Materials Research Bulletin 48 (2013) 2111–2116

Contents lists available at SciVerse ScienceDirect

Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Facile preparation of NiS/CdS-t composite photocatalyst for hydrogen evolution

from aqueous solution of sulphide/sulphite under visible light
Jianling Meng, Fengyan Li *, Yiming Hu, Lin Xu **, Zhixia Sun, Jian Liu
Key Laboratory of Polyoxometalate Science of Ministry of Education, Department of Chemistry, Northeast Normal University, Changchun, Jilin 130024, PR China

A R T I C L E I N F O A B S T R A C T

Article history: The nanostructured NiS/CdS-t (t = aging period in day number) composite photocatalysts were prepared
Received 12 July 2012 by a facile two-step synthesis method. The photocatalytic activity of H2 evolution over NiS/CdS could be
Received in revised form 24 January 2013 greatly enhanced by changing the aging period of CdS. The NiS/CdS achieved a maximal rate of H2
Accepted 12 February 2013
evolution when CdS was aged for 6 days before hydrothermal treatment. It was demonstrated that the
Available online 26 February 2013
composite NiS(0.14)/CdS-6 could achieve a H2 evolution rate up to 1517 mmol h1 and show high
photocatalytic stability for H2 evolution under long-term light irradiation. The rate of H2 evolution on
Keywords:
NiS(0.14)/CdS-6 is about 7.5 times that of NiS(0.14)/CdS-3 and 33 times that of CdS-6. The notable
A. Semiconductors
A. Nanostructures
improvement can be attributed to the fast electron transfer from CdS to NiS, which is proved by the
B. Chemical synthesis surface photovoltage spectroscopy and photoluminescent measurements, as well as the increasing
D. Catalytic properties percentage of hexagonal-CdS in the mixture of cubic and hexagonal CdS.
ß 2013 Elsevier Ltd. All rights reserved.

1. Introduction photocatalytic activity of CdS: (i) Coupling CdS with other

Conversion of solar energy into fossil-fuel-independent chem-
istry energy – H2 from water splitting using semiconductor
photocatalysts has become a promising approach to address the
growing problems of green-house effect and energy crisis [1,2].
Most of the developed photocatalysts capable of splitting water
could only be effective under ultraviolet light constituting only 4%
of the incoming solar energy [3,4], while the visible portion
contributes about 50%. To improve the efficiency of utilizing solar
energy, various visible-light-driven semiconductor materials,
including oxides [5], (oxy) nitride [6], (oxy) sulfide [7,8], have
been widely explored in the past decades.
Among various photocatalysts, CdS continues to be the
attractive candidate for hydrogen evolution by visible-light-driven
photocatalytic water splitting due to its relatively narrow band gap
(2.4 eV) and more negative conduction band edge than the H2O/H2
redox potential [9,10]. However, the use of CdS for photocatalytic
water splitting suffers from low hydrogen evolution rate and
serious photocorrosion under a long-term light irradiation. As high
hydrogen evolution activity requires an efficient charge separation
of photogenerated electrons (e) and holes (h+) and the migration
of photogenerated carriers during the photocatalytic reaction. A
number of approaches have been adopted to enhance the
* Corresponding author. Tel.: +86 431 85099765; fax: +86 431 85099765.
** Corresponding author. Tel.: +86 431 85098760; fax: +86 431 85098760.
E-mail addresses: lify525@nenu.edu.cn (F. Li), linxu@nenu.edu.cn (L. Xu).
semiconductors like TiO2 [11–13]. Owing to the favorable position
of conduction bands for the coupled semiconductor, the photo-
generated electrons could transfer easily from one semiconductor
to the other, which will considerably enhance the photocatalytic
activity for hydrogen evolution. (ii) Controlling the crystal phase
and morphology of CdS by different synthesis routes [14–16].
Semiconductor nanoparticles have a shorter bulk-to-surface
diffusion distance for e and h+ compared with the bulk materials,
exhibiting a higher photocatalytic activity by suppressing the
surface/bulk recombination of e and h+. (iii) Preparation of the
sulfide solid solution by mixing with wide band gap semiconduc-
tors [17,18]. The band structure of the solid solution can be
continuously adjusted by changing its composition. Hence, the
photocatalytic properties of CdS could be modified. (iv) Immobili-
zation of CdS over large area supports [19,20], such as zeolites and
polymeric fibers. It has been demonstrated that the supported CdS
exhibits a higher photocatalytic activity without undergoing any
photocorrosion.
Apart from the above methods, the cocatalysts loaded on CdS
play an important role in the hydrogen production from water
splitting. It is well-known that the cocatalyst is essential to
enhance the photocatalytic activities of CdS; this is because not
only the cocatalyst could promote the separation of photogener-
ated electrons and holes, but also could lower the activation
potentials for H2 generation [21]. In most work reported so far,
however, mainly noble metals or their oxides, such as Pt, Pd, Ru,
and RuO2 [22,23], have been employed as the cocatalysts, while
inexpensive cocatalysts are rarely used in photocatalytic H2

