Materials Science in Semiconductor Processing 16 (2013) 288–294

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Materials Science in Semiconductor Processing

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Preparation and characterization of BiFeO3@Ce-doped

TiO2 core-shell structured nanocomposites
Lixiu Gong a, Zhufa Zhou a,b,n, Shumei Wang a,b,n, Ben Wang a
a
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, PR China
b
National Engineering Laboratory of Modern Silk, Soochow University, Suzhou 215123, PR China

a r t i c l e in f o abstract

Available online 13 November 2012 BiFeO3@TiO2–Ce composite nanoparticles with a BiFeO3 core and a Ce-doped TiO2 shell
Keywords: structure were fabricated via a sol–gel method. The nanoparticles were characterized by
Titania scanning electron microscopy with energy dispersive spectroscopy, X-ray diffraction,
BiFeO3 transmission electron microscopy and UV–vis diffuse reflectance spectroscopy. The
Ce-doped results reveal that core-shell structured BiFeO3@TiO2–Ce nanoparticles show a signifi-
Synergistic effect cant redshift in the UV–vis absorption spectra in comparison with both Ce-TiO2 and
Photocatalysts BiFeO3@TiO2 nanoparticles. The photocatalytic activities of the samples were tested in
the degradation of methyl orange in aqueous solutions under visible light and UV light
irradiations. The core-shell structured BiFeO3@TiO2–Ce sample exhibits higher photo-
catalytic activity, which is attributed to the synergistic effects of BiFeO3 and cerium.
Crown Copyright & 2012 Published by Elsevier Ltd. All rights reserved.

1. Introduction In particular, exploiting a core-shell structured nanoparti-

Titanium dioxide (TiO2) in different forms has attracted
extensive interests in recent years owing to its high photo-
catalytic effects on decomposing various organic pollutants
[1–4], which offers a viable approach to solve the variety of
environmental problems. But the band gap of TiO2 (3.2 eV
for anatase) is so wide that it can only absorb ultraviolet
(UV) light, which is only 5% in the sun source [5]. In
addition, the photogenerated electron–hole pair recombin-
ing easily results in poor photocatalytic activity, and hence
limits its applications. Several efforts have been made, such
as replacing the oxygen position with nonmetallic or metal
element to overcome the barriers [6–10]. Besides, various
modifications have been performed to synthetize nanos-
tructured composites such as Fe3O4/SiO2/TiO2, ZnO/TiO2
and WO3/TiO2, which can efficiently hinder the recombina-
tion of the photogenerated electron–hole pairs [11–13].
n
Corresponding authors at: College of Chemistry, Chemical Engineering
and Materials Science, Soochow University, Suzhou 215123, PR China.
Tel.: þ 86 512 65880963; fax: þ 86 512 65880089.
E-mail address: zhouzhufa@suda.edu.cn (Z. Zhou).
cles in which TiO2 acted as shell and magnetic materials
(such as Fe3O4, MnFe2O4, BaFe12O19) introduced as core is
also an efficient way [14–16].
As we have known, BiFeO3 has an excellent multiferro-
electric properties at room temperature. In addition, It has
been studied widely in the photocatalytic field due to its
small bandgap. Zhang et al. synthesized TiO2/BiFeO3
heterostructures, and their results indicated BiFeO3
weaken the recombination of electrons generated [17].
Shun Li et al. had prepared BiFeO3@TiO2 core-shell struc-
ture and found that the core-shell nanoparticles had a
higher photocatalytic activity in contrast to pure TiO2.
BiFeO3 act as electron carriers that can promote interfacial
charge transfer in the composite systems [18]. Addition-
ally the magnetic property of the composites helps
recycle the photocatalysts from treated water. The core-
shell BiFeO3@TiO2 nanoparticles have a lower energy gap
that enhances visible light absorption. In order to over-
come the recombination of photogenerated electron–hole
pairs of BiFeO3@TiO2, many groups have been involved in
doping rare earth ions into TiO2 [19,20], among which
cerium has been received much attentions because of the

1369-8001/$ - see front matter Crown Copyright & 2012 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mssp.2012.10.009
 L. Gong et al. / Materials Science in Semiconductor Processing 16 (2013) 288–294
following two reasons: (1) the redox couple Ce3 þ /Ce4 þ
with the ability of ceria to shift between CeO2 and Ce2O3
under oxidizing and reducing conditions; and (2) the easy
formation of labile oxygen vacancies (OV) with the
relatively high mobility of bulk oxygen species [21].
