Physicochemical Problems

Physicochem. Probl. Miner. Process. 50(1), 2014, 265−276

of Mineral Processing
ISSN 1643-1049 (print)
www.minproc.pwr.wroc.pl/journal/
ISSN 2084-4735 (online)

Received May 30, 2013; reviewed; accepted, July 23, 2013

SYNTHESIS AND PHYSICOCHEMICAL

CHARACTERISTICS OF TITANIUM DIOXIDE
DOPED WITH SELECTED METALS

Katarzyna SIWINSKA-STEFANSKA*, Dominik PAUKSZTA*,

Adam PIASECKI**, Teofil JESIONOWSKI*

*
Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemical Technology and
Engineering, Marii Sklodowskiej-Curie 2, PL-60-965, Poznan, Poland; e-mail: Katarzyna.Siwinska-
Stefanska@put.poznan.pl, phone: +48 616653626, fax: +48 616653649
**
Poznan University of Technology, Faculty of Mechanical Engineering and Managment, Institute of Materials
Science and Engineering, Jana Pawla II 24, PL-60-965, Poznan, Poland

Abstract: The paper details with of the preparation and physicochemical characterisation of nano- and
microstructured TiO2 doped with Fe and Co produced by the sol-gel method using titanium alkoxide as
the precursor of titania as well as iron or cobalt nitrates as dopant sources. Fe and Co doped TiO2
materials were successfully prepared with two different methods. The effect of the dopant type on the
synthesis of TiO2 powders was investigated. The physicochemical properties of the studied samples were
determined. The characterisation included determination of the dispersion and morphology of the systems
(particle size distribution, SEM images), characteristics of porous structure (BET isotherms), crystalline
structure (XRD), surface composition (EDS), as well as thermal stability (TG/DTA).

Keywords: titanium dioxide, sol-gel method, doping, TiO2 surface modification, Fe and Co dopant

Introduction
Titanium dioxide (TiO2) has emerged as one of the most fascinating materials in the
modern era. It has captured the attention of physical chemists, physicists, material
scientists, and engineers exploring distinctive semiconducting and photocatalytic
properties (Wu, 2007; Huang, 2009; Wang, 2009; Xu, 2011; He, 2012). Inertness to
the chemical environment and long-term photostability has made TiO2 an important
component in many practical applications and in commercial products. From drugs to
doughnuts, cosmetics to catalysts, pigments to pharmaceuticals, and sunscreens to
solar cells, TiO2 is used as a desiccant, brightener, or reactive mediator.

http://dx.doi.org/10.5277/ppmp140122
266 K. Siwinska-Stefanska, D. Paukszta, A. Piasecki, T. Jesionowski

Titanium dioxide represents an effective photocatalyst for water and air

purification and for self-cleaning surfaces. Additionally, it can be used as an
antibacterial agent because of strong oxidation activity and superhydrophilicity
(Fujishima, 2006). TiO2 shows relatively high reactivity and chemical stability under
ultraviolet light (λ < 387 nm), whose energy exceeds the band gap of 3.3 eV in the
anatase crystalline phase. The development of photocatalysts exhibiting high reactivity
under visible light (λ > 400 nm) should allow the main part of the solar spectrum to be
used, even under poor illumination of interior lighting. Several approaches to
modifying TiO2 have been proposed: metal-ion implanted TiO2 (using transition
metals: Cu, Co, Ni, Cr, Mn, Mo, Nb, V, Fe, Ru, Au, Ag, Pt) (Anpo, 2000; Fuerte,
2001; Yamashita, 2001), reduced TiOx photocatalysts (Takeuchi, 2000; Ihara, 2001),
non-metal doped-TiO2 (N, S, C, B, P, I, F) (Ohno, 2003; Yu, 2003; Liu, 2005),
composites of TiO2 with semiconductor having lower band gap energy (e.g., Cd-S
particles (Hirai, 2001), sensitizing of TiO2 with dyes (e.g., thionine) (Chatterjee, 2001)
and TiO2 doped with upconversion luminescence agent (Zhou, 2006; Wang, 2007).
The aim of the study was verification of preparation methods of TiO2 doped with
metallic species, including two types of dopants and doping methods. The effect of the
doping process on the fundamental physicochemical properties for all obtained
samples was evaluated.

