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Metal sulphide semiconductors for photocatalytic

Cite this: DOI: 10.1039/c3cy00018d
hydrogen production
Kai Zhangab and Liejin Guo*a
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D

Photocatalytic hydrogen production using semiconductor materials is one of the ideal processes for
direct solar energy conversion. Sulphide semiconductor photocatalysts have attracted much attention
Downloaded by University of Queensland on 24/04/2013 07:43:45.

Received 7th January 2013,
Accepted 18th February 2013
DOI: 10.1039/c3cy00018d
www.rsc.org/catalysis
due to their excellent solar spectrum responses and high photocatalytic activities. This article presents
recent research progress in the development of visible light driven sulphide photocatalysts, focusing on
the expansion of solar spectrum response and enhancement of charge separation efficiency. As is
known, the ultimate goal of photocatalytic hydrogen production is to meet the practical energy
demand of human beings. Thus, design of highly efficient and low cost sulphide photocatalysts with
excellent sunlight response is highly desired. So we also highlight the crucial issues in the development
of highly efficient sulphide photocatalysts without noble metal cocatalysts. The present paper is
expected to provide important scientific reference for future works. Finally, the challenges and
perspectives in this area are also discussed.

1. Introduction have been reported to be effective for photocatalytic hydrogen

Since the first discovery by Fujishima and Honda in 1972, photo-
catalytic hydrogen production using semiconductor materials has
been considered as one of the ultimate solutions for energy and
environmental issues.1 During the past 50 years, great progress
has been made in this exciting field, numerous semiconductors
a
International Research Centre for Renewable Energy, State Key Laboratory of
Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an 710049,
P. R. China. E-mail: lj-guo@mail.xjtu.edu.cn; Fax: +86 29 82669033;
Tel: +86 29 82663895
b
National Centre for Nanoscience and Technology, No. 11 Zhongguancun Beiyitiao,
Beijing 100190, P. R. China
production.2 However, Maeda and Domen have reported that to
meet 1/3 of the energy requirement of human beings by 2050
through photocatalytic hydrogen production, ten thousand
photocatalytic water splitting systems with energy conversion
efficiency above 10% should be established.2 Fig. 1 shows the
relationship between energy conversion efficiency and quan-
tum yield of photocatalysts with different absorption edges.
Photocatalysts with a photoresponse of up to 600 nm should
have an average quantum yield as high as 60% in the whole
absorption range to achieve the requirement of practical appli-
cation. To the best of our knowledge, photocatalysts satisfying
the above minimum requirement have not yet been obtained.

Kai Zhang received his PhD Liejin Guo is a full professor at

degree under the supervision of
Prof. Liejin Guo from Xi’an
Jiaotong University in 2012, and
joined Prof. Jianru Gong’s group
as a research assistant professor
in the National Center for Nano-
science and Technology, China
in 2013. His current research
concentrates on the synthesis
and properties of nanostructured
materials for photocatalysis/
Kai Zhang photoelectrochemistry applications.
the institute of Energy and Power
Engineering, and the director of
the State Key Laboratory of
Multiphase Flow in Power
Engineering in Xi’an Jiaotong
University, China. He obtained
his PhD degree in Engineering
Thermophysics from Xi’an
Jiaotong University in 1989. His
research interests include multi-
phase flow, heat transfer and
Liejin Guo renewable energy technologies.

This journal is c The Royal Society of Chemistry 2013 Catal. Sci. Technol.