In this paper, a novel TiO2-based BiFeO3@Ce-doped
TiO2 core-shell nanocomposite was prepared through a
sol–gel method. The crystal structure, optical property
and morphologies of the nanocomposite were system-
atically characterized and investigated as well. Finally, the
photocatalytic activity was measured via the degradation
of MO under both UV light and visible light illuminations.
Due to the synergistic effects of BiFeO3 and Ce, the
photocatalytic activity of these core-shell nanoparticles
was dramatically enhanced. Additionally, under an exter-
nal magnetic field, the nanocomposite could be easily
separated and recycled from the treated water.
2. Experimental
2.1. Materials
All the chemicals used in the experiments were analy-
tically pure and used as received without further purifica-
tion. Tetrabutyl titanate (Ti(OC4H9 n)4, 98%), cerium (III)
nitrate hexahydrate (Ce(NO3)3  6H2O, 99%), bismuth nitrate
pentahydrate (Bi(NO3)3  5H2O, 99%), and iron nitrate non-
ahydrate (Fe(NO3)3  9H2O, 98.5%) were obtained from
Shanghai Chemical Corporation (Shanghai, China). Anhy-
drous ethanol (C2H5OH, 99.7%, Jiuyi Chemical Reagent Co.,
Ltd., China), nitric acid (HNO3, 67%) and deionized water
were used in all the experiments.
2.2. Sample preparation
The BiFeO3 was synthesized according to the afore-
published method [22]. The BiFeO3 precursor was pre-
pared from acetic acid based solution, using bismuth
nitrate pentahydrate (5 mol% excess for the bismuth loss
during the heating process), iron nitrate nonahydrate and
acetic acid as the solutes and 2-methoxyethanol as the
solution. After the solution became transparent, the pre-
cursor was dried at 80 1C for about 24 h to obtain the
BiFeO3 xerogel powder. Then the xerogel powder was
annealed at 500 1C for 2 h and the BiFeO3 nanoparticles
were obtained.
The coating of Ce–TiO2 on BiFeO3 is as follows: solu-
tion A consisted of 10 ml tetrabutyl titanate, Ce
(NO3)3  6H2O in the required stoichiometry (0.5%, 1.0%,
2.0% and 4.0%, which was the mole percentage of Ce
element in the theoretical TiO2 samples) and 2 ml acet-
ylacetone in 100 ml anhydrous ethanol, and the pH value
was adjusted to 5–6 by dropwisely adding of HNO3 (70%).
Then the mixture was stirred vigorously until the solution
became transparent. Solution B contained 4.65 g BiFeO3
(BiFeO3:TiO2 ¼ 1:2, molar ratio) and 150 ml anhydrous
ethanol. In order to make the BiFeO3 dispersed uniformly,
the solution B was treated under an ultrasonic bath for
2 h. The Solution A was added dropwise into solution B
under vigorous stirring. Then the mixture solution was
under vigorous stirring at 40 1C for 5 h. The resulting
289
transparent suspension was stirred for another 6 h and
aged for 24 h until the transparent gel was obtained. The
gel was dried at 80 1C for 24 h and then ground to form
semisolid powder before sintering at 500 1C for 2 h in air
condition. The resultant powders were BiFeO3@TiO2–Ce
catalysts. Ce-doped TiO2 was obtained in the same experi-
mental conditions just like solution A. Meanwhile,
BiFeO3@TiO2 was prepared in the absence of Ce(NO3)3 
6H2O.
2.3. Characterizations
The phase structure of the as-synthesized particles
were measured by X-ray diffraction (XRD) (Rigaku Co,
Tokyo, Japan) with a Bragg-Brentano geometry using Cu
Ka radiation (l ¼1.5405 Å). The morphologies were
observed by a scanning electron microscope (SEM, Hitachi
S-4700, Japan) operated at 25 KV and a transmission
electron microscope (TEM, FEI TecnaiG220, USA) with an
accelerating voltage of 200 kV. An energy dispersive
spectroscopy (EDS) was employed to examine the com-
position of the resultant nanocomposite photocatalysts.
