Catalysis Communications 40 (2013) 5154

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Short Communication

A novel noble metal-free ZnSWS2/CdS composite photocatalyst for H2

evolution under visible light irradiation
Guoping Chen a,b, Fan Li a,b, Yuzun Fan c, Yanhong Luo a,b, Dongmei Li a,b,, Qingbo Meng a,b,
a
b
c

Key Laboratory for Renewable Energy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, PR China
Beijing Key Laboratory for New Energy Materials and Devices, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, PR China
Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry and Environment, Beihang University, Beijing 100191, PR China

a r t i c l e

i n f o

Article history:
Received 12 April 2013
Received in revised form 23 May 2013
Accepted 24 May 2013
Available online 4 June 2013
Keywords:
ZnSWS2/CdS
H2 evolution
Synergistic effect
ZnS passivation
Noble metal-free

a b s t r a c t
A novel ZnSWS2/CdS composite photocatalyst for H2 evolution under visible light irradiation has been successfully synthesized. The loading amounts of WS2 and ZnS on the CdS surface were optimized. A H2 evolution rate up to 1224 molh1 has been achieved for the 9.6 mol% ZnS1 mol% WS2/CdS photocatalyst. The
enhancement of the photocatalytic activity is attributed to the synergistic effect of WS2 as co-catalyst and ZnS
as passivation layer.
2013 The Authors. Published by Elsevier B.V. All rights reserved.

1. Introduction
Photocatalytic H2 generation from water has attracted increasing
attention recently [13]. In order to utilize the abundant visible light,
developing visible light driven photocatalysts is indispensable. Sulde
photocatalysts (such as CuInS2 [4], CdS [5], ZnIn2S4 [6], etc.) are generally attractive candidates due to their suitable band gaps and good catalytic activities for H2 evolution. In particular, CdS is widely studied as an
important sulde for its suitable band positions as well as its low cost.
However, its photocatalytic efciency is extremely low due to severe recombination, and it's not stable under irradiation due to photocorrosion.
Generally, the above problems can be greatly solved by loading
noble metals or their oxides (such as Pt, Pd, RuO2, etc.) as co-catalysts,
which facilitate the separation of photo-generated electrons and holes
and afford the redox reaction sites [79]. However, the noble metals
are not appropriate for practical application. In order to reduce the
cost, some metal suldes as co-catalysts, such as MoS2 [10], WS2 [11]
and NiS [12], have been recently reported to replace noble metals. In

This is an open-access article distributed under the terms of the Creative Commons
Attribution License, which permits unrestricted use, distribution, and reproduction in
any medium, provided the original author and source are credited.
Correspondence to: D. Li, Key Laboratory for Renewable Energy, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, PR China. Tel./fax: +86 10
82649242.
Correspondence to: Q. Meng, Key Laboratory for Renewable Energy, Institute of Physics,
Chinese Academy of Sciences, Beijing 100190, PR China. Tel./fax: +86 10 82649242.
E-mail addresses: dmli@iphy.ac.cn (D. Li), qbmeng@iphy.ac.cn (Q. Meng).

the meantime, for the CdS nanoparticles, some photo-generated carriers are easily captured by its surface states, surface passivation is
thus supposed to be a good modication method to restrain this surface
trapping. In quantum-dot sensitized solar cells, ZnS passivation layer
has been widely used to reduce electron losses of quantum dot sensitizers. That is to say, some surface states of CdS can be passivated by
ZnS with higher conduction band and lower valence band, which is
further favorable for the photocatalytic reaction [1315].
Herein, we report a novel noble metal-free ZnSWS2/CdS composite
photocatalyst for H2 evolution, which is obtained by our recently developed ball-milling (BM) combined calcination method for WS2 loading
[16] and subsequently hydrothermal treatment for ZnS loading on
CdS. A H2 evolution rate up to 1224 molh1 has been achieved for
the 9.6 mol% ZnS1 mol% WS2/CdS photocatalyst. The synergistic effect
of ZnS as passivation layer and WS2 as co-catalyst is supposed to contribute to the increase of the photocatalytic activity.
2. Experimental
2.1. Photocatalyst preparation
CdS powder was from Beijing Shuanghuanweiye Reagent Co., Ltd.
Zn(Ac)22H2O, thiourea and lactic acid were from Sinopharm Chemical
Reagent Co., Ltd. All the chemicals were analytical grade (AR) and used
directly except for the CdS which was thermally treated in advance
[1618]. The (NH4)2WS4 was synthesized according to the literature
(details in Supporting Information) [19].

