Article

pubs.acs.org/JPCC

Characterization of Oxygen Vacancy Associates within

Hydrogenated TiO2: A Positron Annihilation Study
Xudong Jiang,† Yupeng Zhang,† Jing Jiang,† Yongsen Rong,† Yancheng Wang,† Yichu Wu,†
and Chunxu Pan*,†,‡
†
School of Physics and Technology, Hubei Nuclear Solid Physics Key Laboratory and MOE Key Laboratory of Artificial Micro- and
Nano-structures, Wuhan University, Wuhan 430072, China
‡
Center for Electron Microscopy, Wuhan University, Wuhan 430072, China
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ABSTRACT: This paper introduces a novel method for

characterizing the oxygen vacancy associates in hydrogenation-
modified TiO2 by using a positron annihilation lifetime
spectroscopy (PALS). It was found that a huge number of
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small neutral Ti3+−oxygen vacancy associates, some larger size

vacancy clusters, and a few voids of vacancy associates were
introduced into hydrogenated TiO2. The defects blurred the
atomic lattice high-resolution transmission electron micros-
copy (HRTEM) images and brought about the emergence of
new Raman vibration. X-ray photoelectron spectroscopy
(XPS) measurement indicated that the concentration of
oxygen vacancies was 3% in the TiO2 lattice. The photoluminescence (PL) spectroscopy, photocurrent, and degradation of
methylene blue indicated that the oxygen vacancy associates introduced by hydrogenation retarded the charge recombination and
therefore improved the photocatalytic activity remarkably.

1. INTRODUCTION
As one of the promising semiconductors, titania (TiO2) has
grabbed appreciable attention over the past decades, due to its
powerful potential applications in photovoltaics, biomedicine,
and photocatalysis.1−3 However, the photocatalytic efficiency of
TiO2 is limited by its wide band gap and the low efficiency of
recombination of photogenerated electrons and holes.4 Herein,
the methods for enhancing the photocatalytic activity of TiO2
are mainly based on decreasing the band gap and inhibiting the
recombination of photo-generated electrons and holes.
In general, the nonmetal dopants for TiO2, such as N,5 C,6
F, and S,8 were widely used for shifting the photoresponse
7 narrowed bandgap to the synergistic presence of oxygen
toward longer wavelengths. Meanwhile, numerous surface
modifications have been devoted to reduce the recombination
of photogenerated electrons and holes, for example, TiO2/
semiconductor composites,9,10 metallic doping,11 heavy metal
deposition upon TiO2,12 and so on. More current evidence has
demonstrated that oxygen vacancy defects on the TiO2 surface
play an essential part in acting as electron scavengers when
electron−hole pair creation occurs by photoexcitation in the
TiO2.13
Recently, hydrogenation modified TiO2 has triggered
extensive research interest and is considered to have great
potential.14−18 Chen et al.14 reported the preparation of black
hydrogenated TiO2 nanoparticles in a 20 bar hydrogen
atmosphere at 200 °C for 5 days. It exhibited a greatly
enhanced absorption in the visible light and near-infrared
region, due to its narrowed band gap around 1.0 eV, which was
ascribed to the surface disorder of TiO2 nanoparticles.
However, the unclear detailed image of the disorder and the
role of the hydrogenation as well as the mechanism of high
photoactivity are still ambiguous.
In addition, surface-hydrogenated anatase TiO2 nanowire
microspheres were also reported by Zheng and his co-
workers.17 They ascribed the enhanced photocatalytic activities
to the improved optical absorption and efficient photo-
generated electron−hole separation induced by the surface
Ti−H bonds as well as the unique structure. Simultaneously,
Naldoni et al.18 fabricated the black TiO2 nanoparticles with
crystalline core/disordered shell morphology, and ascribed its
vacancies and surface disorder. More examples showed the
decisive role of defects such as oxygen vacancy in hydrogenated
TiO2. However, few studies concern the detection of oxygen-
vacancies induced by hydrogenation in TiO2.
Positron annihilation lifetime spectroscopy (PALS) provides
a sensitive method for investigating vacancy-type defects, and it
has been proven to be useful in determining the intrinsic
defects in semiconductors.19,20 When positrons inject inside
bulk materials, they get thermalized and annihilated with
electrons, and result in the emission of γ rays, which convey
information of the lifetime of positrons. Compared to the bulk
of the material, positrons preferentially distribute in the regions
where electron density is low, e.g., vacancy type defects,
Received: July 31, 2012
Revised: September 30, 2012
Published: October 2, 2012