The UV–visible diffuse reflectance spectra (DRS) were
obtained using a scan UV–vis spectrophotometer (Varian
Cary 500) equipped with an integrating sphere assembly.
The photocatalytic performance was evaluated by the
degradation of methylene orange (MO) in aqueous solu-
tion. The particles were placed in quartz vessels and were
irradiated under UV light (Hg lamp 300 W with a primary
wavelength of 254 nm, Philips, China) and visible light (Xe
lamp, 500 W; Visible cutoff filter 4400 nm), the concen-
tration of the dye solution was measured by a UV–vis
spectrometer (Perkin-Elmer Lambda 900 UV/vis/NIR,
Waltham, MA) at wavelength 500 nm. Magnetic measure-
ments were carried out at room temperature using a
vibrating sample magnetometer (VSM, Lakeshore
7307, USA).
3. Results and discussion
3.1. X-ray diffraction
XRD measurements are performed to identify the
crystalline phases synthesized by the sol–gel process.
The obtained TiO2 and Ce–TiO2 samples consist of anatase
as a unique phase are shown in Fig. 1. No characteristic
peaks of cerium oxides are observed in Ce–TiO2 samples
for the low dosage (Ce 2%) and the extremely high
dispersion [21,23]. The BiFeO3@TiO2–Ce 2% sample shows
that TiO2 and BiFeO3 phases coexistence at the present
synthesis conditions, and there are no extra peaks, indi-
cating that no new phase is formed between TiO2 and
BiFeO3. Additionally, it is worth noting that the anatase
(101) crystal plane peak became broad and weak as
presented in the inset of Fig. 1. The average crystallite
sizes of different samples are calculated by applying the
Scherrer formula on the anatase (101) diffraction peaks.
The values of pure TiO2, TiO2–Ce and BiFeO3@TiO2–Ce 2%
were 11.0, 7.6 and 8.9 nm, respectively, suggesting that
cerium doping inhibits crystal growth. The smaller size is
beneficial to improve the photocatalytic activity.
290 L. Gong et al. / Materials Science in Semiconductor Processing 16 (2013) 288–294
3.2. SEM-EDS and TEM
Scanning electron microscopy (SEM) images of the
products, Fig. 2, reveal that the pure BiFeO3 particles
exhibits an agglomeration and irregular shapes (Fig. 2a),
compared to the uniform spherical particles with smooth
surface for BiFeO3@TiO2–Ce 1% (Fig. 2b). Both samples
have a narrow size distribution range (50–100 nm). The
size observed with SEM is extremely different from the
XRD calculated size, indicating that the particles observed
with SEM is not a single crystallite but the agglomerates
of many single crystallites. The EDS patterns of bare
BiFeO3 and BiFeO3@TiO2–Ce are presented in Fig. 3. It is
clearly seen that BiFeO3 mainly contains Bi, Fe and O
elements (Fig. 3(a)). However, except for Bi, Fe and O,
there are other elements such as Ti and Ce co-exist in
BiFeO3@TiO2–Ce sample (Fig. 3(b)).
The TEM images of typically BiFeO3@TiO2–Ce sample
are shown in Fig. 4. At higher magnification, the inter-
planar spacing of 0.354 nm and 0.397 nm in Fig. 4(a)
corresponding to the (101) plane of anatase TiO2 and
(012) plane of perovskite BiFeO3, respectively, which
agrees with the previously reported values [24,25]. The
inset of Fig. 4(a) displays the TEM image of the sample. It
can be seen that BiFeO3 particles are surrounded by
anatase TiO2–Ce nanocrystallines. The existence of the
Fig. 1. XRD patterns of samples: (a) pure TiO2, (b) Ce–TiO2, (c) BiFe
O3@TiO2–Ce 2.0% and (d) BiFeO3. The inset shows the enlarged (101)
peak of samples (a), (b) and (c).
Fig. 2. SEM images of: (a) pure BiFeO3 and (b) BiFeO3@TiO2–Ce.
core-shell structure is well-supported by the results of
EDS analysis (Fig. 4(b)).