Experimental
Materials
The pure and doped TiO2 powders were synthesized employing the sol-gel method, in
which titanium tetraisopropoxide (Ti(OC3H7)4, 97%) was used as the precursor of
titania, ammonia (NH4OH, 25%) as catalyst, 2-propanol (C3H7OH, 99.5%) as solvent,
iron(III) nitrate (Fe(NO3)3.9H2O, 98%) and cobalt(II) nitrate (Co(NO3)2.6H2O, 98%) as
dopant sources.

Synthesis of TiO2 via sol-gel method

TiO2 powder was prepared by a sol-gel process, in which sol was prepared by mixing
titanium tetraisopropoxide (TTIP), 2-propanol, and ammonia at room temperature. 15
cm3 (0.049 mole) of TTIP as the starting material was dissolved in 100 cm3 (1.304
mole) of 2-propanol. Upon stirring the catalyst, ammonia was introduced at a constant
rate of 1 cm3/min. The titanium alkoxide solution was hydrolysed by adding 15 cm3
(0.033 mole) of ammonia. The initially clear solution turned into a white emulsion.
This solution was vigorously stirred for 1 h. The entire system was transferred to a
round-bottomed flask and placed in a vacuum rotary evaporator, in order to remove
the solvent (water bath temperature 60 °C, pressure 136 mbar). The subsequent stage
involved filtration of the mixture under reduced pressure. The sample obtained in this
way was washed with distilled water. At the terminal stage, the sample was dried by
 Synthesis and physicochemical characteristics of titanium dioxide doped with selected metals 267

convection at 105 °C for 18 h. The sample was then calcined at 600 °C for 2 h. The
proposed method for preparing TiO2 is presented schematically in Fig. 1a.

Synthesis of doped-TiO2
The doped-TiO2 materials were prepared following two different methods.
The first method: solution A was prepared by adding 15 cm3 (0.049 mole) of titanium
tetraisopropoxide to 100 cm3 (1.304 mole) of 2-propanol. A certain amount of
Fe(NO3)3 or Co(NO3)2 was dissolved in 100 cm3 (0.782 mole) of 2-propanol (solution
B). Subsequently, solution B and ammonia (catalyst – solution C) were introduced to
solution A, at a constant rate of 5 and 1 cm3/min, respectively. The resulting solution
was vigorously stirred. When dosing of solutions B and C was terminated, the
emulsion obtained was mixed for 30 min. The second method: solution A was
prepared by adding 15 cm3 (0.049 mole) of titanium tetraisopropoxide to 50 cm3
(0.670 mole) of 2-propanol. At first, a certain amount of Fe(NO3)3 or Co(NO3)2 was
dissolved in 100 cm3 (0.782 mole) of 2-propanol and then the solution obtained
(solution B) was dosed to solution A at a constant rate of 5 cm3/min. The obtained
solution was vigorously stirred. Next, 15 cm3 (0.033 mole) of ammonia was dissolved
in 50 cm3 (0.670 mole) of 2-propanol (solution C) and then the resulting mixture was
introduced to a mixture of solution A and B, at a constant rate of 1 cm3/min. When
dosing of solution C was terminated, the obtained emulsion was mixed for 30 min.
The concentrations of Fe and Co calculated for mass of the dry sample of titania were
0.10; 0.25; 0.57; 0.75; 1.00; 1.70 and 2.80% mass, respectively. Classification of the
obtained products was realised in analogous way as in the case of preparation titanium
dioxide. The final products of Fe- and Co-doped titania have a yellow/orange and
green colour, respectively. Fig. 1 b and c presents two doping methods of titania.