© 2012 American Chemical Society 22619 dx.doi.org/10.1021/jp307573c | J. Phys. Chem. C 2012, 116, 22619−22624
The Journal of Physical Chemistry C
vacancy clusters, and microvoids. Herein, the electron-positron
annihilation photons allow measurement of the lifetime of
positrons, which provides information regarding various
defects.21,22
In this research, commercial P25 was chosen as the pristine
TiO2 photocatalyst and annealed at 400 °C in H2 under
atmospheric pressure for 10 h. The positron annihilation
characterization revealed the existence of a large number of
various oxygen vacancy associates in the hydrogenated TiO2,
which would play the key role of inhibiting the recombination
of holes and electrons during photocatalyzing.
2. EXPERIMETAL SECTION
2.1. Preparation of Hydrogenated TiO2. Commercial
pure white P25 TiO2 nanoparticles purchased from Degussa
were used for the pristine sample. The hydrogenation was
carried out in a tube furnace filled with ultrahigh purity
hydrogen gas (99.99%) under atmospheric pressure, and the
pristine P25 was annealed at 400 °C for 10 h, as described in
earlier reports.15,18 The flow rate of hydrogen is 10 sccm. The
obtained taupe powders were denoted as H-P25, distinguished
from the pristine white P25.
2.2. Characterization. The morphologies of P25 and H-
P25 nanoparticles were observed by using high-resolution
transmission electron microscopy (HRTEM, JEM 2010FEF
HRTEM, JEOL, Japan). An X-ray diffraction spectrometer
(XRD) (D8 Advanced XRD, Bruker AXS, Germany) with a Cu
Kα source was employed to analyze their crystalline structures.
The scanning speed was 4°/m in the range of 20−80°. X-ray
photoelectron spectroscopy (XPS) measurements were per-
formed in a VG Multilab2000 spectrometer to obtain
information on the chemical binding energy of the samples.
The ultraviolet−visible diffuse reflectance spectra (UV−vis
DRS) of the samples were measured by using a diffuse
reflectance accessory of a UV−vis spectrophotometer (UV-
2550, Shimadzu, Japan). The Raman spectra were obtained
using a LabRAM HR spectrometer (HORIBA Jobin Yvon,
France) with a laser excitation of 488 nm. Photoluminescence
(PL) spectra were measured at room temperature on a
fluorescence spectrophotometer (F-4600, Hitachi, Japan) with
an excitation wavelength of 300 nm, a scanning speed of 240
nm/min, and a photomultiplier tube (PMT) voltage of 700 V.
PALS was measured using a conventional ORTEC-265 fast−
fast coincident system at room temperature. The coincidence
spectrometer used had a prompt time resolution of 150 ps
(fwhm) for the γ-rays from a 60Co source selected under the
experimental conditions. Three hundred milligrams of sample
powder was pressed into a disk (diameter: 13 mm, thickness: 1
mm). The source (∼1.3MBq) of 22Na was sandwiched between
two identical sample disks. The positron lifetime spectrum
containing 106 counts was analyzed by the PATFIT program to
decompose several lifetime components.
2.3. Photocurrent Tests. Five milligrams of photocatalysts
was dispersed in 5 mL of ethanol and ultrasonically vibrated for
30 min. The 0.25 mL resultant slurry was then dip-coated onto
a 10 × 20 mm indium−tin oxide (ITO) glass electrode and
dried under high-pressure mercury lamp irradiation to eliminate
ethanol. The prepared TiO2/ITO electrode, platinum elec-
trode, and saturation calomel electrode (SCE) were used as the
working electrode, counter electrode, and reference electrode,
respectively. The electrolyte was 0.5 mol/L Na2SO4 aqueous
solution. The working electrode was activated in the electrolyte
for 0.5 h before measurement. A high-pressure mercury lamp
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(160 W), which generates light with maximum intensity at 365
nm, was used as a light source away from the working electrode
with a distance of 10 cm. The intensity of photocurrent was
measured by an electrochemical workstation (CHI660C,
Chenhua, China).
2.4. Measurement of Photocatalytic Activities. The
photocatalytic activity was evaluated by detecting the
degradation rate of methylene blue (MB). In brief, a 250 W
high pressure mercury lamp was used as a light source for
photocatalytic reaction, 100 mg of photocatalyst was dispersed
into 100 mL of 10 mg/L MB solution, and then the mixture
was stirred constantly under the light at a distance of 250 mm.
The concentration of MB solution was measured by the UV−
vis spectrophotometer (UV-2550, Shimadzu, Japan) every 30