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Fig. 1 Solar energy conversion efficiency as a function of wavelength using
photocatalysts with various quantum efficiencies.
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D
Apparently, we still have a long way to go to achieve a green and
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clean energy future by photocatalytic hydrogen production.
Metal oxides, such as SrTiO3,3,4 TiO2 5 and NaTaO3,6,7 pos-
sess suitable band structures meeting the thermodynamic
requirement for water splitting, and are non-toxic and very
stable during the photocatalytic process, thus they have been
reported to be the most efficient oxide photocatalysts for water
splitting reported up to now. But all of them are only active
under ultraviolet light, which only accounts for B4% of the
solar spectrum. Therefore, (oxy)nitrides as well as oxysulphides,
which possess excellent solar spectrum responses, have been
successfully developed by Domen’s group.8–13 Especially,
(Ga1xZnx)(N1xOx) has been proved to be the most efficient
photocatalyst capable of splitting pure water under visible-
light irradiation.8,14–17 Since many important findings on
this subject have been achieved during the past several
decades, a comprehensive review on the advances in the
development of oxide or non-oxide photocatalysts is already
very large.18–21
However, little attention has been focused on the progress of
sulphide photocatalysts for hydrogen production. Sulphides
always possess relatively high conduction band positions
suitable for H2O reduction and better sunlight responses
than oxides, which are originated from the higher valence band
positions composed of S 3p orbitals. For instance, ZnS–
AgInS2–CuInS2 solid solution has an absorption edge up to
ca. 800 nm, that is, it could utilize the whole ultraviolet and
visible light region of sunlight.22,23 But the excellent visible
light responses are always achieved at the cost of oxidizing
abilities. Thus, thermodynamically, sulphides are not capable
of splitting pure water due to their S 2p containing valance
band. Sacrificial reagents are always needed to achieve photo-
catalytic hydrogen production. For example, sulphides always
exhibit excellent photocatalytic activities in aqueous solution
using Na2S and Na2SO3 as sacrificial reagents. Pt/PdS/CdS,
reported by C. Li et al., show an extremely high apparent
quantum yield of about 93% at 420 nm, almost achieving the
efficiency of natural photosynthesis.24,25 One may consider that
development of photocatalysts that work only for half reactions
of water splitting in the presence of sacrificial reagents is
not meaningful. We cannot agree with this point of view,
as abundant sulphur compounds obtained from chemical
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Fig. 2 Solar hydrogen production using abundant sulfur compounds and metal
sulphide photocatalysts. Reprinted with permission from ref. 18. Copyright 2009
The Royal Society of Chemistry.
industries or natural resources can be used as electron donors.
As shown in Fig. 2, this reaction produces H2 at ambient
temperature and pressure but does not consume fossil fuels
and does not emit CO2.18
Obviously, scientific investigations on photocatalytic hydrogen
production by sulphide photocatalysts are also of great impor-
tance from the viewpoint of practical application. Therefore,
sulphide semiconductor photocatalysts have attracted much
attention in recent years due to their excellent visible-light
responses and outstanding photocatalytic properties. So a
comprehensive review on this issue is timely to provide impor-
tant theoretical guidance and scientific reference for future
studies on this exciting subject. The present paper is focused on
the recent advances in the development of highly efficient
sulphide photocatalysts with different formulations, especially
highlighting the important aspects of the modifications of
non-loaded sulphide photocatalysts. The crucial issues that
should be addressed in the future research activities are also
discussed.
2. General view of sulphide photocatalysts
Numerous metal sulphide photocatalysts have been reported
for water splitting in the presence of different sacrificial
reagents in the past several decades. This section briefly reviews
the efficient sulphide photocatalysts reported to date, with
a focus on materials formulation. As shown in Table 1, over
30 kinds of sulphide materials can act as efficient photo-
catalysts for hydrogen evolution via water splitting. Summarizing
the metal elements that construct these heterogeneous
sulphide photocatalysts, we find that almost all of the sulphide
photocatalysts consist of metal cations with d10 configuration
(Fig. 3). It is reasonable that the conduction bands of sulphide
photocatalysts are always composed of d and sp orbitals,
while the valence bands consist of S 3p orbitals, which are
much more negative than O 2p orbitals, thus resulting in
conduction band positions negative enough to reduce H2O to
H2 and narrow band gaps with suitable response to the solar
spectrum.18
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Table 1 Sulphide semiconductors for photocatalytic hydrogen production

