Design of Nano- Materials for

sustainable Photocatalytic Processes

Using Solar Energy
Dr. Nalini Sundaram
Assistant Professor
 Talk Outline
Part I
• introduction to Nanoscience/Nanotechnology
• Some General Applications of Nanomaterials

Part II
• Introduction to Photocatalysis
• Band Theory
• Visible Light Photocatalysis and Nanomaterials
• Summary
 3

What is Nanoscale Science?

• The study of objects and phenomena at a very small

scale, roughly 1 to 100 nanometers (nm)
– 10 hydrogen atoms lined up measure about 1 nm

An emerging, interdisciplinary science involving

– Physics
– Chemistry
– Biology
– Engineering
– Materials Science
– Computer Science

Source: http://www.cs.utexas.edu/users/s2s/latest/bialt1/src/WhatIsNano/images/molecule.gif
 What Is A Nanometer?

One rupee Hair

coin 100 m
2 cm

(m) 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9

cm mm m nm
Raindrop
1 mm
Red Blood Cell
5 m
 Now Entering The NANO-ZONE

Bacteriophage Gold Particles

60-70 nm 13 nm & 50 nm

100 80 60 40 20 1
(nm)

Flu Virus
100 nm
DNA
Diameter = 2 nm
 Terms and Definitions in the Nanotechnology Language
 Nanoscience: The study of
phenomena and materials at the
atomic, molecular and macro
molecular scales, where
properties differ significantly
from those at the larger scale

 Nanotechnology: design,
characterization, production
and application of structures,
devices and systems by
controlling shape and size at the
Multi-shell Gold nanowire
nanoscale
(TEM micrograph; 1 nm diameter)

 Semiconducting metal junction

formed by two carbon nanotubes
 Nanoscale: having one or more dimensions of the order
of 100nm or less, or having at least one dimension that
affects functional behavior at this scale

Nanomaterials: particles, nanotubes, nanowires, quantum

dots, fullerenes (buckyballs) etc that exist at a scale of
100nm or less, or that have at least one dimension that
affects their functional behavior at this scale

Model of a carbon nanotube

 History of Nanotechnology
Birth of Nanotechnology
The concepts of nanotechnology are not new to nature or to
mankind. An early example of a manmade nanoprocess is stained
glass.

Stained glass windows. Picture of gold nano particles.

 Brief History, Continued
Richard Feynman first
conceived the idea of molecular
manufacturing in his 1959 speech,
“There’s Plenty of Room at the
Bottom.” He is most famous for
saying, “The principles of physics, as
far as I can see, do not speak against the
possibility of maneuvering things atom
by atom.”

:
Ref Richard Feynman gave this famous
speech on December 29th 1959 at the annual
meeting of the American Physical Society at the 
California Institute of Technology (Caltech)
 More History
Professor Taniguchi of Tokyo Science
University used the word “nanotechnology”
to describe the science and technology of
processing or building parts with nanometric
tolerances in 1974
•A nanometer is a unit of length in the metric
system, equal to one billionth of a meter.
Tokyo Science University.

Equivalent Units
 More History
Eric Drexler
• Coined the term “Grey Goo”…the Engines of Creation
potential problem of self-replicating and
autonomous artificial intelligence
machines. The Coming Era
of Nanotechnology

By K. Eric Drexler
Drexler’s book.

DNA damage.
 Nobel Prize in Nanoscience
Buckyballs
• Three gentlemen—Harold Kroto from the
University of Sussex, Robert Curl and
Richard Smalley from Rice University—were
awarded the Nobel Prize in Chemistry in
1996 for their discovery of a new composition Carbon-60 buckyball is shaped like a
of carbon, Carbon 60. soccer ball.

Fullerenes
• Carbon 60 was named after Richard Buckminster Fuller, who went by the
nickname “Bucky

A “Buckyball.” Dome over biosphere in Montreal.

 The 2007 Nobel Prize in Physics for the discovery of
Giant Magnetoresistance"
Albert Fert (France) and Peter Grünberg (germany)

The GMR effect was discovered thanks to new techniques developed during the
1970s to produce very thin layers of different materials.

If GMR is to work, structures consisting of layers that are only a few atoms thick
have to be produced. For this reason GMR can also be considered one of the first
real applications of the promising field of nanotechnology.