min.
3. RESULTS AND DISCUSSION
Figure 1 illustrates the XRD patterns of the pristine and
hydrogenated P25 TiO2 nanoparticles. The strong XRD
Figure 1. XRD patterns of P25 before (a) and after (b) hydrogenation.
diffraction peaks indicated that the pristine P25 was highly
crystallized with a mixture of anatase (70−80%) and rutile
(20−30%), which has been reported elsewhere,23 and no
obvious change was observed for the H-P25 TiO2. The anatase
grain sizes of the P25 TiO2 nanoparticles were around 16 nm
calculated from the Scherrer. By contrast, Figure 2 shows the
absorption spectra of the pristine and hydrogenated P25 TiO2
nanoparticles. The hydrogenation had little effect on the
absorption of P25 in the UV region, while H-P25 exhibited a
remarkable absorption in the visible light region, which was also
similar to the results of Chen et al.14 Nevertheless, the gray
coloration of H-P25 in our experiment was due to the use of
slow cooling rate after hydrogenation.18
HRTEM observations are shown in Figure 3 and Figure 4,
respectively, with related fast Fourier transform (FFT) analysis
images in the inset. It revealed clear lattice fringes and a sharp
FFT image in pristine P25 TiO2, which demonstrated a high
level of crystallization. However, after hydrogenation, the lattice
images and the FFT image of H-P25 became blurred, which
indicated the distortion of the TiO2 atomic lattice structures
during hydrogenation.
Raman spectroscopy is a spectroscopic technique to measure
molecular vibrations. It can be used for detecting the structural
dx.doi.org/10.1021/jp307573c | J. Phys. Chem. C 2012, 116, 22619−22624
The Journal of Physical Chemistry C
Figure 2. UV−vis DRS of P25 and H-P25.
Figure 3. HRTEM micrographs of P25 nanoparticles.
Figure 4. HRTEM micrographs of the hydrogenated P25 nano-
particles.
changes on the surface of P25 TiO2 before and after
hydrogenation. As shown in Figure 5, pristine P25 TiO2
exhibited Eg modes (143 cm−1, 198 cm−1 and 639 cm−1), a
B 1g mode (399 cm −1 ) and an A 1g mode (515 cm −1
superimposed by 519 cm−1), in good agreement with a former
report.24 However, besides the peaks appearing in pristine P25,
the Raman peaks of the hydrogenated P25 TiO2 became
fluctuated more, and two weak peaks emerged at 316 cm−1 and
810 cm−1, as shown in Figure 5b. The band centered at about
320 cm−1 should be assigned to second-order scattering, which
always showed an A1g symmetry component.25 In addition, the
band at 810 cm−1 still could not be assigned to any type of
anatase Raman-active modes. A new band at 321.1 cm−1 was
also observed in the surface-hydrogenated anatase TiO 2
nanowire microspheres.17 Therefore, the phenomena of the
emerging of the second-order scattering and new band at 810
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Figure 5. Raman spectra of P25 before and after hydrogenation: (a)
survey; (b) magnified.
cm−1 might result from the hydrogenation-induced structural
changes at the surface.
XPS analysis of the Ti 2p region evidences a slight shift to
low binding energy. Figure 6 shows the XPS spectra of the Ti
2p doublet region after peak deconvolution and background
removal. Comparing with pristine P25 with symmetrical Gauss
distribution (Figure 6a), the 2p doublet peaks of the
hydrogenated P25 exhibited a tail in the region of lower
binding energy, which indicated the presence of lower valence
states of Ti, as shown in Figure 6b. The small peaks at 457.6 eV
for Ti 2p3/2 and 463.3 eV for Ti 2p1/2 clearly indicate the
presence of Ti3+. In addition, the main sharp peaks of Ti 2p3/2
located at 458.3 eV and Ti 2p3/2 located at 464.0 eV were
assigned to Ti4+ in TiO2. The Ti3+/Ti4+ ratio was calculated to
be approximately 14% from the peak areas. In general, the
existence of Ti3+ in TiO2 indicates the oxygen vacancies will be
generated to maintain electrostatic balance according to the
following chemical equation:
4Ti4 + + O2 − → 4Ti4 + + 2e−/□ + 0.5O2
→ 2Ti4 + + 2Ti 3 + + □ + 0.5O2
The □ represents an empty position originating from the
removal of O2− in the lattice. It can be deduced that an oxygen
vacancy generated companied with two Ti3+ ions from the
equation. Therefore, the concentration of oxygen vacancy in
the TiO2 lattice is calculated to be 3% in H-P25. Naldoni et
al.18 reported a 5% concentration of oxygen vacancy, which
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The Journal of Physical Chemistry C Article