Incident Cocatalyst
Mass light Aqueous and activity Quantum
Photocatalyst Synthetic method (g) (nm) reaction solution (mmol g1 h1) yield (%) Morphology Ref.
CdS Purchased 0.25 >390 Na2SO3 Pt 35@435 nm 26
CdS Purchased 0.1 Na2S Rh/185.3 27
CdS Purchased S2 Rh/185.3 28
CdS Mixing and grinding 0.25 >390 Na2SO3 Pt/B1680 8.2@436 nm 29
CdS Mixing and grinding 0.26 >400 Formic acid, for- 6@400–500 nm 30
maldehyde,
methanol (highest
activity)
CdS Cube CdS deposited on 0.05 >420 Na2SO3, Na2S Pt/668 31
hexagonal CdS
CdS Precipitation method 0.1 UV Na2SO3, Na2S Pt/6000 Particles 32
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D

CdS Precipitation method 0.1 >420 Lactic MoS2/B5200 33

CdS Precipitation method 0.1 Overall Na2SO3, Na2S Pt/13 860 1.3@overall Particles 34
spectrum spectrum
CdS Precipitation method 0.3 >420 nm Na2SO3, Na2S Pt–PdS/29233.33 93@420 nm 24
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CdS Precipitation/hydro- 0.1 >420 Na2SO3, Na2S WC/B1350 Particles 35

thermal method
CdS Solvothermal method 0.05 >420 Formic acid Pt/4603.2 13.9 Nanorods 36
CdS Solvothermal method 0.04 >420 Formic acid Pt/1127.5 Rod-like grains 37
CdS Solvothermal method 0.1 >420 Na2SO3, Na2S Pt/B60 Nanowires 38
CdS Thermolysis method 0.3 >420 Na2SO3, Na2S Pt/83.3 Particles 39
CdS Polymer-inorganic 0.5 >420 KOH (photo- Pt/7856 19.7 Particles 40
solid-state reaction decomposition of
method H2S)
CdS Thermal sulfidation 0.2 >430 Na2SO3, Na2S Pt/5625 24.1@420 nm Particles 41
method
CdS Direct cation exchange 0.1 Visible Na2S B350 42
reaction and a sulfur- light
ization method
CdS Template method 0.1 >420 Na2SO3, Na2S Pt/2600 7.2@420 nm Nanowire arrays 43
CdS Two-step aqueous 0.15 >420 Na2SO3, Na2S Pt/27333.3 60.34@420 nm Nanosheets and 44
route self-templated nanorods
synthesis
CdS Ultrasonic method 0.1 UV Na2SO3, Na2S Pt/14 150 Particles 45
CdS 0.005 >360 EDTA, cysteine Pt/ 4@436 nm 46
CdS S2/H2PO2 Pt/14508.9 34@450 nm Particles 47
CdS/Al-HMS Template, ion 0.2 >420 Formic acid Ru/825.9 1.2@420 nm Particles 48
exchange and sulfur-
ization reactions
CdS/alumina Impregnation method 2 Overall Na2SO3, Na2S 180.8 49
spectrum
CdS/alumina Impregnation method 2 Overall Na2SO3, Na2S 41.3 50
spectrum
CdS/alumina Impregnation method 2 Overall Na2SO3, Na2S 180.8 51
spectrum
CdS/alumina Impregnation method 2 Overall Na2SO3, Na2S 180.8 52
spectrum
CdS/alumina Impregnation method 2 Overall Na2SO3, Na2S 90.4 53
spectrum
CdS/Ag2S Two-step precipitation 0.1 Overall Na2SO3, Na2S Pt/874 Mixed morphology 54
method spectrum of nanosheets and
nanorods
CdS/CeO2 One-pot electro- 0.05 >420 and Na2SO3, Na2S 223@>420 nm Spheres with coarse 55
chemical method UV 782@UV surface
CdS-cluster- Solvothermal method 0.02 >420 Lactic acid Pt/56 000 22.5@420 nm Nanosheets 56
decorated graphene
CdS/CNT Annealing method 0.06 >400 Na2S 92.5 Particles and 57
nanotubes
CdS/CNT Acid-treated 0.06 >400 Na2S Pt/819 57
CdS/colloidal In situ generation >350 PhSH, DHP Rh/low 58
rhodium method
CdS/ETS-4 Hydrothermal 0.1 >420 Na2SO3, Na2S 175 59
synthesis method
CdS–glass Annealing and refining 1 >420 KOH (photo- 3570 17.5@470 nm Nanoparticles (QDs) 60
nanosystem decomposition of
H2S)
CdS-incorporated Two-step thermal 0.2 >430 Na2SO3, Na2S 1549 Particles 61
special glass sulfidation method

