, Phys. Rev. Lett. 74, 1462 (1995)
660. J.R. Hampton, J.-L. Martinez-Albertos, H.D. Abruna, Rev. Sci. Instrum. 73, 3018
(2002)
661. W. Schindler, J. Kirschner, Rev. Sci. Instr. 67, 3578 (1996)
662. K.M. Poduska, S. Morin, Rev. Sci. Instrum. 74, 4723 (2003)
663. W. Schindler, in Solid–Liquid Interfaces: Macroscopic Phenomena – Microscopic
Understanding, ed. by K. Wandelt, S. Thurgate. Topics in Applied Physics, vol. 85
(Springer, Heidelberg, 2003), p. 243
664. W. Schindler, J. Kirschner, Phys. Rev. B 55, r1989 (1997)
665. W. Schindler, T. Koop, J. Kirschner, Z. Physik. Chem. 208, 93 (1999)
666. J.R. Hampton, J.-L. Martinez-Albertos, H.D. Abruna, Langmuir 19, 4309 (2003)
667. W. Schindler, T. Koop, J. Kirschner, Z. Physik. Chem. 208, 93 (1999)
668. A. Gündel, L. Cagnon, A. Morrone, J. Schmidt, P. Allongue, Phys. Chem. Chem. Phys.
3, 3330 (2001)
669. A. Gündel, A. Morrone, J. Schmidt, L. Cagnon, P. Allongue, J. Magn. Magn. Mater.
226, 1616 (2001)
670. Y.P. Ma, J.P. Wiksow, M. Samuleviciene, K. Leinartras, E. Juzeliunas, J. Phys. Chem. B
106, 12549 (2002)
671. J.G. Bellingham, M.L.A. MacVicar, M. Nisenoff, P.C. Searson, J. Electrochem. Soc.
133, 1753 (1986)
672. E. Juzeliunas, J.H. Hinken, Electrochim. Acta 45, 3452 (2000)
673. E. Juzeliunas, M. Samuleviciene, A. Sudavicius, J.H. Hinken, Electrochem. Solid State
Lett. 3, 24 (2000)
674. E. Juzeliunas, J.H. Hinken, J. Electroanal. Chem. 477, 171 (1999)
675. C. Andrieu, F. Dalard, J.J. Rameau, F. Alcouffe, M. Reboul, J. Mater. Sci. 33, 3177
(1998)
676. A. Abedi, J.J. Fellenstein, A.J. Lucas, J.P. Wikswo Jr., Rev. Sci. Instrum. 70, 4640
(1999)
677. H. Richter, A. Knecht, Materialprüfung 39, 390 (1997)
678. G. Skennerton, A. Abedi, R.G. Kelly, J.P. Wikswo Jr., J. Corros. Sci. Eng. 3 (2000)
paper 3 (online journal)
679. D. Li, Y.P. Ma, W.F. Flanagan, B.D. Lichter, J.P. Wikswo Jr., Corrosion 53, 93 (1997)

www.ebook3000.com
 References 223

680. D. Li, Y.P. Ma, W.F. Flanagan, B.D. Lichter, J.P. Wikswo Jr., Corrosion 52, 219 (1996)
681. D. Li, Y.P. Ma, W.F. Flanagan, B.D. Lichter, J.P. Wikswo Jr., J. Miner. Metals Mater.
47, 36 (1995)
682. J.G. Bellingham, M.L.A. MacVicar, M. Nisenoff, IEEE Trans. Magn. 23, 477 (1987)
683. A.D. Hibbs, R.E. Saeger, D.W. Cox, T.H. Aukerman, T.A. Sage, R.S. Landis, Rev. Sci.
Instrum. 63, 3652 (1992)
684. A.D. Hibbs, IEEE Trans. Magn. 139, 2447 (1992)
685. D.E. Williams, A.R.J. Kucernak, R. Peat, Electrochim. Acta 38, 57 (1993)
686. D.E. Williams, A.R.J. Kucernak, R. Peat, Electrochim. Acta 38, 71 (1993)
687. R. Hutton, D.E. Williams, Anal. Chem. 67, 280 (1995)
688. R.S. Hutton, D.E. Williams, Chem. Soc. Faraday Trans. 90, 345 (1994)
689. R.B. Severeyn, R.J. Gale, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New
York, 1988), p. 41
690. A. Brodsky, Yu. Gurevich, Electrochim. Acta 13, 1245 (1968)
691. A. Brodsky, Yu. Pleskov, in Progress in Surface Science, vol. 2, ed. by S. Davidson
(Pergamon, Oxford, 1972), p. 2
692. A.M. Brodsky, Yu.V. Pleskov, Yu.Ya. Gurevich, Z.A. Rotenberg, Modern Photoelec-
trochemistry. Photoemission Phenomena (Sovremennaja Fotoelektrochimija. Fotoemis-
sionnye Yavleniya) (Nauka, Moscow, 1974)
693. Y.Y. Gurevich, Y.V. Pleskov, Z.A. Rotenberg, Photoelectrochemistry (Consultants Bu-
reau, New York, 1980)
694. B. Feuerbacher, B. Fitton, R.F. Willis (eds.), Photoemission (Wiley, Chichester, 1978)
695. Yu.V. Pleskov, Z.A. Rotenberg, J. Electroanal. Chem. 20, 1 (1969)
696. L.M. Peter, A.J. Rudge, Extended Abstracts of the 179th Meeting of the Electrochemi-
cal Society, Washington DC, USA, 05.05–10.05.1991, Ext. Abstr. #675
697. G.C. Barker, A.W. Gardner, D.C. Sammon, J. Electrochem. Soc. 113, 1182 (1966)
698. A.N. Frumkin, O.A. Petrii, B.B. Damaskin, in Comprehensive Treatise of Electrochem-
istry, vol. 1, ed. by J’O.M. Bockris, B.E. Conway, E. Yeager (Plenum, New York, 1980),
p. 221
699. A. Frumkin, Zero Charge Potentials (Nauka, Moscow, 1979)
700. Z.A. Rotenberg, Yu.B. Pleskov, Elektrokhimiya 9, 1419 (1973)
701. V.V. Eletskii, V. Pleskov, Elektrokhimiya 10, 167 (1974)
702. A.M. Brodsky, Yu.Ya. Gurevich, S.V. Sheberstov, J. Electroanal. Chem. 20, 353 (1971)
703. V.A. Benderski, A.S. Kotkin, A.G. Krivenko, Russ. Electrochem. Engl. Tr. 29, 449
(1993)
704. V.S. Bagotzky, A.M. Skundin, Electrochim. Acta 30, 899 (1985)
705. P.A. Kilmartin, G.A. Wright, Electrochim. Acta 41, 1677 (1996)
706. for an introduction and overview see: P.A. Kilmartin, G.A. Wright, Electrochim. Acta
41, 1677 (1996)
707. P.A. Kilmartin, G.A. Wright, Synth. Met. 104, 145 (1999)
708. for an introductory overview see: A.J. Bard, L.R. Faulkner, Electrochemical Methods
(Wiley, New York, 2001)
709. H. Gerischer, Advances in Electrochemistry and Electrochemical Engineering, vol. 1
(1961), p. 139
710. V.A. Myamlin, Yu.V. Pleskov, Electrochemistry of Semiconductors (Plenum, New York,
1967)
711. P.J. Holmes, The Electrochemistry of Semiconductors (Academic Press, New York,
1961)
224 5 Spectroscopy at Electrochemical Interfaces

712. R. Memming, in Electroanalytical Chemistry, vol. 11, ed. by A.J. Bard (Dekker, New
York, 1979), p. 1
713. A.J. Nozik, Annu. Rev. Phys. Chem. 29, 189 (1978)
714. S.A. Campbell, L.M. Peter, J.S. Buchanan, J. Power Sources 40, 137 (1992)
715. G. Waldner, R. Gómez, M. Neumann-Spallart, Electrochim. Acta 52, 2634 (2007)
716. M.W. Peterson, B.A. Parkinson, J. Electrochem. Soc. 135, 1424 (1988)
717. Yu.V. Pleskov, in Advances in Electrochemical Science and Engineering, vol. 8, ed. by
R.C. Alkire, D.M. Kolb (VCH, Weinheim, 2003), p. 209
718. Y.V. Pleskov, Russ. J. Electrochem. 38, 1275 (2002)
719. Yu.V. Pleskov, A.Ya. Sakharova, M.D. Krotova, L.L. Bouilov, B.V. Spitsyn, J. Elec-
troanal. Chem. 228, 19 (1987)
720. R. Tenne, C. Levy-Clement, Isr. J. Chem. 38, 57 (1998)
721. A.Y. Sakharova, Y.V. Pleskov, F. Diquarto, S. Piazza, C. Sunseri, I.G. Teremetskaya,
V.P. Varnin, J. Electrochem. Soc. 142, 2704 (1995)
722. Yu.V. Pleskov, Yu.Ya. Gurevich, Semiconductor Photoelectrochemistry (Consultants
Bureau, New York, 1986)
723. L. Boonma, T. Yano, D.A. Tryk, K. Hashimoto, A. Fujishima, J. Electrochem. Soc. 144,
L142 (1997)
724. E.A. Ponomarev, L.M. Peter, J. Electroanal. Chem. 396, 219 (1995)
725. L.M. Peter, E.A. Ponomarev, D.J. Fermin, J. Electroanal. Chem. 427, 79 (1997)
726. E. Barsoukov, J.R. Macdonald (eds.), Impedance Spectroscopy (Wiley, Hoboken, 2005)
727. R. Peat, L.M. Peter, J. Electroanal. Chem. 228, 351 (1987)
728. E.A. Ponomarev, L.M. Peter, J. Electroanal. Chem. 397, 45 (1995)
729. L. Bay, K. West, Sol. Energ. Mater. Sol. Cells 87, 613 (2005)
730. D.J. Blackwood, A. Borazio, R. Greef, L.M. Peter, J. Stumper, Electrochim. Acta 37,
889 (1992)
731. J. Li, L.M. Peter, J. Electroanal. Chem. 199, 1 (1986)
732. L.M. Peter, Chem. Rev. 90, 753 (1990)
733. D.J. Fermin, E.A. Ponomarev, L.M. Peter, J. Electroanal. Chem. 473, 192 (1999)
734. P.M. DiCarmine, O.A. Semenikhin, Electrochim. Acta 53, 3744 (2008)
735. L.M. Abrantes, L.M. Peter, J. Electroanal. Chem. 150, 593 (1983)
736. J.S. Buchanan, N.P. Freestone, L.M. Peter, J. Electroanal. Chem. 182, 383 (1985)
737. L.M. Peter, J. Electroanal. Chem. 144, 315 (1983)
738. J.S. Buchanan, L.M. Peter, Electrochim. Acta 33, 127 (1988)
739. S.M. Wilhelm, N. Hackerman, J. Electrochem. Soc. 128, 1668 (1981)
740. J.F. McAleer, L.M. Peter, Faraday Disc. Chem. Soc. 70, 67 (1980)
741. J. Nan, Y. Yang, Z. Lin, Electrochim. Acta 51, 4873 (2006)
742. M.W. Peterson, B.A. Parkinson, J. Electrochem. Soc. 135, 1424 (1988)
743. L.M. Peter, J. Electroanal. Chem. 98, 49 (1979)
744. L.M. Peter, Electrochim. Acta 23, 1073 (1978)
745. D.J. Fermin, E.A. Ponomarev, L.M. Peter, J. Electroanal. Chem. 473, 192 (1999)
746. T.B. Cao, L.H. Wei, S.M. Yang, M.F. Zhang, C.H. Huang, W.X. Cao, Langmuir 18, 750
(2002)
747. K. Nonomura, T. Loewenstein, E. Michaelis, D. Wöhrle, T. Yoshida, H. Minoura, D.
Schlettwein, Phys. Chem. Chem. Phys. 8, 3867 (2006)
748. H. Flaisher, R. Tenne, M. Halmann, J. Electroanal. Chem. 402, 97 (1996)
749. Y. Yang, Z.G. Lin, Synth. Met. 64, 43 (1994)
750. Y. Byun, B.W. Wessels, 173rd Meeting of the Electrochemical Society, Atlanta, GA,
USA, May 15–20, 1988, Ext. Abstr. #323

www.ebook3000.com
 References 225

751. Y. Byun, B.W. Wessels, J. Electrochem. Soc. 135, 144c (1988)

752. Yu.V. Pleskov, V.P. Varnin, I.G. Teremetskaya, A.V. Churikov, J. Electrochem. Soc. 144,
175 (1997)
753. J. Schefold, J. Electroanal. Chem. 362, 97 (1993)
754. J. Schefold, J. Electrochem. Soc. 139, 2862 (1992)
755. Y. Byun, B.W. Wessel, Appl. Phys. Lett. 52, 1352 (1988)
756. Z.H. Yang, P. Zhang, D.J. Wang, D. Zhang, X.D. Chai, T.J. Li, Synth. Met. 85, 1293
(1997)
757. P. Zhang, Z.H. Yang, D.J. Wang, S.H. Kan, X.D. Chai, J.Z. Liu, T.J. Li, Synth. Met. 84,
165 (1997)
758. R. Kern, R. Sastrawan, J. Ferber, R. Stangl, J. Luther, Electrochim. Acta 47, 4213
(2002)
759. E.M.M. Sutter, I. Gérard, A. Etcheberry, J. Electrochem. Soc. 146, 1448 (1999)
760. A. Baba, W. Knoll, J. Phys. Chem. B 107, 7733 (2003)
761. G.I. Pennarun, C. Boxall, D. O’Hare, Analyst 121, 1779 (1996)
762. F.P.L. Andrieux, C. Boxall, D. O’Hare, J. Electroanal. Chem. 589, 177 (2006)
763. A. Tadjeddine, A. Peremans, in Spectroscopy for Surface Science, ed. by R.J.H. Clark,
R.E. Hester. Advances in Spectroscopy, vol. 26 (Wiley, Chichester, 1998), p. 159
764. C.T. Williams, D.A. Beattie, Surf. Sci. 500, 545 (2002)
765. G.L. Richmond, J.M. Robinson, V.L. Shannon, Progr. Surf. Sci. 28, 1 (1988)
766. G.L. Richmond, in Electroanalytical Chemistry, vol. 17, ed. by A.J. Bard (Dekker, New
York, 1991), p. 87
767. R.M. Corn, M. Romagnoli, M.D. Levenson, M.R. Philpott, J. Chem. Phys. 81, 4127
(1984)
768. R. Georgiadis, G.L. Richmond, J. Phys. Chem. 95, 2895 (1991)
769. I. Fromondi, D.A. Scherson, Electrochemical Society Spring Meeting 209th, Denver,
Colorado, USA, May 7–11, 2006, Ext. Abstr. #1098
770. D.J. Campbell, R.M. Corn, J. Phys. Chem. 92, 5796 (1988)
771. G.L. Richmond, in Electroanalytical Chemistry, vol. 17, ed. by A.J. Bard (Dekker, New
York, 1991), p. 87
772. G. Richmond, in Advances in Electrochemical Science and Engineering, vol. 2, ed. by
H. Gerischer, C.W. Tobias (VCH, Weinheim), p. 142
773. D.A. Koos, V.L. Shannon, G.L. Richmond, J. Phys. Chem. 94, 2091 (1990)
774. R.M. Corn, in Adsorption of Molecules at Metal Electrodes, ed. by J. Lipkowski, P.N.
Ross (VCH, New York, 1992), p. 391
775. A. Friedrich, B. Pettinger, D.M. Lolb, G. Lupke, R. Steinhoff, G. Marowsky, Chem.
Phys. Lett. 163, 123 (1989)
776. see also: B. Pettinger, C. Bilger, J. Lipkowski, in Topics Appl. Phys., vol. 85, ed. by K.
Wandelt, S. Thurgate (Springer, Berlin, 2003), p. 223
777. R. Srinivasan, I.I. Suni, J. Electrochem. Soc. 146, 570 (1999)
778. S. Lakkaraju, M.J. Bennahmias, G.L. Borges, J.G. Gordon, M. Lazaga, B.M. Stone, K.
Ashley, Appl. Optics 29, 4943 (1990)
779. D.A. Higgins, R.M. Corn, J. Phys. Chem. 97, 489 (1993)
780. A. Tadjeddine, A. Peremans, P. Guyot-Sionnest, Surf. Sci. 335, 210 (1995)
781. A. Tadjeddine, A. Le Rille, Electrochim. Acta 45, 601 (1999)
782. A. Tadjeddine, Surf. Rev. Lett. 7, 423 (2000)
783. G. Rupprechter, Phys. Chem. Chem. Phys. 3, 4621 (2001)
784. Y.R. Shen, Nature 337, 519 (1989)
226 5 Spectroscopy at Electrochemical Interfaces

785. A. Le Rille, A. Tadjeddine, W.Q. Zheng, A. Peremans, Chem. Phys. Lett. 271, 95
(1997)
786. M. Tadjeddine, J.P. Flament, A. Tadjeddine, J. Electroanal. Chem. 408, 237 (1996)
787. G.L. Richmond, Chem. Rev. 102, 2693 (2002)
788. G.L. Richmond, Annu. Rev. Phys. Chem. 52, 357 (2001)
789. K.B. Eisenthal, Chem. Rev. 96, 1343 (1996)
790. Z.D. Schultz, S.K. Shaw, A.A. Gewirth, J. Am. Chem. Soc. 127, 15916 (2005)
791. P. Guyot-Sionnest, A. Tadjeddine, Chem. Phys. Lett. 172, 341 (1990)
792. D.K. Hore, J.L. King, F.G. Moore, D.S. Alavi, M.Y. Hamamoto, G.L. Richmond, Appl.
Spectrosc. 58, 1377 (2004)
793. Z.D. Schultz, S.K. Shaw, A.A. Gewirth, J. Am. Chem. Soc. 127, 15916 (2005)
794. F. Vidal, B. Busson, A. Tadjeddine, Electrochim. Acta 49, 3637 (2004)
795. A. Peremans, A. Tadjeddine, J. Chem. Phys. 103, 7197 (1995)
796. A. Tadjeddine, A. Peremans, J. Electroanal. Chem. 409, 115 (1996)
797. B. Bozzini, C. Mele, A. Fanigliulo, B. Busson, F. Vidal, A. Tadjeddine, J. Electroanal.
Chem. 574, 85 (2004)
798. C. Matranga, P. Guyot-Sionnest, J. Chem. Phys. 112, 7615 (2000)
799. K. Uosaki, H. Noguchi, M. Ito, T. Okada, 210th Electrochemical Society Meeting, Can-
cun, Mexico, 29.10–03.11.2006, Ext. Abstr. #1910
800. C. Rambaud, L. Cagnon, J.-P. Levy, G. Tourillon, J. Electrochem. Soc. 151, E352
(2004)
801. A. Peremans, A. Tadjeddine, P. Guyot-Sionnest, Chem. Phys. Lett. 247, 243 (1995)
802. C. Magnus Johnsson, E. Tyrode, C. Leygraf, J. Electrochem. Soc. 153, B113 (2006)
803. G.Q. Lu, A. Lagutchev, D.D. Dlott, A. Wieckowski, Surf. Sci. 585, 3 (2005)
804. A. Wieckowski, G.-Q. Lu, A. Lagoutchev, D. Dlott, 209th Electrochemical Society
Spring Meeting, Denver, Colorado, USA, 07–11.05.2006, Ext. Abstr. #1070
805. B. Bozzini, B. Busson, G.P. De Gaudenzi, L. D’Urzo, C. Mele, A. Tadjeddine, J. Elec-
troanal. Chem. 602, 61 (2007)
806. M. Tadjeddine, J.P. Flament, Chem. Phys. 240, 39 (1999)
807. S. Baldelli, Electrochemical Society Spring Meeting 209th, Denver, Colorado, USA,
May 7–11, 2006; Ext. Abstr. #1041
808. S. Bruckenstein, R.R. Gadde, J. Am. Chem. Soc. 93, 793 (1971)
809. S. Bruckenstein, R.R. Gadde, J. Electroanal. Chem. 50, 163 (1974)
810. T.J. Brockman, L.B. Anderson, Anal. Chem. 56, 207 (1984)
811. O. Wolter, J. Heitbaum, Ber. Bunsenges. Phys. Chem. 88, 2 (1984)
812. O. Wolter, J. Heitbaum, Ber. Bunsenges. Phys. Chem. 88, 6 (1984)
813. B. Bittins-Cattaneo, E. Cattaneo, P. Königshoven, W. Vielstich, in Electroanalytical
Chemistry, vol. 17, ed. by A.J. Bard (Dekker, New York, 1991), p. 181
814. M. Casciola, R. Clemetini, E. Skou, J. Munk, J. Mater. Chem. 5, 991 (1995)
815. E. Skou, J. Munk, J. Electroanal. Chem. 367, 93 (1994)
816. R. Stadler, Z. Jusys, H. Baltruschat, Electrochim. Acta 47, 4485 (2002)
817. H. Baltruschat, in Interfacial Electrochemistry, ed. by A. Wieckowski (Dekker, New
York, 1999), p. 577
818. D. Tegtmeier, A. Heindrichs, J. Heitbaum, Ber. Bunsenges. Phys. Chem. 93, 201 (1989)
819. S. Wasmus, E. Cattaneo, W. Vielstich, Electrochim. Acta 35, 771 (1990)
820. M. Fujihira, T. Noguchi, J. Electroanal. Chem. 347, 457 (1993)
821. S. Wasmus, S.R. Samms, R.F. Savinell, J. Electrochem. Soc. 142, 1183 (1995)
822. Z. Jusys, H. Massong, H. Baltruschat, J. Electrochem. Soc. 146, 1093 (1999)

www.ebook3000.com
 References 227

823. V. Rao, C. Cremers, U. Stimming, L. Cao, S. Sun, S. Yan, G. Sun, Q. Xin, J. Elec-
trochem. Soc. 154, B1138 (2007)
824. P. Friebe, P. Bogdanoff, N. Alonso-Vante, H. Tributsch, J. Catal. 168, 374 (1997)
825. P. Dubé, G.M. Brisard, J. Electroanal. Chem. 582, 230 (2005)
826. M. Winter, R. Imhof, F. Joho, P. Novak, J. Power Surces 82, 818 (1999)
827. P. Novak, F. Joho, R. Imhof, J.C. Panitz, O. Haas, J. Power Sources 82, 212 (1999)
828. Z. Jusys, A. Vaskelis, Ber. Bunsenges. Phys. Chem. 101, 1865 (1997)
829. V. Rosca, G.L. Beltramo, M.T.M. Koper, J. Electroanal. Chem. 566, 53 (2004)
830. A.D. Modestov, J. Gun, I. Savotine, O. Lev, J. Electroanal. Chem. 565, 7 (2004)
831. V. Rao, C. Cremers, U. Stimming, 209th Electrochemical Society Spring Meeting, Den-
ver, Colorado, USA, May 7–11, 2006, Ext. Abstr. #1102
832. F.J. Vidal-Iglesias, J. Solla-Gullón, J.M. Feliu, H. Baltruschat, A. Aldaz, J. Electroanal.
Chem. 588, 331 (2006)
833. B. Neumann, P. Bogdanoff, H. Tributsch, S. Sakthivel, H. Kisch, J. Phys. Chem. B 109,
16579 (2005)
834. K. Jambunathan, A.C. Hillier, J. Electrochem. Soc. 150, E312 (2003)
835. K. Jambunathan, S. Jayaraman, A.C. Hillier, Langmuir 20, 1856 (2004)
836. H. Budzikiewicz, Massenspektrometrie (VCH, Weinheim, 1992)
837. E. Schröder, Massenspektrometrie – Begriffe und Definitionen (Springer, Berlin, 1991)
838. J.R. Pretty, G.J. van Berkel, Rapid Commun. Mass. Spectrom. 12, 1644 (1998)
839. V. Kertesz, G.J. van Berkel, J. Solid State Electrochem. 9, 390 (2005)
840. F.M. Zhou, G.J. van Berkel, Anal. Chem. 67, 3643 (1995)
841. C. Zettersten, R. Lomoth, L. Hammarström, P.J.R. Sjöberg, L. Nyholm, J. Electroanal.
Chem. 590, 90 (2006)
842. G.J. van Berkel, F.M. Zhou, J. Am. Soc. Mass Spectrom. 7, 157 (1996)
843. T. Guo, A. Illies, V. Cammarata, M. Arndt, W. Sonzogniy, J. Electroanal. Chem. 610,
102 (2007)
844. V. Kertesz, N.M. Dunn, G.J. Van Berkel, Electrochim. Acta 47, 1035 (2002)
845. V. Gutkin, J. Gun, P.V. Prikhodchenko, O. Lev, L. Gonsalvi, M. Peruzzini, A. Romerosa,
T. Campos Malpartida, C. Lidrissic, J. Electrochem. Soc. 154, F7 (2007)
846. A.R. Dolan, E.P. Maziarz, T.D. Wood, Eur. J. Mass Spectrom. 6, 241 (2000)
847. Z.H. Ji, J.J. Li, G. Yuan, S.M. Cai, J. Liu, C. Liu, J. Electroanal. Chem. 570, 265 (2004)
848. H.T. Deng, O.J. van Berkel, H. Takano, D. Gazda, M.D. Porter, Anal. Chem. 72, 2641
(2000)
849. C.R. Blakley, M.L. Vestal, Anal. Chem. 55, 750 (1983)
850. M.L. Vestal, Int. J. Mass Spectrom. Ion Phys. 46, 193 (1983)
851. G. Hambitzer, J. Heitbaum, Anal. Chem. 58, 1067 (1986)
852. G. Hambitzer, P.P. Heinz, I. Stassen, J. Heitbaum, Synth. Met. 55, 1317 (1993)
853. G. Hambitzer, I. Stassen, Synth. Met. 55, 1045 (1993)
854. I. Stassen, G. Hambitzer, J. Electroanal. Chem. 440, 219 (1997)
855. G. Hambitzer, J. Heitbaum, I. Stassen, J. Electroanal. Chem. 447, 117 (1998)
856. K.J. Volk, R.A. Yost, A. Brajter-Toth, Anal. Chem. 61, 1709 (1989)
857. J.R. Pretty, E.H. Evans, E.A. Blubaugh, W.-L. Shen, J.A. Caruso, T.M. Davidson, J.
Anal. Atom. Spetctrom. 5, 437 (1990)
858. J.R. Pretty, E.A. Blubaugh, J.A. Caruso, Anal. Chem. 65, 3396 (1993)
859. J.R. Pretty, E.A. Blubaugh, J.A. Caruso, T.M. Davidson, Anal. Chem. 66, 1540 (1994)
860. J.R. Pretty, E.A. Blubaugh, E.H. Evans, J.A. Caruso, T.M. Davidson, J. Anal. Atom
Spectrom. 7, 1131 (1992)
861. J.J. Gross, Mass Spectrometry (Springer, Heidelberg, 2004)
228 5 Spectroscopy at Electrochemical Interfaces

