Applied Catalysis A: General 319 (2007) 230–236

www.elsevier.com/locate/apcata

Improved photocatalytic activity of Sn4+-doped and undoped TiO2

thin film coated stainless steel under UV- and VIS-irradiation
Hikmet Sayılkan
İnönü University, Faculty of Education, Department of Science, 44289 Malatya, Turkey
Received 20 July 2006; received in revised form 13 November 2006; accepted 10 December 2006
Available online 27 December 2006

Abstract
TiO2 can be used as a photocatalyst because of its semiconductor property. If TiO2 is doped with transition metal ions, its electronic properties
are modified. In this work, nanosized Sn4+-doped and undoped TiO2 (TiO2–Sn4+ and TiO2) particles have been synthesized without organic solvent
by hydrothermal process at low temperature. Nano-TiO2 particulates having a doping ratio of about 5 [Sn4+/Ti(OBun)4; mol/mol%] allowed to coat
the stainless steel substrate by spin-coating technique. The particles and the films were characterized by XRD, SEM, BET and UV/VIS/NIR
techniques. The photocatalytic performance of the films were tested for degradation of Malachite Green dye in solution under UV and VIS-lights.
The results reveal that (a) nano-TiO2 particles are fully anatase crystalline form and are easily dispersed in water, (b) the coated surfaces are
hydrophilic, (c) the photocatalytic activity of the TiO2–Sn4+ film is higher than that of the undoped TiO2 film under UV and VIS-light irradiation
and, (d) TiO2–Sn4+ film can be repeatedly used with increasing photocatalytic activity compared to undoped TiO2 film.
# 2006 Elsevier B.V. All rights reserved.

Keywords: Nano-TiO2; Sn4+-doping; Hydrothermal process; Thin film; Photocatalysis