1566-7367/$ see front matter 2013 The Authors. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.catcom.2013.05.025

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G. Chen et al. / Catalysis Communications 40 (2013) 5154

The WS2/CdS photocatalysts with different WS2 loading amounts

(denoted as x mol% WS2/CdS) were prepared by our recently developed
ball-milling combined calcination method (details in Supporting Information) [16]. ZnS was then loaded on the 1 mol% WS2/CdS as follows:
the slurry containing a proper amount of Zn(Ac)22H2O, 10 mmol of
thiourea, 0.3 g of as-prepared 1 mol% WS2/CdS (treated at 723 K) and
35 mL deionized H2O was ultra-sonicated for 1 h, then transferred into
a Teon-lined autoclave and maintained at 393 K for 5 h. The ultimate
solids (denoted as y mol% ZnS1 mol% WS2/CdS) were collected by centrifugation and washing with distilled water for several times. Here, x or
y means the loading molar quantity of ZnS or WS2 per 100 mol CdS.
For comparison, the 1 mol% WS29.6 mol% ZnS/CdS photocatalyst and
the 9.6 mol% ZnS/CdS photocatalyst were also prepared by the same
method.
2.2. Characterization
The surface morphologies were obtained by a scanning electron
microscope (SEM, XL30 S-FEG, FEI) and a transmission electron microscope (TEM, JEM-2010, JEOL Ltd.). The X-ray diffraction (XRD) patterns
were collected by a rotating-anode diffractometer with Cu K radiation
(M18X-AHF, MacScience). The X-ray photoelectron spectra (XPS) were
recorded on an ULVAC-PHI X-ray photoelectron spectrometer (PHI
Quantera SXM) using Al K radiation. The thermal decomposition behavior was studied by a differential thermal analysis/thermogravimetric
analysis instrument (DTA/TGA, NETZSCH STA 449F3) in N2 atmosphere
with the heating rate of 10 K/min. The photoluminescence spectra
were recorded on an FLS 920 uorescence spectrometer (Edinburgh
Instruments).
2.3. Photocatalytic performance
The reaction was performed in a Pyrex reaction cell connected to a
closed gas circulation and evacuation system. 0.1 g photocatalyst powder
was dispersed in a 150 mL aqueous solution containing 15 mL lactic acid
as the sacricial reagent [12]. The suspension was irradiated by a 300 W
Xenon lamp equipped with an optical cut-off lter ( > 420 nm). The
temperature of the reaction solution was maintained at 293 1.5 K by
a cooling liquid ow. The evolved H2 amount was determined by an
on-line gas chromatography. The photocatalytic activities were compared
by the average H2 evolution rate in the rst 5 h.
3. Results and discussion
The XRD patterns of the WS2/CdS photocatalysts treated at different
temperatures indicate that CdS always keeps the hexagonal phase during
the thermal treatment (see Fig. 1(a)), whereas diffraction peaks assigned
to WS2 are not observed due to low loading amount. The TGDSC curve
of (NH4)2WS4 and XRD patterns of different temperatures treated

(NH4)2WS4 conrm that (NH4)2WS4 is completely decomposed into

WS2 above 673 K (see Fig. S1 and Fig. 1(b)). This is also validated by
XPS spectra (see Fig. 1(c)). The W4f peaks at 35.7 and 37.9 eV are
assigned to W6+ while the peaks at 32.6 and 34.8 eV can be assigned
to W4+ in WS2 [20].
For 1 mol% WS2/CdS photocatalysts, the inuence of calcination temperature on H2 evolution rate was rstly investigated. As illustrated in
Fig. 2(a), with the temperature increasing, the H2 evolution rate of
1 mol% WS2/CdS increases gradually, reaching the maximum value of
780 molh1 at 723 K. However, further increasing the temperature
will decrease the H2 evolution rate instead, which may be ascribed to
the decrease of the surface areas. From SEM images of 1 mol% WS2/CdS
samples calcined at different temperatures, we can see that with the
temperature increasing, the particle sizes increase gradually. It is supposed that some small particles grow together into larger ones, as
shown in Fig. S2.
Fig. 2(b) shows the H2 evolution rates of WS2/CdS photocatalysts
with different WS2 amounts. The H2 evolution rate of bare CdS is only
85 molh1. After loading 0.25 mol% WS2, the H2 evolution rate increases sharply to 262 molh1. With 1 mol% WS2 loaded, the H2 evolution rate reaches the maximum of 780 molh1, which is much
higher than 488 molh1 for 0.2 wt.% Pt/CdS photocatalyst [16,17].
However, further increasing the WS2 amount results in the decrease
of the H2 evolution rate, possibly due to the introduction of recombination sites and the light shading effect of WS2 [16].
In order to further improve the photocatalytic activity, ZnS was loaded on WS2/CdS photocatalysts. As shown in Fig. 2(c), with the increase
of the ZnS amount, the H2 evolution rate increases rstly, reaching the
maximum of 1224 molh1 for 9.6 mol%, then decreases gradually
due to the incident light hinder and the introduction of recombination
centers by excessive ZnS. For comparison, a H2 evolution rate of
104 molh1 is obtained for the 9.6 mol% ZnS/CdS photocatalyst,
slightly higher than that of the bare CdS whereas far lower than the
ZnSWS2/CdS photocatalysts. Obviously, the loadings of WS2 and sequent ZnS are simultaneously benecial to improve the photocatalytic
activity.
Fig. 3(a) and (b) clearly shows that WS2 with a typical layered structure is deposited on the surface of CdS, depicted by the black circles, of
which the lattice spacing of the (002) plane is 6.18 . As shown in Fig.
S3, some small ZnS particles are dispersed at the CdS nanoparticle surface after hydrothermal treatment. The HRTEM images (Fig. 3(c) and
(d)) demonstrate the small particles are ZnS for the lattice spacing of
3.3 is (100) planes (depicted by the white circles).
As we know, the photoluminescence (PL) spectroscopy is an effective way to investigate the photo-generated charge transfer and recombination processes. Herein, at the excitation wavelength of 400 nm, the
PL spectra are presented in Fig. 4. The CdS sample displays the highest
emission band intensity centered at 700 nm, which is ascribed to the
trap-related states that generally serve as recombination centers. As