862. H.W. Buschmann, S. Wilhelm, W. Vielstich, Electrochim. Acta 31, 939 (1986)
863. R.A. De Souza, M. Martin, Bunsen-Magazin 8, 109 (2006) (see for an overview)
864. W.N. Hansen, D.M. Kolb, J. Electroanal. Chem. 100, 493 (1979)
865. S. Wilhelm, Dissertation. Universität Bonn, 1988
866. S. Wilhelm, W. Vielstich, H.W. Buschmann, T. Iwasita, J. Electroanal. Chem. 229, 377
(1987)
867. C. Barbero, M.C. Miras, R. Kötz, Electrochim. Acta 37, 429 (1992)
868. J.D. Rudnicki, F.R. McLarnon, E.J. Cairns, in Techniques for Characterization of Elec-
trodes and Electrochemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York,
1991), p. 127
869. R.E. Russo, F.R. McLarnon, J.D. Spaer, E.J. Cairns, J. Electrochem. Soc. 134, 2783
(1987)
870. M.F. Mathias, J. Electroanal. Chem. 407, 115 (1996)
871. C.A. Barbero, Phys. Chem. Chem. Phys. 7, 1885 (2005)
872. K.S.V. Santhanam, R.N. O’Brien, J. Electroanal. Chem. 160, 377 (1984)
873. K.S.V. Santhanam, R.N. O’Brien, in Techniques for Characterization of Electrodes and
Electrochemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991),
p. 401
874. M.A. Tamor, M. Zanini, J. Electrochem. Soc. 133, 1399 (1986)
875. R. Kötz, C. Barbero, O. Haas, Ber. Bunsenges. Phys. Chem. 97, 427 (1993)
876. A.G. Brolo, S.D. Sharma, Electrochim. Acta 48, 1375 (2003)
877. M.J. Henderson, E. Bitziou, A.R. Hillman, E. Vieil, J. Electrochem. Soc. 148, E105
(2001)
878. E. Vieil, C. Lopez, J. Electroanal. Chem. 466, 218 (1999)
879. C. Barbero, M.C. Miras, R. Kötz, O. Haas, Sol. State. Ionics 60, 167 (1993)
880. C. Lopez, M.F. Mendes Viegas, G. Bidon, E. Vieil, Synth. Met. 63, 73 (1994)
881. M. Kalaji, L. Nyholm, L.M. Peter, A.J. Rudge, J. Electroanal. Chem. 310, 113 (1991)
882. E. Vieil, K. Meerholz, T. Matencio, J. Heinze, J. Electroanal. Chem. 368, 183 (1994)
883. M. El Rhazi, C. Lopez, C. Deslouis, M.M. Musiani, B. Tribollet, E. Vieil, J. Chim.
Phys. Phys. Chim. Biol. 92, 859 (1995)
884. C.W. Liu, G.J. Cheng, J.H. Li, J.G. Jin, S.J. Dong, J. Electroanal. Chem. 407, 243
(1996)
885. C. Barbero, M.C. Miras, R. Kötz, O. Haas, J. Electroanal. Chem. 437, 191 (1997)
886. C. Barbero, M.C. Miras, O. Haas, R. Kötz, J. Electrochem. Soc. 144, 4170 (1997)
887. H. Huang, C.W. Liu, B.F. Liu, G.J. Cheng, S.J. Dong, Electrochim. Acta 43, 999 (1998)
888. M.J. Henderson, A.R. Hillman, E. Vieil, J. Electroanal. Chem. 454, 1 (1998)
889. D. Dini, F. Decker, G. Zotti, Synth. Met. 101, 22 (1999)
890. L.M. Abrantes, J.P. Correia, Electrochim. Acta 44, 1901 (1999)
891. B. Piro, E.A. Bazzaoui, M.C. Pham, P. Novak, O. Haas, Electrochim. Acta 44, 1953
(1999)
892. M.J. Henderson, H. French, A.R. Hillman, E. Vieil, Electrochem. Solid State Lett. 2,
631 (1999)
893. M.J. Henderson, A.R. Hillman, E. Vieil, J. Phys. Chem. B 103, 8899 (1999)
894. V.M. Schmidt, C. Barbero, R. Kötz, J. Electroanal. Chem. 352, 301 (1993)
895. M.J. Henderson, A.R. Hillman, E. Vieil, Electrochim. Acta 45, 3885 (2000)
896. C. Barbero, E.J. Calvo, R. Etchenique, G.M. Morales, M. Otero, Electrochim. Acta 45,
3895 (2000)
897. C. Barbero, M.C. Miras, R. Kötz, O. Haas, Synth. Met. 55, 1539 (1993)
898. C. Barbero, M.C. Miras, E.J. Calvo, R. Kötz, O. Haas, Langmuir 18, 2756 (2002)

www.ebook3000.com
 References 229

899. C. Barbero, M.C. Miras, R. Kötz, O. Haas, Synth. Met. 55, 1539 (1993)
900. P. Novak, R. Kötz, O. Haas, J. Electrochem. Soc. 140, 37 (1993)
901. C. Barbero, M.C. Miras, R. Kötz, O. Haas, Sol. State Ionics 60, 167 (1993)
902. R. Kötz, C. Barbero, O. Haas, Ber. Bunsenges. Phys. Chem. 97, 427 (1993)
903. V.W. Jones, M. Kalaji, G. Walker, C. Barbero, R. Kötz, J. Chem. Soc. Faraday Trans.
90, 2061 (1994)
904. C. Barbero, O. Haas, M. Mostefai, M.C. Pham, J. Electrochem. Soc. 142, 1829 (1995)
905. M.C. Miras, C. Barbero, R. Kötz, O. Haas, V.M. Schmidt, J. Electroanal. Chem. 338,
279 (1992)
906. C. Barbero, M.C. Miras, O. Haas, R. Kötz, J. Electrochem. Soc. 138, 669 (1991)
907. C. Barbero, M.C. Miras, O. Haas, R. Kötz, J. Electroanal. Chem. 310, 437 (1991)
908. G.M. Brisard, J.D. Rudnicki, F. McLarnon, E.J. Cairns, Electrochim. Acta 40, 859
(1995)
909. O. Haas, J. Rudnicki, F.R. McLarnon, E.J. Cairns, J. Chem. Soc. Faraday Trans. 87,
939 (1991)
910. M. Vilas-Boas, I.C. Santos, M.J. Henderson, C. Freire, A.R. Hillman, E. Vieil, Lang-
muir 19, 7460 (2003)
911. M. Vilas-Boas, M.J. Henderson, C. Freire, A.R. Hillman, E. Vieil, Chem. Eur. J. 6, 1160
(2000)
912. H.J. Salavagione, J. Arias-Pardilla, J.M. Pérez, J.L. Vázquez, E. Morallón, M.C. Miras,
C. Barbero, J. Electroanal. Chem. 576, 139 (2005)
913. J.M. Rosolen, M. Fracastoro-Decker, F. Decker, J. Electroanal. Chem. 346, 119 (1993)
914. Y. Harima, K. Kishimoto, H. Mizota, Electrochim. Acta 53, 657 (2007)
915. R. Muller, in Advances in Electrohemistry and Electrochemical Engineering, vol. 9, ed.
by P. Delahay, C. Tobias (Wiley, New York, 1991), p. 281
916. K. Santhanam, R. O’Brien, in Techniques for Characterization of Electrodes and Elec-
trochemical Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 401
917. C. Léger, J. Elezgaray, F. Argoul, J. Electroanal. Chem. 486, 204 (2000)
918. C.E. Vallet, in Spectroscopic and Diffraction Techniques in Interfacial Electrochem-
istry, ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Acad-
emic, Dordrecht, 1990), p. 133
919. S. Yoshihara, M. Ueno, Y. Nagae, A. Fujishima, J. Electroanal. Chem. 243, 475 (1988)
920. S. Yoshihara, M. Ueno, Y. Nagae, A. Fujishima, Electrochim. Acta 33, 1685 (1988)
921. S. Yoshihara, R. Takahashi, M. Okamoto, E. Sato, A. Fujishima, Electrochim. Acta 36,
1959 (1991)
922. J.E. De Albuquerque, W.L.B. Melo, R.M. Faria, J. Polym. Sci. B-Polym. Phys. 38, 1294
(2000)
923. E. Kubacki, 40(12), 74 (2006) (see for an introduction)
924. R.J. Archer, Manual on Ellipsometry (Gaertner, Chicago, 1968)
925. R.M.A. Azzam, N.M. Bashara, Ellipsometry and Polarized Light (North-Holland, Am-
sterdam, 1977)
926. W.E.J. Neal, Ellipsometry. Theory and Applications (Plenum, New York, 1982)
927. R. Muller, in Techniques for Characterization of Electrodes and Electrochemical
Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 31
928. W. Plieth, W. Kozlowski, T. Twomey, in Adsorption of Molecules at Metal Electrodes,
ed. by J. Lipkowski, P.N. Ross (VCH, New York, 1992), p. 239
929. S. Gottesfeld, in Electroanalytical Chemistry, vol. 15, ed. by A.J. Bard (Dekker, New
York, 1989), p. 143
230 5 Spectroscopy at Electrochemical Interfaces

930. R. Greef, in Comprehensive Treatise of Electrochemistry, vol. 8, ed. by R.E. White,

J.O’M. Bockris, B.E. Conway, E. Yeager (Plenum, New York, 1984), p. 339
931. D.A. Holmes, J. Opt. Soc. Am. 54, 1115 (1964)
932. R. Muller, Surf. Sci. 56, 19 (1976)
933. B.D. Cahan, R.F. Spanier, Surf. Sci. 16, 166 (1969)
934. J.M.M. Droog, G.A. Bootsma, J. Electroanal. Chem. 105, 261 (1979)
935. P.S. Hauge, Surf. Sci. 96, 108 (1980)
936. M. Dornhege, C. Punckt, J.L. Hudson, H.H. Rotermund, J. Electrochem. Soc. 154, C24
(2007)
937. F. Chao, M. Costa, J. Lecoeur, Electrochim. Acta 36, 1839 (1991)
938. S. Gottesfeld, G. Maio, J.B. Floriano, G. Tremiliosi-Filho, E.A. Ticianelli, E.R. Gonza-
lez, J. Electrochem. Soc. 138, 3219 (1991)
939. T. Ohtsuka, K.E. Heusler, J. Electroanal. Chem. 100, 319 (1979)
940. R. Parsons, W.H.M. Visscher, J. Electroanal. Chem. 36, 329 (1972)
941. J.M.M. Droog, P.T. Alderliesten, G.A. Bootsma, J. Electroanal. Chem. 99, 173 (1979)
942. S. Gottesfeld, S. Srinivasan, J. Electroanal. Chem. 86, 89 (1978)
943. J.L. Ord, J. Electrochem. Soc. 129, 335 (1982)
944. K. Kunimatsu, R.H. Parsons, J. Electroanal. Chem. 100, 335 (1979)
945. H. Arwin, D.E. Aspnes, R. Bjorklund, I. Ljundström, Synth. Met. 6, 309 (1983)
946. L.A.A. Pettersson, T. Johansson, F. Carlsson, H. Arwin, O. Inganäs, Synth. Met. 101,
198 (1999)
947. P. Christensen, A. Hamnett, Electrochim. Acta 45, 2443 (2000)
948. D.R. Kim, W. Cha, W.K. Paik, Synth. Met. 84, 759 (1997)
949. M. Tagliazucchi, D. Grumelliz, E.J. Calvo, Phys. Chem. Chem. Phys. 8, 5086 (2006)
950. M. Hernández Ubeda, M.A. Pérez, H.T. Mishima, H.M. Villullas, J.O. Zerbino, B.A.
López de Mishima, M. López Teijelo, J. Electrochem. Soc. 152, A37 (2005)
951. N.W. Ashcroft, N.D. Mermin, Festkörperphysik (Oldenbourg, München, 2001)
952. W. Knoll, Annu. Rev. Phys. Chem. 49, 569 (1998)
953. M. Mansuripur, A.R. Zakharian, J.V. Moloney, OPN Opt. Photonics News 18(4), 44
(2007)
954. D.G. Hanken, C.E. Jordan, B.L. Frey, R.M. Corn, in Electroanalytical Chemistry,
vol. 20, ed. by A.J. Bard (Dekker, New York, 1998), p. 141
955. N. Zhang, R. Schweiss, Y. Zong, W. Knoll, Electrochim. Acta 52, 2869 (2007)
956. A. Tadjeddine, D.M. Kolb, R. Kötz, Surf. Sci. 101, 277 (1980)
957. A. Tadjeddine, A. Rahmani, Electrochim. Acta 36, 1855 (1991)
958. B.L. Frey, C.E. Jordan, S. Kornguth, R.M. Corn, Anal. Chem. 67, 4452 (1995)
959. L.E. Bailey, D. Kambhampati, K.K. Kanazawa, W. Knoll, C.W. Frank, Langmuir 18,
479 (2002)
960. J.G. Gordon II, S. Ernst, Surf. Sci. 101, 499 (1980)
961. Y. Iwasaki, T. Horiuchi, M. Morita, O. Niwa, Electroanalysis 9, 1239 (1997)
962. M. Vasjari, Y.M. Shirshov, A.V. Samoylov, V.M. Mirsky, J. Electroanal. Chem. 605, 73
(2007)
963. S. Szunerits, R. Boukherroub, Electrochem. Commun. 8, 439 (2006)
964. A. Baba, J. Lübben, K. Tamada, W. Knoll, Langmuir 19, 9058 (2003)
965. A. Bund, A. Baba, S. Berg, D. Johannsmann, J. Lübben, Z. Wang, W. Knoll, J. Phys.
Chem. B 107, 6743 (2003)
966. P. Taranekar, T. Fulghum, A. Baba, D. Patton, R. Advincula, Langmuir 23, 908 (2007)
967. R. Schweiss, J.F. Lübben, D. Johannsmann, W. Knoll, Electrochim. Acta 50, 2849
(2005)

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 References 231

968. A. Baba, M.K. Park, R.C. Advincula, W. Knoll, Langmuir 18, 4648 (2002)
969. A. Otto, in Optical Properties of Solids – New Developments, ed. by B.O. Seraphin
(North-Holland, Amsterdam, 1976), p. 677
970. H. Raether, in Physics of Thin Films, vol. 9, ed. by G. Hass (Academic Press, New York,
1977), p. 145
971. A. Baba, R.C. Advincula, W. Knoll, J. Phys. Chem. B 106, 1581 (2002)
972. P.W.J.M. Boumans, Inductively Coupled Plasma Emission Spectrometry Part 1 (Wiley,
New York, 1987)
973. K. Ogle, S. Weber, J. Electrochem. Soc. 147, 1770 (2000)
974. P.J. Schultz, K.G. Lynn, Rev. Mod. Phys. 60, 701 (1988)
975. X. Wu, P. Asoka-Kumar, K.G. Lynn, K.R. Hebert, J. Electrochem. Soc. 141, 3361
(1994)
976. K. Hebert, M. Fomino, H. Wu, P. Asoka-Kumar, K. Lynn, ECS Fall Meeting, Boston
1–6.11.1998, Ext. Abstr. #281
977. K.G. Lynn, H. Lutz, Rev. Sci. Instrum. 51, 977 (1980)
978. I.I. Bardyshev, Yu.M. Polukarov, Russ. J. Electrochem. 40, 9 (2004)
979. V.S. Subrahmanyam, S.K. Das, B.N. Ganguly, A. Bhattacharya, A. De, Mater. Res.
Bull. 32, 1063 (1997)
980. B. Das, S. Kar, D. Sanyal, D. Banerjee, R. Bhattacharya, J. Appl. Polym. Sci. 89, 930
(2003)
981. R.W. Wilson, R. Cubitt, A. Glidle, A.R. Hillman, P.M. Saville, J.G. Vos, J. Electrochem.
Soc. 145, 1454 (1998)
982. R.M. Richardson, M.J. Swann, A.R. Hillmann, S.J. Roser, Faraday Discuss. 94, 295
(1992)
983. A.R. Hillman, L. Bailey, A. Glidle, J.M. Cooper, N. Gadegaard, J.R.P. Webster, J. Elec-
troanal. Chem. 532, 269 (2002)
984. L. Bailey, M.J. Henderson, A.R. Hillman, N. Gadegaard, A. Glidle, Physica B 276, 373
(2000)
985. R.W. Wilson, R. Cubitt, A. Glidle, A.R. Hillman, P.M. Saville, J.G. Vos, Electrochim.
Acta 44, 3533 (1999)
986. A. Glidle, L. Bailey, C.S. Hadyoon, A.R. Hillman, A. Jackson, K.S. Ryder, P.M. Saville,
M.J. Swann, J.R.P. Webster, Anal. Chem. 73, 5596 (2001)
987. I. Burgess, V. Zamlynny, G. Szymanski, A.L. Schwan, R.J. Faragher, J. Lipkowski, J.
Majewski, S. Satija, J. Electroanal. Chem. 550–551, 187 (2003)
988. L. Bailey, A. Glidle, R.M. Richardson, S.J. Roser, P.M. Saville, M.J. Swann, J.R.P.
Webster, J. Am. Chem. Soc. 120, 12882 (1998)
989. C. Riekel, in Techniques for Characterization of Electrodes and Electrochemical
Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 279
6 Diffraction and Other X-Ray Methods

A beam of X-ray (i.e. electromagnetic radiation with a wavelength between λ = 0.01

and 10 nm) interacts with matter in three different ways:
1. It may be transmitted basically unchanged
2. It may be scattered or reflected either elastically or inelastically
3. It may be absorbed.
Although the first case looks rather unimportant at first glance, the transparency
of a given medium for X-rays is of considerable importance for the application of
any method based on X-rays because the construction of a spectroelectrochemical
cell and the influence of the medium around the interface or the interphase to be
investigated by any X-ray method depends on this transparency. At a wavelength
λ = 0.154 nm (this is copper Kα radiation, which is most commonly used in X-ray
experiments), a layer of 0.1 mm water will absorb 20% of the incoming X-ray pho-
tons and a layer of 1 mm will absorb about 90%. Thus any cell design and ex-
perimental setup must take into account even this seemingly unattractive feature.
Increasing the energy of the X-rays, i.e. decreasing the wavelength, results in lower
absorption. With molybdenum Kα radiation (λ = 0.071 nm), even several centime-
ters of water pose no serious absorption problem. Unfortunately, X-rays with such
high energies pose other challenges and problems related to the availability of suit-
able detectors.
X-rays are basically scattered or absorbed by all atoms in their path, thus they
are not inherently surface sensitive. Depending on the type of interaction employed
in a given method, various approaches are possible to confer this surface sensitivity
when desired, as outlined below.

6.1 X-Ray Diffraction Methods

Besides the use of X-ray absorption for the elucidation of adsorbates and adsorbate–
surface interactions (see Chap. 5), X-ray diffraction is a tool that is useful particu-
larly for the determination of structural data at a very high level of precision pro-
vided the presence of a minimum level of structuring. The advent of synchrotron
radiation that provides an intense source of electromagnetic radiation in the range of
X-rays has greatly stimulated the application of X-ray diffraction methods. A broad

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234 6 Diffraction and Other X-Ray Methods

overview of experimental approaches and recent results has been provided else-
where [1–4].

6.1.1 X-Ray Diffraction

Fundamentals. A wavefront of electromagnetic radiation arriving at an array of

atoms that act as scattering centers causes these centers to emit (scatter) spheric
waves of electromagnetic radiation of the same energy as the incoming radiation.
Depending on the wavelength of the employed radiation and the angle of incidence
and the spatial arrangement of the scatterers, the emitted radiation of the different
scatterers will interfere constructively or destructively. With a crystalline sample
containing a considerable number of scatterers, the conditions for constructive in-
terference will be fulfilled only when the angle of incidence relative to the crystal-
lographic plane in which the scatterers are located is matched very precisely. The
relationship is given by Bragg’s equation, nλ = 2d hkl sin ϑ, with n being the order
of the reflection, λ the wavelength of the used radiation, d hkl the crystallographic
spacing and ϑ the angle of diffraction (i.e. the angle of incidence). From the num-
ber and intensities found at different values of values of ϑ, the crystallographic data
of the sample under investigation can be derived. In order to obtain a diffractogram,
a crystal is illuminated with X-rays of a fixed wavelength λ. The angle of incidence
is varied by turning the crystal and the diffracted intensity is measured. For further
details, see [5, 6].
X-ray diffraction, as described above, is done in an angular dispersive way
(ADXD). The diffracted X-ray intensity is displayed as a function of the scattering
angle 2ϑ. This diffractogram is correct only for the single wavelength used during
its acquisition. Any change of the incident wavelength causes a nonlinear stretching
of the diffractogram. A more general display is obtained by displaying the scattered
intensity as a function of the scattering parameter q. Further details and advantages
of this approach have been discussed elsewhere [7, 8]. Consequently, two different
ways to obtain a diffractogram are possible:
1. Use of light with a fixed wavelength and measurement of the diffracted intensity
as a function of the scattering angle
2. Use of polychromatic light (Bremsstrahlung) and detection of the diffracted
radiation with a solid-state detector connected to a multichannel analyser
Instrumentation. A setup includes a source for X-rays (usually a fixed or a rotating
anode source; more recently, synchrotron radiation has become an attractive choice
as a source of radiation), a monochromator or at least a filter to select the desired
wavelength, the spectroelectrochemical cell and the detector (for an overview on
detectors see [3, 9]).
The cell has to fulfill three general requirements:
1. The path for the incident and the reflected beam should not be obstructed.
 6.1 X-Ray Diffraction Methods 235

2. The number of scattering or absorbing particles beyond the sample under inves-
tigation in the beam path should be kept at a minimum.
3. The electrochemical characteristics of the cell (like even current distribution,
reliable potential control, low iR-drop) should be as perfect as possible.
For X-ray diffraction experiments, two basic designs are possible: The Bragg (or
reflection) and the Laue (or transmission) mode. In electrochemical investigations,
the former is better suited for studies of adsorbates or of other features parallel to
the electrode surface, whereas the second mode is suitable for thick films or layers.
In both cases, a cell window as transparent as possible for X-rays with sufficient
stability towards this radiation is needed. Thin polymer foils (Mylar® or Melinex® )
are most commonly used. A typical design of a cell of the Laue type as depicted
in Fig. 6.1 shows the X-ray passing through two polymer film windows and the
electrolyte solution.
The working electrode is coated onto one of the windows. In order to keep the
scattering from the electrolyte solution low, one window is mounted on the end of a
hollow syringe barrel. For electrochemical measurements, it is retracted to provide
acceptable current distribution; for X-ray measurements, the barrel is moved as close
as possible towards the fixed window. The poor electrochemical properties of the
cell in the latter position are an obvious drawback of the cell design.
A spectroelectrochemical cell of the Bragg (reflection) type, as used for the
investigation of materials that are chemically or electrochemically deposited onto
a gold film that was sputtered first onto a porous membrane foil, has been de-
scribed [10]. The cross section as displayed in Fig. 6.2 shows the Prussian blue-
coated membrane assembly with its coating towards a polyethylene film that is
transparent and amorphous for X-rays.
The electrolyte penetrates the porous membrane via the porous glass body and
the glass fiber paper connection is provided with the silver chloride-coated silver
plate that acts both as a reference and a counter electrode. The electrochemical be-
havior of the cell as demonstrated with cyclic voltammetry is fairly close to standard
electrochemical cells. Results show changes of lattice constants of Prussian blue as

Fig. 6.1. Spectroelectrochemical cell for X-ray diffraction studies in transmission mode

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236 6 Diffraction and Other X-Ray Methods

Fig. 6.2. Spectroelectrochemical cell (for better identification of components in exploded

arrangement) for in situ X-ray diffraction studies according to [10]

Fig. 6.3. In situ X-ray diffraction pattern of TiS2 recorded during charging/discharging ex-
periments (based on data in [12]; see also [13])

a function of the electrode potential and the transferred charge. Because of the pen-
etration depth of X-rays and the need for a minimum of crystallinity, this approach
is not exactly surface sensitive; instead, it probes the interphase between the current
collector (i.e. the gold layer) and the electrolyte solution. Results obtained during
charging/discharging of TiS2 (as proposed for use in secondary lithium batteries bat-
tery [11]) that involve formation of LiTiS2 are displayed in Fig. 6.3; the employed
cell is depicted schematically in Fig. 6.4.
Upon discharge lithium is intercalated. This results in shifts of the (101), (002)
and (100) Bragg peaks. Detailed studies of the various shifts as functions of the
state of charge/discharge reveal further information on the mechanism of the dif-
ferent phase transitions [12]. Reactions of lithium with S8 in a secondary Li/S cell
have been tracked with in situ X-ray diffraction [15]. The electrochemical reaction
 6.1 X-Ray Diffraction Methods 237