1. Introduction many years to find suitable and efficient photocatalysts to

TiO2 has attracted extensive attention due to its effective
photodegradation activity for organic pollutants in water and air
under illumination of UV-light [1–3]. Recently, most of the
investigations have focused on preparing TiO2 catalysts that can
be activated by VIS-light because there is much more energy
produced by the sunlight in the visible lights regime compared
to the UV [4–7]. For this purpose, doping or combining TiO2
with various metal or non-metal ions has been considered [8,9].
The first positive results have been demonstrated by Kisch [10–
12] with carbon doped photocatalysts [13] and by Taga from
Toyota with nitrogen doped catalysts. Sn-doped titania also
shows enhanced day-light activity [14]. Lin et al. [15] have also
studied the effect of Sn doping (up to 1 mol%) in rutile TiO2
and found that the photocatalytic activity has increased. Due to
the large number of possible variations, it is rather difficult to
find out the appropriate compositions and concentrations of
dopants, especially if lattice doping should be avoided. For
these reasons, it is likely that investigations will continue for
E-mail address: hsayilkan@inonu.edu.tr.
0926-860X/$ – see front matter # 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2006.12.012
function under day-light conditions.
Sol–gel process [16], ultrasonic technique [17], microemul-
sion or reverse micelles and hydrothermal process [18–20] have
been reported for synthesizing of TiO2. A multitude of polar or
non-polar solvents have been used in these processes. High
calcination temperature above 450 8C is usually required to
form regular crystal structure in these processes, except for the
hydrothermal process. However, in the meantime, the high
temperature treatment can decline the surface area and surface
hydroxyl or alkoxide groups on the surface of TiO2, which
prevent easy dispersion, are lost. Thus, in this work, the
hydrothermal process was applied to synthesize nanosized TiO2
particles at low temperatures, which seems to be really
attractive to further improve the photocatalytic activity of TiO2.
Compared with the other TiO2 powders, these TiO2 nanopar-
ticles have several advantages, such as being fully in pure
anatase crystalline form, having fine particle size with more
uniform distribution and high-dispersion ability either in polar
or non-polar solvents, stronger adsorption and easy coating on
different supporting material. Moreover, the hydrothermal
process which employs aqueous solvents as reaction medium is
environmentally friendly since the reactions are carried out in a
 H. Sayılkan / Applied Catalysis A: General 319 (2007) 230–236
closed system, and the contents can be recovered and reused
after cooling down to room temperature. In this work, nano-
sized anatase-TiO2 particles have been hydrothermally
synthesized without organic solvent at low temperature and
photocatalytic activity of Sn4+ doped and undoped TiO2 thin
films supported on stainless steel were examined for
the degradation of Malachite Green (MG) in aqueous
solutions under UV and VIS-lights and the results were
compared.
2. Experimental
2.1. Chemicals and apparatus
As starting precursors, the following reagents were employed:
tetrabutylorthotitanate, [Ti(OBun)4, 97%, Fluka], as TiO2 source;
hydrochloride acid (Merck, 37%) as catalyst; tin (IV) chloride
(Alpha, 98%) as dopant; deionized water as hydrolysis agent; 3-
glycidoxypropyltrimethoxysilane (GLYMO, Aldrich, 98%) and
tetraethylorthosilicate (TEOS, Aldrich, 98%) as binder reagents;
2-butoxyethanol (2-BuOEtOH, Aldrich, 99%) and ethyl alcohol
(EtOH, 96%) as solvents.
Berghoff model hydrothermal unit interfaced with a
temperature controller (up to 240 8C) and timer unit was used
for synthesizing of nano-TiO2 photocatalyst. In order to
determine the crystal phase, Rigaku Geigerflex D Max/B model
X-ray diffractometer (XRD) with Cu Ka radiation
(l = 0.15418 nm) in the region 2u = 10–708 with a step size
of 0.048 was used. The average crystallite size of TiO2
nanoparticles were estimated according to the following
Scherrer’s equation:
kl
dh k l ¼
ðb cosð2uÞÞ
where dh k l is the average crystallite size (nm), l the
wavelength of the Cu Ka radiation applied (l = 0.154056 nm),