Fig. 1. Preparation of (a) TiO2 and doped-TiO2 by (b) first method, (c) second method via sol-gel method
268 K. Siwinska-Stefanska, D. Paukszta, A. Piasecki, T. Jesionowski

Determination of physicochemical properties

The doped-TiO2 samples were subjected to comprehensive characterisation using the
most advanced analytical methods and techniques. The dispersive properties of
TiO2/Fe and TiO2/Co samples were evaluated based on the particle size distributions
and polydispersity index (PdI) determined using a Zetasizer Nano ZS made by
Malvern Instruments Ltd. operating based on non-invasive back scatter technique. The
samples of doped-TiO2 were also subjected to morphological and microstructural
analysis using a scanning electron microscope – Zeiss EVO40. In order to characterise
their porous structure, nitrogen adsorption/desorption isotherms at 77 K and
parameters such as surface area (ABET), pore volume (Vp) and average pore size (Sp)
were determined using an ASAP 2020 instrument (Micromeritics Instrument Co.). All
samples were degassed at 120 °C for 4 h prior to measurement. The surface area was
determined by the multipoint BET (Brunauer–Emmett–Teller) method using the
adsorption data in the relative pressure (p/p0). The BJH (Barrett–Joyner–Halenda)
method was applied to determine the pore volume and the average pore size. The
doped-TiO2 samples were also subjected to crystalline structure determination using
the WAXS method (wide-angle X-ray scattering). X-ray diffraction measurements
were performed using Cu Kα (λ=1.54056 Å) radiation. The accelerating voltage and
the applied current were 30 kV and 15 mA respectively. The samples were scanned at
a rate of 0.04° over an angular range of 5–60°. Moreover, the surface composition of
the obtained materials was analysed using an EDS technique (energy dispersive X-ray
spectroscopy) using a Princeton Gamma-Tech unit equipped with a prism digital
spectrometer. Thermogravimetric analysis was performed using a Jupiter STA 449 F3
(Netzsch GmbH). Samples weighing approximately 10.0 mg were placed in an Al2O3
crucible, and heated at a rate of 10 °C/min from 30 to 1000 °C in a nitrogen
atmosphere.

Results and discussion

The aim of the first stage of the study was to characterise the dispersive properties and
morphology of the pure TiO2 obtained via the sol-gel method. The titanium dioxide is
characterised by a monomodal particle size distribution with a relatively wide band
covering the diameter range of 955-2670 nm. The maximum volume contribution of
28.4% corresponds to agglomerates of 1720 nm in diameter (Fig. 2a). The
polydispersity index of TiO2 is 0.153, which means that this sample is rather
homogeneous. The SEM microphotograph of the titanium dioxide studied presented in
Fig. 2b confirms the presence of particles of micro-sized diameter (corresponding to
those indicated in the particle size distribution), their almost spherical shape and high
homogeneity.
The structure of obtained sample was studied using the WAXS method. The
crystalline structure of sample determines their suitability for particular applications
(catalysis, paints, lacquers, and polymer fillers). Titania of well-defined crystalline
 Synthesis and physicochemical characteristics of titanium dioxide doped with selected metals 269

structure shows diffraction maxima at certain specific 2-theta values. Figure 2c shows
the WAXS pattern of prepared TiO2 sample of the anatase structure, characterised by
the presence of maxima at 2Θ values of 25, 38, 48, 54 and 55, which is a confirmation
of the effective preparation process (JCPDS, Card 21-1272.).
Characterisation of the porous structure of pure TiO2 included determination
of the nitrogen adsorption/desorption isotherms and calculation of the surface area,
size and volume of pores. Synthetic TiO2, obtained via the sol-gel method, has defined
surface activity, which is indicated by its specific surface area of 17.4 m2/g. It can be
classified as mesoporous adsorbent as its pore volume is Vp = 0.013 cm3/g and pore
diameter is Sp = 2.9 nm.