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Table 1 (continued )

Incident Cocatalyst
Mass light Aqueous and activity Quantum
Photocatalyst Synthetic method (g) (nm) reaction solution (mmol g1 h1) yield (%) Morphology Ref.
CdS/LaMnO3 Reverse micelle method 0.1 >420 Na2SO3, Na2S 595 Particles 62
CdS/M-MCM-41 Hydrothermal, 0.2 >430 Na2SO3, Na2S 47.11 63
ion-exchange and
sulfidation process
CdS/Ti-MCM-41 Ion-exchange and 0.2 >430 Na2SO3, Na2S 250 Pt/2.6@420 nm Particles and 64
sulfidation Pt/875 nanotubes
CdS/MgO Etching treatments 0.5 Overall Na2SO3, Na2S Pt/290 Particles 65
spectrum
CdS/MoO3 Sonochemistry method >400 Na2SO3, Na2S 5250 28.86@420 nm Core(MoO3)– 66
shell(CdS)
CdS/Ni/NiO/KNbO3 Solid-state reaction 0.2 >400 Isopropanol 150 4.4@>400 nm Particles 67
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D

method
CdS/pani Precipitation 0.2 >420 Na2SO3, Na2S 299.1 Particles 68
CdS/silicas Direct reaction of Cd2+ 0.2 >400 Ethanol 33 Rod-like 69
and aqueous sulphide
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CdS/SrS Coprecipitatation 0.2 >430 Na2SO3, Na2S 615 9.63@480 nm Particles 70

method
CdS/TiO2 Sol–gel method 0.1 >450 EDTA Pt/8.4 13.4@>450 nm 71
CdS/TiO2 Solvothermal method 0.1 >420 Na2SO3, Na2S Pt/B107 Nanowires and 72
and sol–gel synthesis nanoparticles
CdS/TiO2 Precipitation method 0.1 >420 Na2SO3, Na2S Pt/6400 Particles 73
and sol–gel synthesis.
CdS/TiO2 Precipitation method 0.1 >420 KOH (photo- Pt/9800 40.9@420 nm Particles(TiO2 nano 74
and sol–gel synthesis. decomposition of with CdS bulk)
H2S)
CdS/TiO2 Two step method 0.1 >420 Na2SO3, Na2S Pt/4224 Particles(TiO2 nano 75
with CdS bulk)
CdS/TiO2 Two step method 0.1 >420 Na2SO3, Na2S Pt/B5500 Particles 76
CdS/(Pt–TiO2) Sol–gel and precipita- 0.0125 >420 Na2SO3, Na2S 2670 Particles 77
tion method
CdS/TiO2NTs Two-step chemical 0.1 >400 Na2SO3, Na2S 12.7 0.1@420 nm Nanoparticles and 78
solution method nanotubes
CdS/TiO2NTs Ultrasonic stirring 0.15 >420 Na2SO3, Na2S Pt/2680 43.4@420 nm Nanoparticles and 79
method nanotubes
CdS/ Partial ion-exchange 0.2 >430 Na2SO3, Na2S Pt/B1080 2.7@430 nm Nanoparticles and 80
Na2Ti2O4(OH)2 method nanotubes
CdS/zirconium Two-step thermal 0.2 >430 Na2SO3, Na2S Pt/B2300 27.2@420 nm Particles 81
titanium sulfidation method
phosphate
CdS/zeolite Ion exchange and >330 Na2SO3, Na2S ZnS/2455 82
sulfidation
CdS/ZnO A wet two-step 0.2 Na2SO3, Na2S 1805 83
chemistry method Pt/3870
CdS/ZnO A two-step method 0.2 Na2SO3, Na2S RuO2/B6200 Core–shell nanorods 84
CdS–ZnO–CdO Sequential precipita- 0.1 Visible Na2SO3, Na2S Ru/B75 85
tion method light
CdS/N-doped Calcination method 0.2 >420 Na2SO3, Na2S 1050 Nanoparticles and 86
graphene nanosheets
In doped CdS on The polyol method 0.05 Na2SO3, Na2S Pd/B800 3.6(overall Particle 87
ZrO2 spectrum)
Cd1xZnxS Coprecipitation method 0.1 o400 Na2SO3, Na2S 16 320 2.17@UV Particle 88
Cd1xZnxS Precipitate–hydro- 0.1 >430 Na2SO3, Na2S 17 900 43@425 nm Particles with nano- 89
thermal method twins
Cd1xZnxS Thermal sulfuration 0.2 >430 Na2SO3, Na2S B850 10.23@420 nm Particles 90
method
Cd1xZnxS Hydrothermal 0.1 >420 Na2SO3, Na2S 2640 Nanoparticles 91
reduction
Cd1xZnxS Coprecipitation 0.1 Visible Na2SO3, Na2S B350 Particles 92
light
Cd0.1Zn0.9S Hydrothermal method 0.2 >420 Na2SO3, Na2S 403.75 14.36@420 nm Nanoparticles and 93
microspheres
Cd0.1Zn0.9S Hydrothermal method 0.2 Visible Na2SO3, Na2S 21 850 Nanospheres 94
light
Cd0.2Zn0.8S Coprecipitation 0.2 >420 and Na2SO3, Na2S 965@>420 nm Particles 95
method overall 1260@Overall
spectrum spectrum
Pt/2290@>420 nm
Pt/3200@Overall
spectrum

