Abstract. Vanadium doped TiO2 nanoparticles were synthesized by solgel and hydrothermal methods. The samples were characterized by X-ray
diffraction, transmission electron microscopy, Raman spectroscopy, X-ray
photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The
Vanadium doped TiO2 nanoparticles had identical anatase phase with average crystal size of 15-20nm and exhibited the long tailed absorption in the
visible light region above 380nm. The photocatalystic activity under the irradiation of visible light was evaluated by the degradation of phenol aqueous
solution . The samples synthesized by hydrothermal method show better
photocatalystic activity: Under the condition of 360 min of Vis-irradation
the photolacatalyst TiO2:0.5%V makes the phenol concentration decreased
to 0.3%.
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JOURNAL OF SCIENCE OF HNUE
2011, Vol. 56, N◦. 1, pp. 11-20
A VISIBLE LIGHT ACTIVITY OF TiO2 BASED PHOTOCATALYSTS
Nguyen Minh Thuy(∗), Le Thi Hong Hai
Duong Quoc Van and Bui Thi Hau
Hanoi National University of Education
(∗)E-mail: thuynm@hnue.edu.vn
Abstract. Vanadium doped TiO2 nanoparticles were synthesized by sol-
gel and hydrothermal methods. The samples were characterized by X-ray
diffraction, transmission electron microscopy, Raman spectroscopy, X-ray
photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The
Vanadium doped TiO2 nanoparticles had identical anatase phase with aver-
age crystal size of 15-20nm and exhibited the long tailed absorption in the
visible light region above 380nm. The photocatalystic activity under the ir-
radiation of visible light was evaluated by the degradation of phenol aqueous
solution . The samples synthesized by hydrothermal method show better
photocatalystic activity: Under the condition of 360 min of Vis-irradation
the photolacatalyst TiO2:0.5%V makes the phenol concentration decreased
to 0.3%.
Keywords: semiconductors, nanocrystals, photocatalysts, absorp-
tion, irradiation.
1. Introduction
Titanium dioxide (TiO2) photocatalysts have been investigated with consid-
erable attention because they can be applicable for the decomposition of undesired
compounds in air as well as waste water, solar energy conversion and production of
clean energy resources through the water splitting reaction. Especially, applications
for environmental issues such as purification of waster water using natural solar light
are vital interest to practical utilizations and challenging topics. However, the ap-
plication of TiO2 as a photocatalyst for visible light-induced chemical reactions was
hampered by its large band-gap energy (3.2 eV for anatase TiO2), which requires
ultraviolet (UV) light to activate and leads to the lower energy efficiency. Widening
the absorption edge of TiO2 from UV to visible spectral range could provide the
groundwork to develop TiO2 catalysts with visible light activity.
Many studies had been attributed to the doping of transition metals into TiO2
to develop vis-photocatalysts, such as V, Cr, Mo, Fe... [1-5]. Different methods had
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Nguyen Minh Thuy, Le Thi Hong Hai, Duong Quoc Van and Bui Thi Hau
been chosen to prepare V-doped TiO2 catalysts, such as sol-gel method, metal ion-
implantation method, co-precipitation method, hydrothermal method and so on[2-
4]. It is promising to synthesize V-doped TiO2 powders economically and practically
by the hydrothermal method for its low-cost, effectiveness and easy execution.
In this work, V-doped TiO2 nanopoders were successfully synthesized by two
synthesized methods: sol-gel citrate and hydrothermal. The samples prepared by
hydrothermal method exhibited highest photocatalystic activity. The visible light
phototcatalystic activity of V-doped TiO2 prepared by hydrothermal method sug-
gested an application for an environmental treatment of waste water.
2. Content
2.1. Experimental
The used chemicals were TiCl4, acid Citric (CA), NH4NO3, NH3 10 %, V2O5/HCl
0.03 M. All chemicals were of analytical reagent grad. Pure titanium catalyst was
prepared using the hydrothermal method with the following procedure: Firstly 3.0
ml TiCl4 was added drop by drop to 100 ml distilled water vigoroustirring, which
was continuously stirred for 20 minutes. Afterwards, ammonia aqueous solution
NH3 (25%) was added to adjust the pH value to 7-8, and then stirred for 30 min-
utes. Then the distilled water was added and the mixture was transferred into an
autoclave and kept at 2000C for 5h. After centrifugation, washing and drying, the
samples were calcined at 6500C for 1h (see Figure 1a).