Fig. 6.4. In situ X-ray diffraction electrochemical cell (based on [14])

of lithium with crystalline silicon was monitored [16]. Various Lix Siy phases were
identified. The transition from the crystalline into the amorphous state in the first
lithium intercalation was observed [17]. For alternate cell constructions, see [18].
For a cell used in studies of ion insertion into electrode materials, see [19]. A com-
plete cell that has not been modified in any way has been used with high energy
X-rays from a synchrotron source for simultaneous measurement of lithium ion bat-
tery cell component diffraction patterns; recorded diffraction peaks were assigned
to cathode and anode material [20]. A cell that is particularly suitable for measure-
ments under ultrapure conditions has been described [21].
Basically the same design has been employed in a study of the solid state elec-
trochemistry of PbO and Pb(OH)Cl (laurionite) [22]. The particles of red PbO
(litharge) were attached to a paraffin-impregnated graphite (PIG) rod that was used
as a working electrode. X-ray diffraction patterns obtained at various electrode po-
tentials (see Fig. 6.5) show peaks indicative of PbO, a mix of PbO and Pb and
finally of Pb as a function of reduction potential and time. Reflexes of graphite were
also observed and could be distinguished easily from those of the electrochemically
active material. The reduction proceeded entirely as a solid state reaction and no
evidence of solution phase intermediates was observed.
Improved surface specificity can be obtained by making measurements at the
grazing angle of incidence. The structure of small two-dimensional clusters and
linear nanostructures of copper and cadmium deposits on Pt(533) at characteris-
tic electrode potentials in the upd-range has been studied with GIXD combined
with GIXAFS [23]. Using X-rays provided by a synchrotron (the method is now
named SR-GIXRD), the corrosion of mild steel in the presence of carbon diox-
ide containing brine electrolyte solutions was studied. The mechanism of corro-
sion, particularly corrosion products that are present as thin films like Fe2 O2 CO3 ,
Fe2 O2 CO3 and Fe2 (OH)2 CO3 , was identified with SR-GIXRD [24]. Investigations
of iron chalcogenide glasses suitable for ion selective electrodes (ISE) with a combi-
nation of electrochemical impedance measurements and GIXRD have been reported
together with a description of a suitable electrochemical cell [25, 26]. Selective dis-
solution of various crystallographic surfaces of iron chalcogenides associated with

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238 6 Diffraction and Other X-Ray Methods

Fig. 6.5. In situ X-ray diffraction pattern of PbO and its reduction products: before reduction,
at E Ag/AgCl = −0.5 V (top); during reduction at E Ag/AgCl = −1 V, after reduction, at
E Ag/AgCl = −1.3 V (based on data by [22])

the electrode potential shifts of these materials that are employed in ion selective
electrodes have been monitored with SR-GIXRD [27]; results were found to be in
agreement with those obtained with AFM.
The cell designs and examples discussed above pertain to X-ray diffraction per-
formed in the angular dispersive mode, i.e. the angle of incidence is varied by turn-
ing the electrochemical cell with respect to the radiation source.
As already mentioned, energy dispersive measurements are possible when the
spectroelectrochemical cell stays in place, whereas the wavelength of the incident
radiation is varied. An additional advantage of EDXD is the high intensity of X-ray
radiation in the employed energy range with an upper limit only given by the power
supply of the X-ray tube. The strong X-ray absorption of standard K- and L-lines in
the range of lower energies caused by electrochemical cell components is no prob-
lem, because the construction materials that are employed usually show only weak
absorption at higher wavelengths [8]. The poor resolution of the solid-state detector
causes a broadening of the peaks in the measured diffractogram [8]. Results reported
so far deal with intercalation materials as used in batteries [8].
The application of time-resolved high energy X-ray diffraction on platinum
nanoparticles in fuel electrodes has been described [28]. Results indicate severe
surface reconstruction of the nanoparticle surface showing at least three types of
Pt–O bonds (adsorbed OH, adsorbed atomic O and amorphous PtOx ) under oxida-
tive conditions.
X-ray diffraction has also been used in studies of solid electrolytes as reviewed
elsewhere [29]. Diffraction techniques (including X-ray and neutron diffraction), as
applied in electrolyte solution studies, are described in [30].
 6.1 X-Ray Diffraction Methods 239

6.1.2 Surface X-Ray Diffraction (SXD)

Fundamentals. X-ray diffraction as applied to the elucidation of the crystallo-

graphic structure of thick layers, films or other three-dimensional samples can also
be applied to basically1 two-dimensional structures on surfaces or at interfaces
based on various instrumental advances, particularly the use of synchrotron radi-
ation. This way, information on the two-dimensional periodicity of surface layers
can be obtained. The required surface sensitivity can be obtained primarily by em-
ploying an angle of incidence that is less than or in the order of the critical angle.
This results in a significantly reduced depth of penetration of the X-rays and scat-
tering from the bulk of the sample is also diminished. Under these conditions, the
ratio of the signal from the surface vs. the signal from the bulk (or substrate) can
be enhanced by a factor of 2/θ c (with θ c being the critical angle of total external
reflection in radians). At X-ray frequencies typical for metals in contact with trans-
parent incident phases, θ c is about 0.5◦ (or 9 milliradians). These conditions are also
known as total reflection Bragg diffraction [31]. If grazing angle conditions (i.e. an-
gle of incidence θ about 3.5◦ or lower) are employed, the method is also called
grazing incidence X-ray diffraction (GIXRD). Further enhancement of general and
surface sensitivity can be achieved by applying an electrode potential modulation
procedure combined with an appropriate data treatment. This way, only potential de-
pendent features in the diffractogram will become visible, whereas features (Bragg
reflexes) of the bulk that are not affected by the electrode potential will be canceled
out. Because of fluctuations in the intensity of the X-ray source and other experi-
mental components, it is insufficient to record complete diffractograms sequentially;
instead, a slow potential modulation (with the frequency set to a value resulting in
a time constant that is sufficiently longer than that of the occurring electrochemical
process) is applied. Using computer-based data acquisition, the respective data are
stored and treated; for further details and an overview, see [32].
Instrumentation. The electrochemical cells described in the preceding section can
be used. A cell design with a significantly reduced radiation absorption of the elec-
trolyte solution film as used for specular X-ray reflectivity measurements (see de-
scription below Fig. 6.10) can also be used. Electrode potentials are selected based
on standard electrochemical experiments (e.g. cyclic voltammetry) with respect to
well-defined changes of the electrode–solution interface (e.g. potential steps be-
tween potentials of complete desorption and maximum adsorption). Control of the
potentiostat and the X-ray diffractometer as well as data acquisition, storage and
manipulation are done with a suitably programmed computer.
Typical examples include studies of the underpotential deposition of various
metals on metallic substrates. The structure of the upd-layer [33, 34], the position
of adsorbed anions and water molecules on top of the upd-layer and the respective
bond angles and lengths could be elucidated [35, 36]. Surface reconstruction caused
by weakly adsorbed hydrogen [37], surface expansion effects of low-index platinum
and gold surfaces correlated with adsorption/desorption of solution species [38] and
1 The slightly gradual distinction implies possible overlap between both groups of methods.

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240 6 Diffraction and Other X-Ray Methods

crystallographic transformations in layers of NiOH2 have been studied [39]. In a

corrosion study of a Cu3 Au(111) alloy single crystal that was used as a model sys-
tem, initial stages of corrosion, particularly structure formation, was elucidated with
surface XRD [40]. Evidence of the diffusion of gold atoms into the upd-Te layer on
top of a Au(111) has been reported [41]. A study of the water layer structure on a
Cu(111) electrode surface during hydrogen evolution combining SXD and IRRAS
showed a stacked, close-packet structure with significantly different inter- and intra-
layer specific oxygen–oxygen nearest neighbor distances [42]; the infrared spectra
indicated the presence of both free and hydrogen-bonded hydroxyl ions.

6.1.3 Surface Differential X-Ray Diffraction (SDD)

Fundamentals. The scattered X-ray from crystal planes or a thin metal film can in-
terfere coherently with scattered X-rays from an adsorbate layer. This phenomenon
is called surface differential X-ray diffraction (SDD) or Bragg peak interference.
The theory has been described elsewhere in detail [43, 44]. Information on the rela-
tive amount of material in the adsorbate layer (coverage) and the distance between
atoms in the top layer of the substrate and in the adsorbate layer as a function of
electrode potential can be derived from SDD measurements.
Instrumentation. The experimental setup uses a working electrode prepared from
mica coated with the metal to be investigated (e.g. silver) by vapour deposition.
Because of the mode of growth, a certain monocrystalline orientation will result
(e.g. (111) in the case of silver). The working electrode is attached to an electro-
chemical cell equipped with counter and reference electrode and the standard ancil-
lary equipment for electrochemical measurements. The X-ray of well-defined wave-
length from a standard laboratory source or from a synchrotron (selected with e.g. a
Si(220) monochromator) impinges on the working electrode through the mica sub-
strate. Diffracted intensity is collected with a multichannel analyser, which can be
done in real time during electrode potential scans. Investigated systems include pre-
dominantly metal adlayers (upd-layers) on metal surfaces [44, 45]. Data on modes
of layer growth, adsorbate–atom and substrate–atom distance and relaxation of in-
volved atom layers were obtained.

6.1.4 Neutron Diffraction

Fundamentals. Neutrons of low energy have wavelengths similar to those of X-

rays (e.g. a neutron with 1 eV energy has a wavelength of λ = 0.027 nm, a neutron
moderated by graphite down to a speed of about 4 km·s−1 has a wavelength of about
λ = 0.1 nm). They show diffraction like X-rays as predicted in 1936 by Elsasser.
Contrary to X-ray diffraction, where electromagnetic radiation (the X-rays) inter-
acts with electrons of the involved atoms, neutrons will interact with the nuclei of
these atoms. Thus the diffraction of neutrons does not depend on the number of
electrons in the atom. The rapid increase of X-ray scattering factors with increas-
ing numbers of electrons in the atoms is consequently not observed with neutrons.
 6.2 Miscellaneous Methods 241

Scattering factors depend only weakly on this number and do not depend at all on
the direction of the scattering. Scattering is not dominated by heavy atoms. Thus
neutron scattering is much better suited for detection of light atoms like hydro-
gen atoms. Atoms with very similar X-ray scattering factors, e.g. nickel and cobalt
atoms, can be distinguished with neutron scattering. Since neutron fluxes tend to be
very small (typically about 10−5 of X-ray radiation) and are more difficult to han-
dle, neutron diffraction is possible only with powerful neutron sources like nuclear
reactors. They are of particular use in structural studies of metals and solids wherein
the position of light atoms like hydrogen has to be identified.
Instrumentation. The experimental setup is similar to that employed for in situ
X-ray diffraction. The material under investigation is pressed into a thin sheet and
mounted together with suitable counter and reference electrodes into a silica cell.
In order to decrease the large incoherent scattering contributions from protons in
aqueous electrolyte solutions, deuterated solutions are used. In a typical study, the
reaction mechanism of Ni(OH)2 (employed in nickel accumulators) was studied
with neutron powder diffraction NPD [46]. A direct and continuous structural trans-
formation of both the γ - and β-NiOOH phases into β-Ni(OH)2 was observed during
reduction with no direct relationship or discontinuity related to the transition from
the first discharge electrode potential to the second one, which was located about
0.4 V lower.

6.2 Miscellaneous Methods

6.2.1 X-ray Standing Wave Fluorescence Analysis (XSW)

Fundamentals. Dynamical reflection of a monochromatic, longitudinally coherent

planar X-ray wave at a perfect (or almost perfect) single crystal surface results in
the formation of an interference field of low thickness on both sides of the interface
when incident and reflected waves interfere. For every reflection, this standing wave
(XSW) field has the same spatial periodicity as the respective diffraction planes. The
antinodal planes of the electric field intensity lie parallel to the diffraction planes.
The movement of the standing wave field, which is controlled by changing the angle
of incidence, can be used to determine the position of foreign atoms on a surface by
measuring their characteristic fluorescence radiation together with the shift of the
antinodal planes (for further details, see [47–51]) because only those atoms inside an
antinode show X-ray fluorescence. The obtained plot shows fluorescence intensity
as a function of the angle of incidence for the selected wavelength of the X-rays.
Instrumentation. The necessary γ -radiation is usually supplied by a synchrotron.
Selection of the proper monochromatic radiation is done with germanium and/or
silicon single crystals. The angle of incidence of the radiation on the electrode
surface under investigation can be varied; the reflected and scattered intensity are
measured with suitable detectors. Further experimental details have been reported
elsewhere [52, 53]. In the studies reported so far, underpotential deposited layers

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242 6 Diffraction and Other X-Ray Methods

have been investigated and distances between the adlayers and the underlying metal
surface were determined [54, 48]. Closely related studies of membranes have been
described [56]. The use of layered synthetic microstrucutures (LSM) [57] for XSW
measurements has been described [58]. Layered synthetic microstructures are pre-
pared by sequentially depositing materials that are typically of low and high elec-
tron density (e.g. W/C, Mo/C, W/Si or Pt/C) onto a smooth surface like silicon or
cleaved mica, avoiding typical difficulties encountered when handling bulk metal
single crystals. The latter system (Pt/C) was employed in an investigation of iodine
and subsequent competitive adsorption of copper ions on platinum.

6.2.2 Surface X-ray Scattering (SXS)

Fundamentals. X-rays scattered at a surface are reflected from a crystal like any
light from a reflecting surface. The specular (mirror-like) reflection is strongest
when the incident beam arrives at the glancing angle2 (typically less than 1◦ at
the metal/air interface). It falls off rapidly with an increase of the angle of incidence
beyond this critical angle for total external reflection. When the angle of incidence
passes the various Bragg angles (as given by the crystallographic data of the mate-
rial under study), the intensity rises again because scattering amplitudes from every
atomic layer in the crystal are in-phase and signals are added. At intermediate an-
gles, the signals are out-of-phase and show destructive interference. A weak inten-
sity can nevertheless be observed at these intermediate angles, which are caused by
scattering from the surface layers. Atoms in the surface layer have a slightly dif-
ferent crystallographic environment because the crystal is truncated; the atoms in
the topmost layer have dangling (unsaturated) bonds. Consequently, their scattering
conditions are different from those in the bulk of the crystal. In this specular reflec-
tion, the momentum transfer of X-rays is surface normal. The measured intensity
represents the square of the Fourier amplitude of the surface normal electron den-
sity. Since Fourier phases cannot be measured, a direct inversion of the measured
intensities is impossible. Instead, a fit of calculated intensity based on surface struc-
ture models to the actually measured intensity provides an accurate description of
the surface-normal structure.
Besides crystal planes parallel to the surface, further planes exist that might re-
flect impinging X-rays. The scattered X-rays are not in the plane of reflection and
are called off-specular reflections. Their intensity is also high at the Bragg angles.
As with the specularly reflected X-rays, the weak signal between these peak intensi-
ties contains surface-relevant information. A combined analysis of these reflections
often leads to a complete picture of the surface structure.
In reciprocal space, these reflections form streaks of scattered X-ray intensity
with a narrow but elongated cross section in the direction of the surface normal.
With a flat surface parallel to a crystallographic axis, these streaks connect the Bragg
2 Unfortunately there is some confusion with the use of angle of incidence. Sometimes the
angle between beam and surface, sometimes the angle between beam and surface normal are
meant. Here the angle between beam and surface is considered.
 6.2 Miscellaneous Methods 243

reflection peaks. These Bragg reflections essentially contain the crystallographic

information of the bulk and the streaks (sometimes also called “rods”) contain the
surface-relevant information. Surface X-ray scattering measurements are sometimes
called crystal truncation rod (CTR) measurements with respect to the various aspects
mentioned above [59, 60]. The method is capable of providing two-dimensional and
three-dimensional information at resolutions better than 0.1 Å. Further details have
been reported elsewhere [61–65].
Instrumentation. Investigations require an X-ray source of sufficient intensity that
provides monochromatic radiation, usually a synchrotron. The schematic setup is
shown in Fig. 6.6. Typically, X-rays in the energy range 6 to 17 kV (λ = 70 to
200 pm) are used.
Two basically different cell geometries can be used. In Fig. 6.7 these designs are
shown together with their analogous arrangements for single crystal studies.
In the reflection geometry (or in analogy, the Bragg geometry), the cell win-
dow is parallel to the electrolyte surface. The current distribution and iR-drop is

Fig. 6.6. Schematic setup for X-ray scattering experiments

Fig. 6.7. Schematic cell designs for X-ray scattering experiments: (a) reflection (Bragg)
geometry; (b) transmission (Laue) geometry

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244 6 Diffraction and Other X-Ray Methods

Fig. 6.8. Electrochemical cell for X-ray scattering experiments in reflection geometry
(schematic cross section)

considerable because of the thin electrolyte layer between the electrode surface and
the cell window, which is kept at minimum thickness by employing membranes as
cell windows that were kept as close to the electrode as possible. By expanding
the membrane during electrochemical manipulation, this drawback can be reduced
somewhat. This is illustrated in Fig 6.8, showing a simplified cell cross section.
The electrolyte solution is pumped into the cell before electrochemical manipu-
lation, causing the flexible membrane to rise. The solution is removed before starting
X-ray measurements and the membrane collapses down on the electrode surface,
leaving only a thin electrolyte solution film in place. Further typical cell designs
have been described elsewhere [59, 60, 66]. In the transmission (Laue) geometry,
the electrochemical properties of the cell are almost perfect and the free access of
the solution/metal interface even allows for flushing the electrolyte solution in order
to remove radiolysis products. Unfortunately, the beam is attenuated considerably.
This situation can be improved somewhat by keeping the cell thickness as small as
possible. Only X-rays reflected from the interface will reach the detector, because
the X-rays impinge on the cell window at an angle excluding any reflections from
the window from reaching the detector. Because the beam path through the elec-
trolyte volume hardly changes when the angle of incidence is varied, little or no
absorption correction with the reflection geometry is necessary. Typical cell designs
can be found elsewhere [59, 60]. A wide-angle accessible cell [67] and an experi-
mental setup for measurements at elevated temperatures [68] have been described.
Investigated systems include various metal deposits, like underpotentially de-
posited silver on Au(111) [69], thallium on a Pt(111) surface as a function of solu-
tion pH and bisulfate coadsorption [70] and other upd-systems [36, 59]. Evidence
of dealloying of Cu3 Au(111) has been reported [71]. Near-neighbor distances be-
tween atoms in upd-monolayers of various transition metals deposited on Ag(111)
and Au(111) surfaces have been measured as a function of electrode potential [72].
Typical results of a study of thallium-upd showing the changing Tl–Tl distance as a
function of electrode potential are shown in Fig. 6.9.
The incommensurate, hexagonal monolayers are compressed compared to the
bulk metal and they are rotated from the substrate by several degrees. From the
results, the monolayer compressibility could be calculated. The restructuring (i.e.
surface reconstruction) of top layers of single crystal metal surfaces as a function
of solution composition and electrode potential has been studied [73]. The induced
charge density was found to be the critical parameter [74]. Structural changes during
 6.2 Miscellaneous Methods 245

Fig. 6.9. Thallium monolayer near-neighbor distance as a function of electrode potential,

aqueous electrolyte solution 0.1 M Na2 SO4 + 2.5 mM Tl2 SO4 (based on data in [72])

oxidation/reduction of copper surfaces and passivation have been investigated [75].

Dissolution and passivation of a Ni(111) surface have been studied with surface
X-ray scattering combined with in situ STM measurements [76]. By combining sur-
face X-ray diffraction and X-ray scattering, the palladium–gold bond length in a
palladium monolayer on a Au(111) surface was determined to 28.2 pm, which is
close to the sum of the atomic radii of the involved atoms [77]. A study of copper-
upd layers on Au(111) revealed sulfate ions bound via three oxygen atoms to the
copper atoms; this seems to correct previous scanning probe microscopy studies re-
sulting in the claim, that these microscopies probed copper atoms as topmost layer
constituents [78]. The coverage of monocrystalline surfaces with various adsorbates
and the adsorbate structure, including the position of adsorbed ions, have been deter-
mined [79, 80]. A more detailed picture of adsorbate–substrate interactions emerges
when polarization dependencies of the scattered intensity and resonant scattering are
taken into account [81]. Using suitable cell designs, time-resolved measurements on
a second scale have become possible; results pertaining to phase transitions of upd-
layers and the kinetics of oscillating reactions have been reported [82].

6.2.3 Small Angle X-ray Scattering

Fundamentals. Particles like macromolecules in solution or particles in a heteroge-

neous solid scatter X-rays. Information about the particle size can be obtained from
measurements of the scattered intensity as a function of scattering angle; the term
“small angle” refers to the fact that the scattering is investigated at angles of only
a few degrees, corresponding to particle sizes in the nanometer range. In addition,
information about the shape can be derived. Scattering vectors from the atoms of
interest can be selected with X-rays of tunable wavelength (e.g. from synchrotrons).
The use of a microbeam of 5-μm diameter enables laterally resolved studies of lay-
ered systems [83].

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246 6 Diffraction and Other X-Ray Methods

Instrumentation. In studies reported so far [84], polymer nanocomposites as used

in lithium batteries prepared from poly(ethylene oxide) and lithium hectorite have
been investigated. Using a sample holder that could be heated, structural changes of
the nanocomposites as a function of temperature could be monitored in situ. Ex situ
studies of electrodeposited amorphous NiP coatings have been described [85].

6.2.4 Specular X-ray Reflection

Fundamentals. The reflectivity of a surface with respect to electromagnetic radia-

tion in the X-ray range for a beam with equal incident and outgoing angles and both
beams in one plane can be described in a kinematic approximation [73, 86, 87]. The
structure factor included in this relation contains information pertaining both to the
surface layer of the reflecting electrode surface and the bulk of the material, par-
ticularly to interlayer spacings and sample morphology. The parameters describing
the electron density profiles and further structure-related details are optimized un-
til the calculated reflectivity fits the experimentally observed one (for an example,
see [88]).
Instrumentation. In most studies reported so far, X-ray radiation of a synchrotron
collimated and monochromatized with suitable optics is used. An electrochemical
cell with a moving working electrode is employed in order to minimize X-ray ab-
sorption by the electrolyte solution. A typical cell design is depicted in Fig. 6.10.

Fig. 6.10. Schematic spectroelectrochemical cell for in situ X-ray specular reflection mea-
surements. Top: Position of central working electrode down for electrochemical measure-
ments; Bottom: Working electrode up for X-ray measurements (based on [88])
 References 247

For electrochemical measurements, the electrode is lowered away from the

Mylar® film that serves as a cell cover and X-ray window. After moving the elec-
trode upwards, an electrolyte solution film of about 10 μm remains with only small
radiation absorption.
The surface-normal structure of epitaxially grown Te and Cd upd-layer was stud-
ied [89] and other upd-systems have been the subject of investigations [33, 88]. Ki-
netic studies of passive oxide formation on iron and iron alloys [90] and of Au(001)
reconstruction have been reported [73].

References
1. Special issue of Electrochim. Acta 47, 3035 ff. (2002)
2. J. Robinson, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 313
3. J. Robinson, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New York, 1988),
p. 9
4. J. Zegenhagen, F. Renner, Nachr. Chem. 54, 847 (2006)
5. W. Massa, Kristallstrukturbestimmung (Teubner, Stuttgart, 1996)
6. W. Clegg, Crystal Structure Analysis (Oxford University Press, Oxford, 2001)
7. R. Caminiti, V. Rossi Albertini, Int. Rev. Phys. Chem. 18, 263 (1999)
8. V. Rossi Albertini, P. Perfetti, F. Ronci, B. Scrosati, Chem. Mater. 13, 450 (2001)
9. J. Robinson, in Spectroelectrochemistry, ed. by R.J. Gale (Plenum, New York, 1988),
p. 9
10. T. Ikeshoji, T. Iwasaki, Inorg. Chem. 27, 1123 (1988)
11. M.S. Whittingham, Science 192, 1126 (1976)
12. R.R. Chianelli, J.C. Scanlon, B.M.L. Rao, J. Solid State Chem. 29, 323 (1979)
13. R.R. Chianelli, J.C. Scanlon, B.M.L. Rao, J. Electrochem. Soc. 125, 1563 (1978)
14. R.R. Chianelli, J.C. Scanlon, B.M.L. Rao, J. Solid State Chem. 29, 323 (1979)
15. V. Puglisi, M. Simoneau, Y. Geronov, 210. Electrochemical Society Meeting, Cancun,
Mexico, 29.10–03.11.2006, Ext. Abstr. #164
16. J. Li, J.R. Dahn, 210. Electrochemical Society Meeting, Cancun, Mexico, 29.10–
03.11.2006, Ext. Abstr. #261
17. J. Li, J.R. Dahn, J. Electrochem. Soc. 154, A156 (2007)
18. M. Nishizawa, I. Uchida, Denki Kagaku 66, 991 (1998)
19. O. Bergström, T. Gustafsson, J.O. Thomas, J. Appl. Cryst. 31, 103 (1998)
20. Z.G. Li, R.L. Harlow, F. Gao, P. Lin, R. Miao, L. Liang, J. Electrochem. Soc. 150, A1171
(2003)
21. Th. Koop, W. Schindler, A. Kazimirov, G. Scherb, J. Zegenhagen, Th. Schulz, R. Fei-
denhans’l, J. Kirschner, Rev. Sci. Instr. 69, 1840 (1998)
22. B. Meyer, B. Ziemer, F. Scholz, J. Electroanal. Chem. 392, 79 (1995)
23. H. Prinz, H.H. Strehblow, Electrochim. Acta 47, 3093 (2002)
24. R. De Marco, Z.-T. Jiang, B. Pejcic, E. Poinen, J. Electrochem. Soc. 152, B389 (2005)
25. R. de Marco, B. Pejcic, K. Prince, A. van Riessen, Analyst 128, 742 (2003)
26. R. De Marcoa, Z.-T. Jiang, J. Martizano, A. Lowe, B. Pejcic, A. van Riessen, Elec-
trochim. Acta 51, 5920 (2006)

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248 6 Diffraction and Other X-Ray Methods