u the Bragg’s angle of diffraction, b the full-width at half
maximum intensity of the peak observed at 2u = 25.24
(converted to radian) and k is a constant usually applied as
0.9. The BET surface area, average pore diameter and
micropore volume of the nanosized-TiO2 particle was
calculated from the N2 adsorption isotherm using ASAP
2000 model BET analyzer at liquid N2 temperature. During the
BET analysis, sample was degassed at 130 8C for 4 h before N2
adsorption. Pore size distribution of nano-TiO2 was computed
by DFT plus method. Surface morphologies of the particles and
coated surfaces were investigated using Scanning Electron
Microscopy (SEM, LEO EVO 40 Model). The amount of Sn
(mol/mol%) in Sn4+ doped TiO2 particles was determined by
AAS analysis (Perkin-Elmer, Analyst 800 model) in centrifu-
gated solution after the hydrothermal treatment. Contact angles
of coatings with water were measured by using a goniometer
(RAME HART 100-00 model). Film thickness of coated
surfaces were measured by Perthometer (MAHR-M1 Model).
Dye concentration in the aqueous solution after irradiation
was measured by a Varian Carry 5000 model UV-VIS-NIR
spectrophotometer. Coated stainless steel/dye solution was
231
irradiated with and without 400 nm cut-off filter without
shaking in Solar Box 1500 model radiation unit with Xe-lamp
(690 W/m2) and a controller for timing and power input (390–
1100 W/m2).
2.2. TiO2 particle synthesis
The method employed for synthesis of TiO2 particles in this
work is similar to that described in a previous paper [21], which
employs a hydrothermal process in which Ti(OBun)4 was used
as starting material. Ti(OBun)4 was cooled in an ice-bath, then
HCl was slowly added into cooled solution dropwise using a
burette. After stirring a few minute at ambient temperature,
required amount of tin (IV) chloride was suddenly added. The
last solution was stirred until a clear and homogeneous solution
formed at ambient temperature. Then, required amount of water
was added into the last solution dropwise by burette within
10 min. The gelation occured after adding water. The reaction
was allowed to continue for 2 h, then the viscous solution was
obtained. Sol-solution was then transferred into a 250 ml Teflon
crucible, then left in a pre-heated (200 8C) stainless steel
autoclave device. The reaction was allowed to occur at 200 8C
for 1 h. After this time, autoclave was removed from the
hydrothermal unit and cooled to room temperature. As-
obtained powders were separated through centrifuging and
dried in a vacuum sterilizer. Thus, Promrise Yellow TiO2
particle was obtained. The undoped TiO2 with a white color was
synthesized without using dopant as described above. HCl/
Ti(OBun)4, SnCl4/Ti(OBun)4 and H2O/Ti(OBun)4 mol/mol
ratios were 0.3, 0.05 and 2, respectively.
2.3. Preparation of the coating solution
Before preparing coating solution, the TiO2 sol was prepared
by ultrasonically dispersing the TiO2 in deionized water
without using dispersant. For preparing coating solution, (mol/
mol ratios of each component are presented in parentheses),
GLYMO was first reacted with TEOS for 10 min (GLYMO/
TEOS: 1), then EtOH was added to this mixture (EtOH/
GLYMO: 10.3) and stirred for 10 min. HCl was allowed to react
with GLYMO/TEOS/EtOH for 10 min (HCl/GLYMO: 0.055)
and finally H2O was added to GLYMO/TEOS/EtOH/HCl and
allowed to react for 10 min (H2O/GLYMO: 6.5). Thus, the
coating solution was prepared. TiO2 sol (5 g) was added into the
coating solution (5 g) and this mixture was stirred for 5 min
before adding 2-BuOEtOH (4 g) stirring for 40 h. Finally,
transparent and colorless solution was obtained. Stainless steel
plate surfaces were coated with this solution using spin-coating
apparatus operated at 1000 rpm for 10 s. For curing, the coated
surface was treated at 80 8C for 40 min. For obtaining
hydrophilic surface, the coated plates was irradiated under
UV lamp operating at 8 W. Film thickness of the coated
surfaces was measured by Perthometer. For this purpose, half of
the plate area was coated. Film thickness was automatically
measured from the thickness differences between coated and
uncoated surfaces sides. The amount of TiO2 in the coatings
prepared from doped and undoped TiO2 was 52.50%, as
232 H. Sayılkan / Applied Catalysis A: General 319 (2007) 230–236