A series of V-doped TiO2 hydrosol were prepared by changing the V/Ti ratio.
The Vanadium doping content was calculated by following equation:
%V = nV /(nV + nTi)
where nV and nTi were the mole of Vanadium and Titanium respectively.
Pure TiO2 was prepared using the sol-gel citrate method with the following
procedure.
The starting solutions were prepared by addition of aqueous solution of citric
acid (CA) and NH4NO3 with the molar ratio of 1:9. Then TiCl4 was added drop by
drop to the solution vigoroustirring, which was continuously stirred for 30 min. The
molar ratio CA: TiCl4 was 1.2:1. Afterwards, ammonia aqueous solution NH3 was
added to adjust the pH value to 7-8, then the mixture was strong stirred at 800C to
completely get a sol. The sol was burned and then calcined at 6500C for 3h.
A series of V-doped TiO2 hydrosol were prepared by changing the V/Ti ratio.
The V-doped samples prepared by the sol-gel citrate method were designated as S0;
S1; S3; S5; S7 and S9 with the yields of the V doping contents of 0.0; 0.1; 0.3; 0.5;
0.7 and 0.9%, respectively. The samples prepared by the hydrothermal method were
designated as T0; T1; T3; T5; T7 and T9 with the yields of the V doping contents
of 0.0; 0.1; 0.3; 0.5; 0.7 and 0.9%, respectively.
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A visible light activity of TiO2 based photocatalysts
Figure 1. Preparation processes of Vanadium doped TiO2
by sol-gel citrate (a) and hydrothermal (b) methods
The structure and crystalline characters were analyzed by X- ray diffraction
(XRD) SIEMENS D5005 and by Raman scattering measurements with LABRAM
micro-Raman spectroscopy.
The morphology was investigated by scanning electron microscope (SEM) and
transmission electron microscope (TEM). Absorption measurements were obtained
with JASCO V-670 spectrometer. X-ray photoelectron spectroscopy (XPS) mea-
surements were performed in a commercial Microlab 350 XPS system equipped with
an Al Kα source, in the UHV chamber (∼ 10−9Torr) with 600-take off angle.
The irradiation was performed with a 100 W-wolfram lamp being used for
visible light sources. The photocatalytic activity of samples was evaluated by degra-
dation of phenol (C6H5OH) diluted in water. 80 ml phenol solution (5.10
−5 mol/l)
was stirred under dark condition. Then 200 mg TiO2 -based photocatalysts was
added to the phenol solution and the mixture was stirred for 60 min under dark
condition. And then, visible light irradiation was carried out using 100 W-wolfram
lamp. The progress of the reactions was monitored by High performance liquid
Chromatography - HPLC for 360 min.
2.2. Results and discussion
2.2.1. Sample characterization
Figure 2 presented the XRD patterns of V-doping TiO2 powder prepared by
hydrothermal methods. For all doping samples (up to 0.9%) the XRD patterns show
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Nguyen Minh Thuy, Le Thi Hong Hai, Duong Quoc Van and Bui Thi Hau
Figure 2. The XRD patterns of TiO2 (a in left); TiO2:0.05V (b in left)
and TiO2:0.09V (in right) nanoparticles prepared by hydrothermal method
Figure 3. The XRD patterns of TiO2 and TiO2:V nanoparticles prepared
by sol-gel method and the 101-peaks by different preparation methods
only anatase TiO2 peaks. The average crystallite size calculated using the Scherers
formula gave a value of about 15 nm.
The XRD patterns of V-doped TiO2 powder prepared by sol- gel method are
presented in Figure 3a, b, which showed that the nanoparticles present the anatase
phase. The average crystallite size is about 20 nm. The inserted picture in Figure
3 shows the XRD-(101) peaks of the samples TiO2:0.5%V prepared by different
methods. One can see that the (101) peak of sample prepared by hydrothermal
method is clearly broadened than that by sol-gel method. This indicated a smaller
grain size in the samples prepared by the hydrothermal method.
Figure 4 shows the SEM image of TiO2:0.5%V powder (a) and their TEM
image (b). The sample is composed of cubic grains. The average size of particles is
about 20 nm.