0025-5408/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.materresbull.2013.02.013
2112 J. Meng et al. / Materials Research Bulletin 48 (2013) 2111–2116
production [14,21]. Only recently, several noble metal-free
compounds have been found to be effective cocatalysts like noble
metals [24,25].
Sulfides and sulfites are undesirable and polluting byproducts
in hydrogenation and flue gas desulfurization processes at
chemical industries. Hence the hydrogen production from sulfide
and sulfite aqueous solution is very attractive both for promoting
the photocatalytic hydrogen evolution and improving the envi-
ronmental problems caused by the petrochemical industries.
Therefore, it would be of great interest to study the synthesis
procedures of CdS, the effect of NiS cocatalyst and Na2SO3 and Na2S
sacrificial agents on the photocatalytic performance of the CdS
photocatalyst.
In this work, the nanosphered CdS catalysts were prepared by a
facile two-step method. Then the cocatalyst NiS was deposited on
the thus-prepared CdS. When CdS was aged for 6 days, the NiS/CdS-
t (t = aging period in day number) composite photocatalyst could
achieve the highest photocatalytic activity. The rate of H2 evolution
on NiS(0.14)/CdS-6 reached up to 1517 mmol h1 under the
simulated solar light irradiation using sulfide and sulfite as
sacrificial reagents. It is increased to 33.4 times that of pure CdS.
Fig. 1. XRD patterns of CdS-3, NiS(0.14)/CdS-3, CdS-6 and NiS(0.14)/CdS-6.
Meanwhile the NiS/CdS catalyst did not show any deactivation for
photocatalytic H2 evolution for 12 h.
2. Experimental
2.1. Preparation of photocatalysts
All the reagents were of analytical grade, and used without
further purification. The CdS nanoparticles were prepared as
follows: an aqueous solution of Na2S (160 mL, 0.14 M) was added
dropwise to CdCl2 solution (200 mL, 0.14 M) under vigorous
stirring. The yellow suspension was stirred for 6 h and kept
overnight. The resulting yellow slurry was filtered and washed
with water. The wet solid was suspended in pure water (80 mL),
then transferred to a Teflon-lined stainless steel autoclave
(150 mL) and kept aging for different days. Then the mixture
was treated hydrothermally at 473 K for 72 h (slowly increase the
temperature), and cooled to room temperature naturally. The
yellow solid was filtered and washed with water, then kept in oven
at 343 K for 2 h. The final products were denoted as CdS-t, where t
represents the aging period (t = 3, 4, 6, and 12 days).
 J. Meng et al. / Materials Research Bulletin 48 (2013) 2111–2116 2113

NiS(m)/CdS-t was prepared by deposition of NiS on the

surface of pre-prepared CdS (m represents the weight concen-
tration (wt%) of NiS loaded onto the CdS-t, m = 0, 0.09, 0.14, 0.19,
0.22, 0.29, and 0.59 wt%). The content of NiS in NiS(m)/CdS-t was
investigated by inductively coupled plasma atomic emission
spectroscopy. Certain amount of Ni(NO3)26H2O was dissolved in
deaired distilled water (3 mL). CdS-t (0.260 g) and Na2SO3
(8.174 g) were dissolved with deaired distilled water (100 mL)
under moderate stirring in N2 atmosphere, then followed with
the addition of Na2S9H2O (21.798 g). The solution of Ni(NO3)2
was added dropwise to the above solution and kept stirring for
30 min under N2 atmosphere just before the photocatalytic
reaction.