Figure 7. Positron lifetime spectra with fitting lines of P25 (blue) and
H-P25 (red).

Table 1. Positron Lifetimes and Relative Intensities with

Their Deviations of Pristine P25 and H-P25
τ3 I3
sample τ1 (ps) τ2 (ps) (ns) I1 (%) I2 (%) (%)
P25 value 140.5 376.9 NA 11.22 88.78 NA
deviation 14.1 2.1 NA 1.08 1.08 NA
H-P25 value 188.1 378.7 19.3 14.30 85.45 0.25
deviation 19.9 3.8 10.7 2.74 2.75 0.07

a straight line, because they closed to the time resolution. The

Figure 6. Ti 2p XPS spectra of P25 (a) and H-P25 (b).
indicated the fast cooling rate could be a plus to keep the
concentration of oxygen vacancy in hydrogenation.
PALS provides information including size, type, and relative
concentration of various vacancies according to the lifetime of
the positrons.21,22 Generally, the positions would undergo rapid
thermalization by dissipation of their energy to the surrounding
medium and then diffuse through the medium with an average
diffusion length after entering into solid. For anatase TiO2, the
position diffusion length is approximately 45 nm referring to
the previous report,26 which is much longer than the grain size
of our sample (about 16 nm of anatase). Herein, the positron
can diffuse throughout the lattice and reach the grain surface to
annihilation.
The time-dependent positron decay spectrum D(t) = ∑iIi
exp(−t/τi) was analyzed as the sum of exponential decay
components convoluted with the Gaussian resolution function
of the spectrometer. Figure 7 illustrates the typical positron
lifetime spectra from the samples P25 and H-P25. The positron
lifetime spectrum N(t) = ∑iIi/τi exp(−t/τi) and the absolute
value of the time were the deconvolution of the positron decay
spectrum D(t) by the PATFIT program. The fitting results are
listed in Table 1 with three positron lifetime components, τ1, τ2,
and τ3, and the relative intensities, I1, I2, and I3, for pristine P25
and H-P25. The obtained lifetime components τ2 for both P25
and H-P25 and τ3 for H-P25 were added as straight lines in the
plots for illustration. The τ1 components were not indicated as
22622
slop of the straight line was according to λ = Δ ln D(t) /Δt
strictly. The λ represents annihilation rate, which is the
reciprocal of the τ.
The shorter component (τ1) is generally due to the free
annihilation of positrons in a defect-free crystal, denoted as the
first lifetime of positrons.27 In a disordered system, smaller
vacancies (such as monovacancies, etc.) or shallow positron
traps (such as oxygen vacancies associated in CeO2) may
reduce the surrounding electron density,19 which increases the
lifetime of τ1. In pristine P25, some monovacancies exist
naturally in the crystal lattice. Herein, the τ1 for pristine P25
was 140.5 ps, which could be ascribed to the inherent free
positron lifetime in pristine TiO2. However, the τ1 for H-P25
was remarkably longer at 188.1 ps, 33% greater than in pristine
P25. Therefore, the prolonged τ1 of H-P25 demonstrates that a
huge number of small neutral Ti3+−oxygen vacancy associates
were introduced into the TiO2 lattice by hydrogenation.
Correspondingly, the relative intensity (I1) of H-P25 was also
increased dramatically, i.e., from 11.22% in pristine P25 to
14.3% in H-P25.
The longer lifetime component (τ2) is attributed to positrons
captured by defects of larger size.27 The average electron
density in larger-sized defects is lower than that in small size
defects, which decreases the annihilation rate and increases the
positron lifetime correspondingly. Therefore, the values of τ2
were much larger than the values of τ1. In our samples, both
P25 and H-P25, the positions could diffuse throughout the
lattice and reach the grain boundaries, where there existed a
huge number of boundary-like defects. So the longer lifetime
was generated with larger proportion. For pristine P25, the τ2
was 376.9 ps with the intensity (I2) of 88.78%. Obviously, the
boundary-like defect accounts for more proportion than that of
natural monovacancies in pristine P25 due to I2 > I1. For H-
dx.doi.org/10.1021/jp307573c | J. Phys. Chem. C 2012, 116, 22619−22624
The Journal of Physical Chemistry C Article