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Table 1 (continued )

Incident Cocatalyst
Mass light Aqueous and activity Quantum
Photocatalyst Synthetic method (g) (nm) reaction solution (mmol g1 h1) yield (%) Morphology Ref.
Cd0.5Zn0.5S Hydrothermal method 0.1 >420 Glucose, NaCl Pt/B350 96
CdZnS (containing Coprecipitation 0.4 Na2SO3, Na2S Pt/39062.5 0.37 97
Ag2S) method
Cd0.1Zn0.9S–CNT Hydrothermal method 0.05 >420 Na2SO3, Na2S 1563.2 7.9@40 nm Particles 98
Cd0.5Zn0.5S/TNTs One-step hydrothermal 0.2 >430 Na2SO3, Na2S 13 200 38.1@420 nm Particles and 99
method nanotubes
Cd0.8Zn0.2S/ Successive intercala- 1 >290 and Na2S Pt/ 100
HNbWO6 tion reactions and >400 B625@>290 nm
coprecipitation Pt/536@>400 nm
method
ZnxCd1xS–CuS A one-step method 0.3 >420 Na2SO3, Na2S 2080 15.7@420 nmPt/ Nanospheres 101
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Pt/2466.7 19.1@420 nm
Reduced graphene Coprecipitation–hydro- Na2SO3, Na2S 1824 23.4@420 nm Nanoparticles and 102
oxide–ZnxCd1xS thermal reduction nanosheets
method
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CdS QDs sensitized Hydrothermally syn- 0.05 >400 Na2SO3, Na2S 2128 6.3@420 nm Particles 103
Zn1xCdxS thesize and cation
exchange method
CdSZnS ZnS precipitated on >400 Benzyl alcohol 1.86@404 nm ZnS coated CdS 104
CdS
CdSZnS Coprecipitation 0.0413 Sunlight Na2SO3, Na2S 2283.9 105
method
CdS/ZnS/n-Si Coprecipitation 0.1 Na2SO3, Na2S 1584.8 106
method
CdSZnS/silica 0.05 UV + S 2
B268 0.4@488 nm Particles 107
visible
light
[Pt/(CdS/n-Si)]/ZnS Physical mixing 0.1 Overall Na2SO3, Na2S Pt/647.3 108
method spectrum
Sr-doped CdSZnS Coprecipitation 0.2 >430 Na2SO3, Na2S B500 Nanoparticles 109
method
Ba doped Thermal sulfuration 0.2 >430 Na2SO3, Na2S B700 17.4@425 nm Nanoparticles 110
Cd0.8Zn0.2S method
ZnIn2S4 Hydrothermal method 0.3 >420 Na2SO3, Na2S Pt/257 111
ZnIn2S4 Hydrothermal method 0.5 KOH (photo- 10 574 Flower-like 112
decomposition of structures, nano-
H2S) plates and nanostips
ZnIn2S4 Hydrothermal method 0.1 >420 Na2SO3, Na2S Pt/8420 34.3@420 nm Floriated micro- 113
spheres comprised of