Fig. 1. (a) X-ray diffraction patterns of 1 mol% WS2/CdS photocatalysts calcined at different temperatures, along with thermally treated CdS for comparison; (b) X-ray diffraction
patterns of (NH4)2WS4, (NH4)2WS4 (BM), and WS2 prepared by calcining (NH4)2WS4 (BM) at different temperatures; and (c) XPS spectra of the W4f regions for 1 mol% WS2/CdS
photocatalysts prepared at (I) 573 K, (II) 673 K, (III) 723 K, (IV) 773 K and (V) 9.6 mol% ZnS1 mol% WS2/CdS photocatalyst.

G. Chen et al. / Catalysis Communications 40 (2013) 5154

53

Fig. 2. The H2 evolution rates of (a) 1 mol% WS2/CdS photocatalysts prepared at different temperatures; (b) WS2/CdS photocatalysts loaded with different amount of WS2 at 723 K;
and (c) y mol% ZnS1 mol%WS2/CdS photocatalysts loaded with different amount of ZnS. The composition of the photocatalyst system: 0.1 g photocatalyst dispersed in 150 mL
solution containing 15 mL lactic acid as the sacricial reagent; light source, xenon lamp (300 W) with a cut-off lter ( > 420 nm).

expected, the PL intensity is dramatically quenched after the load of

WS2, indicating that WS2 can efciently capture electrons which is
favorable for the photocatalytic reaction. After the load of ZnS, the PL
intensity is even lower. Interestingly, the variation tendency between
the PL intensity and ZnS amount is the same as that between the H2 evolution rate and the ZnS amount, for excessive ZnS will introduce recombination centers again.
Because ZnS and CdS have similar crystal structures, ZnS is prone
to grow on CdS to eliminate its interfacial defects. The higher conduction band and lower valence band of ZnS demonstrate the type
I heterojunction of ZnS/CdS. This heterojunction can effectively passivate the electron loss at the CdS surface, as shown in Scheme 1, which
has also been found in many quantum-dot sensitized solar cells
[21,22]. Moreover, because of the presence of ZnS on the CdS surface,
the ZnSWS2/CdS photocatalyst exhibits good photostability, only a

slight drop of the evolved H2 amount was observed in the third 5 h reaction (details in Supporting Information). It should be noted that as we
can see from the TEM image (Fig. 3), the ZnS layer is not compact and
very thin, which is in agreement with the above hypothesis in some extent. By the way, the photocatalytic activity of the 1 mol% WS2
9.6 mol% ZnS/CdS photocatalyst with an opposite deposition order of
ZnS and WS2 only accounts for 66.3% of that of the 9.6 mol% ZnS
1 mol% WS2/CdS photocatalyst, for rstly deposited ZnS decreases the
electrons to react with the protons. The exact mechanism needs further
investigation.
4. Conclusions
In summary, a novel noble metal-free ZnSWS2/CdS photocatalyst for
photocatalytic H2 evolution under visible light irradiation was prepared

Fig. 3. HRTEM images of (a, b) 1 mol% WS2/CdS photocatalyst prepared at 723 K and (c, d) 9.6 mol% ZnS1 ml% WS2/CdS photocatalytst. The black circles depict the WS2 while the
white circles depict the ZnS.

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G. Chen et al. / Catalysis Communications 40 (2013) 5154

Acknowledgments
The work was nancially supported by NSFC (21173260 and
51072221), the MOST (973) (2012CB932903 and 2012CB932904) and
the Knowledge Innovation Program of the Chinese Academy of Sciences.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.catcom.2013.05.025.
References

Fig. 4. Photoluminescence spectra of CdS, 1 mol% WS2/CdS and ZnSWS2/CdS

photocatalysts with different loading amounts of ZnS.

Scheme 1. Proposed mechanism for photocatalytic H2 evolution on ZnSWS2/CdS

photocatalyst.

by a two-step method. WS2 was rstly loaded on the CdS surface by a

simple ball-milling combined calcination method, and then ZnS was deposited on WS2/CdS by the hydrothermal method. The H2 evolution rate
of 9.6 mol%ZnS1 mol% WS2/CdS is 1224 molh1, much higher than
that of 0.2 wt.% Pt/CdS. The synergistic effect of ZnS as passivation layer
and WS2 as co-catalyst results in the high photocatalytic activity. Besides,
the ZnSWS2/CdS photocatalyst exhibits good anti-photocorrosion
property.

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