27. R. de Marco, Z.T. Jiang, B. Pejcic, A. van Riessen, Electrochim. Acta 51, 4886 (2006)
28. H. Imai, K. Izumi, Y. Kubo, K. Kato, Y. Imai, Extended Abstracts of the 209th Meeting
of the Electrochemical Society Spring Denver, Colorado, USA, 07.05–11.05.2006, Ext.
Abstr. #302
29. J.B. Wagner Jr., in Techniques for Characterization of Electrodes and Electrochemical
Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 3
30. J.E. Enderby, in Techniques for Characterization of Electrodes and Electrochemical
Processes, ed. by R. Varma, J.R. Selman (Wiley, New York, 1991), p. 327
31. W.C. Marra, P. Eisenberger, A.Y. Cho, J. Appl. Phys. 50, 6927 (1979)
32. J. Zegenhagen, F. Renner, Nachr. Chem. 54, 847 (2006)
33. H. Kawamura, M. Takahasi, N. Hojo, M. Miyake, K. Murase, K. Tamura, K. Uosaki,
Y. Awakura, J. Mizuki, J. Electrochem. Soc. 149, C83 (2002)
34. M. Fleischmann, B.W. Mao, J. Electroanal. Chem. 247, 297 (1988)
35. M. Nakamura, O. Endo, T. Ohta, M. Ito, Y. Yoda, Surf. Sci. 514, 227 (2002)
36. E. Herrero, S. Glazier, H.D. Abruna, J. Phys. Chem. B 102, 9825 (1998)
37. M. Fleischmann, B.W. Mao, J. Electroanal. Chem. 247, 311 (1988)
38. C.A. Lucas, Electrochim. Acta 47, 3065 (2002)
39. M. Fleischmann, A. Oliver, J. Robinson, Electrochim. Acta 31, 899 (1986)
40. F.U. Renner, A. Stierle, H. Dosch, D.M. Kolb, T.-L. Lee, J. Zegenhagen, Nature 439, 707
(2006)
41. H. Kawamura, M. Takahasi, N. Hojo, M. Miyake, K. Murase, K. Tamura, K. Uosaki,
Y. Awakura, J. Mizuki, J. Electrochem. Soc. 149, C83 (2002)
42. M. Ito, M. Yamazaki, Phys. Chem. Chem. Phys. 8, 3623 (2006)
43. T. Rayment, R.K. Thomas, G. Bomchil, J.W. White, Mol. Phys. 43, 601 (1981)
44. E.D. Chabala, T. Rayment, Langmuir 10, 4324 (1994)
45. A.R. Ramadan, E.D. Chabala, T. Rayment, Phys. Chem. Chem. Phys. 1, 1591 (1999)
46. F. Bardé, M.R. Palacin, Y. Chabre, O. Isnard, J.-M. Tarascon, Chem. Mater. 16, 3936
(2004)
47. M.J. Bedzyk, D. Bilderback, J. White, H.D. Abruna, M.G. Bommarito, J. Phys. Chem.
90, 4926 (1986)
48. G. Materlik, M. Schmäh, J. Zegenhagen, W. Uelhoff, Ber. Bunsenges. Phys. Chem. 91,
292 (1987)
49. H.D. Abruna, G.M. Bommarito, H.S. Yee, Acc. Chem. Res. 28, 273 (1995)
50. M.J. Bedzyk, G.M. Bommarito, M. Caffrey, T.L. Penner, Science 248, 52 (1990)
51. H.D. Abruna, G.M. Bommarito, D. Acevedo, Science 250, 69 (1990)
52. A. Krolzig, G. Materlik, J. Zegenhagen, Nucl. Instrum. Methods 208, 613 (1983)
53. A. Krolzig, G. Materlik, M. Swars, J. Zegenhagen, Nucl. Instrum. Methods 219, 430
(1984)
54. G. Materlik, J. Zegenhagen, W. Uelhoff, Phys. Rev. B 32, 5502 (1985)
55. H.D. Abruna, J.H. White, M.J. Albarelli, G.M. Bommarito, M.J. Bedzyk, M. McMillan,
J. Phys. Chem. 92, 7045 (1988)
56. M. Caffrey, J. Wang, Faraday Discuss. 94, 283 (1992)
57. for an introduction to LSM see: T.W. Barbee, in Low Energy X-ray Diagnostics, ed. by
D.T. Atwood, B.L. Henke (AIP, New York, 1981)
58. H.D. Abruna, J.H. White, M.J. Albarelli, G.M. Bommarito, M.J. Bedzyk, M. McMillan,
J. Phys. Chem. 92, 7045 (1988)
59. H. You, Z. Nagy, Curr. Top. Electrochem. 2, 21 (1993)
60. Z. Nagy, H. You, Electrochim. Acta 47, 3037 (2002)
 References 249

61. B.M. Ocko, J. Wang, in Synchrotron Techniques in Interfacial Electrochemistry, ed. by

C.A. Melendres, A. Tadjeddine (Kluwer Academic, Dordrecht, 1994), p. 127
62. B.M. Ocko, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 343
63. M. Takahashi, Y. Hayashi, J. Mizuki, K. Tamura, T. Kondo, H. Naohara, K. Uosaki, Surf.
Sci. 461, 213 (2000)
64. J.X. Wang, R.R. Adzic, B.M. Ocko, in Interfacial Electrochemistry, ed. by A. Wieck-
owski (Dekker, New York, 1999), p. 175
65. D.M. Kolb, Angew. Chem. Int. Ed. [Angew. Chem.] 40[113], 1162[1199] (2001[2001])
66. K.M. Robinson, W.E. O’Grady, Rev. Sci. Instr. 64, 1061 (1993)
67. Z. Nagy, H. You, R.M. Yonco, Rev. Sci. Instr. 65, 2199 (1994)
68. V. Stamenkowvic, C. Lucas, D. Tripkovic, D. Strmenik, N.M. Markovic, 210. Elec-
trochemical Society Meeting, Cancun, Mexico, 29.10.–03.11.2006, Extended Ab-
stract #1913
69. T. Kondo, J. Morita, M. Okamura, T. Saito, K. Uosaki, J. Electroanal. Chem. 532, 201
(2002)
70. R.R. Adzic, J.X. Wang, O.M. Magnussen, B.M. Ocko, J. Phys. Chem. 100, 14721 (1996)
71. F.U. Renner, T.L. Lee, S. Warren, B.C.C. Cowie, D.M. Kolb, A. Stierle, I. Costina, H.
Dosch, R. Felici, Extended Abstracts of the 203rd Meeting of the Electrochemical Soci-
ety, Paris, France, 27.04–02.05.2003, Ext. Abstr. #287
72. M.F. Toney, J.G. Gordon, M.G. Samant, G.L. Borges, O.R. Melroy, D. Yee, L.B.
Sorensen, J. Phys. Chem. 99, 4733 (1995)
73. B.M. Ocko, J. Wang, A. Davenport, H. Isaacs, Phys. Rev. Lett. 65, 1466 (1990)
74. J. Wang, B.M. Ocko, A.J. Davenport, H.S. Isaacs, Phys. Rev. B 46, 10321 (1992)
75. H. You, C.A. Melendres, Z. Nagy, V.A. Maroni, W. Yun, R.M. Yonco, Phys. Rev. B 45,
11288 (1992)
76. J. Scherer, B.M. Ocko, O.M. Magnussen, Electrochim. Acta 48, 1169 (2003)
77. H. Furukawa, M. Takahashi, M. Ito, J. Electroanal. Chem. 256, 213 (1988)
78. M.F. Toney, J.N. Howard, J. Richer, G.L. Borges, J.G. Gordon, O.R. Melroy, D. Yee,
L.B. Sorensen, Phys. Rev. Lett. 75, 4472 (1995)
79. T. Wandlowski, J.X. Wang, B.M. Ocko, J. Electroanal. Chem. 500, 418 (2001)
80. B.M. Ocko, G.M. Watson, J. Wang, J. Phys. Chem. 98, 897 (1994)
81. Y.V. Tolmachev, A. Menzel, A. Tkachuk, Y.S. Chu, H. You, Extended Abstracts of the
203rd Meeting of the Electrochemical Society, Paris, France, 27.04–02.05.2003, Ext.
Abstr. #2840
82. J.X. Wang, K. Tamura, B.M. Ocko, R.R. Adzic, Extended Abstracts of the 203rd Meeting
of the Electrochemical Society, Paris, France, 27.04–02.05.2003, Ext. Abstr. 2839
83. S.V. Roth, P. Müller-Buschbaum, M. Burghammer, H. Walter, P. Panagiotou, A. Diethert,
C. Riekel, Spectrochim. Acta B 59, 1765 (2004)
84. G. Sandi, H. Joachin, R. Kizilel, S. Seifert, K.A. Carrado, Chem. Mater. 15, 838
(2003)
85. D. Tatchev, R. Kranold, S. Armyanov, J. Electrochem. Soc. 150, C502 (2003)
86. D. Gibbs, B.M. Ocko, D.M. Zehner, S.G.J. Mochrie, Phys. Rev. B 38, 7303 (1988)
87. B.M. Ocko, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 343
88. H. Kawamura, M. Takahasi, J. Mizuki, J. Electrochem. Soc. 149, C586 (2002)

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250 6 Diffraction and Other X-Ray Methods

89. H. Kawamura, M. Takahasi, J. Mizuki, Extended Abstracts of the 203rd Meeting of the
Electrochemical Society, Paris, France, 27.04–02.05. 2003, Ext. Abstr. #2837
90. D.H. Kim, S.S. Kim, H.W. Jang, D.Y. Noh, Extended Abstracts of the 203rd Meeting of
the Electrochemical Society, Paris, France, 27.04–02.05. 2003, Ext. Abstr. #270
7 Surface Analytical Methods

In previous chapters a broad variety of methods has been treated which could be
easily grouped into spectroscopic methods or techniques employing some sort of in-
teraction between electromagnetic radiation and the electrochemical interface. Var-
ious techniques remain which are hard to assign to any of the families of methods
presented so far. This is partly caused by the fact, that some of these methods com-
bine optical, i.e. spectroscopic, details with experimental features providing spatial
resolution or to the fact, that surface properties like e.g. electrical conductivity are
measured which have no direct or obvious relationship to spectroscopic methods.
The advent of ever smaller electrochemically cells (microcells, capillary cells)
which can be placed on selected areas of an electrode surface allows spatially re-
solved measurements of local properties. Spectroscopic methods modified in such a
way like e.g. locally resolved electrochemical mass spectrometry have been treated
in previous sections. Optical methods incorporating scanning probes will be treated
below. Classical electrochemical methods like e.g. impedance measurements em-
ploying these miniaturized cells [1] thus providing localized information will not be
treated in this book. The same applies to scanning electrodes employed in localized
electrochemical impedance measurements (LEIS).

7.1 Topographic Methods

A topographic picture of a surface can be obtained in various ways. Mostly optical

methods yielding pictures based on secondary electrons that are emitted from the
investigated surface or other probes and signals have been employed so far. Most
of these methods are applicable only under vacuum and the obtained pictures are
indirect, i.e. they are based upon the interaction between the surface and a probe
(e.g. an electron beam). Directly scanning the surface on a microscopical scale using
an appropriately small probe (tip) has become possible with micromanipulators of
sufficient mechanical resolution and reproducibility (see [2, 3]). A first approach that
closely resembles the well-known technology employed in phonographic pickup
cartridges has been described [4, 5]. The device employs piezoelectric actuators.
Its operation is based on the principle of a field emission probe. A field emitter
with a typical radius of 100–10,000 Å that is close to a conducting surface shows
an electric field strength given by the Fowler–Nordheim equation when a constant

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252 7 Surface Analytical Methods

current is passed between tip and surface. The amplified voltage is applied to the Z-
axis piezo actuator. Thus a constant distance between tip and surface are maintained.
The applied voltage is a measure of the altitude of the surface. By scanning the
position of the tip with X- and Y-servos, this altitude can be measured across the
surface; a topographic picture of the surface results. The device operates only under
vacuum conditions. A vertical resolution of 30 Å and a horizontal resolution of
4000 Å have been achieved. Experimental results have been reviewed [6].

7.2 Scanning Probe Methods

The advent of micropositioners capable of moving a probe (e.g. a tiny metal tip) in
closest proximity to the solid surface to be investigated (i.e. in nanometer distance)
with high spatial resolution based predominantly on piezocrystal-driven actuators
has made a variety of scanning probe methods, or scanning probe microscopies
(SPM), possible. Methods are named depending on the principle of measurement
and the type of probe. Several methods can be used in different modes of opera-
tion (e.g. the scanning tunneling microscope can be run in the constant distance and
the constant current mode). In addition, some methods have been developed into
further variations. The following overview of established methods starts with a gen-
eral description of the most often used variant of a method; variations are included
wherever it seemed appropriate. A classification of scanning probe microscopies has
been provided [7, 8].
The use of light (photons) instead of electrons results in the photon scanning
tunneling microscope (PSTM) [9]. A fiber tip with an apex shape similar to the one
used in other SPMs with electrons is positioned close to the investigated surface. As
outlined in Fig. 7.1, the surface is illuminated from the backside with a laser beam
or even with a beam of white light at an angle larger than the critical angle.
On top of the hemispherical cylinder, the sample with the surface to be investi-
gated is mounted with an index matching gel. Thus the upper surface becomes the
interface where internal reflection occurs. Light tunneling through the surface apex
gap is guided via the optical fiber to the photomultiplier. Its intensity is directly re-
lated to the distance in an exponentially decaying way. Thus the intensity can be
used as a height indicator. In advanced setups, Raman spectroscopy or optical ab-

Fig. 7.1. Schematic setup for photon scanning tunneling microscopy

 7.2 Scanning Probe Methods 253

sorption spectroscopy of species at the interface have been proposed. Uses in an

electrochemical environment have not been reported so far.
Scanning the surface with a laser beam in a confocal arrangement can result in
topographic information about the investigated surface; since the confocal arrange-
ment and further optical features dominate this experimental approach, whereas the
scanning feature is of lesser importance, this microscopy is treated in the Sect. 7.3.

7.2.1 Scanning Tunneling Microscopy (STM)

Fundamentals. An STM uses an atomically sharp probe tip of an electronically

conducting material in close proximity (∼ = 1 nm) to the surface under investigation.
The tip is rastered (scanned) relative to the surface using piezoelectric devices. Thus
an STM can be used to directly monitor the local density of electronic surface states
with atomic resolution. The current flowing between the tip and the surface when a
small voltage is applied depends on the exponential dependency on the tip-surface
distance that is characteristic of an electronic tunneling process. This results in the
remarkable vertical resolution of the apparatus. In a simple approximation [10], the
tunneling current I can be given in terms of local density of states (LDOS) ρs (EF )
at the Fermi level, distance d, applied voltage U and decay constant κ:

I ≈ Uρs (EF ) exp(−2κd).

Using average values for a semi-classical square potential barrier and effective bar-
rier height of 4 eV yields a value of κ ∼ = 1 Å−1 . Further details are provided else-
where [11]. This causes the tunneling current to drop by about an order of magnitude
per Å of increased distance, which finally results in the indicated vertical resolution.
The very pronounced distance–current relationship contributes also in a very spe-
cific way to the high resolution: Although tips may be very sharp, they nevertheless
show even in the perfect case a curvature on an atomic scale. Instead, in the real
world the tip is generally composed of several atoms because it is prepared by cut-
ting a wire at an oblique angle or by etching a thin wire [12]. Nevertheless, there
will most likely be one atom protruding somewhat beyond the neighbors. As the tun-
neling currents drops by about an order of magnitude when the distance increases
by 1 Å (100 pm), the dominant fraction of the tunneling current will flow across
this particular atom. In the case of extremely blunt tips, the image of the tip will be
recorded instead of the investigated surface.
Probing the LDOS can be done in two fundamentally different ways:
1. The tip can be scanned at constant height (distance) over the surface. This is
possible only when the surface is smooth on an atomic scale, otherwise the tip
might crash into surface features.
2. Alternatively the tip can be scanned in a constant tunneling current mode. In this
case the actually measured current is fed into an electronic regulation circuit
which adjusts the actual tip-surface distance to a value resulting in a constant
value of the tunneling current at all probed places. The signal fed into the z-axis
piezodrive provides information about the local elevation. This mode works

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254 7 Surface Analytical Methods

Fig. 7.2. Scheme of scanning tunneling microscopy in the constant height mode (left) and the
constant current mode (right); X, Y and Z designate the respective piezodrives, dashed line
indicates tip position

well even with strongly structured surfaces; it is inherently slower because of

the employed feedback circuitry.
At first glance, both methods seem to be equivalent, i.e. the results should be the
same. Upon closer inspection, differences appear. The first method, which operates
at constant height, yields results wherein the observed tunneling current taken as a
measure of the tip-surface distance is influenced by the distance–current relation-
ship mentioned above. Interpreting the observed pictures requires a sophisticated
understanding of this relationship for the system under investigation.1 This problem
is absent in the second mode. In order to get a correct topographic picture, a precise
knowledge of the relationship between LDOS and actual atomic surface structure
on an atomic level is needed. Both modes of operation are shown schematically in
Fig. 7.2.
Both designs were initially developed and applied under vacuum conditions,
yielding microscope pictures with atomic resolution [13, 14]. Very soon it was found
that this design was also suitable for measurements at ambient temperature or even
in the presence of an electrolyte solution [15]. The need to maintain the tip at a cer-
tain potential (bias) with respect to the surface (i.e. the electrode) under investigation
and to keep this electrode itself at a selected potential adds to the complexity of the
experiment. The tip acts as a probe for tunneling microscopy and as an ultramicro-
electrode in the electrolyte solution. Attention has to be paid to conceivable Faradaic
processes occurring at the tip. This current is usually minimized by coating the tip
with an insulating material with only its apex exposed to the solution. A typical cur-
rent of the STM of about 1 to 10 nA corresponds to 106 A cm−2 flowing between the
tip and the probed section of the surface under investigation (typically 10−14 cm2 ).
Any Faradaic current at the tip that is caused by an electrochemical process would
flow across the whole exposed surface area of the tip (about 10−8 to 10−10 cm2 ),2
thus 10 nA would correspond to about 10 to 100 A cm−2 . This Faradaic current
1 This plays a major role in scanning tunneling spectroscopy (see p. 277).
2 In addition, the tip is covered with an insulating material (wax, resin) that leaves only the
apex of the tip exposed to the electrolyte solution.
 7.2 Scanning Probe Methods 255

density is much smaller than the tunneling current and no distortion of the tunneling
current should be expected.
Chemical modification of the microscope tip most frequently prepared from
metals like tungsten or gold results in surface properties that are useful for transfer-
ring “chemical sensitivity” to the tip. Chemical modification of the tip (by coating
with polypyrrole or with self-assembled monolayers (SAM) [16]) resulting in en-
hanced hydrogen bond or coordination bond interaction with species on the scanned
surface results in enhanced tunneling electron transfer and increased brightness of
the observed surface location or in higher contrast [17].
Instrumentation. In order to operate a STM under in situ conditions, i.e. in the
presence of an electrolyte solution, some conditions have to be fulfilled. The design
of the STM must allow investigation of a horizontal surface at the bottom of the
microscope. The tip has to be coated as completely as possible in order to minimize
the Faradaic current. Since the potential of the electrode surface under investiga-
tion has to be maintained at a fixed, controlled potential with respect to a reference
electrode, a four-electrode arrangement requiring a corresponding bipotentiostat is
necessary. The schematic drawing of the electrochemical cell as depicted in Fig. 7.3
shows the major components.
The peripheral components necessary for this experiment are indicated in
Fig. 7.4.
An experimental setup specifically dedicated to electrochemical in situ investi-
gations has been described in detail [18]. The preparation of suitable tips preferably
prepared from metals like Pt, Pt–Ir, Ir, and W has been reviewed elsewhere [10].
The importance of operation under a controlled gas atmosphere, in particular the

Fig. 7.3. Scheme of an electrochemical cell for in situ investigations with an STM

Fig. 7.4. Scheme of a setup for electrochemical in situ investigations with an STM

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256 7 Surface Analytical Methods

Fig. 7.5. STM pictures of a Au(111) electrode surface in contact with an aqueous solution
of 0.1 M H2 SO4 at various electrode potentials as indicated (picture provided by D. Kolb,
University of Ulm)

influence of dioxygen, has been examined extensively [19]. An experimental setup

for measurements at elevated temperatures [20] has been described.
Fast scan measurements, i.e. for investigations of the dynamics of surface diffu-
sion or reconstruction are done preferably in constant height instead of constant cur-
rent mode because no electronic feedback circuit, limiting response time and scan
speed, is involved in this mode. Obviously this works only with very smooth elec-
trode surfaces. An electronic setup (bipotentiostat) that allows fast transient methods
combined with scanning probe microscopies has been reported [21].
The formation of a well-ordered adsorbate layer could be demonstrated using
an STM. The dependence of the formation of the adsorbate layer on the electrode
potential, i.e. in the case of an anion at a sufficiently positive electrode potential, is
obvious in Fig. 7.5.
Scanning tunneling microscope pictures (Fig. 7.6) obtained during the deposi-
tion of copper on Au(111) electrode surfaces provide evidence that copper deposi-
tion proceeds almost exclusively at the steps [22].
The hexagonal arrangement of surface atoms after reconstruction of a Au(111)
surface in contact with an aqueous solution of 0.1 M H2 SO4 can be shown with
STM (Fig. 7.7).
General overviews of STM studies of metal electrodes have been provided [10,
23–25]; in addition, an extensive review that focused on ordered anion monolay-
ers on metal electrode surfaces has been published [26]. Charge-induced surface
phase transitions on ordered Au(111) caused by increasing iodide adsorption from
an aqueous electrolyte solutions have been observed [27]. The formation of copper
sulfide nanostripe patterns on a Au(111) electrode surface formed by exposure of
a single copper monolayer on this electrode and exposed to bisulfide ions in the
electrolyte solution has been studied with in situ STM [28]. Correlations between
 7.2 Scanning Probe Methods 257

Fig. 7.6. STM pictures of a Au(111) electrode surface before (top) and during (bottom) copper
deposition from an aqueous solution of 5 mM H2 SO4 + 0.05 mM CuSO4 (pictures provided
by D. Kolb, University Ulm; for further details see [22])

Fig. 7.7. STM picture of a reconstructed Au(100) surface (picture provided by D. Kolb, Uni-
versity of Ulm)

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258 7 Surface Analytical Methods

STM and SEM pictures have been discussed [29] and implications for reversible
oxidative roughening have been pointed out [30]. Relationships between observed
topography, electrochemical roughening parameters and Raman spectroscopic fea-
tures have been discussed [31]. Metal deposition, including underpotential deposi-
tion processes on metal substrates [32–35] and on highly ordered pyrolytic graphite
[36], has been frequently studied. The influence of solution additives (both organic
molecules and inorganic anions) has been investigated [37–39] and organic adsor-
bate layers have been reviewed elsewhere [40]. Applications of STM to disordered
(polycrystalline) materials, including metallic glasses, have been described [41].
Topography and local barrier height of metallic glass surfaces were measured. Step
and island dynamics at liquid/solution interfaces have been studied and comparisons
with the solid/gas interface were drawn [42]. Step and kink energies on Au(100)
electrode surfaces could be derived from island studies with an STM [43]. Real-
time observations of surface reactivity and mobility that were initially made ex situ
only [44] have been extended to in situ observations3 recently. Reported examples
included CO adsorption on Au(111) electrodes [45], adsorption of alkanethiols on
Au(111) [46] and reductive desorption of self-assembled monolayers of hexanethiol
from Au(111) surfaces [47, 48]. In the latter study it was observed that desorption
initiates at defects in the SAM, at missing rows and edges of vacancy islands. Both
formation and final structure of self-assembling osmium-bipyridine complexes were
monitored [49]. Adsorption and subsequent monolayer film formation of various
protoporphyrins on a HOPG surface have been studied with both STM and AFM
[50]. Studies of active metal dissolution [51] have been reported. In an investigation
of electrodeposition of bismuth on a graphite surface, formation of small particles
of about 10 nm diameter was observed initially [52]. Upon making contact with
neighbors, these particles coalesce. The coarsening of platinum island deposits in
the electrochemical double layer potential region has been studied with STM [53].
Underpotential deposition of lead on a Cu(100) electrode surface initially revealed a
high surface mobility [54]. Subsequent deposition of lead caused numerous changes
of both structure and dynamics at the interface. Copper deposition and stripping at
a gold electrode has been investigated [55]. Dissolution of highly polished copper
surfaces showed roughening and formation of facets [56]. During selective dissolu-
tion of copper from Cu–Au alloys, pit formation and finally porosity were observed.
AuCN-adlayers were found during adsorption from aqueous solutions of KAu(CN)2
on Au(111) surfaces [57]. Adsorption of NO from a KNO2 -containing electrolyte
solution on a Rh(111) surface and the subsequent reduction were monitored in real
time [58]. The reaction proceeds preferably at atomically flat terraces, not at surface
defects. Initial reaction fronts were spatially concentrated, not randomly distributed.
3 There seems to be some debate over the limit between static and dynamic measurements
related to the question of the frequency of image registration (frames per second) at which a
true real time observation is done. Obviously this judgement—if it is necessary at all— has to
be made with reference to the rate of change at the surface. No attempt is made in this text to
enter this discussion. Consequently, no attempt is made in this text to enter into this debate:
“video STM” will not be separated from other “real time STM”.
 7.2 Scanning Probe Methods 259

Fig. 7.8. STM pictures of a Au(111) in contact with an aqueous solution of 0.1 M H2 SO4 at
various electrode potentials as indicated (picture provided by D. Kolb, University of Ulm)

A computational tool for analysing observations obtained with STM based on a

self-consistent semiempirical molecular orbital model has been described [59]. The
electrodeposition of aluminum and titanium–aluminum alloys that are potentially
useful as corrosion protection layers from room temperature molten salt electrolytes
has been studied with STM [60]. Underpotential deposition of cadmium on Ag(111)
surfaces from ionic liquids has been monitored in situ with STM [61], spinodal de-
composition and surface alloying were observed. The use of STM beyond simple
surface imaging, including molecular identification, investigation of molecular reac-
tivity, electron transfer kinetics and nanofabrication have been reviewed elsewhere
[62, 63]. Investigations of the semiconductor/solution interface beyond topographic
ones [64] with varied tunnel gap distances and tip potentials allowed the separation
of the effects of the tunneling barrier and the Schottky barrier at this interface [65].
An STM can be used to study the effects of illumination of a semiconductor sur-
face by measuring local photovoltages resp. photocurrents [66]; surprisingly, this
approach has been employed so far only in ex situ studies. Gold/n-Si(111) nanocon-
tacts (interface area about 10−12 cm2 ) that were prepared by electrodeposition of
gold onto n-Si(111):H substrates have been studied with an STM [67] in the pres-
ence of an aqueous solution of 0.02 M HClO4 . By varying the tip voltage and
the electrode potential of the silicon substrate, a Schottky diode behavior of the
nanocontact was verified.
An emerging application of the STM is the structuring of an electrode surface
on a nanometer scale (nanostructuring). In a representative example (see Fig. 7.8),
selective copper deposition resulted in a regular arrangement of metallic tips [68].
The use of an STM to deposit silver inside a polymer electrolyte film (Nafion® )
has been reported [69]. A combination of an STM with an SECM (see also below for

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260 7 Surface Analytical Methods

this method) has been described [70]. The specifically adapted tip can be operated
both in tunneling mode and as a probe electrode for scanning the surface over a
large distance in the feedback mode, measuring diffusion-controlled oxidation of a
mediator. This way, the topography and local reactivity can studied with a single
instrument and with high spatial reproducibility. The influence of the geometry of a
nanometer-sized electrode has been discussed [71].