large interleaving
flakes
ZnIn2S4 (CTAB)-assisted hydro- 0.2 >430 Na2SO3, Na2S Pt/562.25 18.4@420 nm Microsphere with 114
thermal method numerous petals
ZnIn2S4 CPBr-assisted hydro- 0.1 Visible Na2SO3, Na2S 766.8 Flowerlike micro- 115
thermal method light spheres composed of
nanosheets
ZnIn2S4 Surfactant-assisted 0.2 >430 Na2SO3, Na2S Pt/612.5 11.9@420 nm Microsphere with 116
hydrothermal method numerous petals
ZnIn2S4 Microwave-assisted 0.1 >430 Na2SO3, Na2S Pt/692 Microspheres 117
hydrothermal method composed of numer-
ous petals/sheets
ZnIn2S4 Solvothermal/hydro- 0.2 >430 Na2SO3, Na2S Pt/136.5 4.2@420 nm Flowering-cherry 118
thermal method sphere-like structure
with numerous petals
ZnIn2S4 Thermal sulfidation 0.2 >430 Na2SO3, Na2S Pt/B55 Irregular lumps in 119
micron-scale size
ZnmIn2S3+m Hydrothermal method 0.2 >430 Na2SO3, Na2S Pt/159.5(Zn2In2S5) 11.1@420 nm Microspheres 120
composed of numer-
ous petals/sheets
ZnIn2S4/MWCNTs Facile hydrothermal 0.1 >420 Na2SO3, Na2S 6840 23.3@420 nm Floriated micro- 121
method spheres comprised of
large interleaving
flakes
ZnIn2S4/ Solvothermal method 1.02 Na2SO3, Na2S B398.3 Particles and fibers 122
fluoropolymer and hydrothermal
synthesis
polymerization

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Table 1 (continued )

Incident Cocatalyst
Mass light Aqueous and activity Quantum
Photocatalyst Synthetic method (g) (nm) reaction solution (mmol g1 h1) yield (%) Morphology Ref.
ZnIn2S4 loaded (CTAB)-assisted hydro- 0.05 Na2SO3, Na2S Pt/4000 Microspheres 123
with transition- thermal synthetic
metal sulphides method
Cu doped ZnIn2S4 Facile hydrothermal 0.2 >430 Na2SO3, Na2S Pt/757.5 14.2@420 nm Microspheres 124
method composed of numer-
ous petals/sheets
Ni doped ZnIn2S4 Hydrothermal method 0.2 >420 Na2SO3, Na2S Pt/B45 Microspheres 125
comprised of petals
CdIn2S4 Hydrothermal method 0.5 >420 KOH (photo- 6960 17.1@500 nm Microspheres 126
decomposition of composed of nano-
H2S) petals and nanotubes
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CdIn2S4 Surfactant-assisted 0.5 >420 KOH (photo- 6476 Microspheres 127