Scheme 1. Photoreactor system. (A) UV irradiation applied without filter, (B) VIS irradiation applied with UV cut-off filter, (C) UV measurement after irradiation. (a)
Solar Box irradiation unit, (b) Sn doped TiO2 coated glass plate, (c) dye solution, (d) control unit of the Solar Box, (e) UV lamp, (f) UV lights, and (g) glass UV filter.

calculated by taking into consideration the amount of SiO2 3. Results and discussion
originating from GLYMO and TEOS, and TiO2 from TiO2 sol.
3.1. Characterization
2.4. Photocatalytic degradation of Malachite Green
XRD patterns of hydrothermally synthesized TiO2 are
shown in Fig. 1. When the XRD patterns were compared with
The photocatalytic performance of the films was determined
PDF#21-1272 data files it was found that all peaks observed at
by the degradation of Malachite Green (MG) dye solution. The
25.168, 37.918, 48.198, 55.018 (for undoped TiO2) and 25.128,
photocatalytic degradation intermediates of MG were not
37.888, 48.078 and 54.528 (for Sn-doped TiO2) 2-Theta values
determined. The coated stainless steel plate (5 cm  5 cm) was
are consistent with anatase (1 0 1), (0 0 4), (2 0 0) and (2 1 1)
immersed into 25 ml aqueous MG solution with a concentration
spacing [22]. The other crystalline forms of TiO2, rutile and
of 5 mg/l in a polystyrene reaction cell which has twelve
brookite, have not been detected. In addition, no Sn phase, as
separate sample compartments and one cover. The cell was
examined according to the sensitivity of XRD method, was
immediately located in the Solar Box ready for UV-irradiation.
found in XRD pattern. Based on the main chemical state of
The coated plate and dye solution system was irradiated in the
Sn4+, it can be concluded that Sn ions completely disperse in the
vertical direction without shaking and the distance between the
anatase crystallite in the studied composition [23]. In the region
UV lamp and plate/dye solution system was kept within 20 cm.
of 10–808, the shape of diffractive peaks of the crystal planes of
The change of MG concentration with respect to irradiation
Sn-doped TiO2 (curve b) is almost similar to that of undoped
time was measured by UV/VIS/NIR spectrophotometer. The
photocatalytic performance was determined without cut-off
filter for UV irradiation, and with 400 nm cut-off filter for VIS
irradiation. The photocatalytic reactor system used for testing
the photocatalytic performance of Sn doped and undoped TiO2
coated surfaces is shown in Scheme 1.