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A visible light activity of TiO2 based photocatalysts
Figure 4. SEM and TEM images of TiO2:0.5%V nanoparticles prepared
by hydrothermal method
Figure 5 i) and ii) present the Raman patterns of undoped TiO2 and V-doped
TiO2. The observed peaks showed that the nanoparticles were complete anatase
phase. Figure 5 iii) and iiii) below show more detailed Raman peaks of the doped
samples.
Figure 5. The Raman spectra of TiO2 and TiO2:V prepared
by hydrothermal method
15
Nguyen Minh Thuy, Le Thi Hong Hai, Duong Quoc Van and Bui Thi Hau
Compared with the undoped sample, the Eg-vibrations at 146 and 197 cm−1
presented a lightly blue-shift after V doping. The other vibrations presented no
changed with the doping effect up to 0.9%V. All peaks became wide and lightly
unsymmetrical after V doping. As well-known for the nanomaterials the blue-shift of
Raman peaks can be attributed to the quantum size effect that comes from the small
particle size, which implied that the smaller the grain size, the more noticeable the
blue-shift. In this study the observed blue shift can not be ascribed to the decrease
of grain sizes because the grain size increased with the doped V concentration, we
supposed the blue shift can be ascribed to the TiO2 lattice structure distortion due
to V doping. According to [3], the blue shift can be partly attributed to the oxygen
defects. The lattice structure distortion due to V doping can be remarked also in
the absorption spectra.
Figure 6. The Raman spectra of TiO2 and TiO2:V prepared
by hydrothermal method
Figure 7. The Ti 2p and O 1s XPS spectra of undoped
and vanadium doped samples
16
A visible light activity of TiO2 based photocatalysts
The optical absorption spectra of TiO2 and V-doped TiO2 samples prepared
by sol-gel (left) and hydrothermal (right) methods are presented in Figure 6. Pure
TiO2 (curve a) exhibited the absorption edge at around 380 nm, which corresponded
to the band gap of anatase type of TiO2. The V-doped TiO2 exhibited the long
tailed absorption in the visible light above 380 nm. Compared with the spectrum
of undoped TiO2 (curve a), the red (curve b) shift was observed in doped samples.
The tailing of the absorption band of doped samples can be assigned to the charge-
transfer transition from the d orbital of V4+ to the conduction band of TiO2 [4,5].
The weak absorption band in 650-700 nm can due to the d-d transitions of V3d
electrons. Reference [6] shown that besides the d-d transition, the gap states intro-
duced by V doping was another important reason that resulted in the visible light
absorption. The Reference [7,8] obtained that the weak band tail of undoped TiO2
was from the momentary localization of excitons due to the phonon interaction, and
the strong band tail of the V-doped TiO2 nanoparticles can mainly contributed to
the impurities and lattice disorder, which also indicated the formation of gap states,
in accordance with the result of calculation performed by [9]. In present work we
suppose that the strong band tail in the visible light of V-doping TiO2 nanopow-
ders is related to the d-d transition of V4+ in the host TiO2 and also to the lattice
disorder. The evidence of the V4+ in host TiO2 and lattice disorders can be also
observed in XPS spectra (see Figure 7).
The oxygen defects and lattice disorder can be seen by the XPS spectra. Figure
7a shows the Ti 2p core-level spectra of undoped and vanadium doped samples. As
well known, the Ti 2p peak split into Ti 2p3/2 (∼459 eV) and Ti 2p1/2 (∼ 464.5
eV) due to self-orbital coupling effect. For the undoped sample, these peaks were
symmetrical, that indicates that Ti+4 was mainly presented in the undoped sample.
The Ti 2p peak became wide and unsymmetrical after V doping, which may be
related to more oxygen defects after V doping (it can lead to Ti2O3 formation).
Figure 7b illustrates the O 1s core level XPS spectra of undoped and vanadium
doped samples. The O 1s peak (from 530 to 532 eV) is often believed to be composed
of several different oxygen species, such as Ti-O bonds in TiO2 or Ti2O3, hydroxyl
groups, C-O bonds and adsorbed H2O. In the spectra this peak is broaden, which
can be analyzed to three components: (i) the man peak (of undoped and doped
samples) at ∼531 eV could be ascribed to lattice oxygen in TiO2 (Ti-O-Ti); (ii) the
other peak at 532.3 eV could be associated to surface hydroxyl (Ti-OH) groups [10];
and (iii) for the doping samples there could be other peak at ∼533 eV of V-O groups
[7]. The latest is increased with the doping effect. The V doping lead to the O 1s
peak shifting to higher binding energy, indicative of the O valence increase.