hydrothermal method decomposition of composed of
H2S) nanopetals
CdxIn2S4– Hydrothermal method 0.2 >400 Na2SO3, Na2S 590 Particle 128
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Zn1xIn2S4
CuInS2 Situ formed template 0.25 >420 Na2SO3, Na2S Pt/59.4 Microsphere built by 129
solvothermal route many flakes
AgIn5S8 Coprecipitation and 0.3 >420 K2SO3, Na2S Pt/B133.3 5.3@411.2 nm 130
heat-treatment
CuGa3S5 Coprecipitation and 0.05 >420 Na2SO3, Na2S B300 NiS/1.3@ Particles(some of 131
heat-treated method Rh/800 420–520 nm which are pyramidal)
NiS/1000
AgGaS2 Coprecipitation and 0.1 >420 Na2SO3, Na2S Pt/B3000 Particles 132
annealing method
AGa2In3S8(A = Cu Heat-treated solid-state 0.3 >420 K2SO3, Na2S Cu: Rh/10666.7 15@Cu = 560 nm 133
or Ag) reaction method Ag: Rh/3433.3 or Ag = 460 nm
Zn1xCuxS Coprecipitation 1 >420 Na2SO3 B370 3.7@420 nm 134
sulfidation
Cu-doped ZnS Sulfidation and ion 0.2 Overall Na2SO3, Na2S B210 Shell structure 135
exchange spectrum particles
(CuIn)xZn2(1x)S2 Hydrothermal method 0.2 >430 Na2SO3, Na2S Ru/990.45 15.45@420 nm Microspheres 136
(CuIn)xZn2(1x)S2 Coprecipitation and 0.3 >420 K2SO3, Na2S Pt/2280 12.5@420 nm Particles with 137
heat-treated method hexagonal plane
(AgIn)xZn2(1x)S2 Coprecipitation and 0.3 >420 K2SO3, Na2S 320(x = 0.29) Pt/20@420 nm Particles with nano- 138
heat-treated method Pt/1413.3(x = 0.22) steps structure
AgInZn7S9 Coprecipitation and 0.3 >420 Na2SO3, Na2S Pt/3133 35@420 nm 139
heat-treated method
(CuIn)xCd2(1x)S2 Low-temperature 0.1 >420 Na2SO3, Na2S 649.9 Pt/26.5@420 nm Microspheres 140
hydrothermal method Pt/2456
(AgIn)xCd2(1x)S2 Hydrothermal method 0.1 >420 K2SO3, Na2S 274.5 Nanosphere 141
Pt/1172.5
ZnS-coated Solvothermal method 0.1 >420 Glucose Pt/103 Micospheres and 142
ZnIn2S4 rod-like grains
ZnS–CuInS2– Coprecipitation and 0.3 >420 K2SO3, Na2S Ru/7733.3 Particles(most of 22
AgInS2 heat-treated method which have sharp
edges and clear
planes)
ZnS–CuInS2– Coprecipitation and 0.3 >420 K2SO3, Na2S Ru/1208 Average = Particles(some of 23
AgInS2 heat-treated method 7.4@440/480/ which are platelike)
520 nm
(CuxAg1x)2ZnSnS4 Coprecipitation and 0.02 Overall K2SO3, Na2S Ru/B750 0.18– Particles 143
heat-treated method spectrum 0.25@o700 nm
AI2–Zn–AIV– Coprecipitation and 0.3 >420 K2SO3, Na2S Ru/ 3@500/540/ Particles 144
I
S4(A = Cu and Ag; heat-treated method 1606.7(Ag2ZnSnS4) 580 nm
AIV = Sn and Ge)

The genealogy of these reported sulphide photocatalysts is
illustrated in Fig. 4. Sulphide photocatalysts can be divided into
several groups, such as IIB–VIA, IIB–IIIA–VIA, IA–IIIA–VIA and
IB–IIB–IVA–VIA sulphide photocatalysts, according to their
elemental compositions and material formulations. All these
sulphide semiconductors can be considered as derivatives of
zinc-blende structure, which are obtained through substituting
IIB atoms with other metallic elements. Due to the variety of
metal elements, the symmetries of corresponding crystal struc-
tures are reduced. Thus tetragonal crystal systems, the symme-
tries of which are obviously lower than cubic crystal systems,
are gradually presented in sulphides such as chalcopyrite
and stannite structures. Therefore the significant progress
in the development of sulphide photocatalysts will be reviewed
in the following sections with reference to their material
formulations.