Fig. 2. Particle size distribution (a), SEM microphotograph (b) and WAXS pattern (c)
of TiO2 obtained via sol-gel method

At the next stage, the titanium dioxide preparation process was supplemented with
doping using selected metals (Fe and Co). The main aim of the study was to evaluate
the efficiency of the doping process of synthetic titanium dioxide and to determine its
influence on the fundamental physicochemical properties of the obtained systems.
Samples of TiO2 doped with Fe and Co were subjected to dispersive and
morphological characterisation. Table 1 presents the dispersive characteristics of
doped-TiO2 samples. The results prove that the doping process caused significant
changes in the dispersive character of the obtained systems.
270 K. Siwinska-Stefanska, D. Paukszta, A. Piasecki, T. Jesionowski

Table 1. Dispersive properties of doped-TiO2 obtained via sol-gel method

Amount of metal Particle size distributions by volume (nm) and

Polydispersity index
dopant (% mass) maximum volume contribution (%)
TiO2/Fe (first method)
0.10 295–1110 (531 nm – 24.9) 0.329
0.57 255–825 (459 nm – 25.5) 0.191
1.00 220–615 (396 nm – 27.3) 0.298
190–825 (396 nm – 8.7)
2.80 0.424
3090–6440 (5560 nm – 25.7)
TiO2/Fe (second method)
0.10 342–955 (615 nm – 29.2) 0.079
0.57 342–1280 (712 nm – 23.4) 0.342
1.00 531–1990 (1280 nm – 20.2) 0.099
2.80 396–1480 (712 nm – 23.7) 0.264
TiO2/Co (first method)
0.10 531–1480 (955 nm – 26.3) 0.098
0.57 615–1720 (1110 nm – 25.3) 0.247
1.00 255–615 (459 nm – 28.6) 0.417
2.80 295–825 (531 nm – 27.7) 0.205
TiO2/Co (second method)
0.10 531–2300 (1280 nm – 19.7) 0.267
0.57 459–1720 (955 nm – 23.4) 0.305
1.00 531–1990 (1110 nm – 22.4) 0.195
2.80 342–1280 (615 nm – 22.8) 0.260

The substantial differences in the mean diameters of TiO2 particles doped with two
different metals in different amounts, imply that the dopant type have a great effect on
the dispersive parameters of the final products. The dispersive characteristics show
that noticeable changes in the particle size of all doped TiO2 appear independently of
the type and quantity of the dopant as well as the doping method. According to the
results, by far the best dispersive properties are shown by materials doped with iron.
All samples of the doped materials have particles of smaller diameter than those
determined in the sample of pure titanium dioxide. In most samples, the doping of
pure TiO2 with selected dopant (in relation to the amount of dopant used) contributed
to a decrease in the sample’s homogeneity (higher polydispersity index) – see Table 1
– compared to that of pure titania.
The SEM microphotographs of the samples studied presented in Fig. 3 confirm the
presence of particles of microsized diameter (corresponding to those indicated in
particle size distributions), high homogeneity, almost spherical shape and showing a
small tendency to form agglomerate structures.
 Synthesis and physicochemical characteristics of titanium dioxide doped with selected metals 271

Fig. 3. SEM microphotographs of TiO2 doped with 1.0% mass of Fe (first method – a),
1.0% mass of Fe (second method – b), 1.0% mass of Co (first method – c)
and 1.0% mass of Co (second method – d)

The XRD patterns of different TiO2 samples (pure, Fe and Co doped) are shown in
Fig. 4. The XRD pattern of pure TiO2 shows five primary peaks at 25, 38, 48, 54 and
55, which can be attributed to different diffraction planes of anatase. The XRD
patterns of doped samples show different peaks at 28, 36, 39, 41, 44, 54 and 57, which
resulted from different diffraction planes of the rutile form of TiO2. Results show that
the addition of iron or cobalt to the titania preparation process has a significant effect
on crystalline structure formation. The XRD patterns of Fe and Co doped TiO2
samples almost coincide with that of pure TiO2, showing no diffraction peaks related

Fig. 4. WAXS patterns of TiO2 doped with Fe (a) and Co (b)

272 K. Siwinska-Stefanska, D. Paukszta, A. Piasecki, T. Jesionowski

with iron and cobalt. Our observations are in agreement with previous research
(Amadelli, 2008; Ambrus, 2008; Hamadanian, 2010). It can be concluded that selected
dopants are not incorporated directly onto titania structure, but are placed onto the
TiO2 surface. Fe3+ and Co2+ ions influence the crystalline structure formation of TiO2
and cause the transformation of the anatase phase to rutile.
At the next stage of the study, the adsorption abilities of the doped titanium dioxide
samples were characterised. The fundamental parameters determining the surface
activity of the doped samples, the surface area (BET) and pore size distribution, are
given in Table 2.