2.5. Catalyst re-use studies

Plates coated with Sn doped and undoped TiO2 were

repetitively used to degrade MG under UV-light. After the first
use, so-used plates were again employed to degrade a fresh MG
solution under the same conditions. The process was repeated
for seven times under UV light. Fig. 1. XRD patterns of: (a) undoped TiO2 and (b) Sn-doped TiO2.
 H. Sayılkan / Applied Catalysis A: General 319 (2007) 230–236 233

TiO2 (curve a), however the position of the diffraction peaks

between of Sn-doped TiO2 and undoped TiO2 are slightly shifts
to smaller diffraction angles. It is known that there are two
kinds of doping modes; interstitial and substitutional, for doped
metal ions in oxides, depending primarily on the electro-
negativity and ionic radius of the doping metal ions. If the
electronegativity and ionic radius of the doping metal ions
match those of the lattice metal ion in oxides, the doping metal
ion will substitute itself for the lattice in the doping reactive
process (substitutional mode). If the electronegativity of the
doping metal ion approaches that of the lattice metal ion and its
ionic radius is smaller than that of the lattice metal ion, the
oxide lattice spacing will be larger than the ionic radius of the Fig. 2. UV–VIS absorption spectra of undoped and Sn-doped TiO2 particles.
lattice metal ions, which will enter into the crystal cell of the
oxide (interstitial mode) [4,24]. Since the electronegativity and
the ionic radius of Sn4+ ion (1.8, 69 pm) approach those of Ti4+ obtained almost as 98.6%. Total pore volume was estimated
ion (1.5, 53 pm) in TiO2 [24], it is expected Sn4+ ions will from nitrogen adsorption at a relative pressure of 0.995. The
replace lattice Ti4+ ions and thus occupy lattice Ti4+ positions in mesoporosity was obtained almost as 1.4%. The mesoporosity
the doping reactive process. The ionic radius of the doping Sn4+ and microporosity for Sn-doped TiO2 were obtained as 79 and
ion is larger than that of the lattice and increment the lattice 21%, respectively.
parameters and cell volume of Sn-doped TiO2 compared with UV/VIS absorption spectra of Sn-doped and undoped TiO2
those of TiO2. As a result, the position of all the diffraction particles are presented in Fig. 2. The doping Sn4+ results in a
peaks of Sn-doped TiO2 should slightly lower diffraction sharp increase in the absorption of TiO2 photocatalyst in visible
angles. region, leaving unaffected intrinsic band gap of anatase TiO2.
According to Sn analysis carried out by AAS in the The band edge absorption at <380 nm is accompanied by a
centrifuged solution obtained after the hydrothermal treatment, broad and continuously degreasing absorption in the range
the doping ratio was obtained as 4.92 [Sn4+/Ti(OBun)4; mol/ 380–560 nm. The greatly red-shift (380–560 nm) can be
mol%]. This result shows that, the Sn4+ ions was almost doped attributed to the electron transfer transition between conduction
into TiO2 lattice. band (CB) and/or valance band (VB) of SnO2 and conduction
Some physicochemical characteristics of the undoped and band (CB) and/or valance band (VB) of TiO2. The extended
Sn-doped TiO2 are shown in Table 1. absorbance of Sn-doped TiO2 photocatalyst in the visible
As can be seen from Table 1, while the BET surface area and region provides a possibility for enhancing the photocatalytic
adsorption average pore diameter of the undoped TiO2 are performance of TiO2.
smaller, crystallite size, micropore area and micropore volume While the spectral responses of SnO2 and TiO2 are quite
are bigger than Sn-doped TiO2. According to the result of DFT similar as both are large bandgap semiconductors (Eg, bandgap
plus method [25], microporosity (percentage of micropore to energy, for SnO2 = 3.8 eV while Eg for TiO2 = 3.2 eV) [26].
total pore volume, Vmi/Vtot) dominated and distributed very Though the band gap of SnO2 is wider than that of TiO2, its
little in the range of 1.4–2.0 nm for undoped TiO2. Whereas, conduction band is at a lower energy level than that of TiO2 as
mesoporosity (percentage of mesopore to total pore volume, shown in Scheme 2. The electrical conductivity of SnO2 is
Vms/Vtot) dominated and distributed large area in the range of better than that of TiO2. Hence, in a mixture of TiO2 and SnO2,
1.2–3.2 nm for Sn-doped TiO2. The microporosity was it could be expected that the photogenerated electrons from
TiO2 is transferred easily into the SnO2 underlayer,
[(TiO2)eCB ! (SnO2)eCB], and holes oppositely flow into
Table 1
Some physicochemical characteristics of the synthesized undoped and Sn-
doped TiO2
Undoped-TiO2 Sn-doped TiO2
Particle property
Crystalline type Anatase Anatase
Crystallite size (nm) 9.76 9.24
BET Surface area (m2 g1) 40.84 97.83
Micropore area (m2 g1) 39.3095 19.87
Micropore volume (cm3 g1) 0.022 0.011
Adsorption average pore diameter (Å) 13.12 21.16
Film property
Film thickness (mm) * 15 21
Contact angles with water 608/88 698/258
(before/after irradiation) * Scheme 2. Schematic representation of the electron transfer process in case of
SnO2–TiO2.
234 H. Sayılkan / Applied Catalysis A: General 319 (2007) 230–236
the TiO2 overlayer, [(SnO2)hVB+ ! (TiO2)hVB+], as shown in
Scheme 2 [27,28]. Consequently, more holes reach the TiO2
surface to oxidation thereat in surface. The electrons would be
accumulated in the SnO2 underlayer. In addition, as the molar