2.2. Photocatalytic Reaction

NiS(m)/CdS-t suspension was transferred into the photocata- Fig. 2. UV–visible diffuse reflectance spectra of the (a) CdS-6, (b) NiS(0.14)/CdS-6
lytic instrument, and kept the solution to 160 mL with deaired nanoparticles.
distilled water. The photocatalytic reaction was irradiated by a Xe
lamp (250 W). The temperature of the reaction solution was
maintained at 25–27 8C by providing a flow of cooling water during 3. Results and discussion
the photocatalytic reaction. The photocatalytic reaction process of
CdS-t was just the same with that of NiS(m)/CdS-t. 3.1. X-ray diffraction studies

2.3. Characterization The XRD measurement of the synthesized photocatalysts was

The phase of the as-prepared CdS was examined by X-ray
diffraction (XRD) (D/max 2200 VPC diffractometer with a Cu Ka
irradiation source). Diffraction patterns were collected from 208 to
808 at a speed of 68 min1. The Ultraviolet–visible diffuse
reflectance spectra were obtained using a CARY 500 scan UV–
vis–NIR spectrophotometer. The size and morphology were
examined with transmission electron microscopy (TEM). TEM
images were obtained on a JEM-2100F microscope with an
accelerating voltage of 200 kV. The surface photovoltage spectros-
copy (SPS) measurement of the samples was carried out with a
home-built apparatus. Monochromatic light was obtained by
passing light from a 500 W xenon lamp through a double prism
monochromator. The slit width of the entrance and exit is 1 mm. A
lock-in amplifier synchronized with a light chopper was employed
to amplify the photovoltage signal. The raw SPS data were
normalized using the illuminometer (Zolix UOM-1S, made in
China). The photoluminescent (PL) properties were measured on
an FLSP920 Edinburgh Fluorescence Spectrometer at room
temperature. The inductively coupled plasma atomic emission
spectroscopy (ICP-AES) results were obtained on a leamain
inductively coupled plasma (ICP) spectrometer. The hydrogen
evolved was sampled and analyzed periodically by using a gas
chromatograph (Agilent 6890GC, thermal conductivity detector, Ar
carrier).
carried out on the powder samples. Fig. 1 shows the XRD
patterns of pure CdS-t (t = three days and six days) and
NiS(0.14)/CdS-t catalysts. For all the samples, the diffraction
patterns of CdS-t are indexed as a mixture of cubic and
hexagonal CdS. With increasing aging days from three to six
days, the relative peak intensity of (1 0 3) facets at 47.8 nm for
hexagonal CdS increases indicates that the percentage of
hexagonal CdS increases in the mixture. No characteristic peaks
associated with NiS were observed in these heterogeneous
semiconductors. NiS prepared under the same condition shows
amorphous state. The diffraction peaks would shift to higher
angles when Ni2+ is doped into the lattice of CdS, as the ionic
radius of Ni2+ (0.69 Å) is smaller than that of Cd2+ (0.97 Å)
[26,27]. However, the XRD data indicates no significant lattice
deformation when the concentration of NiS is 0.14 wt%. These
observations suggest that NiS is highly dispersed on the surface
of CdS-t, but not doped into the lattice of CdS-t. The intense XRD
peaks for CdS crystallines reveal their good crystallinity [15].
3.2. Optical absorption spectra
The UV–visible diffuse reflectance spectra of CdS-6 and
NiS(0.14)/CdS-6 are displayed in Fig. 2. The CdS-6 sample has an
absorption edge at about 540 nm, with an energy gap estimated to
be 2.3 eV. The absorption edge of the composite NiS(0.14)/CdS-6

Fig. 3. TEM images of the photocatalysts. (a) CdS-3, (b) NiS(0.14)/CdS-3.