Table 2. Porous structure parameters of native and doped-TiO2

Amount Vp Sp ABET Sp
ABET (m2/g) Vp (cm3/g)
of metal (cm3/g) (nm) (m2/g) (nm)
dopant TiO2/Fe TiO2/Co
(% mass) (first method) (first method)
0.10 10.2 0.009 3.1 9.9 0.008 3.0
0.57 8.7 0.006 2.9 8.4 0.006 2.6
1.00 6.7 0.005 2.8 6.9 0.004 2.5
2.80 4.5 0.003 2.8 4.3 0.004 2.5
TiO2/Fe TiO2/Co
(second method) (second method)
0.10 12.8 0.012 3.2 14.5 0.013 3.3
0.57 6.2 0.004 2.8 13.6 0.009 2.7
1.00 5.8 0.004 2.8 9.8 0.008 2.6
2.80 4.7 0.003 2.8 7.3 0.007 2.6

A considerable decrease in the surface area relative to that of the pure sample was
observed for all doped samples. Addition of any of dopants also resulted in a decrease
in the pore diameters relative to those of native TiO2, irrespective of the quantity of
dopant. The BET surface areas decrease was observed together with increasing Fe and
Co amount in the sample structure. The TiO2 doped with Co obtained via first method
has the lowest BET surface area as compared to Co doped TiO2 obtained according to
second method.
The surface composition of the obtained samples was studied by the EDS
technique. EDS results are given in Table 3. From the elemental mapping mode,
highly and uniformly dispersed Fe and Co on the TiO2 support were observed. This
implies good interaction between dopant and support in the preparation process using
the sol-gel method. The EDS technique was used to detect the amount of Fe and Co in
the titania structure. Doped titania samples contain ca. 0.12 and ca. 0.56% mass of Fe
were produced via first method using 0.10 and 0.57% mass of Fe as a dopant. It can be
seen that Fe amount is very close to the initial values. Wen et al. (2012) have observed
 Synthesis and physicochemical characteristics of titanium dioxide doped with selected metals 273

the analogous results. The EDS analysis of Fe and Co doped TiO2 confirmed the
presence of Fe and Co ions in the powder structure, as the opposite of XRD patterns.
The XRD patterns do not show any peaks related to Fe and Co, presence in TiO2
structure.

Table 3. Surface composition of doped-TiO2

Amount Compound content (%)

of metal Ti O Fe Ti O Co
dopant TiO2/Fe TiO2/Co
(% mass) (first method) (first method)
0.10 54.92 44.95 0.12 52.10 47.85 0.05
0.57 51.08 48.36 0.56 55.44 44.13 0.43
1.00 50.06 49.12 0.82 51.63 47.74 0.63
2.80 54.13 43.82 2.05 55.86 42.18 1.96
TiO2/Fe TiO2/Co
(second method) (second method)
0.10 50.61 49.19 0.20 50.11 49.83 0.06
0.57 48.77 50.62 0.61 50.80 48.78 0.42
1.00 52.32 46.79 0.89 52.01 47.41 0.58
2.80 51.07 46.83 2.10 51.13 47.08 1.79

Investigation of the effectiveness of the doped process has been broadened by

thermal analysis TG/DTA (Fig. 5) of the pure TiO2, and selected doped materials. The
results of TG/DTA analysis allowed for an estimate of the temperature range that
corresponds to important chemical and structural transitions of the obtained systems.
Figure 5a shows TGA thermograms of pure titanium dioxide and systems obtained
by doping titania with 2.8% mass of Fe. Analysis of the obtained systems was
performed in order to determine thermal stability. In case of pure titania, first mass
loss is observable in a temperature range of 30 to 300 °C, and most likely corresponds
to loss of physically and chemically bound water. At this point mass loss is slightly
above 0.4%. Total mass loss of pure TiO2 is equal to ~0.9%. The TGA thermograms of
doped-TiO2 with iron show similar changes in thermal stability in comparison to pure
titania. Total mass loss of doped samples via first and second method is equal to ~0.7
and ~1.2%, respectively. A similar change of thermal stability was observed of Co-
doped TiO2 (Fig. 5b). Total mass loss of Co-doped samples via the first and second
method is equal to ~0.75 and ~0.8%, respectively.
274 K. Siwinska-Stefanska, D. Paukszta, A. Piasecki, T. Jesionowski