7.2.2 Differential Conductance Tunneling Spectroscopy (DCTS)

Fundamentals. Modulation of the tip bias voltage of an STM at a frequency much

larger than the time constant of the STM’s tip-positioning constant-current feedback
circuit results in a modulation of the tunneling current. At a small amplitude mod-
ulation, this signal corresponds to the density of tunneling states at the bias voltage
[72]. This signal forms the basis of DCTS. The DCTS image of a surface obtained
in this way can be understood as the variation of the density of tunneling states on
the surface.
Instrumentation. An STM is equipped with suitable additional electronics to gen-
erate the desired bias modulation and to detect the modulation of the tunneling cur-
rent [72]. Differential Conductance Tunneling Spectroscopy data that was obtained
for a platinum film electrode have been interpreted in terms of step density and
surface disorder [72].

7.2.3 Atomic Force Microscopy (AFM)

Fundamentals. Beyond the tunneling current flowing between the tip and the sur-
face, further interactions are effective between the tip and the surface. Spence et al.
[73] have observed strain fringes on a graphite surface interacting with an STM tip
that extends 200 nm from the tunnel junction. This observation led to the develop-
ment of the atomic force microscopy (AFM)4 by Binnig et al. [74]. Depending on
the design (including surface coating) of the tip van der Waals forces, electrosta-
tic or magnetic forces can be monitored [75]. Generally, forces between 10−9 and
10−6 N are measured; there have been reports describing measurements down to
3 10−13 N [76]. They can be attractive or repulsive. When considering interatomic
interactions, the force reaches a minimum at the mechanical point contact and, at
smaller distances, the repulsive interactions measured in the contact mode dom-
inate; at greater distances, the attractive interactions observed in the non-contact
mode dominate. In the contact mode, the tip actually touches the surface. Obviously
the electronic conductivity of the surface and the tip play no role in the operation,
thus non-conducting surfaces that are not suitable for the use of STM can be studied.
The presence of a liquid between tip and surface provides no fundamental problem;
4 The terms SFM (scanning force microscopy) and AFM (atomic force microscopy) are
used synonymously; the former term is used less frequently. In the initial stages of develop-
ment, the latter term was exclusively used for setups providing atomic (or better) resolution.
 7.2 Scanning Probe Methods 261

of course, the mechanical properties of the whole setup are changed. Nevertheless
electrochemical measurements in situ are possible.
Chemical sensitivity can be conferred to AFM by coating the tip with covalently
linked monolayers which affect the tip–surface interaction; the method is called
chemical force microscopy [77]. Additional modulation of the piezo actuator oper-
ating in z-direction and evaluation of the force signal can be used to measure the
adhesion force between a surface and a chemically modified AFM tip [78]. Metal
coated AFM tips can be used in a scanning electrochemical microscopy (SECM, see
p. 264) mode [79] in studies of crystal dissolution or growth where surface processes
are associated with considerable fluxes of species.
Instrumentation. A cantilever with a sharp tip interacting with the surface under
investigation is used. The actual bending of the cantilever is measured with a laser
beam deflected from a mirror-like surface spot on the back of the cantilever towards
a position-sensitive photodetector. The measured signal is used to control the piezo
actuators. A constant force mode in which the cantilever–surface distance is kept
at a preset interaction force and a constant height mode of scanning operation are
possible. The principle of operation is schematically outlined in Fig. 7.9.
The mechanical properties of the tip-cantilever assembly are of central impor-
tance. Caused by the forces that are effective between surface and tip, the cantilever
is deformed. This deformation controls the overall performance of the microscope.
The spring constant k and the resonance frequency ω0 of the cantilever are particu-
larly important. In order to be insensitive to mechanical noise from the environment,
a high resonance frequency is desirable. A small spring constant in turn is required
to detect weak forces. To obtain high resonance frequencies, stiff materials (silicon,
silicon oxide or silicon nitride) are used for the cantilever. A small spring constant
can be maintained by limiting the mass of the device to a minimum by microfabri-
cation techniques. A typical cantilever has a length of 0.1 mm, a thickness of 1 μm,
a spring constant around 0.1 to 1 nm−1 and a resonance frequency around 10 to 100
kHz. The development of single-wall carbon nanotubes (SWNT) as tips for AFM to
also be used in electrochemical investigations has been described [80]. An alterna-
tive mode of operation without optical detection as described above employs a tip
attached to a vibrating fork-like assembly. This approach has resulted in very high
resolution; unfortunately it cannot be employed in an electrochemical environment
because of the dampening effect of the electrolyte solution. The integration of an
ultramicroelectrode into a tip for atomic force microscopy has been accomplished

Fig. 7.9. Scheme of an atomic force microscope

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262 7 Surface Analytical Methods

[81]. The electrochemically active area is located as a ring around the tip. It has been
used in SECM measurements; an AFM picture was simultaneously obtained.
In actual operation in the contact mode, the tip touches the surface like the stylus
of a record player. In the non-contact mode, the cantilever is oscillated at a frequency
close to the resonance frequency with a large amplitude. In this mode, vertical long-
range forces are probed, whereas lateral forces (friction-like forces in the plane of
the sample surface) are almost non-effective. These forces have been employed in
lateral force microscopy (LFM).
Investigations published so far include metal dissolution studies (relevant to cor-
rosion and corrosion inhibition) [82], underpotential metal deposition (upd) [83] and
overpotential deposition (opd) [84]. Structural features of deposits, the influence of
electrolyte composition, electrode potential, etc. were reported. In a study employ-
ing both AFM and LFM, specific adsorption and phase changes at the polycrys-
talline silver/halide-containing electrolyte solution were investigated [85]. Whereas
AFM provided topological imaging, LFM enabled detailed studies of adsorption
and chemical reactions in adsorbate layers. Specifically, adsorbed halide anions with
their hydration shells stripped provided higher friction values probed with LFM and
hydrated anions in the outer Helmholtz layer that were not adsorbed to specific sites
and maintained intact hydration shells caused lower friction values. Using a col-
loidal probe (a silica particle attached to the cantilever of an AFM), the diffuse layer
properties of a thiol-modified gold electrode has been investigated [86].
With chemically modified AFM tips, adhesion forces between the tip and a two-
component self-assembled monolayer on a gold electrode have been studied [87].
Utilizing the different strengths of interaction between the modified tip (methyl and
carboxyl terminating group functionalized), SAM areas with methyl and carboxyl
end groups could be distinguished.
Several reviews dealing with the fundamentals, experimental aspects and appli-
cations have been published [88–90]. Operated in the constant force mode, the AFM
can monitor changes in the thickness of a film (e.g. a metal hydroxide, which shows
swelling/shrinking during redox processes) [91]. Dimensional changes of highly
oriented pyrolytic graphite (HOPG) during lithium ion intercalation/deintercalation
have been studied with an AFM [92]. During the first intercalation cycle, an irre-
versible increase of layer spacing was found. In the following cycles, a reversible
change of 17% of the layer spacing was measured. Roughness effects caused by
the formation of a solid electrolyte interface were taken into account by statistical
analysis of the data. Electrochemical deposition and dissolution of molecular crys-
tals of organic conductors have been studied [93]. Morphological changes occurring
during electropolishing of stainless steel in an ionic liquid have been identified with
AFM [94].
Atomic force microscopy has been combined with nano-indentation and nano-
scratching studies [95]. The hardness (and, to a similar extent, the friction coeffi-
cient) of passivated titanium was three to four times higher under in situ conditions,
this was assigned to a much faster repassivation process in the presence of the passi-
vating electrolyte solution. Nanotribology, particularly surface friction forces mea-
 7.2 Scanning Probe Methods 263

surements of electrode surfaces modified with submonolayer foreign metal (upd de-
posits with AFM have been reported [96]). An AFM operated in the contact mode
was used to scratch a surface of the aluminum alloy AA2024-T3 in contact with
electrolyte solutions of different compositions (with/without chloride, dichromate)
and under varying experimental conditions (stagnant/flowing solution) to gain in-
sights into corrosion, protection and breakdown [97].

7.2.4 Scanning Kelvin Probe Force Microscopy (SKPFM)

Fundamentals. An AFM can also be used to probe the local Volta potential. Us-
ing a metal-coated silicon tip (e.g. Co–Cr40), first the topography of the surface
under investigation is mapped using the tapping mode. In a second scan, the tip is
moved along and kept at a constant distance of 50 nm above every point on the
surface. An AC voltage is applied to the tip, generating an oscillating dipole. In the
presence of an external field this will in turn create a mechanical oscillation of the
cantilever, which can be detected using the standard features of the AFM. At every
point of the scan a DC ramp is added to the AC modulation. At the DC voltage,
where the oscillation of the cantilever vanishes, the potential on the tip and on the
surface are the same. Thus a map of the surface Volta potentials with respect to the
tip is created. Because the potential of the tip might be unstable and could vary from
experiment to experiment, calibration is necessary. A particularly reproducible ref-
erence is a nickel surface exposed to deionized water before the measurement [98].
In the absence of further calibration this is the point of reference. The method cannot
be applied in the presence of an electrolyte solution because of the large voltages
applied to the tip, which would cause Faradaic reactions. Data from measurements
of Volta potentials at corroding surfaces could be related to corrosion potentials of
the same surface in contact with a solution because the linear correlation has been
established before [98]. Nevertheless studies at air or in the presence of ultrathin
electrolyte films (i.e. under conditions frequently encountered in atmospheric cor-
rosion) are possible. The general advantages of SKPFM in comparison with SKP, in
particular the greatly enhanced spatial resolution, have been discussed in detail [99].
A critical review of the applications of SKPFM that focuses on corrosion science
with particular attention to possible artifacts and a comparison with SKP has been
provided [100].
Instrumentation. The experimental procedure for an AFM equipped with a suit-
ably coated tip has been outlined above. In a study of an aluminum alloy AA2024-
T3, intermetallic particles and the matrix phase could be separated clearly [98]. The
different surface films on these phases could be associated with their corrosion be-
havior. Inclusions and their corrosive behavior have been studied with a combination
of SKPFM and AFM [101]. The effect of chloride-containing solution on corrosion
at the matrix and the intermetallic particles was studied with SKPFM, in addition,
light scratching with the AFM in the contact mode was applied to study the effect
of the mechanical destabilization [102]. The intermetallic particles dissolved imme-
diately after the film on their surface had been destabilized by mechanical abrasion.

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264 7 Surface Analytical Methods

A general study of the influence of experimental parameters applied during emer-

sion of the electrode, distance between tip and surface, influence of oxide coverages,
etc. on the observed Volta potentials has been reported [103]; relationships to previ-
ous studies at emersed electrodes (see [104–107]) and the topic of the adherence of
the electrochemical double layer on an emersed electrode have been discussed. The
influence of aluminum in magnesium alloys on atmospheric corrosion (in the ab-
sence/presence of CO2 ) was studied with SKPFM [108] and a corrosion mechanism
was suggested. Applications and limitations of SKPFM in studies of the surface of
aluminum alloys have been reviewed thoroughly [109]. The surface of cast AlSi(Cu)
alloys has been characterized with SKPFM [110]. Numerous particles of different
composition were detected and they showed a positive Volta potential difference
relative to the matrix with the actual value depending on the matrix composition.
Filiform corrosion on epoxy-coated 1045 carbon steel was investigated with
SKPFM [111]. Under coatings of 150 and 300 nm thickness at 93% relative humid-
ity, samples were studied under air. Separation of active anode and cathode locations
in the head of the filament could be identified. Microscopic and even submicroscopic
aspects of electrochemical delamination have been studied with SKPFM [99].

7.2.5 Scanning Electrochemical Microscopy (SECM)

Fundamentals. A microelectrode5 with a small diameter (e.g. 10–20 μm, such an

electrode is sometimes also called ultramicroelectrode (UME) [112–116]) is ex-
posed to an electrolyte solution containing an electrochemically active substance.
The electrode potential is adjusted to a value sufficiently negative to drive the elec-
trochemical reaction O + ne− → R under diffusion control. Diffusion of reactive
species to the electrode surface is hemispherical instead of planar, as in the case of
large electrodes. The current I flowing across the solid/electrolyte solution inter-
face of the microelectrode tip quickly reaches a steady state value IT∝ = 4nF Dcr
with n as the number of electrons transferred in the electrochemical reaction step,
F the Faraday constant, D the diffusion coefficient of the reacting species, c its con-
centration and r the tip radius. The experimental setup is pictured schematically in
Fig. 7.10.

Fig. 7.10. Schematic setup for voltammetry with an ultramicroelectrode (UME); CE: counter
electrode; RE: reference electrode
5 A microelectrode is a conductive material with an active surface area of a few μm2 that is
embedded in an insulating material. Microelectrodes are commonly fabricated by coating a
metal or carbon fiber with a polymer or glass sheath.
 7.2 Scanning Probe Methods 265

Fig. 7.11. Principle of SECM with the UME far away from a surface (top), approaching an
insulating surface (middle) and approaching a conductive surface kept at a suitable electrode
potential (bottom)

When the UME is moved close to an insulating surface, the current drops to
a lower value I T because the surface and the insulating sheath of the UME block
transport of active species O. This effect is sometimes called negative feedback and
is further enhanced by the fact that no reoxidation of R can occur at insulating
parts of the surface. Approaching a conductive surface kept at an electrode potential
where reoxidation of R is possible causes an opposite effect (positive feedback) and
I T is enhanced with a closer distance. Both possibilities are schematically depicted
in Fig. 7.11. A similar effect may be observed with an unbiased (not kept at any spe-
cific potential, but instead at open circuit) surface. Because the large surface area is
in contact with the solution containing a supply of O, the surface electrode potential
is essentially controlled by the Nernst equation. At the potential established by the
concentration of O, the reduced species R created at the UME will be reoxidized,
whereas further O is reduced elsewhere on the surface.
In an operational mode where species R are generated at the surface and col-
lected and reduced at the UME, an SG/TC experiment is done (substrate genera-
tion/tip collection). This mode is particularly interesting when localized phenomena
or properties of an inhomogeneous surface are studied. The change of the current I
normalized with respect to the current at infinite distance as a function of the dis-
tance d of the microelectrode from the surface normalized with respect to the radius
of the microelectrode is depicted in Fig. 7.12 for a conductive and an insulating
substrate (for a brief overview of the associated mathematics, see also [117]). An
introductory overview has been published [118]. This rather general description of
the principles of an SECM will become more complicated when further constraints
(e.g. electron transfer at the tip or surface is charge transfer controlled instead of
diffusion controlled) are considered [119–121]. The described mode of operation
is based on current measurement and is called amperometric mode. Localized cat-
alytic acitivity of the particles of a catalyst deposited on an inert current collector
support can be monitored with SECM in the redox competition mode (RC-SECM)

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266 7 Surface Analytical Methods

Fig. 7.12. Current I measured at a microelectrode normalized with respect to the current at
infinite distance between tip and surface as a function of distance d between microelectrode
and surface (normalized with respect to the radius of the microelectrode) for a conductive
substrate (top) and an insulating substrate (bottom)

[122]. With an SECM positioned above a surface with deposited nanoparticles of

dioxygen reduction electrocatalysts in a solution saturated with dioxygen, signifi-
cant decreases of tip current are observed. Variations in the nature of catalyst spots,
including inhomogeneities, could be localised. Further modes include the potentio-
metric mode with an ion selective UME that is used to probe the local composition
of the solution. This method is basically equivalent to the scanning ion-sensitive
electrode technique SIET (see p. 270, particularly pH microscopy).
An AC voltage can be applied to the UME and a counter electrode (AC-SECM).
The AC current response can be evaluated and it can provide information about
local surface conductivity of the surface under investigation [123–125]. This setup
has been applied to interrogate living cells [126]. Enhanced spatial resolution may
be obtained by using a shear force-based distance control to operate the UME at
submicrometer distance.
Instrumentation. A suitable microelectrode [119] or nanoelectrode [127] is at-
tached to a piezo-driven micropositioner. It is connected as the working electrode
with a potentiostat. A counter electrode and a reference electrode are wired in a
three-electrode arrangement. Investigations with conducting substrates require the
use of a bipotentiostat. The surface to be investigated is immersed into the electro-
chemical cell together with the other electrodes. The position of the microelectrode
and the flowing current are controlled and monitored by a computer equipped with
 7.2 Scanning Probe Methods 267

Fig. 7.13. SECM picture of a polycarbonate membrane

necessary interface cards and software [128]. As an example, the SECM image of a
filtration membrane prepared from polycarbonate with an average hole size of 10 μm
in a solution containing [Fe(CN)6 ]4− -ions scanned with a 2 μm UME is shown in
Fig. 7.13.
Lateral charge propagation in a monolayer of polyaniline has been monitored
with an SECM [129]; kinetic data could be extracted by modeling. The charge
transfer between a dissolved redox mediator and polyalkylterthiophene films has
been studied [130]. In the oxidized (p-doped) state of the film, redox reactions pro-
ceeded at the film/solution interface, not inside the film. In the reduced state the film
behaved like a completely passivating film and penetration of redox mediator ions
into the film was obviously completely inhibited.
The combination of SECM and a quartz microbalance has been reported [119].
The amount of information obtained at any given point of the electrode surface
can be greatly increased by recording a cyclic voltammogram at every spot [131,
132]. At a high scan rate (about 100 V s−1 ), the actual SECM picture acquisition
rate is not impeded significantly. A microelectrode array that is useful for parallel
imaging has been described [133]. A broad variety of systems has been investigated
with SECM; for examples and reviews, see [119–139]. These studies cover electron
transfer processes [140], mapping of local reactivities [141], local conductivities
of intrinsically conducting polymer film layers [142] and efficiency of corrosion in-
hibitors [117], including formation of inhibitive benzotriazole films on copper [143]
and coupled measurements of electrolyte solution resistance [144]. The SECM has
also been used for surface modification and microstructuring of carbon surfaces
[145]. Improvements in the preparation and application of small microelectrodes,
i.e. nanoelectrodes or nanodes, have enabled nanostructuring of surfaces with an
SECM [146]. A combination of AFM and SECM as described [147] has been used
to study the dissolution of calcite in an aqueous solution; the dissolution of the
(100) cleavage plane of potassium bromide has also been investigated [148]. The
platinum-coated tip of the AFM serves both as topographical sensor and as an elec-
trode for a SECM. Alternatively, a partially paint-coated platinum tip was used for
this purpose [149]. The integration of an ultramicroelectrode into a tip for atomic

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Fig. 7.14. Current (right) and topographic (AFM, left) pictures of a track-etched polycarbon-
ate membrane in contact with an aqueous solution of [IrCl6 ]3− , AFM tip of platinum coated
with Si3 N4 (pictures kindly provided by J.V. Macpherson, University of Warwick, UK)

Fig. 7.15. Scheme of gold deposition with an SECM (picture kindly provided by D. Mandler,
Hebrew University, Jerusalem, Israel)

force microscopy has been accomplished in a third way [81]: The electrochemically
active area is located as a ring around the tip. This method has been used in SECM
measurements; simultaneously, an AFM picture was obtained (for an example, see
Fig. 7.14). An introductory overview of the AFM/SECM combination has been pro-
vided [150].
A combination of an STM with an SECM (see also below for this method)
has been described [70]; for details, see above. The SECM can also be used for
surface structuring. In order to deposit gold on a surface that is spatially resolved,
the experimental setup schematically depicted in Fig. 7.15 was used. The current
flowing between the ultramicroelectrode and the surface is displayed in Fig. 7.16.
Its distance dependence resembles exactly the behavior observed with a conductive
surface, as discussed above. The deposited gold microdots are shown in Fig. 7.17.
The generation of palladium clusters on a surface of Au(111) with an SECM
has been reported [152]. More stable and larger clusters were found at closer tip–
surface distances. Associated computer simulations suggest that larger clusters are
composed of a gold–palladium mixture. The dissolution of clusters proceeds from
 7.2 Scanning Probe Methods 269

Fig. 7.16. Normalized current vs. normalized distance plot for the SECM setup depicted in
Fig. 7.15 (figure kindly provided by D. Mandler, Hebrew University, Jerusalem, Israel)

Fig. 7.17. Gold dots deposited from a solution of 0.01 M HCl and 0.01 M HBr with an SECM
(Picture kindly provided by D. Mandler, Hebrew University, Jerusalem, Israel) [151]

the edges, not layer-by-layer. The formation of polypyrrole towers of about 150 μm
diameter and 120 μm height using an SECM has been described [153]; without an
SECM, localized electropolymerization at a considerably lower spatial resolution
can be obtained with short voltage pulses [154]. An overview of the use of SECM
for the modification of surfaces has been provided [155].
In a study of the corrosion of stainless steel with MnS inclusions, dissolution
products of the sulfide could be localized and identified using the redox couple io-
dide/triiodide as mediator [156]. Pitting corrosion starting in the vicinity of sulfide
inclusions on Ni200 was also studied with SECM [157]. Other applications of the
SECM include the characterization of thin films and membranes, liquid/liquid in-
terfaces, the fabrication of nanostructured devices [158], the characterization of mi-
croelectrode arrays [159] and the imaging of biological systems (like photosystem
I) on surfaces patterned with discrete regions of methyl- and hydroxyl-terminated
self-assembled monolayers [160]. The use of an SECM in a study of superoxide
generation during the electroreduction of dioxygen in aprotic media has been re-
ported [161].
The use of an SECM to probe the surface conductivity of ultrathin films has
been proposed [162]. Lateral conductivity of poly(3-hexylthiophene) films contain-
ing gold nanoparticles in addition was measured with an SECM in the feedback
mode [163].
A microelectrode scanned in the vicinity of a macroelectrode surface has been
employed in an investigation of concentration profiles and the associated electro-
chemical processes of organic species being created and/or consumed at the inter-

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270 7 Surface Analytical Methods

face has been described [164]. In an early study, the concentration profiles within
the diffusion layer adjacent to an electrode were mapped with a spatial resolution of
2 μm [165].

7.2.6 pH-Microscopy6

Fundamentals. Based on the functional principles of the scanning electrochemi-

cal microscope, other scanning probe methods used to determine localized surface
properties of the electrode under investigation or of the solution phase adjacent to
this surface have been developed utilizing suitable microelectrodes. A pH-sensitive
microelectrode based on a glass capillary filled with a pH-constant buffer solution
and containing an internal reference electrode that has a tip filled with a proton-
selective ionophor cocktail is scanned across the surface. The potential of the in-
ternal reference electrode with respect to an external reference electrode is directly
correlated to the local pH value. A schematic cross section of this microelectrode is
shown in Fig. 7.18.
Instrumentation. A setup employing the described microelectrode positioned at a
distance of about 1 μm [166] above the investigated steel surface has been used to
study pH-gradients developing in front of a corroding surface as a function of ni-
trite concentration [167]. The microelectrode showed Nernst factors ranging from
−58 mV at room temperature to −69 mV at 60◦ C. pH shifts of 0.8 pH units at a con-
centration c = 11.6 mM of NaNO3 were found. Localized acidification in a neutral
aqueous solution of 0.5 M Na2 SO4 over reinforced 6092 aluminum composites in-
dicating anodic regions were identified with SIET [168]. The corrosion of zinc and
iron at cut edges of galvanized steel have been studied with a pH-microelectrode

Fig. 7.18. Schematic cross section of a pH-sensitive microelectrode (left); tip details (right)
6 This device is also called a scanning ion-sensitive electrode technique (SIET).
 7.2 Scanning Probe Methods 271

[169]. Large pH variations between 7 < pH < 11 were observed and assigned to
hydroxyl ions formed in the cathodic reaction occurring on the steel surface. Lo-
calization of corrosion product deposition and pH-change could be identified in the
presence of a solution of NaCl [170]; in the case of a solution of (NH4 )2 SO4 , no
such direct correlation was seen.
A somewhat similar approach with an open “pipette”-like tip has been suggested
for imaging and controlled release of species on a nanometer scale [171].

7.2.7 Scanning Ion-Conductance Microscopy

Fundamentals. A micropipette having an aperture of about 0.25 μm diameter is

placed above the sample under investigation, which is immersed in an electrolyte
solution. On the bottom of the cell vessel, two electrodes (one besides the sam-
ple, one underneath the sample) are mounted (see Fig. 7.19). The electrical current
flowing between the electrode inside the micropipette and the two electrodes on
the cell bottom is measured. It is used as a feedback signal for the standard scan-
ning probe microscope electronics operating the piezoactuators that are moving the
micropipette across the sample surface. The vertical movement of the z-actuator
follows the topography of the sample, thus providing its image [172, 173].
Instrumentation. A setup has been reviewed [172]. A modified setup using a vi-
brating micropipette and an AC electronic circuitry that allows better (more precise)
position control of the tip and its aperture has been described [174]. Applications
reported so far deal with living cells [175, 176] and the internal and external pore
structure of membranes [177].

7.2.8 Scanning Reference Electrode Technique

Fundamentals. Localized very small variations of the electrode potential that are
caused by current flow across the metal/solution interface over the surface of an
electrochemically active material (e.g. a corroding metal) can be measured with a
scanning reference electrode [178]. The local variations are picked up by a pair
of very fine tips about 10 μm above the surface. The response of a twin platinum
electrode has been modelled and results could be matched satisfactorily with real

Fig. 7.19. Schematic of a scanning ion conductance microscope

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272 7 Surface Analytical Methods

scans across localized events [179]. Instead of real reference electrodes, pseudo-
reference electrodes like platinum or iridium tips or wires may be used. The tips
pick up potential gradients normal to the current flux lines, which are caused by
the current flowing across the interface and subsequently amplified and displayed.
By scanning the tips across the surface, a map of local potential variations emerges.
In more recent versions, a single tip is used. It vibrates at a frequency of 80 Hz
using a piezocrystal. The potential change is picked up and amplified using a lock-
in amplifier. A spatial resolution of 0.5 μm is possible [180]. At high electrolyte
concentrations, the effect of ion flux caused by localized corrosion is swamped out
and the sensitivity of the method is diminished.
Instrumentation. A commercial setup has been reported [181]. Operation with a
fixed reference electrode and a rotating sample or a flat, fixed sample and a moving
electrode has been described and the particular advantages and limitations have been
reviewed [182]. In most applications the rotating electrode systems appeared to be
superior. Reported studies include investigations of corrosion protection coatings
[180, 183], weld metal corrosion [184], pit initiation [185] (including hydrogen-
promoted pitting [186]) and localized corrosion [187–189]. The method has been
identified as being highly sensitive, compared to other methods in short time results
can be obtained [190]. For inherent limitations and a comparison with SVET see
below. Measurements of electrode potentials at higher resolution with a scanning
probe setup as used for STM and AFM have been reported [191].