3.3. UV–vis diffuse reflectance spectra
The UV–vis diffuse reflectance spectra (DRS) of TiO2,
BiFeO3@TiO2, Ce–TiO2 and BiFeO3@TiO2–Ce 1% catalysts
are shown in Fig. 5. The results demonstrate that the
broad band gap of pure TiO2 shows narrow absorption
edges below 385 nm. Additionally, Ce–TiO2 samples exhi-
bit a significant light absorption in the range from 400 to
500 nm. Cerium ion has two possible oxidation states,
Ce3 þ and Ce4 þ . The absorption range from 400 to 500 nm
cannot be ascribed to Ce4 þ because the 4f state of Ce4 þ
does not contain any electron. Although Ce3 þ ion pos-
sesses a single optically-active electron in the 4f1 orbital,
which has an excited state 2F7/2 and a ground state of 2F5/2,
the light absorption in visible region also cannot be
attributed to 4f–4f transitions, because the characteristic
4f–4f transitions only be observed in the infrared spectral
region [26]. Therefore, the absorption range from 400 to
500 nm is due to 4f–5d transition of Ce3 þ [21,27]. The
band gap energy of the sample could be calculated by the
equation (ahu)n ¼ k(hu Eg), where a is the absorption
coefficient, k is the parameter related to the effective
masses associated with the valence and conduction bands,
n is 1/2 for a direct transition, hu is the absorption energy,
and Eg is the band gap energy [28]. Plotting (ahu)1/2; versus
hu based on the pattern response, as shown in Fig. 4(a),
gives the extrapolated intercept corresponding to the Eg
value as shown in Fig. 4(b). The band gaps of TiO2, Ce–TiO2,
BiFeO3@TiO2 and BiFeO3@TiO2–Ce are about 3.13 eV,
2.76 eV, 2.58 eV and 2.41 eV, respectively. The Ce–TiO2
sample has a lower Eg than pure TiO2. This is ascribed to
the formation of Ce 4f and oxygen defect levels. Ce 4f and
oxygen defect states are expected to hybridize and to form
an impurity band, leading to the decrease of bandgap.
Compared with the peaks of pure TiO2 sample, the
BiFeO3@TiO2 displays the Eg of 2.58 eV, which is exactly the
same as that of the pure BiFeO3 [29]. The spectral response in
the visible region of the BiFeO3@TiO2 is mainly attributed to
the photosensitization of BiFeO3. BiFeO3, as a semiconductor,
has photocatalytical active in visible light for narrow band
gap. When the two semiconductors are in contact, electronic
interaction occurs at their contact point. The spontaneous
 L. Gong et al. / Materials Science in Semiconductor Processing 16 (2013) 288–294 291

Fig. 3. EDX analysis images of: (a) the pure BiFeO3 powder and (b) the core-shell structured BiFeO3@ TiO2–Ce nanoparticles.

Fig. 4. (a) A HRTEM micrograph of the BiFeO3@TiO2–Ce composite nanoparticles. the inset: a TEM micrograph of the BiFeO3@TiO2–Ce composite
nanoparticles and (b) the corresponding EDS spectra.

polarization in the ferroelectric domains of BiFeO3 leads to
band bending that transports photoinduced electrons and
holes in opposite directions. Because the photogenerated
carriers are separated by the internal polarization, they are
less likely to recombine, and this may enhance photocatalytic
efficiency [17]. The absorption of BiFeO3@TiO2–Ce samples in
the visible region is stronger than the undoped and doped
sample with Ce4 þ or modified with BiFeO3 alone. The
enhanced visible light absorption may be attributed to the
synergistic effect of Ce3 þ /Ce4 þ and BiFeO3.
3.4. Photocatalytic activity analysis
The photocatalytic performance of the samples is
tested in the degradation of MO in aqueous suspensions
under UV and visible light irradiation. Before the reaction,
the samples in MO solution are kept in dark for 30 min to
reach adsorption/desorption equilibrium. As shown in
Fig. 6(a) and (b), no evident difference of the adsorption
percentage is found, suggesting that the adsorption ability
of different samples is not the key factor to determine the
photodegradation rate. MO solution does not have any
self-degradation under the radiation of UV or visible light.
It can be seen that the photocatalytic activity of BiFeO3@-
TiO2 is much better than pure TiO2, which is owing to the
interfacial effect between BiFeO3 and TiO2. The photo-
electrons in BiFeO3@TiO2 could easily transfer from the
conduct band (CB) of BiFeO3 to the neighboring CB of TiO2.