Fig. 5. Thermograms of doped TiO2 with Fe (a) and Co (b) obtained by sol-gel method

Conclusions
According to the results presented above, the systems obtained after doping of selected
dopants (Fe and Co) on titania were characterised by particles of smaller diameter and
lower homogeneity compare to pure TiO2.
The XRD patterns show that the addition of iron or cobalt to the titania preparation
process has a significant effect on crystalline structure formation. The XRD patterns of
Fe and Co doped TiO2 samples almost coincide with that of pure TiO2, showing no
diffraction peaks related with iron and cobalt.
The type of dopant and doping method has a significant influence on the surface
activity of the systems obtained by sol-gel method. The porous structure of the doped
titania decreased proportionally with increasing concentration of the dopant. Surface
area measurements were carried out on TiO2 samples doped with Fe and Co,
indicating that the adopted doping procedure brought some surface area change with
respect to the pristine oxide.
Iron and cobalt were found to be effectively doped on the surface of synthetic the
TiO2 sample. EDS analysis of Fe and Co doped TiO2 confirmed the presence of Fe and
Co ions in the powder structure,
The Fe and Co doped titania acquired via doping of selected dopants are
characterised by a small shift in thermal stability. However, a small change in the
mass loss of doped samples, in comparison to pure titania, was observed.

Acknowledgements
This work was supported by Polish National Centre of Science research grant no. 2011/01/B/ST8/03961.
 Synthesis and physicochemical characteristics of titanium dioxide doped with selected metals 275

References
AMADELLI R., SAMIOLO L., MALDOTTI A., MOLINARI A., VALIGI M., GAZZOLI D., 2008,
Preparation, characterisation, and photocatalytic behaviour of Co-TiO2 with visible light response,
International Journal of Photoenergy, Article ID 853753, 9 pages, doi: 10.1155/2008/853753.
AMBRUS Z., BALÁZS N., ALAPI T., WITTMANN G., SIPOS P., DOMBI A., MOGYORÓSI K.,
2008, Synthesis, structure and photocatalytic properties of Fe(III)-doped TiO2 prepared from TiCl3,
Applied Catalysis B: Environmental 81, 27–37.
ANPO M., 2000, Use of visible light. Second-generation titanium dioxide photocatalysts prepared by the
application of an advanced metal ion-implantation metod, Pure and Applied Chemistry 72, 1787–
1792.
CHATTERJEE D., MAHATA A., 2001, Demineralization of organic pollutants on the dye modified TiO2
semiconductor particulate system using visible light, Applied Catalysis B: Environmental 33, 119–
125.
FUERTE M.D.H.A., MAIRA A.J., MARTINEZ-ARIAS A., FERNADEZ-GARCIA M., CONESA J.C.,
SORIA J., 2001, Visible light-activated nanosized doped-TiO2 photocatalysts, Chemical
Communications 24, 2718–2719.
FUJISHIMA X., ZHANG C.R., 2006, Titanium dioxide photocatalysis: Present situation and future
approaches, Chimie 9, 750–760.
HAMADANIAN M., REISI-VANANI A., MAJEDI A., 2010, Sol-gel preparation and characterization
of Co/TiO2 nanoparticles: application to degradation of Methyl Orange, Journal of the Iranian
Chemical Society 7, S52–S58.
HE Z.L., QUE W.X., XIE H.X., CHEN J.,Y. YUAN, P. SUN., 2012, Facile synthesis of self-sensitized
TiO2 photocatalysts and their higher photocatalytic activity, Journal of the American Ceramic Society
95, 3941–3946.
HIRAI T., SUZUKI K., KOMASAWA I., 2001, Preparation and photocatalytic properties of composite
CdS nanoparticles-titanium dioxide particles, Journal of Colloid and Interface Science 244, 262–265.
HUANG D.G., LIAO S.J., ZHOU W.B., QUAN S.Q., LIU L., HE Z.J., WAN J.B., 2009, Synthesis of
samarium- and nitrogen-co-doped TiO2 by modified hydrothermal method and its photocatalytic
performance for the degradation of 4-chlorophenol, Journal of Physics and Chemistry of Solids 70,
853–859.
IHARA T., MIYOSHI M., ANDO M., SUGIHARA S., IRIYAMA Y., 2001, Preparation of a visible-
light-active TiO2 photocatalyst by RF plasma treatment, Journal of Materials Science 36, 4201–4207.
JCPDS International Center of Diffraction Data (1980), JCPDS Powder Diffraction File, Card 21-1272.
LIU Y., CHEN X., LI J., BURDA C., 2005, Photocatalytic degradation of azo dyes by nitrogen-doped
TiO2 nanocatalysts, Chemosphere 61, 11–18.
OHNO T., MITSUI T., MATSUMURA M., 2003, Photocatalytic activity of S-doped TiO2 photocatalyst
under visible light, Chemistry Letters 32, 364–365.
TAKEUCHI K., NAKAMURA I., MATSUMOTO O., SUGIHARA S., ANDO M., IHARA T., 2000,
Preparation of visible-light-responsive titanium oxide photocatalysts by plasma treatment, Chemistry
Letters 29, 1354–1355.
WANG J., MA T., ZHANG G., ZHANG Z., ZHANG X., JIANG Y., ZHAO G., ZHANG P., 2007,
Preparation of nanometer TiO2 catalyst doped with upconversion luminescence agent and
investigation on degradation of acid red B dye using visible light, Catalysis Communications 8, 607–
611.
276 K. Siwinska-Stefanska, D. Paukszta, A. Piasecki, T. Jesionowski