7.2.9 Scanning Vibrating Electrode Technique7 (SVET)

Fundamentals. A small electrode (typically a microelectrode of about 20 μm diam-

eter) is scanned across the surface under investigation in a distance of about 100 μm.
Any current flow across the sample/solution interface causes a potential drop in the
solution that is probed by the microelectrode. Using previously established calibra-
tion data (with known current densities from a point source electrode), the mea-
sured voltage vectors are converted into current vectors [192]. Magnitude and di-
rection of currents above the interface can thus be mapped. Cathodic and anodic
processes can be localized; overlaying the obtained maps onto optical micrographs
allows detection of visible surface features related to localized corrosion phenomena
[193, 194]. The technique is similar to the scanning reference electrode technique
(SRET) (see above). In comparison to the initially used two microreference elec-
trodes with SRET, which were later replaced by a single vibrating microelectrode,
the actual way of vibrating the scanning electrode is different in SVET [195]. This
results in a limitation to measurement of DC currents only, which in turn have re-
stricted the use of SRET to bare metals or coated metals with defects [196, 197].
Instrumentation. Various possibilities for manufacturing the required microelec-
trodes and their piezoelectric drivers as well as the associated electronics have been
described [194, 198]. Reported studies deal mainly with corrosion processes. With
7 This method is also called current density probe (CDP).
 7.2 Scanning Probe Methods 273

chromate-containing epoxy coatings on both steel and aluminium surfaces, a signif-

icant delay in the onset of anodic corrosion currents at a defect site was observed,
whereas chromate-free epoxy coatings did not show this delay [194]. With the steel
sample, the cathodic current was observed at the defect site only with the chromate-
free coating; on a chromate-containing epoxy, a cathodic current was also observed
on this coating. With coatings of an intrinsically conducting polymer (ICP), e.g.
poly(3-octyl pyrrole), a further onset of any detectable current was observed both
with coated steel and aluminum alloy [199]. Current density maps with the coated
steel sample showed reduction currents on the polymer surface and oxidation was
confined to the defect site. With the coated aluminum alloy sample, no significant
oxidation was observed at the defect. Instead, reduction was observed both on the
polymer coating and the defect site and concomitant oxidation was observed locally
under the coating. The localization of this process seemed to be associated with
specific interactions between the polymer and locally enriched copper (an alloy con-
stituent). With pure aluminum, the oxidation current was more distributed over the
coated surface, but still as far away from the defect as possible. The metal surface
showed no pitting after removal of the coating. The influence of the application of
the ICP coating (direct deposition by anodic electropolymerization onto the sample
or casting from a polymer solution) was apparent in a study of polypyrrole-coated
aluminum and aluminum alloys [200]. The former method yielded better corrosion
protection because of stronger electronic (conductive) coupling. The action of dis-
solved cerium ions as corrosion inhibitors on steel has been investigated [201]. Con-
trary to previously published assumptions, these ions act as anodic inhibitors. Cor-
rosion studies at metal matrix composites (MMC, reinforced 6092 aluminium com-
posites) with SVET revealed corrosion initiation at localized anodic regions [168].
In a study of the corrosion at cut edges of galvanized steel zinc oxide, zinc carbonate
and zinc hydroxide were suggested as reaction products of the anodic current ob-
served with SVET over the zinc surface [169]. The cathodic current observed over
the steel surface showed a behavior typical of a diffusion limited oxygen reduction
current; consequently, localized pH-shifts were observed with a pH-microelectrode.
In the presence of SrCrO4 in the electrolyte solution, an increase of the Tafel slope
of the anodic current was found, which is indicative of the passivating effect of this
inhibitor. In a solution of NaCl the spatial patterns of deposition of corrosion prod-
ucts and anodic/cathodic currents could be matched with the SVET [170]. No such
localized behavior was found with an aqueous solution of (NH4 )2 SO4 .
Localized impedance measurements with an SVE have been described [202]
and limitations and artifacts observed when using an SVE under specific corrosion
conditions were discussed in detail [203].

7.2.10 Scanning Kelvin Probe (SKP)

Fundamentals. The surface (or contact) potential of a solid or a liquid film cov-
ered solid can be measured with a Kelvin probe [204, 205]. Essentially, the Volta
potential difference ΔΨ between the two employed surfaces, as described below,
is measured. In common abbreviation, this is also called measurement of a Volta

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274 7 Surface Analytical Methods

Fig. 7.20. Scheme of Kelvin probe measurement

potential Ψ (e.g. in [206]). As depicted in Fig. 7.20, a probe tip is brought close to
the surface under investigation.
The tip and the adjacent surface form a condenser. When the distance between
the tip and the surface is changed by vibrating the probe, an AC current flows; its
magnitude depends on the existing potential difference. By adjusting the external
bias voltage U comp , this potential difference can be compensated. As a consequence
the AC current vanishes. In most cases, relative changes of the local surface potential
are of interest. In order to remove any unwanted influence of the probe surface po-
tential, a material with constant surface potential is used (typically an etched Ni/Cr
wire tip or a cylindrical probe of this material), thus the measured local Volta poten-
tial depends only on the surface potential of the sample. A calibration of the probe
is accomplished by measuring the corrosion potential with a conventional reference
electrode that touches the electrolyte film-covered surface under investigation with a
Luggin capillary [207]. Simultaneous measurements with an SKP yield the desired
Volta potential difference, which differs from the measured corrosion potential only
by a constant difference that is typical of the experimental setup. The Volta potential
is thus closely and directly related to the local corrosion potential [207–210]. Thus
spatially resolved measurements are useful in studies of localized processes like
corrosion on heterogeneous surfaces. The required resolution can be obtained with
piezodrives. The required compensation voltages are high enough to cause Faradaic
processes in aqueous solution in the gap between tip and surface; obviously this
method will work only in the absence of bulk solution. It works well with thin elec-
trolyte solution films coating the corroding surface under investigation as frequently
encountered in atmospheric corrosion [211, 212]. In its described setup, the distance
between the tip (needle) and the surface is kept constant on a macroscopic level. In
the case of very rough, bent or otherwise deformed surfaces, this might prove in-
sufficient. A mode of operation with a height-regulated probe has been proposed
(HR-SKP) [213].
Instrumentation. Reported examples are mostly related to corrosion studies; the
particular problems in relating Volta potential differences as measured with an SKP
and local corrosion potentials have been treated in detail [209]. The effect of barrier
layers and metal surface pretreatment has been investigated [214, 215]. In a study of
the effect of a corrosion protection primer that contains the intrinsically conductive
 7.2 Scanning Probe Methods 275

Fig. 7.21. Potential profile measured with a SKP at a steel surface coated alternatively with
standard primer and a new primer (see text for details) and top coat (based on data in [206])

polyaniline (CORRPASSIV™) [206], the positive shift of the potential of the steel
surface coated with this primer in comparison to the surface coated with a standard
primer is evident and the positive effect of the primer on the extent of the (much
narrower) delamination zone is obvious (see Fig. 7.21). The delamination zone is
larger by a factor of two with the standard primer.
In a study of zinc-coated steel covered with a polymer topcoat, the mechanism of
topcoat delamination was elucidated with high spatial resolution [216]. Depending
on the details of the defect and the composition of the corroding atmosphere, the
rate and type of delamination could be described. A similar study with a coated
iron surface has been reported [217]. A comparison of results obtained with SKP,
electrochemical impedance measurements and cyclic voltammetry with respect to
validity as a corrosion prediction tool has been reported [218].
Differences in detected Volta potentials between pristine and corroded Al–Mg
alloy surfaces could be related to the factors influencing thickness and conductivity
of the corrosion product layers [219]. Corrosion layers developed in the presence
of ion-containing solutions yielded lower Volta potentials and showed higher con-
ductivity. Cathodic delamination of polyaniline-based organic coatings on iron have
been studied with SKP [220]. The role of dioxygen reduction and of the polyaniline
fraction in the coating were included in a proposed corrosion mechanism.
The surface topography (i.e. the distance between the actual surface and the
needle when the latter is kept at a constant distance from the sample itself) can
be mapped simultaneously with the local potentials with a Kelvin probe equipped
with an additional modulation setup [213]. A typical example of a zinc-coated iron
surface with a thin polymer top coat shows the change of height (about 8 μm based
on the deposition data) at the edge of the zinc coating (see Fig. 7.22). The expected
change of the Volta potential upon changing from zinc to iron is also observed. The
roughness of the metal surface is visible in the plot.

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276 7 Surface Analytical Methods

Fig. 7.22. Height and potential profile measured with a HR-SKP at an iron surface coated
partially with zinc (based on data in [213])

Fig. 7.23. Height and potential profile measured with an HR-SKP at an iron surface coated
with layers of latex (based on data in [213])

An iron surface coated with layers of latex of varying thickness yields a consid-
erably different topographic picture (Fig. 7.23). The change of height is registered
when an edge in the coating is passed. The changes of height (5 μm for every step)
is well defined; the potential remains unchanged because the polymer coating has
no influence.
 7.2 Scanning Probe Methods 277

Fig. 7.24. Height and potential profile measured with a HR-SKP at an iron surface with a
drop of an aqueous solution of 0.5 M NaCl (based on data in [213])

In a setup similar to the Evans drop experiment, the height and the potential of
an iron surface with a drop of an aqueous solution of 0.5 M NaCl were scanned;
results are displayed in Fig. 7.24.
The lowest potential is measured in the center, where corrosion (i.e. anodic dis-
solution of iron) attacks most aggressively. At the edges, the potential increases
somewhat; in this zone oxygen reduction proceeds. The potential changes around
the drop imply the presence of an ultrathin electrolyte film because the potential
reaches values of the bare iron surface only at a considerable distance from the
edges of the macroscopically observed drop [213]. Filiform corrosion of automo-
tive aluminium alloy AA6016 has been studied with SKP [221].
In earlier studies using a fixed Kelvin probe, corrosion kinetics and mechanisms
were studied without the spatial resolution possible with the SKP [222, 223]. The
use of a Kelvin probe as a reference electrode in corrosion studies with very thin
electrolyte films (2 μm) has been described [224]. The use of Kelvin probes to con-
trol and to monitor the potential has been reviewed [225].

7.2.11 Scanning Tunneling Spectroscopy8 and Related Methods

Fundamentals. The tunneling current depends at fixed voltage across the gap be-
tween tip and probed surface on the distance and the local probability of electron
transfer. This in turn is a function of local electron density, work function or re-
lated localized electronic properties (for an overview of tunneling spectroscopies,
8 Although this method is a spectroscopy, the obtained vibrational spectra and other data
contain localized information pertaining to the probed point of the surface. Thus it can also
be considered surface analytical and spatially resolved.

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278 7 Surface Analytical Methods

see [226]). Depending on the polarity of the applied voltage (also called bias) the
tunneling electrons probe different surface atomic states (see a study of the sur-
face of n-doped TiO2 [227]). With positive sample bias, the net tunneling current
is caused by electrons tunneling from occupied states of the negatively biased tip
into empty states of the surface (this may include LUMOs of molecules, too). At
negative sample bias, electrons tunnel from occupied (HOMO) states of the sample
into empty tip states. Because the states with the highest energy have the longest
decay lengths into vacuum, in both cases electrons close to the Fermi level of the re-
spective emitter are most likely to contribute to the tunneling current. Consequently
STM pictures obtained at the two possible bias polarities can be obtained and must
be interpreted accordingly. With continuous modulation of voltage (in addition to
switching polarity), densities of state (DOS) can be probed quantitatively [volt-
age tunneling spectroscopy (VTS)]. Any desired chemical contrasts beyond DOS
require far greater energetic resolutions, as are generally required in inelastic tun-
neling spectroscopy (IETS, which is also known as ITS) [226]. A few meV are
generally assumed to be necessary (see also HREELS [228]). This would require
operation at liquid helium temperature or lower. Examples of feasibility seem to be
limited so far. Obviously, since measurements at modulated bias voltage may result
only in data of DOS or possibly also other localized information, the term “scanning
tunneling spectroscopy” is used in ambiguous ways, including both possibilities. An
STM can definitely be operated in a way that yields data of the local surface density
of states (so-called I –V spectroscopy with modulation of the bias between tip and
sample) and the effective barrier height (I –S characteristics) can be obtained [11,
229]. An overview of STM and related spectroscopies as applied to electrochemical
systems has been provided [230].
Instrumentation. For electrochemical measurements of DOS and effective barrier
height, a standard setup as used for STM is employed. In a study of the Au(111)
surface in contact with a solution containing copper ions and chloride ions with
distance tunneling spectroscopy (i.e. measurements of I –S characteristics, abbre-
viated DTS) the double layer outside the inner Helmholtz layer was probed [59].
Examples of double layer studies employing DTS have been briefly reviewed [231].
The electrical conductance of n-alkanethiol and α,ω-alkanedithiols has been studied
with DTS [232]. Molecules of the latter type assume two distinctly different orien-
tations in the gap between the STM tip and the surface (break junction), resulting
in significantly different electrical conductivities. On the contrary, n-alkanethiols
show only one conductivity value for a given alcohol, which is almost identical
with the lower value of the respective α,ω-alkanedithiol. In a study of decanethi-
olate adsorbed on a Au(111) electrode, an electronic model of the thiol layer and
possible conduction mechanism are proposed [233]. Investigations of distance and
voltage dependencies of tunneling currents have suggested indirect tunneling via in-
termediate states [234]. These states are related to dipole resonances of well-ordered
water dipoles located in the electrochemical double layer at the tip-solution and the
solution–substrate interface. The chemical nature and the crystallographic orienta-
tion of the substrate and (when present) of 2-D upd adlayers influence the effective
 7.3 Near Field and Confocal Optical Methods 279

barrier height. Energetic inhomogeneities on single-crystal and textured platinum

surfaces were detected with a combination of DTS and VTS measurements [235].
For a brief overview of methods for the generation and investigation of nanostruc-
tures at electrochemical interfaces, with particular attention paid to DTS and VTS,
see [231]. In an ex situ study of electropolymerized polypyrrole, the band struc-
ture was studied as a function of polymer doping [236]. Currently, results of true
scanning tunneling spectroscopy under electrochemical conditions have not been
reported; the described fundamental requirements and conditions make this actually
rather unlikely.

7.3 Near Field and Confocal Optical Methods

The optical resolution of a microscope is traditionally described based on the Abbé
equation [237] as being equal to half the wavelength of the employed electromag-
netic radiation, i.e. in the visible part of the spectrum, the resolution amounts to
250–300 nm. Actual values might be better, but generally experimental conditions
might conspire towards worse results. Methods to overcome this limitation include
the use of near field optics. Figure 7.25 shows a schematic comparison of the situ-
ation with an optical device, which is limited by the Abbe equation and in addition
to possible near field approaches.
The use of confocal microscopy is predominantly driven by the investigation
of localized phenomena beyond the simple investigation of structures and topogra-
phies. The resolution in this case is not necessarily better than the optical resolution
discussed initially above. A serious problem, and even a limitation, is the need to
prepare a tip with an aperture of the required diameter right at the tip apex. The light
passing through the aperture stays confined for a length approximately equal to the
aperture diameter. As has been reported elsewhere, the resolution is limited to λ/10
or 50 nm [238]. The same arguments apply to the use of a scanning near field opti-
cal microscope (SNOM), where the tip is scanned over the surface and in scanning
near field infrared (spectroscopy) microscopy (SNIM). A practical resolution limit
in the middle infrared is about 1 μm. A promising alternative, not yet explored in
electrochemical studies, is the use of apertureless tips. A sharp, metallic needle that
acts like an optical antenna supplying a concentrated electric field at its apex is used

Fig. 7.25. Focusing principles in microscopy: left: classical objective; middle: near field with
aperture, right: near field scattering tip; resolution as indicated, arrow indicates path of light

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280 7 Surface Analytical Methods

[239]. Infrared radiation is focused on the tip–surface gap and the scattered light is
detected using standard techniques [240].

7.3.1 Near Field Methods

Fundamentals. Based on a suggestion by Synge [241], a light beam created by a

hole in an opaque material very close to the specimen to be studied, with a diame-
ter much smaller than the optical wavelength, is used to image the sample surface.
Using single mode optical fibers acting as tips in a scanning atomic force micro-
scope (AFM), this illumination has become possible. The light passing the sample
or created at the interface by fluorescence is collected by suitable optics of an optical
microscope. Further details of the method, instrumentation, etc. have been reported
elsewhere [242, 243]. Scanning near field optical microscopy (SNOM) has been em-
ployed in material sciences using fluorescence images in studies of polymer blends
[244].

7.3.2 Confocal Optical Methods

Fundamentals. In a confocal optical arrangement, light coming from the surface/

interface under investigation is collected and guided by suitable (e.g. microscopy)
objectives towards an optical detector (a photomultiplier, a photodiode, etc.). In
front of this detector a pinhole is placed. If properly located, this pinhole will only
allow light to pass from the focal point on the surface and all other light that is “out
of focus” will be rejected. By scanning the surface in x- and y-directions and storing
the optical information (e.g. scattered light intensity), an image of the surface can
be generated [245–247]. Illumination of the investigated surface can be done in var-
ious ways; this of course includes monochrome laser light. In this case, laser light
is focused with suitable lenses to a diffraction limited spot [confocal laser scanning
microscopy (CLSM)]. Optical properties of this spot are investigated with an opti-
cal microscope or other means. These applications include microscope-assisted flu-
orescence photon correlation measurements [related to and based on fluorescence
correlation spectroscopy (FCS)]. This technique is a method used to study inter-
molecular interaction. It is based on the statistical evaluation of the fluctuation of
concentration based on measurements of fluorescent light [248]. Although it has no
direct and obvious relevance to electrochemists, this method has been used starting
from locally resolved surface enhanced Raman spectroscopy (see Sect. 5.2.12). The
closely related confocal Raman microscopy is treated in Sect. 5.2.15.
Instrumentation. In a typical CLSM experiment, a narrow laser beam scans a sur-
face horizontally, i.e. at constant height, in x- and y-directions using piezo-driven
mirrors. A small pinhole is located in front of an optical detector at a position con-
jugate to the focal point in the sample plane. This way, the detector measures the
intensity of light reflected from the surface at every scanned position. Light scattered
from out-of-focus positions is focused outside the pinhole and thus does not reach
the detector. An image of scattered and/or reflected laser light intensity is created
 7.4 Surface Conductivity Measurements 281

Fig. 7.26. Schematic setup of a confocal scanning laser microscope; for details, see text

for one height z for every point. Repetition of this procedure at different values of
z results in a three-dimensional image of the sample. In electrochemical investiga-
tions this can be helpful in corrosion studies of rough surfaces [249]. The distance
between the surface and the front end of the optical arrangement is about 1 mm.
A schematic setup is shown in Fig. 7.26.
In a study of the effect of thiourea (an additive to electroplating solutions) on
copper deposition it was observed that thiourea acted as a mediator in the electro-
chemical reactions; cathodic consumption was found to be negligible. The additive
acted as a brightening agent and did not show any leveling capability [250]. The
adsorption of the organic dye 3,3
-dihexyloxacarbocyanine iodide, DiOC6 (3), on a
polycrystalline gold surface was tracked with CLSM [251]. The dye inhibited ca-
thodic processes (copper deposition) at sites where it was adsorbed. At sufficiently
negative electrode potentials, a distinctive influence of the dye on copper deposition
was observed. Besides CLSM, with the scanning of the illuminating laser light beam
as an important feature, confocal laser-assisted microscopy has been used to in-
vestigate two- and three-dimensional samples as reviewed elsewhere [252]. Under-
film corrosion of epoxy-coated steel AA2024-T3 has been investigated with CLSM
[253]. Corrosion metrology could be described in detail.

7.4 Surface Conductivity Measurements

Fundamentals. According to the Drude equation, the electrical resistance of a con-
ducting material depends on the concentration, the specific charge and the mobility
of charge carriers in the conducting medium. A more thorough examination of the
mobility takes into account the way the charged species (electron, hole) are mov-
ing in the conductor. Any distortion of the material, particularly in the solid phase
(defects in crystals, etc.), will affect the conductivity. In the case of a very thin
conducting film on an insulating substrate, the influence of particles sitting on the
surface (e.g. adsorbed molecules) of the thin film will be particularly strong because
their effect will extend into almost the complete conducting layer. Consequently the

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282 7 Surface Analytical Methods

electrical resistance is called surface resistance9 . Species adsorbed on the surface

will introduce additional “defect-like” changes in the film, resulting in changes of
the film conductivity. More recently, the change of the DC resistance was explained
by Schumacher et al. [254] by considering the adsorbate-induced density of states at
the Fermi level and the half-width of the Newns–Anderson resonance corresponding
to the lowest unoccupied orbital of the adsorbate molecule. Because the adsorption
of neutral species depends on the electrode potential and reaches a maximum around
the potential of maximum adsorption, measurements of the thin film resistance (or
conductance) as a function of adsorbate concentration in the solution phase and
electrode potential will provide the necessary information to construct an adsorp-
tion isotherm (see also [255–259]). As the mode and intensity of adsorbate–surface
interaction may be different for different surface places (differing in local energy,
topography, atomic arrangement), results may differ from those of other methods
not sensitive to local differences in surface properties. In addition to studies of very
thin metal films, conductivity measurements of layers of intrinsically conducting
polymers have been made frequently [260, 261]. Changes of polymer conductivity
result from a multitude of causes: degree of oxidation (doping), type and composi-
tion of electrolyte solution and pH-value are only a selection. The use of a SECM
as a probe for the conductivity of ultrathin films has been proposed [162].
Instrumentation. Thin films of the material to be studied (mostly metals) are de-
posited onto insulating substrates (glass, mica); for a typical setup, see Fig. 7.27.
Films of intrinsically conducting polymers are deposited by casting from their solu-
tion or by electropolymerization [262, 263].
The electronic resistance of polyaniline changes reversibly from the poorly con-
ducting reduced (undoped) through the medium oxidized (doped) state to the strongly
oxidized state and back without any significant difference between the initial and

Fig. 7.27. Two band electrode as used for in situ DC conductivity measurements with poly-
mer films deposited on the gap between the two electrodes; A: cross section after finished
preparation; B: top view after preparation; C: after embedding, before grinding [262]
9 The terms “surface conductivity” and “surface resistance” are used equally.
 7.4 Surface Conductivity Measurements 283

Fig. 7.28. Resistance of a film of polyaniline (left) and polythiophene (right) measured in situ
as a function of electrode potential in a nonaqueous electrolyte solution [264]

Fig. 7.29. Resistance of a film of a 1:1 copolymer of aniline and thiophene measured in situ
as a function of electrode potential in a nonaqueous electrolyte solution [264]

the final state (Fig. 7.28, left). Polythiophene shows an irreversible change when
exposed to electrode potentials as positive as established before with polyaniline
(Fig. 7.28, right). A different situation emerges when an electrochemically formed
copolymer of both thiophene and aniline is used (Fig. 7.29).
A lower resistance in the oxidized state and a broader electrode potential range
wherein no irreversible change occurs are observed.
Adsorbates of molecules or ions from solution onto the electrode as a function
of electrode potential or concentration in solution can be investigated. The electrode
to be investigated is prepared as a thin film by vapor deposition onto a suitable
insulating (monocrystalline, if desired) substrate. For simultaneous measurements
of film resistance and electrode potential an electrode design as depicted in Fig. 7.30
provides an optimum compromise between current distribution and a minimum of
interference between both measurements [258].
The highly conductive silver cement contact between the strips providing con-
nection to the electrochemical circuitry (i.e. potentiostat) does not interfere with the
conductivity measurements and any conceivable contribution of the electrochemical

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284 7 Surface Analytical Methods

Fig. 7.30. Electrode array for in situ thin film conductivity measurements (according to [258])

Fig. 7.31. Cyclic voltammogram and thin film resistance of a Au(111) electrode in contact
with an aqueous solution of 0.1 M H2 SO4 (according to [258])

current flowing across the metal film/solution interface will compensate because of
opposite signs at both strips. The electrode array is pressed towards an opening of
the electrochemical cell vessel with the rubber ring providing an adequate seal.
Besides adsorption of ions and organic molecules on metal surfaces [265], stud-
ied systems include underpotential metal deposition [266, 267], intercalation pro-
cesses [268] and surface reconstruction phenomena. Interactions between various
metal adsorbates (e.g. upd-Zn on polycrystalline gold with Cu adatoms already
present [269]) have been studied. The application of surface resistance measure-
ments in heavy metal analysis in aqueous solution has been reported10 [270]. A rule
(surface Linde rule) correlating the surface concentration of a species with the rela-
tive resistance change has been found to be effective in many cases [269]. In the case
of specifically adsorbed halide ions, the resistance seems to depend on the number
of ions directly adsorbed on the surface, as determined with surface X-ray scatter-
ing (see Chap. 6) and not with the coverage determined by classical thermodynamic
electrochemical methods like chronocoulometry [271]. Figure 7.31 shows results
with features in the CV, including the current peak around EAg/AgCl = 230 mV,
which is indicative of the lifting of surface reconstruction; a broad current wave
10 The method has been called voltohmmetry by the author.
 7.5 Interfacial Conductivity Measurements 285

around EAg/AgCl = 400 mV, which is assigned to sulfate adsorption; and a peak
pair around EAg/AgCl = 695 mV, which is associated with the ordering/disordering
of the sulfate adsorbate layer. The simultaneous increase of the film resistance is
caused by sulfate ion adsorption [258].