 Nanotechnology gives sensitive read-out heads for compact hard disks

The 2010 Nobel Prize for Graphene Nanotechnology

Andre Geim and Konstantin Novoselov won the 2010 Nobel Prize in Physics
“for groundbreaking experiments regarding the two-dimensional material
graphene”, and their work has opened a broad frontier in nanotechnology.
 Nanofabrication
• Bottom-up: Assemble nanoscale objects out of
even smaller units (e.g., atoms and molecules)
• Top-down: Chisel away material to make
nanoscale objects

 Ultimate Goal: Dial in the properties that you

want by designing and building at the scale of
nature (i.e., the nanoscale)
 How do nanoparticles form?

Chemical reaction Critical concentrantion,

takes place nucleation begins
Aggregation happens
due to its lowering the
free energy

Particles grow and

consume all the solute

Best time to synthesize

nanoparticles

Subsequent growth of the nuclei

lowers the solute concentration

Img by deMello, J. & deMello, A. Microscale reactors: nanoscale products. Lab Chip 4, 11N–15N(2004).
Schematic diagram of the Bottoms-Up Approach
Nan05.pdf
 So What?

Is nanoscience just seeing

and moving really small
things?

• Yes, but it’s also a whole lot more. Properties of

materials change at the nanoscale!
 Nanogold
• Well… strange things happen at the small scale
– If you keep cutting until the gold pieces are in the nanoscale
range, they don’t look gold anymore… They look RED!
– In fact, depending on size and type of structure, they can
turn red, blue, yellow, and other colors

12 nm gold particles look red

Other sizes are other colors

• Why?
– Different thicknesses of materials
reflect and absorb light differently

Source: http://www.nano.uts.edu.au/pics/au_atoms.jpg
 QD
• A quantum dot, also called a semiconductor nanocrystal or
artificial atom is a semiconductor crystal whose size is on the
order of just a few nanometers and which reemit the light in a
different colour according to the particle size.

Img from: http://www.answers.com/topic/fluorescence-in-various-sized-cdse-quantum-dots-png

 21

Carbon Buckyballs (C60)

• Profile
• Full name: Buckministerfullerine
• 60 Carbon atoms in interlocking
hexagons and pentagons, cousins of
graphite and diamond
• 1996 Nobel Laureate for chemistry
• Nanoscale single element hollow
spheroid
• Resistant to high speed collisions
• Superconducting
• Incredible strength due to their bond
structure and “soccer ball” shape
• Could be useful “shells” for drug
delivery
• Can penetrate cell walls
• Are nonreactive (move safely
through blood stream) Model of Buckminsterfullerene

Source: http://digilander.libero.it/geodesic/buckyball-2Layer1.jpg
 22

Carbon Nanotubes
• Using new techniques,
amazing structures like
carbon nanotubes have
been created
• 100 time stronger than
steel and very flexible
• If added to materials
like car bumpers,
increases strength and
flexibility

Model of a carbon nanotube

Source: http://www.library.utoronto.ca/engineering-computer-science/news_bulletin/images/nanotube.jpeg
 Potential Impacts of
Nanotechnology
• Materials • Technology
– Stain-resistant clothes – Better data storage
• Health Care and computation
– Chemical and biological • Environment
sensors, drugs and
delivery devices
– Clean energy, clean
air

Thin layers of gold are used Carbon nanotubes can be Possible entry point for
in tiny medical devices used for H fuel storage nanomedical device
 Materials: Stain Resistant
Clothes
• Nanofibers create cushion of air around
fabric
– 10 nm carbon whiskers bond with cotton
– Acts like peach fuzz; many liquids roll off

Nano-Care fabrics with water, cranberry juice,

Nano pants that refuse to stain; vegetable oil, and mustard after 30 minutes
Liquids bead up and roll off (left) and wiped off with wet paper towel (right)

Sources: http://www.sciencentral.com/articles/view.php3?article_id=218391840&cat=3_5
http://mrsec.wisc.edu/Edetc/IPSE/educators/activities/nanoTex.html
 Environment: Paint That Cleans
Air
• Nanopaint on buildings
could reduce pollution
– When exposed to
ultraviolet light, titanium
dioxide (TiO2)
nanoparticles in paint
break down organic and
inorganic pollutants that Buildings as air purifiers?

wash off in the rain

– Decompose air pollution
particles like formaldehyde

Sources: http://english.eastday.com/eastday/englishedition/metro/userobject1ai710823.html
 Technology: A DVD That Could
Hold a Million Movies
• Current CD and DVD media have storage
scale in micrometers
• New nanomedia (made when gold self-
assembles into strips on silicon) has a
storage scale in nanometers
– That is 1,000 times more storage along
each dimension (length, width)…

…or 1,000,000
times greater
storage density
in total!