2.2.2. Photocatalytic activity measurement
The photocatalystic degradation of phenol has been chosen as a model reac-
tion to evaluate the photocatalystic activities of the obtained TiO2 based catalysts.
17
Nguyen Minh Thuy, Le Thi Hong Hai, Duong Quoc Van and Bui Thi Hau
Phenol was selected as a model pollutant for the photocatalytic oxidation experi-
ments because it was a common toxicant in waste water. All phenol diluted water
samples were prepared as following: 80 ml (C6H5OH) solution (5.10
−5 mol/l) was
stirred under dark condition. Then 200 mg TiO2 -based photocatalysts was added
to the phenol solution and the mixture was stirred for 60 min under dark condition.
And then, visible light irradiation was carried out using 100 W wolfram lamp with
emission spectral range from 400 to 800 nm.
Figure 8 presented the chromatographs of phenol degradation of phenol pol-
lution water using TiO2:0.5%V as photocatalysts, which were recorded by HPLC at
0 and 360 min after a visible irradiation.
Figure 8. Chromatographs of phenol
degradation using TiO2:0,5%V
under vis-irradiation at 0 (over)
and 360 min(below))
Figure 9. Photocatalytic phenol
degradation curves of the 0,5%
doped TiO2 prepared by different
method
By calculating and comparing the squares of phenol peaks (at trent.=5.6 min.)
in the chromatographs we obtained the phenol degradation in water samples in
photocatalyctic process. Using result of our previous study, the 0.5%V doped TiO2
sample was chosen for the photocatalystic investigation. Figure 9 described the
photocatalystic activity of the 0.5%V- doped TiO2 samples prepared by different
methods. One can see that the sample prepared by hydrothermal method (c curve)
exhibited highest photocatalystic activity. After 360 min irradiation, the current
normalized phenol concentration decreased to 0.43%. This result can be related to
the smaller grain size of the samples prepared by hydrothermal method, which is
agreed with the XRD result above.
Toward practical use of these materials we have measured its photocatalystic
degradation of phenol in waste water of Vanphuc textile village in Hanoi. We choose
18
A visible light activity of TiO2 based photocatalysts
the 0.5%V doped TiO2 samples prepared by sol gel (S5) and hydrothermal (T5)
methods. The current phenol concentrations in waste water sample after visible
irradiation are presented in Table 1.
Table 1. The visible light photocatalystic degradation of phenol
in waste water by using TiO2:0.5%V powders
Irradiation time (min) 0 60 120 180 240
Phenol content (mg/l) case of S5 sample 0.9106 0.7318 0.5714 0.2739 0.0036
Phenol content (mg/l) case of T5 sample 0.7712 0.6992 0.6271 0.3135 0.0030
The current phenol content in waste water decreased to 0.003 mg/l after 240
min. of visible irradation.This value is less than the allowable phenol value on
industrial waste water by discharge standards (TCVN5945-2005: < 0.1mg/l). The
visible light phototcatalystic activity of V doped TiO2 suggested an application for
an environmental treatment of waste water.
3. Conclusion
The pure and vanadium doping TiO2 nanopowders were prepared by sol-gel
citrate and hydrothermal methods. The dopant V-concentration is in a range from
0.1% to 0.9%. All obtained samples are single anatase crystal phase. The average
crystal size is about 15-20 nm, the grain are cubic form and have the size dis-
tributed of 15-25 nm. The doped samples exhibited long tailed absorption in the
visible light above 380 nm. This can be related to the charge- transfer transitions
from the d-d orbital of V to the conduction band of TiO2 or the impurities and
lattice disorder. The first reason is important for the photocatalyst activity of the
samples. The HPLC measurements show that the phenol- photooxidation rate un-
der Vis-irradation increased with vanadium concentration and reached maximum in
the doped sample with 0.5%V. After 360 min of Vis-irradation the photolacatalyst
TiO2:0.5%V lead the phenol concentration degrading less than 0.5%.
Acknowledgements
The authors would like to thank Hanoi National University of Education and
the Ministry of Education and Training for financial support. This work is financially
supported by the Ministerial-level project on the science and technology.
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Nguyen Minh Thuy, Le Thi Hong Hai, Duong Quoc Van and Bui Thi Hau
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