7.5 Interfacial Conductivity Measurements11

Fundamentals. The electric (i.e. generally the Ohmic) resistance observed between
the connection to the electrochemical measuring device (e.g. a potentiostat) and the
Faradaic impedance assigned to the entirety of the electrochemical process and the
double layer (or interfacial) capacitance coupled in parallel to the latter impedance
is generally assumed to be constant. As depicted in Fig. 7.32, it is connected in an
equivalent circuit in series with both latter elements.
The resistance is composed of the electrical resistance of the wiring and the bulk
of the electrode, both of which are assumed to be constant and independent of time
and electrode potential. The solution phase resistance encountered between the outer
electrode surface (i.e. the actual interface between the electronically conducting and
the ionically conducting phase) and the reference electrode is also an entity assumed
to be constant in most experiments. (It should be kept in mind that gas evolution or
rapid creation or depletion of ionic species by electrochemical reactions might cause
totally different observations.) A third component is the Ohmic resistance of films
or deposits present, formed or removed during electrochemical reactions and thus
causing changes of the resistance as a function of time and/or electrode potential.
A method to determine this change, called cyclic resistometry, has been reported
[272].
Instrumentation. Using a fast electronic switching circuit short (45 μs) galvanos-
tatic (100 mA) pulses with fast risetime (<1 μs) are applied to the electrochemical
cell; the potentiostat is switched to a dummy cell for this time [272]. Under these
conditions, the observed potential drop is essentially caused only by R comp . From
the acquired voltage response, the desired value R comp is calculated. This proce-
dure is repeated frequently enough to yield continuous R comp vs. electrode potential
plots. After the measurement pulse an inverted galvanostatic pulse was applied to
avoid unwanted leakage of charge into the double layer.

Fig. 7.32. Simplified equivalent circuit of the electrochemical interphase containing the
Faradaic impedance Z interface , the double layer capacitance C DL and the composed Ohmic
resistance R comp
11 This method is sometimes also called the contact electroresistance (CER) method.

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286 7 Surface Analytical Methods

Investigated examples include film formation on lead electrodes, various metal

dissolution processes, redox electrochemistry of electrochromic films of IrO3 [272]
and various intrinsically conducting polymers [273–276]. A review covering exper-
imental aspects and results pertaining to ion adsorption, hydride and oxide film for-
mation and hydrophilicity of metals has been provided elsewhere as well as further
reports [277–284].

7.6 Microradiology
Fundamentals. Using suitably selected monochromatic synchrotron radiation, the
local absorption caused by a selected species (e.g. an ion) can be monitored in real
time with high lateral resolution. This method is closely related to X-ray microscopy
and tomography with X-rays (see Chap. 6). Further resolution and mapping, using
suitably focused synchrotron radiation, has been described [285, 286]; applications
seem to be limited so far to non-electrochemical environments.
Instrumentation. A miniaturized cell used for studies of metal-deposition dynam-
ics has been described [287]. Results pertaining mostly to metal-deposition pro-
cesses have revealed that zinc can deposited on hydrogen bubbles developed at
sufficiently negative electrode potentials, thus explaining common defects in zinc
plating.

References
1. M. Pilaski, T. Hamelmann, A. Moehring, M.M. Lohrengel, Electrochim. Acta 47, 2127
(2002)
2. G. Binnig, H. Rohrer, Angew. Chem. 99, 622 (1987)
3. R. Wiesendanger, Scanning Probe Microscopy (Springer, Heidelberg, 1998)
4. R. Young, J. Ward, F. Scire, Rev. Sci. Instr. 43, 999 (1972)
5. R. Young, J. Ward, F. Scire, Phys. Rev. Lett. 27, 922 (1971)
6. R.D. Young, Physics Today 1971 (11) 42
7. G. Friedbacher, H. Fuchs, Pure Appl. Chem. 71, 1337 (1999)
8. G. Friedbacher, H. Fuchs, Angew. Chem. 115, 5804 (2003)
9. S.L. Sharp, R.J. Warmack, J.P. Goudonnet, I. Lee, T.L. Ferrell, Acc. Chem. Res. 26,
377 (1993)
10. T.P. Moffat, Electroanalytical Chemistry, vol. 21, ed. by A.J. Bard, I. Rubinstein
(Dekker, New York, 1999), p. 211
11. D.A. Bonnel (ed.), Tunneling Microscopy and Spectroscopy (VCH, New York, 1993)
12. G. Legett, Surface Analysis – The Principal Techniques, ed. by J.C. Vickerman (Wiley,
Chichester, 1997), p. 393
13. G. Binnig, H. Rohrer, Ch. Gerber, E. Weibel, Phys. Rev. Lett. 49, 57 (1982)
14. G. Binnig, H. Rohrer, Phys. Bl. 39, 176 (1983)
15. P. Lustenberger, H. Rohrer, R. Christoph, H. Siegenthaler, J. Electroanal. Chem. 243,
225 (1988)
16. T. Ito, P. Bühlmann, Y. Umezawa, Anal. Chem. 71, 1699 (1999)
 References 287

17. T. Nishino, T. Ito, Y. Umezawa, J. Electroanal. Chem. 550–551, 125 (2003)

18. M. Wilms, M. Kruft, G. Bermes, K. Wandelt, Rev. Sci. Instrum. 70, 3641 (1999)
19. J. Zhang, J. Ulstrup, J. Electroanal. Chem. 599, 213 (2007)
20. V. Stamenkovic, C. Lucas, D. Tripkovic, D. Strmenik, N.M. Markovic, 210th Electro-
chemical Society Meeting, Cancun, Mexico, 29.10–03.11.2006, Ext. Abstr. #1913
21. W. Schindler, E. Bucharsky, C. Behrend, Extended Abstracts of the 203rd Meeting of
the Electrochemical Society, Paris, France, 27.04–02.05. 2003, Ext. Abstr. #2314
22. D.M. Kolb, Angew. Chem. 113, 1199 (2001)
23. A.A. Gewirth, K.J. Hanson, Interface 2, 37 (1993)
24. R. Sonnenfeld, J. Schneir, P.K. Hansma, Modern Aspects of Electrochemistry, vol. 21,
ed. by R.E. White, J.O’M. Bockris, B.E. Conway (Plenum, New York, 1990), p. 1
25. A.J. Arvia, in Spectroscopic and Diffraction Techniques in Interfacial Electrochemistry,
ed. by C. Gutiérrez, C. Melendres. NATO ASI Series C, vol. 320 (Kluwer Academic,
Dordrecht, 1990), p. 449
26. O.M. Magnussen, Chem. Rev. 102, 679 (2002)
27. X.P. Gao, G.J. Edens, M.J. Weaver, J. Phys. Chem. 98, 8074 (1994)
28. D. Friebel, C. Schlaup, P. Broekmann, K. Wandelt, Phys. Chem. Chem. Phys. 9, 2142
(2007)
29. J. Gómez, L. Vázquez, A.M. Baró, C. Alonso, E. González, J. Gónzalez-Velasco, A.J.
Arvía, J. Electroanal. Chem. 240, 77 (1988)
30. E. Holland-Moritz, J. Gordon II, G. Borges, R. Sonnenfeld, Langmuir 7, 301 (1991)
31. L.M. Siperko, J. Electrochem. Soc. 137, 2791 (1990)
32. D. Carnal, U. Müller, H. Siegenthaler, J. Phys. IV 4, 297 (1994)
33. W. Obretenov, U. Schmidt, W.J. Lorenz, G. Staikov, E. Budevski, D. Carnal, U. Müller,
H. Siegenthaler, E. Schmidt, J. Electrochem. Soc. 140, 692 (1993)
34. W. Obretenov, U. Schmidt, W.J. Lorenz, G. Staikov, E. Budevski, D. Carnal, U. Müller,
H. Siegenthaler, E. Schmidt, J. Electrochem. Soc. 140, 692 (1993)
35. R.J. Nichols, D. Schröer, H. Meyer, Scanning 15, 266 (1993)
36. Z.F. Chen, J. Li, E.K. Wang, J. Electroanal. Chem. 373, 83 (1994)
37. W. Haiss, D. Lackey, J.K. Sass, H. Meyer, R.J. Nichols, Chem. Phys. Lett. 200, 343
(1992)
38. R.J. Nichols, C.E. Bach, H. Meyer, Ber. Bunsenges. Phys. Chem. 97, 1012 (1993)
39. Z.L. Wu, Z.H. Zang, S.L. Yau, Langmuir 16, 3522 (2000)
40. K. Itaya, Progr. Surf. Sci. 58, 121 (1998)
41. R. Wiesendanger, M. Ringger, L. Rosenthaler, H.R. Hidber, P. Oelhafen, H. Rudin, H.J.
Güntherodt, Surf. Sci. 181, 46 (1987)
42. M. Giesen, Prog. Surf. Sci. 68, 1 (2001)
43. S. Dieluweit, M. Giesen, J. Electroanal. Chem. 524, 194 (2002)
44. X.C. Guo, R.J. Madix, Acc. Chem. Res. 36, 471 (2003)
45. C.-H. Shue, L.-Y.O. Yang, S.-L. Yau, K. Itaya, Langmuir 21, 1942 (2005)
46. R. Yamada, K. Uosaki, Langmuir 14, 855 (1998)
47. H. Wano, K. Uosaki, Langmuir 17, 8224 (2001)
48. H. Wano, K. Uosaki, Langmuir 21, 4024 (2005)
49. J.E. Hudson, H.D. Abruna, J. Phys. Chem. 100, 1036 (1996)
50. N.J. Tao, G. Cardenas, F. Cunha, Z. Shi, Langmuir 11, 4445 (1995)
51. R.S. Robinson, J. Electrochem. Soc. 135, 143C (1988)
52. R. Nishitani, A. Kasuya, Y. Nishina, Z. Phys. D 26, S42 (1993)
53. Q. Xu, T. He, D.O. Wipf, Langmuir 23, 9098 (2007)
54. H.C. Wu, S.L. Yau, J. Phys. Chem. B 105, 6965 (2001)

www.ebook3000.com
288 7 Surface Analytical Methods

55. J.E.T. Andersen, P. Møller, J. Electrochem. Soc. 142, 2225 (1995)

56. Y.C. Wu, H.W. Pickering, D.S. Gregory, S. Geh, T. Sakurai, Surf. Sci. 246, 468 (1991)
57. T. Sawaguchi, T. Yamada, Y. Okinaka, K. Itaya, J. Phys. Chem. 99, 14149 (1995)
58. Z.H. Zang, Z.L. Wu, S.L. Yau, Langmuir 15, 8750 (1999)
59. T. Kawamoto, Phys. Chem. Chem. Phys. 6, 4913 (2004)
60. C.L. Aravinda, I. Mukhopadhyay, W. Freyland, Phys. Chem. Chem. Phys. 6, 5225
(2004)
61. G.-B. Pan, W. Freyland, Phys. Chem. Chem. Phys. 9, 3286 (2007)
62. N.J. Tao, C.Z. Li, H.X. He, J. Electroanal. Chem. 492, 81 (2000)
63. A. Gonzalez-Martin, R.C. Bhardwaj, J.O’M. Bockris, J. Appl. Electrochem. 23, 531
(1993)
64. K. Uosaki, M. Koinuma, Faraday Discuss. 94, 361 (1992)
65. R. Hiesgen, M. Krause, D. Meissner, Electrochim. Acta 45, 3213 (2000)
66. R. Hiesgen, D. Meissner, Adv. Mater. 10, 619 (1998)
67. M. Hugelmann, W. Schindler, Appl. Phys. Lett. 85, 3608 (2004)
68. for further details see e.g.: D.M. Kolb, R. Ullmann, T. Will, Science 275, 1097 (1997)
69. D.H. Craston, C.W. Lin, A.J. Bard, J. Electrochem. Soc. 135, 785 (1988)
70. T.H. Treutler, G. Wittstock, Electrochim. Acta 48, 2923 (2003)
71. O. Sklyar, T.H. Treutler, N. Vlachopoulos, G. Wittstock, Surf. Sci. 597, 181 (2005)
72. for an overview see: R.S. Robinson, C.A. Widrig, Langmuir 8, 2311 (1992)
73. J.C.H. Spence, W. Lo, M. Kuwabara, Ultramicroscopy 33, 69 (1990)
74. G. Binnig, C.F. Quate, C. Gerber, Phys. Rev. Lett. 63, 2669 (1989)
75. N.A. Burnham, R.J. Colton, in Scanning Tunneling Microscopy and Spectroscopy, ed.
by D.A. Bonnell (VCH, New York, 1993), p. 191
76. Y. Martin, C.C. Williams, Y. Wickramsinghe, J. Appl. Phys. 61, 4723 (1987)
77. for a review see: A. Noy, D.V. Vezenov, C.M. Lieber, Annu. Rev. Mater. Sci. 27, 381
(1997)
78. A. Rosazeiser, E. Weilandt, S. Hild, O. Marti, Meas. Sci. Technol. 8, 1333 (1997)
79. M.N. Holder, C.E. Gardner, J.V. Macpherson, P.R. Unwin, J. Electroanal. Chem. 585,
8 (2005)
80. N.R. Wilson, D.H. Cobden, J.V. Macpherson, J. Phys. Chem. B 106, 13102 (2002)
81. C. Kranz, G. Friedbacher, B. Mizaikoff, A. Lugstein, J. Smoliner, E. Bertagnolli, Anal.
Chem. 73, 2491 (2001)
82. B.J. Cruickshank, A.A. Gewirth, R.M. Rynders, R.C. Alkire, J. Electrochem. Soc. 139,
2829 (1992)
83. C.H. Chen, S.M. Vesecky, A.A. Gewirth, J. Am. Chem. Soc. 114, 451 (1992)
84. S. Manne, P.K. Hansma, J. Massie, V.B. Elings, A.A. Gewirth, Science 251, 183 (1991)
85. W. Kautek, S. Dieluweit, M. Sahre, J. Phys. Chem. B 101, 2709 (1997)
86. S. Rentsch, H. Siegenthaler, G. Papastavrou, Langmuir 23, 9083 (2007)
87. K.M. Balss, G.A. Fried, P.W. Bohn, J. Electrochem. Soc. 149, C450 (2002)
88. R. Sonnenfeld, J. Schneir, P.K. Hansma, in Modern Aspects of Electrochemistry, vol.
21, ed. by R.E. White, J.O’M. Bockris, B.E. Conway (Plenum, New York, 1990), p. 1
89. T.R.I. Cataldi, I.G. Blackham, G.A.D. Briggs, J.B. Pethica, H.A.O. Hill, J. Electroanal.
Chem. 290, 1 (1990)
90. H. Takano, J.R. Kenseth, S.-S. Wong, J.C. O’Brien, M.D. Porter, Chem. Rev. 99, 2845
(1999)
91. P. Häring, R. Kötz, J. Electroanal. Chem. 385, 273 (1995)
92. F.P. Campana, R. Kötz, J. Vetter, P. Novak, H. Siegenthaler, Electrochem. Commun. 7,
107 (2005)
 References 289

93. A.C. Hillier, M.D. Ward, Science 263, 1261 (1994)

94. A.P. Abbott, G. Capper, K.J. McKenzie, A. Glidle, K.S. Ryder, Phys. Chem. Chem.
Phys. 8, 4214 (2006)
95. M. Seo, Y. Kurata, Electrochim. Acta 48, 3221 (2003)
96. M. Nielinger, H. Baltruschat, Phys. Chem. Chem. Phys. 9, 3965 (2007)
97. P. Schmutz, G.S. Frankel, J. Electrochem. Soc. 146, 4461 (1999)
98. P. Schmutz, G.S. Frankel, J. Electrochem. Soc. 145, 2285 (1998)
99. M. Rohwerder, E. Hornung, M. Stratmann, Electrochim. Acta 48, 1235 (2003)
100. M. Rohwerder, F. Turcu, Electrochim. Acta 53, 290 (2007)
101. P. Leblanc, G.S. Frankel, J. Electrochem. Soc. 149, B239 (2002)
102. P. Schmutz, G.S. Frankel, J. Electrochem. Soc. 145, 2295 (1998)
103. V. Guillaumin, P. Schmutz, G.S. Frankel, J. Electrochem. Soc. 148, B163 (2001)
104. D.M. Kolb, D.L. Rath, R. Wille, W.N. Hansen, Ber. Bunsenges, Phys. Chem. 87, 1108
(1983)
105. W.N. Hansen, D.M. Kolb, J. Electroanal. Chem. 100, 493 (1979)
106. E.M. Stuve, A. Krasnopoler, D.E. Sauer, Surf. Sci. 335, 177 (1995)
107. D.L. Rath, D.M. Kolb, Surf. Sci. 109, 641 (1981)
108. D. Bengtsson Blücher, J.-E. Svensson, L.-G. Johansson, M. Rohwerder, M. Stratmann,
J. Electrochem. Soc. 151, B621 (2004)
109. T.H. Muster, A.E. Hughes, J. Electrochem. Soc. 153, B474 (2006)
110. L.E. Fratila-Apachitei, I. Apachitei, J. Duszczyk, Electrochim. Acta 51, 5892 (2006)
111. P.P. Leblanc, Frankel, J. Electrochem. Soc. 151, B105 (2004)
112. A.M. Bond, Analyst 119, R1 (1994)
113. F. Magno, I. Lavagnini, Anal. Chim. Acta 305, 96 (1995)
114. R.J. Forster, Chem. Soc. Rev. 23, 289 (1994)
115. K. Aoki, Electroanalysis 5, 627 (1993)
116. J. Heinze, Angew. Chem. 105, 1327 (1993)
117. K. Mansikkamäki, P. Ahonen, G. Fabricius, L. Murtomäli, K. Kontturi, J. Electrochem.
Soc. 152, B12 (2005)
118. P. Sun, F.O. Laforge, M.V. Mirkin, Phys. Chem. Chem. Phys. 9, 802 (2007)
119. A.J. Bard, F.F. Fan, M.V. Mirkin, in Electroanalytical Chemistry, vol. 15, ed. by A.J.
Bard (Dekker, New York, 1994), p. 243
120. J.L. Amphlett, G. Denuault, J. Phys. Chem. B 102, 9946 (1998)
121. A.J. Bard, F.-R.F. Fan, M.V. Mirkin, in Physical Electrochemistry, ed. by I. Rubinstein
(Dekker, New York, 1995), Chap. 5
122. K. Eckhard, X. Chen, F. Turcu, W. Schuhmann, Phys. Chem. Chem. Phys. 8, 5359
(2006)
123. M. Etienne, A. Schulte, W. Schuhmann, Electrochem. Commun. 6, 288 (2004)
124. see also: M.A. Alpuche-Aviles, D.O. Wipf, Anal. Chem. 73, 4873 (2001)
125. P.M. Diakowski, A.S. Baranski, Electrochim. Acta 52, 854 (2006)
126. P.M. Diakowski, Z. Ding, Phys. Chem. Chem. Phys. 9, 5966 (2007)
127. B.B. Katemann, W. Schuhmann, Electroanalysis 14, 22 (2002)
128. A.J. Bard, F.-R.F. Fan, D.T. Pierce, P.R. Unwin, D.O. Wipf, F. Zhou, Science 68, 254
(1991)
129. D. Mandler, P.R. Unwin, J. Phys. Chem. B 107, 407 (2003)
130. M. Tsionsky, A.J. Bard, D. Dini, F. Decker, Chem. Mater. 10, 2120 (1998)
131. D.O. Wipf, M. Alpuche-Aviles, L. Diaz-Ballote, 205th Electrochemical Society Meet-
ing, San Antonio, USA, 09–13.05.2004, Ext. Abstr. #837
132. L. Diaz-Ballote, M. Alpuche-Aviles, D.O. Wipf, Electrochim. Acta 52, 17 (2007)

www.ebook3000.com
290 7 Surface Analytical Methods

133. A.L. Barker, P.R. Unwin, J.W. Gardner, H. Rieley, Electrochem. Commun. 6, 91 (2004)
134. A.J. Bard, F.R. Fan, Faraday Discuss. 1992, 1
135. A.J. Bard, D.E. Cliffel, C. Demaille, F.R.F. Fan, M. Tsionsky, Ann. Chim. Rome 87, 15
(1997)
136. K. Borgwarth, C. Ricken, D.G. Ebling, J. Heinze, Ber. Bunsenges. Phys. Chem. 99,
1421 (1995)
137. G. Nagy, L. Nagy, Fresenius J. Anal. Chem. 366, 735 (2000)
138. C. Ricken, K. Borgwarth, J. Heinze, Nachr. Chem. Tech. Lab. 44, 502 (1996)
139. A.L. Barker, M. Gonsalves, J.V. Macpherson, C.J. Slevin, P.R. Unwin, Anal. Chim.
Acta 385, 223 (1999)
140. I. Turyan, B. Orel, R. Reisfeld, D. Mandler, Phys. Chem. Chem. Phys. 5, 3212 (2003)
141. G. Wittstock, in Appl. Phys., vol. 85, ed. by K. Wandelt, S. Thurgate (Springer, Berlin,
2003), p. 335
142. J. Kwak, C. Lee, A.J. Bard, J. Electrochem. Soc. 137, 1481 (1990)
143. K. Mansikkamäki, U. Haapanen, C. Johans, K. Konturri, M. Valden, J. Electrochem.
Soc. 153, B311 (2006)
144. C. Gabrielli, F. Huet, M. Keddam, P. Rousseau, V. Vivier, 205th Electrochemical Soci-
ety Meeting, San Antonio, USA, 09–13.05.2004, Ext. Abstr. #848
145. R.C. Tenent, D.O. Wipf, J. Electrochem. Soc. 150, E131 (2003)
146. J. Ufheil, C. Heß, K. Borgwarth, J. Heinze, Phys. Chem. Chem. Phys. 7, 3185 (2005)
147. C.E. Jones, P.R. Unwin, J.V. Macpherson, Chem. Phys. Chem. 4, 139 (2003)
148. J.V. Macpherson, P.R. Unwin, A.C. Hillier, A.J. Bard, J. Am. Chem. Soc. 118, 6445
(1996)
149. J.V. Macpherson, P.R. Unwin, Anal. Chem. 72, 276 (2000)
150. C.E. Gardner, J.V. Macpherson, Anal. Chem. 74, 576A (2002)
151. E. Ammann, D. Mandler, J. Electrochem. Soc. 148, C533 (2001)
152. M. Del Popolo, E. Leiva, H. Kleine, J. Meier, M. Mariscal, W. Schmickler, Appl. Phys.
Lett. 81, 2635 (2002)
153. C. Kranz, H.E. Gaub, W. Schuhmann, Adv. Mater. 8, 634 (1996)
154. M.T. Giacomini, R. Schuster, Phys. Chem. Chem. Phys. 7, 518 (2005)
155. V. Radtke, J. Heinze, Z. Phys. Chem. 218, 103 (2004)
156. C.H. Paik, H.S. White, R.C. Alkire, J. Electrochem. Soc. 147, 4120 (2000)
157. C.H. Paik, R.C. Alkire, J. Electrochem. Soc. 148, B276 (2001)
158. J.F. Zhou, D.O. Wipf, J. Electrochem. Soc. 144, 1202 (1997)
159. C.G. Zoski, N. Simjee, O. Guenat, M. Koudelka-Hep, Anal. Chem. 76, 62 (2004)
160. M. Ciobanu, H.A. Kincaid, G.K. Jennings, D.E. Cliffel, Langmuir 21, 692 (2005)
161. S. Bollo, P. Jara-Ulloa, S. Finger, L.J. Nunez-Vergara, J.A. Squella, J. Electroanal.
Chem. 577, 235 (2005)
162. A.L. Whitworth, D. Mandler, P.R. Unwin, Phys. Chem. Chem. Phys. 7, 356 (2005)
163. P.G. Nicholson, V. Ruiz, J.V. Macpherson, P.R. Unwin, Phys. Chem. Chem. Phys. 8,
5096 (2006)
164. R.C. Engstrom, T. Meaney, R. Tople, R.M. Wightman, Anal. Chem. 59, 2005 (1987)
165. R.C. Engstrom, M. Weber, D.J. Wunder, R. Burgess, S. Winquist, Anal. Chem. 58, 844
(1986)
166. E. Klusmann, J.W. Schultze, Electrochim. Acta 42, 3123 (1997)
167. E. Klusmann, J.W. Schultze, Electrochim. Acta 48, 3325 (2003)
168. H. Ding, L.H. Hihara, J. Electrochem. Soc. 152, B161 (2005)
169. K. Ogle, V. Baudu, L. Garrigues, X. Philippe, J. Electrochem. Soc. 147, 3654 (2000)
170. K. Ogle, S. Morel, D. Jacquet, J. Electrochem. Soc. 153, B1 (2006)
 References 291