2114 J. Meng et al. / Materials Research Bulletin 48 (2013) 2111–2116
Fig. 4. TEM images of the photocatalysts. (a) CdS-6, (b) NiS(0.14)/CdS-6.
sample is not shifted compared with that of CdS. However, an
enhanced absorption was observed in the spectrum of NiS(0.14)/
CdS-6 in the visible light region from 550 nm to 800 nm. It is due to
NiS loaded on CdS-6 which exhibits visible light absorption from
550 to 800 nm. These results imply that the Ni2+ is not doped into
the CdS lattice by Ni2+/Cd2+ cation exchange, but highly dispersed
on the surface of NiS(0.14)/CdS-6, which is in accordance with the
XRD results. Considering that NiS has a much larger solubility than
CdS, thus the reaction Ni2+ + CdS ! Cd2+ + NiS is not favorable [28].
3.3. Morphology observation
The morphologies of CdS-t and NiS(0.14)/CdS-t (t = 3 and 6)
were investigated by HRTEM and high-resolution Fourier trans-
form. The size distributions of the samples are calculated by
counting at least 200 particles from the TEM images. The average
size of particles is determined by computing the average size of
many particles with the similar volume. By the observation and
statistical measure from HRTEM image, CdS-3 particles appears in
irregular spherical and conical patterns with size distribution
range from 26 to 69 nm (Fig. 3a), while the size distribution of CdS-
6 particles with sphere-like morphology is in the range of 27–
48 nm (Fig. 4a). The morphologies of CdS-6 and NiS(0.14)/CdS-6
are more uniform and highly dispersed, compared with that of
CdS-3 and NiS(0.14)/CdS-3. This suggests that aging period also
affects the morphologies of the photocatalysts. After the loading of
0.14 wt% NiS, the morphologies of NiS(0.14)/CdS-t are similar to
that of CdS-N (Figs. 3b and 4b). The HRTEM image (Fig. 5) exhibits
clear and continuous crystal lattice fringes with interlayer
distances of 3.59 and 3.28 Å respectively, close to the lattice
spacing of the (1 0 0) planes in hexagonal CdS and the (1 1 1) plane
Fig. 5. HRTEM images of the heterogeneous photocatalysts NiS(0.14)/CdS-6.
in cubic CdS [29]. The lattice fringes with a distance of 2.22 Å could
be assigned to the (3 0 0) plane of rhombohedral NiS [25]. This
implies that NiS particles have been loaded onto the surface of the
mixture of cubic and hexagonal CdS.
Generally, the good photocatalytic activity of CdS requires that
CdS sample has good crystallinity, short bulk-to-surface diffusion
distance for photogenerated electrons and holes, and monodis-
persed cocatalyst surface [14]. Based on the results of XRD, UV–
visible adsorption spectra and TEM, NiS(0.14)/CdS-6 would be
expected to exhibit superior photocatalytic activity in hydrogen
production from water splitting.
3.4. Evaluation of photocatalytic activity
Fig. 6 displayed the rate of H2 evolution on pure CdS-6 and
NiS(m)/CdS-6 with different amount of NiS loading. No H2 was
detected when NiS alone was used as the catalyst, suggesting that
NiS is not active for photocatalytic H2 evolution. CdS-6 alone shows
activity in photocatalytic H2 evolution, but the rate of H2 evolution
is very slow (ca. 45.4 mmol h1). After loading only 0.09 wt% of NiS
on CdS-6, the activity in H2 evolution is increased up to 23.6 times.
With increasing the amount of NiS loaded on CdS, the rate of H2
evolution on NiS/CdS-6 is enhanced to 1517 mmol h1 when the
loading amount of NiS is about 0.14 wt%.
The H2 production rate increased up to 33.4 times that of pure
CdS after loading 0.14 wt% of NiS on CdS. The realization of such a
high efficiency might be due to the following reasons. First, NiS acts
as an effective cocatalyst for CdS photocatalyst in the hydrogen
production. In the photocatalytic reactions for H2 production,