Source: Images adapted from http://uw.physics.wisc.edu/~himpsel/nano.html

 Part II: Photocatalysis
Energy and Environmental Issues:

Chem. Soc. Rev., 2009, 38, 1999–2011

Photocatalysis - Need of the day
 What is Photocatalysis
• The role of photocatalysis is to initiate or accelerate
specific reduction and oxidation (redox) reactions in
the presence of irradiated semiconductors.

• Materials that show photocatalytic capability are called

Photocatalysts

• The most popular and economically viable example is

titanium dioxide
 Photocatalysis

CO2 + H2O

CO2
Chlorophyll

Photocatalyst

Organic
Compound

H2O Starch + O2 + H2O + O2

Organic compound
 Photocatalysts Requirements
1) Efficient conversion of sunlight to electron-hole pairs.
2) Surface trapping of electrons and holes before recombination.
3) Catalyst photostability.
4) Inexpensive, chemically-stable, environmentally benign materials.
Electromagnetic Spectrum
 How much Solar Energy?

The surface receives about 47% of the

solar energy that reaches the earth.
Only this amount is usable
Three chemical ways to exploit Sun Light by Photocatalysis:

1.Production of Hydrogen by Water splitting

2. Activating chemical processes Organic

transformations

3. Destroying undesired chemicals

 Sources of effluents:
 industries
 Textile industries
 Paper and ink
manufacturing
industries
 Cosmetics
 Dyeing and printing
 Pharmaceuticals
 Food
Mechanism of Photocatalysis

Adv. Mater. 2012, 24, 229–251

• The highest energy band completely filled with
electrons (at T = 0 K) is called the Valence Band
• The next band is called the Conduction Band

• The energy difference

between the bottom of
the Conduction and
the top of the Valence
bands is called the
Band Gap
 Benchmark Photocatalyst; TiO2
Influence of structural and
electronic characteristics on
TiO2 photoactivity
Phases: Anatase (tetragonal),
Rutile (tetragonal), Brookite (orthorhombic)
and TiO2 (B) (monoclinic)

Anatase --- below 400 C BG – 3.0eV

Rutile ------ above 400 C BG – 3.2eV

VB – O 2p orbitals, CB – 3d orbitals with t2g symmetry of Ti4+ cation

Anatase Rutile mixture - Degaussa P25 ; Biphasic TiO2 Superior than Anatase
 Wavelength

Band Gap – 3.2eV UV active

Utilises less than 6% of solar energy

300nm> Wavelength < 400nm Catalysis Today ., 2009 ,147 ,1–59

Visible Light Driven Photo Catalysis

The Separation of photo induced electron-hole pairs by

dispersion
 Advantages of Nanomaterials in Photocatalysis

Quantum size (confinement) effects

- Energy levels of atoms vs. energy band in bulk
- Conductor, semiconductor, insulator
Conduction Band: white

Band gap
No gap

Valence Band
in red

Conductor Insulator Semiconductor 42

As size decreases(<de Broglie wavelength)
electrons (and holes) are confined → “particle in a box”
→ electrons: discrete energy level or level spacing > kBT
•It is called size quantisation and arises because the size
of a nanoparticle is comparable to the de Broglie
wavelength of its charge carriers (i.e. electrons and holes).
•Due to the spatial confinement of the charge carriers, the
edge of the valance and conduction bands split into
discrete, quantized, electronic levels. These electronic
levels are similar to those in atoms and molecules.
Semiconductors
•Electron-hole pairs
(excitons)

-Due to much longer

wavelength of excitons in
semiconductor(1um
compared to 0.5nm for
metal) size confinement
appears for N=10,000
atoms

- Discrete energy levels

- Increase in bad gap
 Ways for Developing Nano Photocatalysts:
Energy Band Engineering:

1. Modification of VB

2. Adjustment of CB

3. Modulation of VB and CB
 Modification of VB
1.Doping 3d transition element to multimetal oxides

In1-xNixTaO4 (x = 0–0.2)