Thus, the recombination between photoelectrons and holes
could be effectively inhibited, leading to a higher decom-
position rate. The results also demonstrate that all cerium
doped samples achieve a higher degradation than pure
292 L. Gong et al. / Materials Science in Semiconductor Processing 16 (2013) 288–294
Fig. 5. UV–vis absorption spectra (a) and the optical absorption edges
(b) of TiO2, Ce–TiO2, BiFeO3@TiO2 and BiFeO3@TiO2–Ce.
TiO2, and the MO degradation rate increase with the
increase of the concentration of cerium initially. However,
the photocatalytic activity decrease, as well as the concen-
tration of cerium, achieve a higher level. Under UV light
irradiation, the optimal doping levels of cerium is 2%, and
the MO color changes dramatically as shown in the inset of
Fig. 6(a); While under visible light illumination, the sample
doped with 1% cerium shows the best performance. The
best degradation rate under UV light irradiation and visible
light irradiation is 93.5% and 74.8%, respectively. These
results are closely related to the smaller particle size, larger
surface area and higher concentration of hydroxy groups on
the surface of TiO2. On the contrary, when the doping
concentration exceeds the doping levels (2% under UV light
and 1% under visible light), the photoinduced electrons will
be trapped by Ce4 þ in the interstitial lattice of TiO2 rather
than transferred to the surface [23]. Meanwhile, many
introduced holes can be also trapped by Ce3 þ , the trap
center become the recombination center, resulting in the
decrease of photoactivity of Ce doped TiO2 [30]. Besides, the
excessive cerium induce the agglomeration, which will
weaken the incident light, hence reduce the photoquantum
efficiency [31].
Clearly, BiFeO3@TiO2–Ce exhibits the highest photo-
catalytic activity for the degradation of MO. In order to
explain the enhanced visible light activity of BiFeO3@-
TiO2–Ce, possible mechanisms are proposed. The bandgap
value of p-type semiconductor (BiFeO3) is assume as
Fig. 6. Photodegradation of MO with different catalysts under (a) UV
light and (b) visible light irradiation, (a): blank; (b): TiO2; (c): TiO2–Ce;
(d):BiFeO3@TiO2; (e): BiFeO3@TiO2–Ce 0.5%; (f): BiFeO3@TiO2–Ce 1.0%;
(g): BiFeO3@TiO2–Ce 2.0%; (h): BiFeO3@TiO2–Ce 4.0%. The inset is the
MO color change of BiFeO3@TiO2–Ce 2.0%.
2.5 eV like reported in the previous work [29], TiO2 is
considered as n-type semiconductor with a band gap of
3.2 eV, the details are shown in Fig. 7. Fe3 þ existence at
the interface of BiFeO3@TiO2 sample is reported pre-
viously [18]. Therefore, electrons can be excited from
the partially filled d orbitals of Fe3 þ to the Ti 3d orbitals
in TiO2 under lower energy visible light condition. It is
reported that the excitation of one semiconductor results
in an electron injection into the lower lying CB of the
second semiconductor [32]. The core-shell structured
BiFeO3@TiO2–Ce systems consist of two semiconductors.
BiFeO3 has relatively higher conduction band (CB), hence
the photoinduced electrons on the BiFeO3 nanoparticle
can transfer to the lower lying CB of TiO2 via the interface.
Subsequently, the electrons are promoted to the surface
of TiO2 and then trapped by Ce4 þ /Ce3 þ . The cerium has
better electron scavenging capacity than oxygen vacancies.
Its unoccupied 4f orbital can accept electron and undergo
strong interaction with the chromophore of dye molecule.
Due to the presence of Ce3 þ , the labile oxygen vacancies
and mobility of bulk oxygen species are increased [33]. On
the other hand, the particle size of samples decreased
significantly. In this aspect, the larger surface area is
efficient for absorbing O2 and H2O. The trapped electrons
absorb O2 molecules, and the holes accumulate in the
valence band of BiFeO3 react with the absorbed H2O which
 L. Gong et al. / Materials Science in Semiconductor Processing 16 (2013) 288–294
Fig. 7. Schematic diagram of proposed mechanism for the synergistic
effect of Ce and BiFeO3 under visible light irradiation. In the figure, the
Fermi level, conduction band edge and valence band edge are given by
the symbols Ef, CB and VB, respectively.