Fig. 6. The rate of H2 evolution on NiS/CdS-6 with different amount of NiS loaded on
CdS-6. Experiment conditions: CdS-N (0.260 g); 160 mL aqueous solution
containing 0.57 M Na2S + 0.4 M Na2SO3; light source, Xe lamp (250 W).
 J. Meng et al. / Materials Research Bulletin 48 (2013) 2111–2116
Fig. 7. The surface photovoltage spectroscopy (SPS) spectra of CdS-6 and NiS(0.14)/CdS-6.
photogenerated electrons could transfer from CdS to NiS. NiS
accommodates the photogenerated e transferred from CdS, and
provides the active sites for proton reduction. However, when the
amount of NiS loaded on CdS is above 0.14 wt%, the hydrogen
evolution rate of NiS(m)/CdS-6 decreases. It is supposed that
excessive NiS will become the recombination centers for photo-
generated carriers as found in the literature [22–24]. Hence too
much NiS loaded on CdS will cause an adverse effect on the
photocatalytic activity of hydrogen production. Second, the
intimate contact between NiS and CdS-6 is crucial for the high
photocatalytic activity of NiS/CdS-6. In a control experiment, a
mechanical mixture of NiS and CdS-6 with the same ratio as that in
the NiS(0.14)/CdS-6 demonstrates a H2 evolution rate of
789 mmol h1. It is higher than that of CdS-6, but lower than that
Fig. 8. The photoluminescent emission spectra of CdS-6 and NiS(0.14)/CdS-6.
2115
of NiS(0.14)/CdS-6. The result demonstrates that the intimate
contact between NiS and CdS-6 is crucial for the high photo-
catalytic activity of NiS/CdS-6 [24]. Compared with the mechanical
mixture, the intimate contact leads to a more efficient electron
transfer from CdS phase to NiS phase. Hence the recombination of
the photogenerated carriers in NiS/CdS-6 is more effectively
suppressed than that in the mechanical mixture. Therefore, NiS/
CdS-6 displays higher rate of hydrogen evolution than that of the
mechanical mixture. The important role of the intimate contact in
facilitating the transfer of photogenerated electrons from one
phase to the other is also proved in anatase–rutile mixed TiO2 [30].
Furthermore, the transfer of photogenerated carriers is also
responsible for enhancing the photostability of CdS. During the
photocatalytic experiment, the rate of H2 evolution over NiS(0.14)/
CdS-6 did not show any deactivation under continuous photo-
catalytic reaction for 12 h.
The SPS is effective to evaluate the photocatalytic activity of
semiconductor materials, since it can provide information such as
the separation, recombination and transfer of the photoinduced
charge carriers under illumination [31]. In order to investigate the
effect of NiS on the photocatalytic activity of hydrogen evolution,
SPS an PL measurements were performed on the powder samples
of the CdS-6 and NiS(0.14)/CdS-6. As shown in Fig. 7, the
photovoltaic response band of NiS(0.14)/CdS-6 appears at about
Table 1
The rate of H2 evolution on NiS(0.14)/CdS-N.a
Samples Rate of H2 evolution (mmol h1)
NiS(0.14)/CdS-3 202
NiS(0.14)/CdS-4 759
NiS(0.14)/CdS-6 1517
NiS(0.14)/CdS-12 379
a
N: the aging days of CdS (N = 3, 4, 6,j and 12 days). Experiment conditions: NiS/
CdS-N (0.260 g); 160 mL aqueous solution containing 0.57 M Na2S + 0.4 M Na2SO3;
light source, Xe lamp (250 W).
2116 J. Meng et al. / Materials Research Bulletin 48 (2013) 2111–2116
520 nm, which can be mainly assigned to the electron transition
from the valence band (S 2p) to the conduction band (Cd 3d). While
the intensity of photovoltaic response band of CdS is weak, and no
photovoltaic signal can be observed for NiS. The intensity of
photovoltaic response band for NiS(0.14)/CdS-6 exhibits 3 orders
of magnitude stronger than that of pure CdS, though the amount of
NiS loaded on CdS-6 is only 0.14 wt%. These results demonstrate