Challenges:
1. Creates defects which increase the recombination probability
2. Suppress the migration of the carriers
2. Cations with d10 and d10s2 electronic configuration
Bismuth based photocatalysts CaBi2O4 degrades Acetaldyhyde and Methylene Blue
in gaseous phase
Bi 6p states at the CB O2p and Bi 6s hybrid states at VB …………… Upshift of VB

ref .J. W. Tang, Z. G. Zou, J. H. Ye, Angew. Chem. Int. Ed. 2004, 43,4463J.
H. Ye, Z. G. Zou, J. Phys. Chem. Solids 2005, 66, 266.
Z. G. Zou, J. H. Ye, K. Sayama, H. Arakawa, Nature 2001, 414, 625
 3. Doping with non metals: N, C, B, S

• N- doped HNb3O9 showed superior catalytic activity

to commercial TiO2 (P25) as well as to N-doped TiO2

The crystal structure is destroyed when the proportion of substituted

anions increases

X. K. Li, N. Kikugawa, J. H. Ye, Adv. Mater. 2008, 20,

3816.
 .Nano Assemblies

Electronic coupling assembly

a. TiO2 Nanoparticles a. TiO2 Nanoparticles

assembly crushed
Adv. Mater. 2012, 24, 229–251
 Advantages of Nanomaterials in
Photocatalysis
– huge surface area
• Effcient surface trapping of electrons and holes
– small particle size
• particle size is generally beneficial for surface-dependent
photocatalysis because it leads to quadratic growth of the
specific surface area and hence reactive sites

Ag.NanoWires BiVO4 Nanoplatelets: active

Facets
 Morphology Control: Crystallinity and particle size effect

Effects of particle size on photocatalytic activity.

However, it is not always the case that the smaller the particle size, the higher
the efficiency

a strong quantum confinement effect appears to increase the recombination

rate

Chem. Soc. Rev., 2009, 38, 253–278

SEM images of Ag3PO4 sub-microcrystals with different morphologies: (A) rhombic
dodecahedrons and (B) cubes. The photocatalytic activities of Ag3PO4 rhombic
dodecahedrons,cubes, spheres, and N-doped TiO2 are shown for the degradation of
(C) MO and(D) RhB under visible light irradiation (λ > 400 nm).
 Bi –Based Oxychlorides as an
efficient photo catalysts

Oxychlorides: BiOCl Eg=2.9eV

Bi3O4Cl Eg=2.80eV

Anatase: TiO2 Eg=3.2eV

Shows better catalytic Performance than

Anatase
J. Phys. Chem. B 2006, 110, 24629-24634
Aurivillius-Sillen intergrowths

[Bi2O2][An-1BnO3n+1][Clm]
(n=1,m=1,B= Nb)

Sillen phase:[M2O2][Xm]

Aurivillius phase: [Bi2O2][An-1BnO3n+1]

Aurivillius-Sillen phase materials are

important for ferroelectric, piezoelectric
properties
CB consists of Bi 6p and Nb 4d orbitals
VB consists of O 2p and Cl 3p orbitals
Experimental
Combustion Synthesis(CS) of Bi4TaO8Cl

Precursor
+ Fuel
(Urea))
Oxidizer
Solid State(SS) synthesis of Bi4MO8Cl [M = Nb,Ta]
Bi2O3
Calcined Bi4MO8Cl
+
M2O5
7000C, 15 hrs
+
BiOCl
X-Ray Diffraction for phase purity
 Band Gap by UV-Vis DRS

Band gap of Bi4TaO8Cl SS Band Gap of Bi4TaO8Cl CS

Eg=2.80eV
Eg=2.59eV

Band gap for Bi4TaO8Cl CS is larger than that of Bi4TaO8Cl SS

 “Seeing” at the nanoscale
• Characterization tools of nanoscience
 Microscopy
 Transmission Electron Microscopy
 Scanning Electron Microscopy
 Scanning Probe Microscopy

Atomic Force Microscopy Scanning Tunneling Microscopy

 SEM Analysis

SEM image of BulkBi4TaO8Cl

SEM image of Nano Bi4TaO8Cl
 Size of the Particles range from 30-70nm for Nano Bi4TaO8Cl
 Size of particle range from 400-900nm for Bulk Bi4TaO8Cl
 Forms nano structure with interconnected particle(Nano Bi4TaO8Cl )
 Forms microstructure (Bulk Bi4TaO8Cl)
 SEM Analysis

SEM image of Nano Bi4NbO8Cl

 Forms porous nano structure

SEM image of Bulk Bi4NbO8Cl

 Micrometer regime
Photocatalytic Reactor Setup:
 Photo catalytic measurement:

Quartz cell Mercury Lamp

Reaction Temperature: Room

Temperature
Volume of MO: 300ml
Powder concentration
in MO aqueous solution:0.2g per 100ml
Solution is magnetically stirred in the dark for
50mins
 Dye Degradation(Congo Red)
Under UV irradiation

Dye = 30mg/L
Catalyst = 0.2g/100ml

Congored degradation by Bi4TaO8Cl

Nano particles degrade the Dye faster than the bulk

 Dye Degradation(Congo Red)
Under Sun light

Dye = 30mg/L
Catalyst = 0.2g/100ml

Congored degradation by Bi4TaO8Cl

Nano particles degrade the Dye faster than the bulk

 Degradation Efficiency

Recyclability of Bi4TaO8Cl CS

Bi4TaO8Cl CS removes 95% of the dye

Bi4TaO8Cl SS removes 80% of the dye

After the reuse, Photocatalytic activity

will not fade to the greater extent
 Recyclability of nano and bulk Bi4TaO8Cl

 Little fading of photocatalytic activity observed for nano Bi 4NbO8Cl

Removal of Congo Red

FTIR spectra of a) CR b) Catalyst c)CR+Catalyst (UV Light) and

d)CR + Catalyst (Sun light)
UV-Vis Absorpiton Spectra

Successive UV-Vis Spectra of CR degradation at different time

interval in presence of Nano Bi4TaO8Cl
Development of alternative Photocatalysts for
water Splitting:

Chem. Soc. Rev., 2009, 38, 253–278

Mechanism:

Chem. Soc. Rev., 2009, 38, 253–278

The system that can promote both these reactions simultaneously is essential

2H+ + 2e- → H2 2OH- + 2h+ → H2O + 1/2O2

Relationship b/n Band structure and Redox potential for water splitting

Chem. Soc. Rev., 2009, 38, 253–278

 Multilayer Photocatalysts are the alternatives

Water splitting over K4Nb6O17 photocatalyst with layered structure

A. Kudo, A. Tanaka, K. Domen, K. Maruya, K. Aika and T. Onishi, J.Catal., 1988, 111, 67.
Effect of Distortion of Crystal structure on band Gap

H. Kato and A. Kudo, J. Phys. Chem. B, 2001, 105, 4285.

 Effect of Co-Catalyst

H. Kato, K. Asakura and A. Kudo, J. Am. Chem. Soc., 2003, 125,

3082 H. Kato and A. Kudo, J. Phys. Chem. B, 2001, 105, 4285.
Alternative photocatalysts for Water Detoxification

Mechanism Of Detoxification

Oxidative reaction:
h+ + Organic(R) Intermediates CO2 þ H2O
h+ + H2O OH + h+

Reductive reaction:
OH - Organic (R) Intermediates CO2 +
H2O
Pictorial Representation
Photocatalytic Applications
Antimicrobial Effect
Antimicrobial Effect
Self-Cleaning Effect
 “Sense
“Sense and
and Shoot”
Shoot”
Approach Nanosized zinc oxide (ZnO) “senses”
Approach to
to Pollution
Pollution
Treatment organic pollutants indicated by change
Treatment
in visible emission signal.

Dual role of ZnO semicondouctor

film as a sensor and photocatalyst The ZnO “shoots” the pollutants via
photocatalytic oxidation to form more
environmentally benign compounds.
>300 nm

Sensing capability means that the

UV energy-consuming oxidation stage only
occurs when the pollutants present.

Multifunctionality and “smartness” is

highly desirable for environmental
applications.
mat, P.V, et al. J.Phys.Chem. B 2002, 106,788-794.
 RAKO self cleaning ceramic tiles

Ref: http://www.powershow.com/view/154754-
MGZjN/Photocatalytic_titania_nanosurfaces_application_progress_problems_international_cooperation_powerpoint_ppt_prese
ntation
Applications of TiO2/cement (CTG Italcementi Grp)
Summary: Solar Photocatalysis
at the Nanoscale
• An emerging, interdisciplinary science
– Integrates chemistry, physics, biology, materials
engineering, earth science, and computer science

• The power to collect data and manipulate particles

at such a tiny scale will lead to
– New areas of research and technology design
– Better understanding of matter and interactions
– New ways to tackle important problems in energy, the
environment, and technology
– Many emerging practical applications