171. L. Ying, A. Bruckbauer, D. Zhou, J. Gorelik, A. Shevchuk, M. Lab, Y. Korchev, D.

Klenerman, Phys. Chem. Chem. Phys. 7, 2895 (2005)
172. P.K. Hansma, B. Drake, O. Martio, S.A.C. Gould, C.B. Prater, Science 243, 641 (1989)
173. C.B. Prater, P.K. Hansma, M. Tortonese, C.F. Quate, Rev. Sci. Instrum. 62, 2634 (1991)
174. D. Pastre, H. Iwamoto, J. Liu, G. Szabo, Z.F. Shao, Ultramicroscopy 90, 13 (2001)
175. Y.E. Korchev, C.L. Bashford, M. Milanovic, I. Vodyanov, M.J. Lab, Biophys. J. 73, 653
(1997)
176. Y.E. Korchev, M. Milovanovic, C.L. Bashford, D.C. Bennett, E.V. Sviderskaya, I.
Vodyanov, M.J. Lab, J. Microsc. 188, 17 (1997)
177. R. Proksch, R. Lal, P.K. Hansma, D. Morse, G. Stucky, Biophys. J. 71, 2155 (1996)
178. K.R. Trethewey, D.A. Sargeant, Metal Mater. 8, 378 (1992)
179. S.J. Badger, S.B. Lyon, S. Turgoose, J. Electrochem. Soc. 145, 4074 (1998)
180. P.J. Kinlen, V. Menon, Y.W. Ding, J. Electrochem. Soc. 146, 3690 (1999)
181. EG&G Instruments, Princeton Applied Research, P.O. Box 2565, Princeton, NJ 08543,
USA
182. D.A. Sargeant, Corros. Prevent. Control 44, 91 (1997)
183. R. Gasparac, C.R. Martin, J. Electrochem. Soc. 148, B138 (2001)
184. V.S. Voruganti, H.B. Luft, D. DeGeer, S.A. Bradford, Corrosion 47, 343 (1991)
185. D.A. Sargeant, C. Ford, J. Corderoy, Corros. Prev. Control 38, 12 (1991)
186. J.G. Yu, J.L. Luo, P.R. Norton, Langmuir 18, 6637 (2002)
187. K.R. Trethewey, D.A. Sargeant, D.J. Marsh, A.A. Tamimi, Corros. Sci. 35, 127 (1993)
188. G. Bellanger, J.J. Rameau, Electrochim. Acta 40, 2519 (1995)
189. D.A. Sargeant, J.G.C. Hainse, S. Bates, Mater. Sci. Technol. 5, 487 (1989)
190. V.S. Voruganti, H.B. Luft, D. DeGeer, S.A. Bradford, Corrosion 47, 343 (1991)
191. VEECO data sheet DS57, Rev. A0, 2003
192. H.S. Isaacs, J. Electrochem. Soc. 138, 722 (1991)
193. H.S. Isaacs, A.J. Davenport, A. Shipley, J. Electrochem. Soc. 138, 390 (1991)
194. J. He, V.J. Gelling, D.E. Tallman, G.P. Bierwagen, J. Electrochem. Soc. 147, 3661
(2000)
195. D.A. Sargeant, Corros. Prevent. Control 44, 91 (1997)
196. I. Sekine, M. Yuasa, K. Tanaka, T. l Tsutsumi, F. Koizumi, N. Oda, H. Tanabe, M.
Nagai, Shikizai 67, 424 (1994)
197. I. Sekine, Prog. Org. Coat. 31, 73 (1997)
198. C. Scheffey, Rev. Sci. Instrum. 59, 787 (1988)
199. J. He, V.J. Gelling, D.E. Tallman, G.P. Bierwagen, G.G. Wallace, J. Electrochem. Soc.
147, 3667 (2000)
200. J. He, D.E. Tallmann, G.P. Bierwagen, J. Electrochem. Soc. 151, B644 (2000)
201. H.S. Isaacs, A.J. Davenport, A. Shipley, J. Electrochem. Soc. 138, 390 (1991)
202. E. Bayet, F. Huet, M. Keddam, K. Ogle, H. Takenouti, J. Electrochem. Soc. 144, L87
(1997)
203. E. Bayet, F. Huet, M. Keddam, K. Ogle, H. Takenouti, Electrochim. Acta 44, 4117
(1999)
204. L. Kelvin, Philos. Mag. 46, 82 (1898)
205. A.W. Adamson, Physical Chemistry of Surfaces (Wiley, New York, 1990)
206. B. Wessling, J. Posdorfer, Electrochim. Acta 44, 2139 (1999)
207. M. Stratmann, H. Streckel, Corros. Sci. 30, 681 (1990)
208. M. Stratmann, M. Wolpers, H. Streckel, R. Feser, Ber. Bunsenges. Phys. Chem. 95,
1365 (1991)
209. S. Yee, R.A. Oriani, M. Stratmann, J. Electrochem. Soc. 138, 55 (1991)

www.ebook3000.com
292 7 Surface Analytical Methods

210. M. Stratmann, M. Wolpers, H. Streckel, R. Feser, Ber. Bunsenges. Phys. Chem. 95,
1365 (1991)
211. G. Grundmeier, W. Schmidt, M. Stratmann, Electrochim. Acta 45, 2515 (2000)
212. M. Stratmann, H. Streckel, R. Feser, Farbe Lack 97, 9 (1991)
213. K. Wapner, B. Schoenberger, M. Stratmann, G. Grundmeier, J. Electrochem. Soc. 152,
E114 (2005)
214. G. Grundmeier, M. Stratmann, Appl. Surf. Sci. 141, 43 (1999)
215. V. Barranco, P. Thiemann, H.K. Yasuda, M. Stratmann, G. Grundmeier, Appl. Surf. Sci.
229, 87 (2004)
216. W. Fürbeth, M. Stratmann, Fresenius J. Anal. Chem. 353, 337 (1995)
217. M. Stratmann, R. Feser, A. Leng, Electrochim. Acta 39, 1207 (1994)
218. J. Posdorfera, B. Wessling, Fresenius J. Anal. Chem. 367, 343 (2000)
219. E. Juzeliunas, A. Sudavicius, K. Jüttner, W. Fürbeth, Electrochem. Commun. 5, 154
(2003)
220. G. Williams, R.J. Holness, D.A. Worsley, H.N. McMurray, Electrochem. Commun. 6,
549 (2004)
221. H.N. McMurray, A.J. Coleman, G. Williams, A. Afseth, G.M. Scamans, J. Electrochem.
Soc. 154, C339 (2007)
222. M. Stratmann, Corros. Sci. 27, 869 (1987)
223. A. Leng, M. Stratmann, Corros. Sci. 34, 1657 (1993)
224. M. Stratmann, H. Streckel, K.T. Kim, S. Crockett, Corros. Sci. 30, 715 (1990)
225. G.S. Frankel, M. Stratmann, M. Rohwerder, A. Michalik, B. Maier, J. Dora, M. Wicin-
ski, Corr. Sci. 49, 2021 (2007)
226. R.J. Hamers, in Scanning Tunneling Microscopy and Spectroscopy, ed. by D.A. Bonnell
(VCH, New York, 1993), p. 51
227. F.-R. Fan, A.J. Bard, J. Phys. Chem. 94, 3761 (1990)
228. H. Ibach, Electron Energy Loss Spectroscopy and Surface Vibrations (Academic Press,
New York, 1982)
229. G. Nagy, T. Wandlowski, Langmuir 19, 10271 (2003)
230. A.J. Bard, F.F. Fan, in Scanning Tunneling Microscopy and Spectroscopy, ed. by D.A.
Bonnell (VCH, New York, 1993), p. 287
231. M. Hugelmann, P. Hugelmann, W.J. Lorenz, W. Schindler, Surf. Sci. 597, 156 (2005)
232. E. Wierzbinski, K. Slowinski, Langmuir 22, 5205 (2006)
233. C. Vericat, I. Diez-Pérez, P. Gorostiza, F. Sanz, Electrochemical Society Spring Meeting
209th, Denver, Colorado, USA, May 7–11, 2006, Ext. Abstr. #1213
234. J. Halbritter, G. Repphun, S. Vinzelberg, G. Staikov, W.J. Lorenz, Electrochim. Acta
40, 1385 (1995)
235. E.V. Kasatkin, E.B. Neburchilova, Russ. J. Electrochem. 34, 1039 (1998)
236. R. Yang, W.H. Smyrl, D.F. Evans, W.A. Hendrickson, J. Phys. Chem. 96, 1428 (1992)
237. E. Abbe, Archiv Mikroskop. 9, 413 (1873)
238. B. Hecht, B. Sick, U.P. Wild, J. Chem. Phys. 112, 7761 (2000)
239. B. Knoll, F. Keilmann, Opt. Commun. 162, 177 (1999)
240. F. Keilmann, Vib. Spectrosc. 29, 109 (2002)
241. E.H. Synge, Phil. Mag. 6, 356 (1928)
242. R.C. Dunn, Chem. Rev. 99, 2891 (1999)
243. A. Bek, R. Vogelgesang, K. Kern, Rev. Sci. Instr. 77, 43703 (2006)
244. R. Stevenson, R. Riehn, R.G. Milner, D. Richards, E. Moons, D.J. Kang, M. Blamire,
J. Morgado, F. Cacialli, Appl. Phys. Lett. 79, 833 (2001)
245. M. Minsky, Scanning 10, 128 (1988)
 References 293

246. T. Wilson, C.J.R. Sheppard, Scanning Optical Microscopy (Academic Press, London,
1984)
247. T.G. Corle, G.S. Kino, Confocal Scanning Optical Microscopy and Related Techniques
(Academic Press, New York, 1996)
248. M. Völcker, A. Schnetz, R. Grub, Tech. Messen 63, 128 (1996)
249. O. Schneider, G.O. Ilevbare, J.R. Scully, R.G. Kelly, Electrochem. Solid State Lett. 4,
B35 (2001)
250. M.A. Alodan, W.H. Smyrl, J. Electrochem. Soc. 145, 957 (1998)
251. D.S. Chung, R.C. Alkire, J. Electrochem. Soc. 144, 1529 (1997)
252. B. Faltermeier, Tech. Messen 63, 4 (1996)
253. O. Schneider, G.O. Ilevbare, R.G. Kelly, J.R. Scully, J. Electrochem. Soc. 154, C397
(2007)
254. D. Schumacher, A. Otto, B.N.J. Persson, Chem. Phys. Lett. 178, 204 (1991)
255. J.O’M. Bockris, B.D. Cahan, G. Stoner, Chem. Inst. 1, 273 (1969)
256. R.I. Tucceri, D. Posadas, Electrochim. Acta 32, 27 (1987)
257. D. Körwer, D. Schumacher, A. Otto, Ber. Bunsenges. Phys. Chem. 95, 1484 (1991)
258. P. Lilie, Cyclovoltammetrische und transiente Messung des Gleichstromwiderstandes
während elektrochemischer Prozesse an Gold- und Silberschichten (Shaker Verlag,
Aachen, 2002)
259. R. Tucceri, Surf. Sci. Rep. 56, 85 (2004)
260. R. Holze, in Handbook of Advanced Electronic and Photonic Materials, vol. 2, ed. by
H.S. Nalwa (Gordon and Breach & OPA N.V., Singapoore, 2001), p. 171
261. R. Holze, in Handbook of Electronic and Photonic Materials and Devices, vol. 8, ed.
by H.S. Nalwa (Academic Press, San Diego, 2000), p. 209
262. R. Holze, J. Lippe, Synth. Met. 38, 99 (1990)
263. R.I. Tucceri, J. Electroanal. Chem. 505, 72 (2001)
264. S. Vogel, R. Holze, unpublished results
265. R.I. Tucceri, D. Posadas, Electrochim. Acta 32, 27 (1987)
266. F.M. Romeo, D. Posadas, R.I. Tucceri, J. Electrochem. Soc. 134, 145C (1987)
267. C. Hanewinkel, D. Schumacher, A. Otto, J. Electroanal. Chem. 554–555, 325 (2003)
268. M.D. Levi, E. Levi, Y. Gofer, D. Aurbach, E. Vieil, J. Serose, J. Phys. Chem. B 103,
1499 (1999)
269. M.H. Fonticelli, D. Posadas, R.I. Tucceri, J. Electroanal. Chem. 565, 359 (2004)
270. M.J. Schöning, in Ultrathin Electrochemical Chemo- and Biosensors in: ed. by O.S.
Wolfbeis, V.M. Mirsky. Springer Series on Chemical Sensors and Biosensors (Springer,
Berlin, 2004), p. 117
271. C. Hanewinkel, A. Otto, T. Wandlowski, Surf. Sci. 429, 255 (1999)
272. R.L. Deutscher, S. Fletcher, J.A. Hamilton, Electrochim. Acta 31, 585 (1986)
273. R. John, G.G. Wallace, J. Electroanal. Chem. 354, 145 (1993)
274. A. Talaie, G.G. Wallace, Solid State Ion. 70, 692 (1994)
275. A. Talaie, Solid State Ionics 74, 219 (1994)
276. A. Talaie, J.Y. Lee, K. Adachi, T. Taguchi, J. Romagnoli, J. Electroanal. Chem. 468, 19
(1999)
277. V.A. Marichev, Surf. Sci. Rep. 44, 53 (2001)
278. V.A. Marichev, Russ. J. Electrochem. 36, 240 (2000)
279. V.A. Marichev, Electrochim. Acta 41, 2551 (1996)
280. V.A. Marichev, Russ. J. Electrochem. 33, 990 (1997)
281. V.A. Marichev, Electrochim. Acta 43, 2203 (1998)
282. V.A. Marichev, Russ. J. Electrochem. 35, 434 (1999)

www.ebook3000.com
294 7 Surface Analytical Methods

283. N.D. Sverdlova, W. Schäfer, G.N. Mansurov, O.A. Petrii, Russ. J. Electrochem. 31, 227
(1995); Elektrokhimiya 31, 250 (1995)
284. V.A. Marichev, Russ. J. Electrochem. 35, 417 (1999)
285. J.-D. Grunwaldt, S. Hannemann, C.G. Schroer, A. Baiker, J. Phys. Chem. B 110, 8674
(2006)
286. S. Hannemann, J.-D. Grunwaldt, N. van Vegten, A. Baikeroer, P. Boye, C.G. Schroer,
Catal. Today 126, 54 (2007)
287. W.L. Tsai, P.C. Hsu, Y. Hwu, C.H. Chen, L.W. Chang, S.K. Seol, J.H. Je, G. Margari-
tondo, Extended Abstracts of the 203rd Meeting of the Electrochemical Society, Paris,
France, 27.04–02.05.2003, Ext. Abstr. #2845
Index

Ab initio calculation 109 CER 285

Adsorption overpotential 10 Charge carrier density 169
ADXD 234 Charge transfer overpotential 9
AFM 238 Chemical effect 106
Aircraft aluminum alloys 163 Chemiluminescence 47, 48
Alternating gradient field magnetometry Chiral 65
162 Cholesteric 65
Anodic stripping voltammetry 183 Circular dichroism 64
Anti-Stokes-shift 71 CLSM 280
Aperture 279 Combinatorial chemistry 78
aSNOM 130 Compensator 193
ASV 183 Confocal laser scanning microscopy 280
Atmospheric corrosion 274 Confocal microscopy 279
Atomic force microscopy 260 Confocal optical methods 279, 280
ATR 92 Confocal optics 121
Attenuated total reflection 37 Confocal Raman spectroscopy 128
Attenuated total reflection spectroscopy 91 Connes advantage 73, 111
Auger electron spectroscopy 24 Contact electroresistance 285
Contact potential 273
Bandgap energy 169
Corrosion 51
Benzotriazole 267
Corrosion compounds 104
Bidimensional UV-Vis-
Corrosion inhibitor 267
spectroelectrochemistry 44
Corrosion layer 16
Bipolaron 18
Cotton effect 64
Bohr magneton 145
Coupling constant 147
Boltzmann distribution 145
Creutz-Traube ion 90
Bragg angle 242
Crystal-truncation-rod 243
Bragg mode 235
Crystallization overpotential 10
Bragg peak 236
CTR 243
Bragg peak interference 240
Current density probe 272
Bragg-geometry 243
Braggs equation 234
D-band 104
Bremsstrahlung 234
Brewster angle 192 DEMS 21
Brewster windows 192 Densities of state 278
Density functional theory 109
Capturing reaction 164 DESERS 105
CDP 272 DFG 173, 175
Centrosymmetric media 173, 176 DFT 109

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296 Index

Diamond 39 ESI-FTMS 181

Diamond electrode 171 ESI-MS 181
Difference frequency generation 175 Ethylene dioxythiophene 198
Differential conductance tunneling Evanescent wave penetration length 46
spectroscopy 260 EXAFS 138
Differential electrochemical mass Expanded metal 40
spectrometry 21, 178
Differential photothermal deflection Far infrared 71
spectroscopy 63 Far infrared spectroscopy 102
Diffuse reflectance infrared spectroscopy FCS 280
100 Felgett advantage 73
Diffuse reflectance spectroscopy 57 Fermi level 107, 253, 278
Diffusion overpotential 9 Fermi resonance 90
Diheptyl viologen 61 Filiform corrosion 264, 277
Distance tunneling spectroscopy 278 Flatband potential 169
Doppler broadening 201 Fluorescence 47
Doppler-effect 132 Fluorescence correlation spectroscopy 280
DOS 278 Fluorescence spectroscopy 48
DRIFT 100 Fluorometer 49
Drude equation 281 Focal plane detector 37
DTS 279 Fowler-Nordheim equation 251
DXAFS 141 Free radicals 143
Dye films 85 Fresnel’s equations 50

ECESR 21 G-band 104

ECL 48 Genzel-Happ design 85
EDOT 198 GIXAFS 139, 142, 237
EDXD 238 GIXD 142
Electrochemical electron spin resonance GIXRD 237
spectroscopy 21 Glowbar 73
Electrochemically modulated infrared Green rust 104
reflectance spectroscopy 83
Electrochromic sites 43 Helmholtz layer 278
Electrogenerated chemiluminescence 48 Heptyl viologen 96
Electromagnetic effect 106 Hidden corrosion 163
Electron magnetogyric ratio 144 Highly oriented pyrolytic graphite 262
Electron spillover 143 HOPG 258, 262
Electron spin resonance spectroscopy 143 HR-SKP 274
Electropolishing 262 HREELS 278
Electroreflectance spectroscopy 50, 173 Hydrophobic porous membrane 179
Electrospray ionization Fourier transform Hyper-Raman scattering 123
mass spectrometry 181 Hyperfine splitting 146
Electrospray mass spectrometry 180
Ellipsometer 194 ICP-AES 200
Ellipsometry 192 IETS 278
Ellipsomicroscopy 195 Immiscible liquids 50
EMIRS 83 IMPS 167
EMLC 181 IMVS 170
EMSI 195 Indigo 40
 Index 297

Indium-doped tin oxide 16, 38 Linear potential scan infrared reflection

Inductively coupled plasma atomic emission spectroscopy 82
spectroelectrochemistry 200 LiTiS2 236
Inductively coupled plasma mass spectrom- Local density of states 253
etry 183 Localized electrochemical impedance
Inelastic tunneling spectroscopy 278 measurements 251
Infrared emission spectroscopy 101 Long optical pathlength 42
Infrared reflection spectroscopy 75 LPSIRS 82
Inner-sphere 106 LSM 242
Intensified multichannel detectors 44 Luggin capillary 84
Intensity modulated photocurrent spec- Luminescence 47, 50, 171
troscopy 167 Luminescence spectroscopy 47
Intensity-modulated photovoltage spec-
troscopy 170, 171 Magnetic circular dichroism 159
Intercalation 122 Magnetic momentum 144
Intercalation material 238 Magnetic resonance spectroscopy 143
Intercalation process 203 Magneto-optical Kerr effect 160
Interfacial conductivity measurements 285 Magnetogyric ratio 144
Interphase 10 Mass spectrometry 178
Inversion symmetry 173 Maxwell equations 77
Ionic liquid 36, 178 Metal matrix composite 273
Ionophor 270 Metal minigrid 74
Iron carbonyl complexes 90 Methylene blue 56
IRRAS 89 Michelson interferometer 102
ITO 16, 38 Micro Raman spectroscopy 122
ITS 278 Micro-optical ring electrode 172
Microdots 268
Jacquinot advantage 73 Microelectrode 264
Micropipette 271
Kelvin probe 273 Micropositioner 252
Kerr effect 161 Microradiology 286
Kretschmann configuration 196 Microroughness 77
Kretschmann design 95 Minigrid electrodes 40
KRS-5 93 Mirage effect 63, 184
Kubelka-Munk-functions 57 MMC 273
MnS inclusion 269
Larmor frequency 145 MOKE 160
Lateral force microscopy 262 Molten electrolytes 203
Laue mode 235 MORE 172
Laurionite 237 Mössbauer spectroscopy 24, 131
Layered synthetic microstrucuture 242 Multiplex advantage 73
LDOS 253
LEIS 251 Nano-indentation 262
LFM 262 Nano-scratching 262
LiFePO4 75 Nanode 267
LIGA 40 Nanoelectrode 267
LIGA-technique 38 Nanostructuring 259, 267
Light reflection method 189 Nanotribology 262
Lightning rod effect 106 NdYAG lasers 111

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298 Index

Near field methods 279, 280 pH-Microscopy 270

Near field Raman microscopy 130 Phase transition 236
Near infrared spectroscopy 65 Phase-shift interferometry 190
Negative feedback 265 Phosphine complexes 75
Nernst glower 73 Phosphorescence 47
Neutron diffraction 240 Photoacoustic methods 190
Neutron reflectivity 202 Photoacoustic spectroscopy 60
Neutron scattering 203, 241 Photocurrent conversion efficiency 169
Newns-Anderson resonance 282 Photocurrent measurements 165
NEXAFS 137 Photocurrent spectroscopy 165
Nickel oxide 129 Photoelastic modulator 64, 84, 160
NIR 71 Photoelectrochemical impedance spec-
Nitropropane 147 troscopy 167
Nitrosobenzene 40 Photoelectrochemical methods 164
Nonlinear optic 173 Photoelectrochemical microscope 172
Nonlinear optical methods 173 Photoelectrooxidation 48
Nonlinear surface susceptibility 174 Photoemission spectroscopy 164
Normal Raman spectroscopy 103 Photoluminescence 47, 48, 171
NRS 103 Photon scanning-tunneling microscope 252
Nuclear g-factor 144 Photosystem I 269
Nuclear magnetic resonance spectroscopy
Photothermal spectroscopy 62, 100
143
Photovoltage spectroscopy 170
Nuclear magnetogyric ratio 144
PIG 237
Plancks law 102
Optical spectroscopy 37
Plasma oscillations 195
Optically active molecule 64
Plasmon surface polariton 173, 195
Optically transparent electrode 16, 38
ORC 111 Platinum nanoparticle 238
ORD 64 PMFTIRRAS 85
Organic conductor 262 Pockels cell 64
Otto arrangement 197 Polaritons 195
Ottoconfiguration 196 Polarization modulated Fourier trans-
Outer-sphere 106 form infrared reflection absorption
Oxidation-reduction electrode potential spectrometry 85
cycling 111 Polaron 18
Poly(3,4-ethylenedioxythiophene) 172
Palladium monolayer 245 Poly(3-octyl pyrrole) 273
Paraffin-impregnated graphite 237 Polyalkylterthiophene 267
PAS 201 Polyaniline 171
PASCA 24 Poly(N-methylaniline) 187
Passivation 51, 103 Polypyrrole 171
PBD 184 Polythiophene 283
PDATRFTIRS 93 Porphyrins 50
PDFTIRRAS 93 Positron annihilation spectroscopy 24, 201
PDS 100 Positrons 201
PECM 172 Potential dependent attenuated total
PEIS 167 reflectance Fourier transform infrared
PEM 64, 84, 142 spectroscopy 93
PERMS 179 Probe beam deflection 184
 Index 299

Prussian blue 235 SEIRAS 94

PSTM 252 Self-assembled monolayer 115, 255, 269
Semiconductor/solution interface 175
Quarter-wave plate 64 SERRS 105, 126
SERS intensity 107, 112
Racemization 65 SERS-active sites 114
Radical cation 47 SFG 173, 175
Raman microscopy 103 SFIRS 102
Raman spectroscopy 103 SHG 173
Rayleigh scattering 105 SIET 266
RC-SECM 265 SIMS 24, 183
Reaction overpotential 9 Single molecule surface enhanced Raman
Reflection anisotropy spectroscopy 58 spectroscopy 128
Refractometer 185 Single-wall carbon nanotube 261
Reticulated vitreous carbon 47 SKP 263, 273
Rhodamine 6G 106 SKPFM 263
Rotational anisotropy 173, 175 SLAPEM 164
Rotational state 71
Sm-SERS 128
Small-angle X-ray scattering 245
Saccharin 121
Snells law 45
SAM 115, 116, 255
SNIFTIRS 79
Scanning electrochemical microscopy 264
SNIM 279
Scanning ion-conductance microscopy 271
SNOM 130, 279
Scanning ion-sensitive electrode technique
Solid electrolyte interface 180
266
Scanning Kelvin probe 273 Solid electrolytes 159, 238
Scanning Kelvin probe force microscopy Solid oxide fuel cell 102
263 Solid oxide fuels 102
Scanning near field infrared microscopy 279 Solvated electron 164
Scanning near field optical microscope 279 Spatially offset Raman spectroscopy 103
Scanning near field optical microscopy 130 Specular X-ray reflection 246
Scanning probe method 252 SPFELS 199
Scanning probe microscopy 252 Spin 144
Scanning reference electrode technique 271 Spin traps 150
Scanning tunneling microscopy 253 Spin–lattice relaxation 146
Scanning tunneling spectroscopy 277 Spin–spin relaxation 146
Scanning vibrating electrode technique 272 Spin–spin-splitting 146
Scavenger 164 Splitting constant 147
SDD 240 SPLS 199
SDEMS 180 SPM 252
SECM 264, 267 Square wave Fourier transform infrared
Second harmonic generation 173 reflection spectroscopy 82
Second-order non-linear optical process 175 SQUID magnetometry 163
Secondary ion mass spectrometry 183 SR-GIXRD 237
Secondary ion mass spectroscopy 24 SRRS 105, 125
Secondary lithium 236 SRS 22
SEHRS 123 Stark effect 109
SEI 180 Stark shift 52
SEIDAS 100 Stark tuning 109, 110

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300 Index

STM 245 SWNT 261

Stokes scattering 107 SXD 239
Stokes-shift 71 SXS 242
Strain fringe 260 Synchrotron 239
Structure factor 246 Synchrotron far infrared spectroscopy 102
Subtractively normalized interfacial Fourier Synthetic diamond discs 39
transform infrared spectroscopy 82 Synthetic diamond electrode 166
SUERS 105
Sum and difference frequency generation Thermodesorption mass spectrometry 183
175 Thermospray mass spectrometry 182
Sum-frequency generation 173, 175 THG 173
Suprabandgap illumination 166 Thin layer cells 38, 74
Surface analytical methods 251 Time-resolved SFG 177
Surface conductivity measurements 281 TiS2 236
Surface differential X-ray diffraction 240 TiSapphire-based laser 176
Surface enhanced hyper-Raman spec- Topcoat 275
troscopy 123 Topographic methods 251
Surface enhanced infrared absorption 78, 91 Transverse collective electron resonance 94
Surface enhanced infrared absorption Trapping 112
spectroscopy 94 Two-dimensional periodicity 239
Surface enhanced infrared difference
absorption spectroscopy 100 UHF-range 148
Surface enhanced Raman spectroscopy 104 Ultramicroelectrode 261, 264
Surface enhanced resonance Raman UME 264
spectroscopy 126 Underfilm corrosion 281
Surface plasmon dispersion curve 53 Underpotential deposition 175
Surface plasmon excitation 199 Upd-Cu 142
Surface plasmon field-enhanced light
scattering 199 Vibrational lifetime 177
Surface plasmon polaritons 94, 195 Vibrational state 71
Surface plasmon resonance angle 196 Volmer-Tafel mechanism 99
Surface plasmon resonance spectroscopy Volta potential 263
195 Voltage function generator 112
Surface plasmons 106 VTS 279
Surface Raman spectroscopy 22, 104
Surface reconstruction 238 Waveguide 148
Surface resistance 282
Surface resonance Raman spectroscopy 105, X-ray 233
125 X-ray absorption spectroscopy 137
Surface selection rules 72 X-ray diffraction 234
Surface sites 24 X-ray standing wave fluorescence analysis
Surface unenhanced surface Raman 241
spectroscopy 105 XANES 137
Surface X-ray diffraction 239 XAS 137
Surface X-ray scattering 242 XSW 241
SVET 272
SW-FTIRS 82 Zeeman effect 159