WANG J., TAFEN D.N., LEWIS J.P., HONG Z.L., MANIVANNAN A., ZHI M.J., LI M., WU N.Q.,
2009, Origin of photocatalytic activity of nitrogen-doped TiO2 nanobelts, Journal of the American
Ceramic Society 131, 12290–12297.
WEN L., LIU B., ZHAO X., NAKATA K., MURAKAMI T., FUJISHIMA A., 2012, Synthesis,
characterization, and photocatalysis of Fe-doped TiO2: a combined experimental and theoretical
study, Internationaal Journal of Photoenergy, Article ID 368750, 10 pages, doi:
10.1155/2012/368750.
WU X.H., QIN W., DING X.B., WEN Y., LIU H.L., JIANG Z.H., 2007, Photocatalytic activity of Eu-
doped TiO2 ceramic films prepared by microplasma oxidation method, Journal of Physics and
Chemistry of Solids 68, 2387–2393.
XU X.J., FANG X.S., ZHAI T.Y., ZENG H.B., LIU B.D., HU X.Y., BANDO Y., GOLBERG D., 2011,
Tube-in-tube TiO2 nanotubes with porous walls: Fabrication, formation mechanism, and
photocatalytic properties, Small 7, 445–449.
YAMASHITA H., HARADA M., MISAKA J., 2001, Application of ion beam techniques for preparation
of metal ion-implanted TiO2 thin film photocatalyst available under visible light irradiation: Metal
ion implantation and ionized cluster beam method, Journal of Synchrotron Radiation 8, 569–571.
YU J.C., ZHANG L., ZHENG Z., ZHAO J., 2003, Synthesis and characterization of phosphated
mesoporous titanium dioxide with high photocatalytic activity, Chemistry of Materials 15, 2280–
2286.
ZHOU W., ZHENG Y., WU G., 2006, Novel luminescent RE/TiO2 (RE=Eu, Gd) catalysts prepared by
in-situation sol-gel approach construction of multi-functional precursors and their photo or
photocatalytic oxidation properties, Applied Surface Science 252, 1387–1392.