ratio of SnO2 is lower than that of TiO2, each SnO2 particle is
surrounded by more TiO2 particles, the photogenerated electron
from TiO2 conduction band may be passed to the SnO2
conduction band or the electrons from the SnO2 valence band
may be excited to its conduction band by illumination.
However, since SnO2 particle is surrounded by many TiO2, to
which it cannot transfer the photogenerated electron, the
electrons cannot further travel to the outer circuit and so. It can
be concluded that this phenomena important plays in the
photocatalytic performances of these type semiconductors.
Typical SEM images of Sn-doped and undoped TiO2
particles are shown in Fig. 3. Shown in Fig. 3a and b indicating
that shape of the particles are quite similar to each other and
likely become spherical in general. In the SEM images seen that
the some TiO2 particles are agglomerates. The agglomeration
may result from the hydrothermal treatment conditions.
However the size distribution of the powder was not
determined, the size of the particles varies in the range of
1.02–8.25 mm for Sn-doped TiO2 and of 1.07–11.72 mm for
Fig. 3. Typical SEM microphotograph of: (a) undoped TiO2 particle, (b) Sn-
doped TiO2 particle.
undoped TiO2, as measured using the SEM images. Introduc-
tion of Sn4+ ion decreased the size of the powder and gained
more spherical shapes.
One interesting result obtained in this work is that the
crystallite size and the particle size (Table 1 and Fig. 3) of the
Sn4+ doped TiO2 were smaller than those of undoped TiO2,
which can signify that the presence of Sn4+ in the reactional
media might be used to control the particle and crystallite sizes
of the oxides. Oliviera et al. [28] reported that the particle size
of (Ti,Sn)O2 mixed oxides prepared by the sol–gel process is
lower than the pure TiO2. Leite et al. [29] also reported a novel
approach to control particle size of Nb2O5 doped (5 mol%)
SnO2 prepared by the polymeric precursors method. They
observed that Nb2O5–SnO2 mixed oxide is formed with lower
crystallite size than the pure SnO2, with a Nb2O5–SnO2 solid
solution restricted to the surface of particles. The lower
crystallite size of doped particles was attributed to this surface
effect, with the Nb2O5 preventing the formation of necks
between particles and the process of coalescence. The similar
effect can be occur in Sn4+ doped TiO2 particle synthesized in
this work. There are important differences between the oxide of
this present study and their oxides. For example, Sn4+ doped
and undoped TiO2 particles are synthesized by the hydro-
thermal process at low temperature (200 8C) and very low
reaction time (1 h), organic solvent is not used during the
synthesis reaction, the obtained particles are fully anatase
crystalline form and easily dispersed in water without using
dispersant.
The results of element analysis (SEM-EDX) carried out
locally on the Sn-doped and undoped TiO2 particles and in three
selected points are given in Table 2. According to the analysis,
the amount of Sn and other elements slightly varies, meaning
that Sn4+ ions are occupied in the crystal structure and varied
with little difference amounts.
Typical SEM image of Sn-doped TiO2 coated stainless steel
surface is shown in Fig. 4. It is seen that the coated surface has
very smooth and transparent image. The film thickness was
measured 15 mm.
As can be also seen from Table 1, the film thickness was
measured 15 and 21 mm for Sn4+ doped and undoped TiO2
coated surfaces, respectively. In addition, the contact angles of
the irradiated surfaces with water were found 88 and 258 for
Sn4+ doped and undoped TiO2 coated plate surface. These
results reveal that the contact angle decreases during the
Table 2
The results of EDX analysis in three selected points on the undoped and Sn-
doped TiO2 particles
Selected point Element wt.%
Undoped-TiO2
1 Ti/C/Cl 87.85/6.30/5.85
2 Ti/C/Cl 82.87/10.37/6.76
3 Ti/C/Cl 84.76/11.17/4.07
Sn-doped TiO2
1 Ti/C/Sn/Cl 58.91/24.57/9.51/5.88
2 Ti/C/Sn/Cl 66.34/14.96/11.75/5.96
3 Ti/C/Sn/Cl 66.48/20.20/7.76/4.47
 H. Sayılkan / Applied Catalysis A: General 319 (2007) 230–236
Fig. 4. Typical SEM image of Sn-doped TiO2 coated stainless steel surface.
irradiation. For example, while the contact angle was 88 and 258
on the irradiated surfaces, they were 608 and 698 on the
unirradiated surface. The decrease in the contact angle can be
attributed to the reaction of produced electrons and holes in a
different way. According to Fujishima et al. [6], the electrons
tend to reduce the Ti(IV) cations to the Ti(III) state and the
holes oxidizes the O2 anions. In the process oxygen atoms are
rejected, creating oxygen vacancies. Water molecules can then
occupy these oxygen vacancies, producing adsorbed OH groups
which tend to make the surface hydrophilic, to form active OH
radicals for further photocatalytic performance. Therefore, we
can conclude that the irradiated surface has almost super-
hydrophilic property and it has an important role for
photocatalytic properties. As can be seen from Fig. 5, water
drop spreads as a thin film on the irradiated stainless steel plate
surface coated with Sn4+ doped TiO2.
The photocatalytic activity results for the Sn-doped and
undoped TiO2 coated surfaces exposed for the photodegrada-
tion of MG under both UV and VIS-lights irradiation are shown
in Fig. 6.
It was found that photocatalytic performance of Sn-doped