that the loaded NiS could facilitate the separation of photoinduced
electron and hole pairs in CdS-6. The separation rate of
photoinduced electron and hole pairs in NiS(0.14)/CdS-6 is higher
than that in pure CdS-6 sample. This corresponds to the higher rate
of hydrogen evolution over NiS(0.14)/CdS-6. As shown in Fig. 8,
both NiS(0.14)/CdS-6 and CdS-6 show fluorescence emission bands
at 480 and 560 nm upon excitation at 237 nm. The characteristic
emission band at 480 nm is ascribed to band to band emission of
CdS, which is blue-shifted in comparison to that of bulk CdS
(512 nm) due to the quantum confinement of CdS nanoparticles
[32]. The broad bands around 560 nm are ascribed to the surface
defects of the CdS sample. While the fluorescence of NiS(0.14)/CdS-
6 is clearly quenched compared to that of CdS-6. The photoinduced
electron transfer from CdS to NiS should be responsible for the
fluorescence quenching. Therefore, it confirms that the introduc-
tion of NiS is effective in enhancing the photocatalytic activity of
CdS.
In addition, the effect of the aging period of CdS was also
studied. Table 1 shows the rate of H2 production on NiS(0.14)/CdS-t
with different aging days (N = 3, 4, 6, and 12). As shown in Table 1,
the aging period for six days of CdS could lead to excellent catalytic
efficiency. The rate of H2 production on NiS(0.14)/CdS-6 is
1517 mmol h1, which is 2 times that of NiS(0.14)/CdS-4, 4 times
that of NiS(0.14)/CdS-12, and about 7.5 times that of NiS(0.14)/
CdS-3. The superior activity of NiS/CdS-6 composite photocatalyst
might be attributed to the higher percentage of hexagonal-CdS in
the mixture of cubic and hexagonal CdS [29,33]. The recombination
probability in NiS(0.14)/CdS-6 is lower than that in NiS(0.14)/CdS-
3. This may be part of the reason for the high photocatalytic activity
of the NiS(0.14)/CdS-6 nanoparticles. Meanwhile, when CdS is aged
for 6 days, the crystallites contain fewer defects, which could
provide the recombination centers for photo-generated carriers.
The less electron-hole recombination in NiS(0.14)/CdS-6 results in
the increase of hydrogen evolution rate. But when CdS is aged for
too long time, the activity will decrease possibly due to the
aggregation of CdS nanoparticles.
Similar to the mechanism of cathodic H2 evolution reactions
(HER) in electrolysis, it is proposed that the NiS co-catalyst in NiS/
CdS photocatalysts plays important roles both in electron transfer
(reaction (1)) and electrochemical desorption (reaction (2)) for H2
evolution [34].
NiS þ e þ H2 O $ HNiS þ OH
HNiS þ e þ H2 O $ NiS þ H2 þ OH
Considering the conduction band of NiS is lower than that of
CdS, the photogenerated electrons in the conduction band of CdS
can be easily transferred to the surface of NiS due to the intimate
contact between the two components. The formation of the
hydride on NiS catalysts has been well reported in hydrotreating
processes [35–37]. Therefore, the introduction of NiS can
effectively enhance the photocatalytic activity of CdS.
4. Conclusions
The rate of H2 evolution on NiS/CdS is significantly enhanced by
controlling the aging procedure of CdS before hydrothermal
treatment. The composite photocatalyst NiS(0.14)/CdS-t shows
the highest activity when CdS is aged for 6 days. Meanwhile, NiS
possessed remarkable cocatalytic effect on CdS. The rate of H2
evolution on NiS(0.14)/CdS-6 is about 7.5 times that of NiS(0.14)/
CdS-3 and 33 times that of CdS-6. The notable improvement can be
attributed to the fast electron transfer from CdS to NiS, as well as
the increasing percentage of hexagonal-CdS in the mixture of cubic
and hexagonal CdS. This work not only presents valuable