P25, the τ2 was increased to 378.7 ps because of hydrogenation,

which demonstrated that some larger size vacancy clusters were
induced inside the hydrogenated TiO2, which resulted from
interaction between the small neutral Ti3+−oxygen vacancy
associates. However, the increase of τ2 was only 0.4% for the
monovacancies introduced predominately by hydrogenation.
The decrease of I2 in H-P25 was due to the dramatic increase of
I1, because of the relationship of I1 + I2 + I3 = 100%.
The longest lifetime component (τ3) was probably assigned
to the annihilation of orthopositronium atoms formed in the
large voids (nanoscale) in materials.27 For the present work, τ3
= 19.3 ns was detected only in H-P25, and no τ3 single in
pristine P25. However, the intensity of τ3 (I3) was also so slight
that it was only 0.25% in the hydrogenated TiO2. That is to say,
few voids of oxygen vacancy associates in nanoscale were
formed in the hydrogenated TiO2 crystalline grains.
Hydrogen gas (H2) is generally used as a reducing agent. By
heating TiO2 in a hydrogen atmosphere, numerous oxygen Figure 8. PL spectra of P25 and H-P25.
vacancies, associated with Ti3+ were introduced in H-P25. Thus
the shorter lifetime component (τ1) of positrons was prolonged TiO2 samples.28 For pristine P25, the intensities of the
by the oxygen vacancy associates, where the surrounding secondary peaks (at 451 and 469 nm) are lower than their
electron density decreased. Some of the oxygen vacancy main peaks (at 400 and 412 nm). However, for H-P25, the
associates tended to flock to larger size vacancy clusters and relative intensity of the secondary peaks was enhanced
few voids in nanoscale, which increased the τ2 and generated τ3 remarkably, when compared with the main peaks. Particularly,
accordingly. Herein, the concentration of the small neutral the intensity of peak at 469 nm reached the summit of the
Ti3+−oxygen vacancy associates, larger size vacancy clusters, survey spectrum, which demonstrated the formation of oxygen
and voids of vacancy associates decreased subsequently. The defects in the TiO2 lattice by hydrogenation. However, for the
vacancy associates also disordered the surface structure of lower intensity of background, the absolute intensity of the
modified TiO2 and thus blurred the atomic lattice HRTEM secondary PL peaks of H-P25 was lower than that of pristine
images, as shown in Figure 4. Moreover, the surface structural P25.
variations were caused by vacancies in the modification of It has been well-known that there is a positive correlation
hydrogenation, thereby the emergence of the second-order between e−−h+ separation efficiency, photocurrent, and
scattering and new band at 810 cm−1 of Raman vibration were photocatalytic activity. Figure 9 illustrates the photocurrent
brought about in the hydrogenated TiO2. Oxygen vacancy
defects on the surface of TiO2 play an essential part in
governing the adsorption of O2 molecules, which interact with
Ti3+ sites or act as electron scavengers.13 Additionally, the Ti3+
species from the removal of oxygen atoms would act as holes
scavengers. These behaviors could retard the charge recombi-
nation and therefore improve the photocatalytic activity.