TiO2 thin film for degradation of MG is higher than that of
undoped TiO2 film under UV and VIS-lights. According to the
results from repeated usage experiments performed under UV
Fig. 5. Images of the water drops on the stainless steel surfaces.
235
Fig. 6. Kinetic curves for photodegradation of MG under UVand VIS lights. (a)
Sn-doped TiO2 coated and (b) undoped TiO2 coated stainless steel.
light, Sn ion doping improves the photocatalytic activity.
Even after the seventh use, the photocatalytic performance of
Sn-doped TiO2 thin film was almost similar to first and
further uses, whereas undoped-TiO2 thin film showed a
decreased photocatalytic activity from first to seventh use.
For the first time of use, 85% of MG was degraded with Sn-
doped TiO2 thin film. After the first use and additional UV-
irradiation for 70 min, 72, 77, 68, 72, 81 and 67% of the same
amount of MG was degraded in the second and further use
with Sn-doped TiO2 thin film. On the other hand, degradation
percentage of the same amount of MG decreased from the
first use to further use with undoped TiO2 thin film as 68, 47,
38, 36, 37, 30 and 30%, respectively. After UV-irradiation for
460 min, 97.5, 97, 97.5, 97, 97, 97.5 and 97% of MG was
degraded at the first and further use with Sn-doped TiO2 thin
film, respectively. On the other hand, the MG was degraded
as 95, 87, 78, 77, 76, 73 and 69% with undoped TiO2 thin
film, respectively. After 250 min of irradiation, the amount of
degraded MG hardly changed with Sn-doped TiO2 film,
whereas it always changed with undoped TiO2 film. It was
observed during the experiments performed under the VIS-
light that the photocatalytic performances of both thin films
increase in the course of time. However, doping of Sn4+ ions
improves the photocatalytic performance under visible light
irradiation. After 430 and 460 min of irradiation time, the
MG concentration did not changed under VIS-irradiation.
80% of MG was degraded with Sn-doped TiO2 film in
430 min, whereas 67% was degraded with undoped TiO2 film
under VIS-irradiation.
236 H. Sayılkan / Applied Catalysis A: General 319 (2007) 230–236
Scheme 3. Schematic representation of electron transfer from MG (LUMO) to
TiO2 (CB).
There are various reasons for increase in the photocatalytic
performance: (a) high photocatalytic activity of Sn-doped TiO2
film may be related to small crystal size, high surface area as well
as its mesoporous structure. It is well known that, as the particle
size decreases, the surface area increases, and as the process is
adsorption dependent, the photocatalytic degradation rates also
increases. Thus, Sn4+-doped TiO2 coated surface, which has a
surface area of 83 m2 g1, showed that higher photocatalytic
performance than undoped-TiO2, which has a surface area of
40.84 m2 g1 (Table 1). Dagan and Tomkiewicz [30] and
Tomkiewicz et al. [31] also showed that TiO2 with a surface area
of 600 m2 g1 showed greater activity then commercial Degussa
P-25 which has a surface area of 55 m2 g1. (b) Dopant Sn4+
improves electron transfer efficiency from the LUMO band of
MG to the conduction band of Sn-doped TiO2, subsequently
increasing the amount of radicals as shown in Scheme 3. (c) High
photocatalytic performance, may be ascribed to the Sn ions
located in the TiO2 lattice. The Sn ions can be in the substitutional
sites of Ti while a solid state compound, Ti1xSnxO2, may be
formed [4,24]. The Ti1xSnxO2 may have a higher photocatalytic
performance than undoped TiO2 and this can result in a high
efficiency to degrade MG. At the same time, the Sn-doped TiO2
has a stronger UV-light absorption ability than the undoped TiO2.
This also denotes that the Sn-doped TiO2 can effectively be
utilized under VIS–irradiation for photocatalytic applications.
(d) All the nano-TiO2 particles in coating can be transferred onto
the Sn-doped TiO2 coated surface during the irradiation resulting
in a high photocatalytic performance. (e) The high photocatalytic
performance of the coated plate can also be related to its surface
which has almost super hydrophilic property. These reasons (d
and e) confirmed with the obtained results by Schmidt et al. [32].
4. Conclusion
Nano-sized Sn-doped and undoped TiO2 particles were
synthesized by hydrothermal process at low temperature. The
particles synthesised in this work and the synthesis process
have much advantages than the others: These particles were
synthesised without using organic solvent such as alcohols,
they were fully anatase crystal form, easily dispersed in polar
and/or apolar solvent system (amfiphilic property) and they can
be easily used to obtain thin or thick films on different surfaces.
Very transparent, hydrophilic and smooth TiO2 based thin films
were prepared by spin-coating technique. Doping of the Sn4+
ion decreased the particle size which resulted in an increases in
the surface area. The photocatalytic performance of Sn-doped
TiO2 thin film for photodegradation of MG is higher than that of
the undoped TiO2 film under UV and VIS-lights. It can be
suggested that Sn-doped TiO2 coated surfaces can be used for
preparing self-cleaning and/or antibacterial surfaces.
Acknowledgement
The author gratefully acknowledges the financial support of
T.R. Prime Ministry State Planning Organization (Project
number: 2005 DPT.120.150).
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