Fig. 8. M–H hysteresis loops of (a) pure BiFeO3 and (b) BiFeO3@TiO2–Ce
2.0% nanocomposites. The inset is a image of BiFeO3@TiO2–Ce 2.0%
suspension under a magnetic field.
can be expressed in the Eqs. (1)–(3). The absorption spectra
and the photo utilization of TiO2 were broadened and
improved by the BiFeO3 core. While Ce-doping retard the
recombination of the photoinduced electron–hole pair and
increase the absorption of MO [34]. Therefore, the photo-
catalytic activity of co-modified TiO2 is efficiently
improved.
Ce4 þ þe  -Ce3 þ (1)
3þ 4þ
Ce þ O2 -O
2 þCe ð2Þ
H2Oþ h -dOHþ H
þ þ
(3)
3.5. Analysis of magnetism of BiFeO3@TiO2–Ce
nanoparticles
The magnetic properties of pure BiFeO3 and BiFeO3@
TiO2–Ce (2%) nanoparticles are shown in Fig. 8. In case of
BiFeO3 nanoparticles, an obvious ferromagnetic (FM) beha-
vior is observed and the saturated magnetization (Ms) is
estimated to be 0.8 emu/g. A similar behavior for the
BiFeO3@TiO2–Ce composites is also observed. In contrast,
Ms of the TiO2–Ce coated BiFeO3 decrease to 0.5 emu/g,
293
which is mainly attributed to the high volume concentra-
tion of the non-magnetic coating layer of TiO2–Ce [12].
In addition, the magnetic separation ability of the
BiFeO3@TiO2–Ce (2%) nanoparticles is tested in water by
placing a magnet near the glass bottle. As displayed in
the inset of Fig. 8, under a magnetic field, the nanoparticles
can be easily attracted towards the magnet, demonstrating
that the resultant magnetic photocatalyst gives it excellent
performance on magnetic recycling.
4. Conclusions
In summary, novel BiFeO3@TiO2–Ce core-shell nanopho-
tocatalysts have been successfully prepared by a sol–gel
method. Photocatalytic experiments show that BiFeO3@
TiO2–Ce has a good photocatalytic activity which may be
attributed to the synergistic effect of Ce and BiFeO3. BiFeO3
plays an important role in extending light absorption into
the visible region and Ce dopant can inhibit the recombina-
tion between photoinduced electron and hole pair. Because
of the ferromagnetism of BiFeO3 core, these core-shell
nanoparticles can be conveniently separated by using an
external magnetic field, which greatly extend their poten-
tial applications.
Acknowledgments
The authors would like to acknowledge the support of the
project funded by the Priority Academic Program Develop-
ment (PAPD) of Jiangsu Higher Education Institutions.
References
[1] L.M. Jiang, G. Zhou, Materials Science in Semiconductor Processing
15 (2012) 108–111.
[2] O. Vázquez-Cuchillo, A. Cruz-López, L.M. Bautista-Carrillo,
A. Bautista-Hernández, L.M. Torres Martı́nez, S. Wohn Lee, Research
on Chemical Intermediates 36 (2010) 103–113.
[3] X. Zhang, X.L. Zhao, H.J. Su, Journal of Chemical Engineering 28
(2001) 1241–1246.
[4] T.C. Cheng, K.S. Yao, Y.H. Hsieh, L.L. Hsieh, C.Y. Chang, Materials and
Design 31 (2010) 1749–1751.
[5] J.L. Gole, J.D. Stout, C. Burda, Y.B. Lou, X.B. Chen, Journal of Physical
Chemistry B 108 (2004) 1230–1240.
[6] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science 293
(2001) 269–271.
[7] H.X. Li, X.Y. Zhang, Y.N. Huo, J. Zhu, Environmental Science and
Technology 41 (2007) 4410–4414.
[8] G.S. Wu, J.P. Wang, D.F. Thomas, A. Chen, Langmuir 24 (2008)
3503–3509.
[9] K. Matsubara, T. Tatsuma, Advanced Materials 19 (2007)
2802–2806.
[10] M.S. Nahar, J. Zhang, K. Hasegawa, S. Kagaya, S. Kuroda, Materials
Science in Semiconductor Processing 12 (2009) 168–174.