The measurement of PL emission was performed to reveal
the efficiency of charge carrier trapping, migration, transfer, and
separation, and to understand the fate of photogenerated
electrons and holes in semiconductors, since PL emission
results from the recombination of free carriers.28 Figure 8
shows the comparison of PL spectra of pristine and
hydrogenated P25 TiO2 in the wavelength range of 350−550
nm with the excitation at 300 nm. The main emission peaks of
pristine P25 and H-P25 appeared at 400 and 412 nm, which
were attributed to the emission of bandgap transition with the
energy of emission corresponding to the bandgap energy of
anatase (3.2 eV) and rutile (3.0 eV), respectively. The PL Figure 9. Photocurrents of P25 and H-P25.
emission intensity of H-P25 at 400 and 412 nm are only one-
third of the pristine P25, which indicated that the profiles of pristine P25 and H-P25. It was found that value of
recombination rate of photogenerated electrons and holes the H−P25 photocurrent was 3 times higher than that of
had been inhibited considerably in H-P25, because of the pristine P25, in good agreement with the PL test.
formation of oxygen vacancies during the hydrogenation. The Figure 10 shows the time profiles of ln(C0/C) under UV−vis
oxygen vacancies actually served as electron capture traps, and irradiation for degradation of MB aqueous solution, where C is
hence separated the charge carriers and reduced the the concentration of MB at irradiation time t, and C0 is the
recombination significantly. concentration in absorption equilibrium of photocatalysts
The secondary PL emission peaks at 451 and 469 nm were before irradiation. The linear relationship between the ln(C0/
equivalent to 2.75 and 2.65 eV, respectively. These PL signals C) and irradiation time confirmed the stability of the TiO2
were attributed to surface oxygen vacancies and defects of the before and after hydrogenation. The line slope of H-P25 was 2
22623 dx.doi.org/10.1021/jp307573c | J. Phys. Chem. C 2012, 116, 22619−22624
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(12) Wang, C.; Pagel, R.; Bahnemann, D. W.; Dohrmann, J. K. J.

Figure 10. Photocatalytic degradation of MB by P25 and H-P25.
times higher than that of pristine P25, which demonstrated the
superior photocatalytic property of H-P25.
4. CONCLUSIONS
As a sensitive approach for measuring vacancy-type defects,
PALS provides an effective route to qualitatively characterize
the oxygen-vacancy-induced defects in TiO2. It will be of
significance to evaluate and understand the importance of
oxygen vacancies, the associated with Ti3+ sites in TiO2 as
electron and hole scavengers, which thus separated the charge
carriers and remarkably improved the photocatalytic activity of
TiO2.
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■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +86-27-68752481 ext. 5201; Fax.: +86-27-68752003; e-
mail: cxpan@whu.edu.cn.
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This research was financially supported by the National Basic
Research Program of China (973 Program) (No.
2009CB939705 and No. 2009CB939704).

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