information for the preparation of photocatalytically efficient
CdS catalyst with high stability but also provides a low-cost
substitute for noble metals cocatalysts.
Acknowledgements
The authors are thankful for the financial support by the Natural
Science Foundation of China (Grant Nos. 20971019 and 21001021),
Jilin Provincial Science and Technology Development Foundation
(Grant No. 201201068) and China Postdoctoral Science Foundation
(20110491283).
References
[1] J.L. Dempsey, B.S. Brunschwing, J.R. Winkler, H.B. Gray, Acc. Chem. Res. 42 (2009)
1995–2004.
[2] L. Hammarström, S.H. Schiffer, Acc. Chem. Res. 42 (2009) 1859–1860.
[3] F.E. Osterloh, Chem. Mater. 20 (2008) 35–54.
[4] A. Kudo, Y. Miseki, Chem. Soc. Rev. 38 (2009) 253–278.
[5] H. Kato, H. Kobayashi, A. Kudo, J. Phys. Chem. B 106 (2002) 12441–12447.
[6] K. Maeda, K. Domen, Chem. Mater. 22 (2010) 612–623.
[7] A. Ishikawa, T. Takata, J.N. Kondo, M. Hara, H. Kobayashi, K. Domen, J. Am. Chem.
Soc. 124 (2002) 13547–13553.
[8] Y.X. Li, G. Chen, C. Zhou, J.X. Sun, Chem. Commun. 15 (2009) 2020–2022.
[9] D. Meissner, R. Memming, B. Kastening, J. Phys. Chem. 92 (1988) 3476–3483.
[10] D.W. Jing, L.J. Guo, J. Phys. Chem. C 111 (2007) 13437–13441.
[11] Y.J. Zhang, W. Yan, Y.P. Wu, Z.H. Wang, Mater. Lett. 62 (2008) 3846–3848.
[12] J.C. Kim, J. Choi, Y.B. Lee, J.H. Hong, J.I. Lee, J.W. Yang, W.I. Lee, N.H. Hur, Chem.
Commun. 48 (2006) 5024–5026.
[13] Y.X. Yin, Z.G. Jin, F. Hou, Nanotechnology 18 (2007) 495608–495613.
[14] S.H. Shen, L.J. Guo, X.B. Chen, F. Ren, S.S. Mao, Int. J. Hydrogen Energy 35 (2010)
7110–7115.
[15] D.W. Jing, L.J. Guo, J. Phys. Chem. B 110 (2006) 11139–11145.
[16] N.Z. Bao, L.M. Shen, T. Takata, K. Domen, Chem. Mater. 20 (2008) 110–117.
[17] C.J. Xing, Y.J. Zhang, W. Yan, L.J. Guo, Int. J. Hydrogen Energy 31 (2006) 2018–2024.
[18] W.J. Luo, Z.S. Li, X.J. Jiang, T. Yu, L.F. Liu, X.Y. Chen, Phys. Chem. Chem. Phys. 10
(2008) 6717–6723.
[19] P.S. Lunawat, S. Senapati, R. Kumar, N.M. Gupta, Int. J. Hydrogen Energy 32 (2007)
2784–2790.
[20] M. Sathish, B. Viswanathan, R.P. Viswanath, Int. J. Hydrogen Energy 31 (2006)
891–898.
[21] J.S. Jang, D.J. Ham, N. Lakshminarasimhan, W.Y. Choi, J.S. Lee, Appl. Catal. A: Gen.
346 (2008) 149–154.
[22] X.L. Fu, X.X. Wang, Z.X. Chen, Z.Z. Zhang, Z.H. Li, D.Y.C. Leung, Appl. Catal. B:
Environ. 95 (2010) 393–399.
[23] H.J. Yan, J.H. Yang, G.J. Ma, G.P. Wu, X. Zong, Z.B. Lei, J. Catal. 266 (2009) 65–68.
[24] X. Zong, H.J. Yan, G.P. Wu, G.J. Ma, F.Y. Wen, L. Wang, J. Am. Chem. Soc. 130 (2008)
7176–7177.
[25] W. Zhang, Y.B. Wang, Z. Wang, Z.Y. Zhong, R. Xu, Chem. Commun. 46 (2010) 7631–
7633.
(1)
[26] I. Tsuji, A. Kudo, J. Photochem. Photobiol. A: Chem. 156 (2003) 249–252.
(2)
[27] S.H. Shen, L. Zhao, Z.H. Zhou, L.J. Guo, J. Phys. Chem. C 112 (2008) 16148–16155.
[28] J.R. Goates, M.B. Gordon, N.D. Faux, J. Am. Chem. Soc. 74 (1952) 835–836.
[29] N.Z. Bao, L.M. Shen, T. Takata, K. Domen, A. Gupa, K. Yanagisawa, C.A. Grimes, J.
Phys. Chem. C 111 (2007) 17527–17534.
[30] L.Q. Jing, X.J. Sun, J. Shang, W.M. Cai, Z.L. Xu, Y.G. Du, Sol. Energy Mater. Sol. Cells
79 (2003) 133–151.
[31] J. Zhang, Q. Xu, Z.C. Feng, C. Li, Angew. Chem. Int. Ed. 47 (2008) 1766–1769.
[32] Z.X. Sun, F.Y. Li, L. Xu, S.P. Liu, M.L. Zhao, B.B. Xu, J. Phys. Chem. C 116 (2012) 6420–
6426.
[33] M. Matsumura, S. Furukawa, Y. Saho, H. Tsubomura, J. Phys. C 89 (1985) 1327–
1329.
[34] N.A. Assuncao, M.J. Giz, G. Tremiliosi, E.R. Gonzalez, J. Electrochem. Soc. 144
(1997) 2794–2800.
[35] M. Breysse, E. Furimsky, S. Kasztelan, M. Lacroix, G. Perot, Catal. Rev. Sci. Eng. 44
(2002) 651–735.
[36] M.Y. Sun, A.E. Nelson, J. Adjaye, J. Catal. 233 (2005) 411–421.
[37] D.Y. Hwang, A.M. Mebel, J. Phys. Chem. A 106 (2002) 520–528.