[11] D.L. Liao, C.A. Badour, B.Q. Liao, Journal of Photochemistry and
Photobiology A: Chemistry 194 (2008) 11–19.
[12] Y.H. Fan, C.H. Ma, W. Li, Y.H. Yin, Materials Science in Semicon-
ductor Processing 15 (2012) 582–585.
[13] H.M. Yang, R.R. Shi, K. Zhang, Y.H. Hu, A.D. Tang, X.W. Li, Journal of
Alloys and Compounds 398 (2005) 200–202.
[14] M.S. Islam, Y. Kusumoto, M. Abdulla-Al-Mamun, Y.J. Horie,
A.C. Photocatalytic, Catalysis Communications 16 (2011) 39–44.
[15] W.Y. Fu, H.B. Yang, M.H. Li, L.X. Chang, Q.J. Yu, J. Xu, et al., Materials
Letters 60 (2006) 2723–2727.
[16] H.M. Xiao, X.M. Liu, S.Y. Fu, Composites Science and Technology 66
(2006) 2003–2008.
[17] Y.L. Zhang, A.M. Schultz, P.A. Salvador, G.S. Rohrer, Journal of
Materials Chemistry 21 (2011) 4168–4174.
294 L. Gong et al. / Materials Science in Semiconductor Processing 16 (2013) 288–294
[18] S. Li, Y.H. Lin, B.P. Zhang, J.F. Li, C.W. Nan, Journal of Applied Physics
105 (2009) 054310.
[19] Q.G. Zeng, Z.M. Zhang, Z.J. Ding, Y. Wang, Y.Q. Sheng, Scripta
Materialia 57 (2007) 897–900.
[20] Y.N. Huo, J. Zhu, J.X. Li, G.S. Li, H.X. Li, Journal of Molecular Catalysis
A: Chemical 278 (2007) 237–243.
[21] T.Z. Tong, J.L. Zhang, B.Z. Tian, F. Chen, D.N. He, M. Anpo, Journal of
Colloid and Interface Science 315 (2007) 382–388.
[22] F. Gao, X.Y. Chen, K.B. Yin, S. Dong, Z.F. Ren, F. Yuan, et al., Advanced
Materials 19 (2007) 2889–2892.
[23] H. Liu, M.Y. Wang, Y. Wang, Y.G. Liang, W.R. Cao, Y. Su, Journal of
Photochemistry and Photobiology A: Chemistry 223 (2011)
157–164.
[24] C.L. Zhu, M.L. Zhang, Y.J. Qiao, G. Xiao, F. Zhang, Y.J. Chen, Journal of
Physical Chemistry C 14 (2010) 16229–16235.
[25] U.A. Joshi, J.S. Jang, P.H. Borse, J.S. Lee, Applied Physics Letters 92
(2008) 242106.
[26] W.M. Yen, M. Raukas, S.A. Basun, W.V. Schaik, U. Happek, Journal of
Luminescence 69 (1996) 287–294.
[27] F.B. Li, Z.X. Li, M.F. Hou, K.W. Cheah, W.C.H. Choy, Applied Catalysis
A: General 285 (2005) 181–189.
[28] M.J. Yoon, M.J. Seo, C.J. Jeong, J.H. Jang, K.S. Jeon, Chemistry of
Materials 17 (2005) 6069–6079.
[29] X. Wang, Y. Lin, C. Zhang, J.Y. Bian, Journal of Sol–Gel Science and
Technology 60 (2011) 1–5.
[30] S.I. Shah, W. Li, C.P. Huang, O. jung, C. Ni, National Academy of
Sciences 99 (2002) 6482–6486.
[31] Z.F. Bian, J. Zhu, S.H. Wang, Y. Cao, X.F. Qian, H.X. Li, Journal of
Physical Chemistry C 112 (2008) 6258–6262.
[32] M.A. Fox, M.T. Dulay, Chemical Reviews 83 (1995) 341–357.
[33] B.M. Reddy, A. Khan, Y. Yamada, T. Kobayashi, S. Loridant, J.C. Volta,
Journal of Physical Chemistry B 107 (2003) 5162–5167.
[34] Q.Q. Wang, S.H. Xu, F.L. Shen, Applied Surface Science 257 (2011)
7671–7677.