Catal. Sci. Technol. This journal is c The Royal Society of Chemistry 2013

Catalysis Science & Technology
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D
Fig. 3 Elements used for constructing most of the sulphide photocatalysts for
hydrogen production.
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Fig. 4 Genealogy of sulphide semiconductor photocatalysts and the corre-
sponding relationship between semiconductors with different formulations.
3. IIB–VIA sulphide photocatalysts
IIB–VIA sulphide semiconductors are one of the most popular
photocatalysts reported up to now, including ZnS, CdS and
Cd1xZnxS solid solutions. As shown in Fig. 5, zinc-blende and
wurtzite structures are the two types of atomic arrangements
adopted by tetrahedral coordinated semiconductors of IIB–VIA
groups. The lattice is FCC in the zinc-blende structure and CPH
in the wurtzite structure, each structure is composed of two
sublattices displaced from each in blende and wurtzite struc-
tures, respectively, metal atoms being at the nodes of one
lattice and S atoms at the nodes of the other lattice. They differ
by the stacking sequence: A-aB-bC-cA-aB-bC-c for the blende
structure and A-aB-bA-aB-b for the wurtzite structure, where
capital letters denote pure metal planes and small letters pure
S planes or vice verse.145
ZnS is a typical IIB–VIA group semiconductor photocatalyst,
exhibiting an extremely high apparent quantum yield of about
90% at 313 nm without noble metal co-catalysts in Na2S–
Na2SO3 aqueous solution because of its high conduction
band position.146 However, ZnS can only utilize ultraviolet
light due to its wide band gap (B3.6 eV). Thus numerous
efforts have been made to realize visible light response
while maintaining the high conduction band of ZnS. Foreign
elements doping has been proved to be one of the most
effective modification methods to develop visible-light active
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Fig. 5 Schematic diagram of zinc-blende and wurzite crystal structures.
Fig. 6 UV-vis absorption spectrum of transition metal doped ZnS. The spectral
shapes indicate that doping cations form donor levels in the forbidden band.
Reprinted with permission from ref. 18. Copyright 2009 The Royal Society of
Chemistry.
ZnS based photocatalysts.18,134,147–149 Fig. 6 shows the UV-vis
absorption spectra of ZnS doped with different transition metal
cations.18,134,147,148 Foreign elements doping successfully
enhances the absorbance of ZnS in the visible-light region,
and the spectral shapes are distinct from those of band gap
transitions, indicating that doping cations form donor levels
in the forbidden band of ZnS. These doped ZnS photo-
catalysts exhibit excellent photocatalytic activities without any
co-catalysts, because the high conduction band of ZnS is
maintained after doping. Additionally, Muruganandham and
Kusumoto successfully synthesized a novel C, N co-doped
porous ZnS photocatalyst by a simple procedure, which was
the first report on non-metal doped sulphide semiconductors,
and the doped ZnS exhibited excellent photocatalytic activity
under visible light.149 Recently, J. G. Yu et al. reported that
surface modification of a ZnS porous nanosheet by CuS could
significantly enhance its photocatalytic activity under visible
light, and they concluded that the interfacial charge transfer
from the valence band of ZnS to CuS caused the reduction
of CuS to Cu2S, thus resulting in much more improved
activity (Fig. 7).150
CdS, another member of IIB–VIA sulphides, is probably the
best-studied metal sulphide photocatalyst for H2 evolution,
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Fig. 7 TEM image of a CuS modified ZnS nanosheet and the schematic diagram
of the interfacial charge transfer mechanism. Reprinted with permission from
ref. 149. Copyright 2011, American Chemical Society.
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because of its narrow band gap (2.4 eV) that suits very well with
the solar spectrum and good band positions for reducing H2O
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to H2, although it is unstable and toxic. However, CdS alone
exhibits very low photocatalytic activity and its good perfor-
mance is always achieved by loading noble metals on the
surface to lower the overpotential for H2O reduction, such as
Pt, Pd, RuO2, etc.46,47,151–155 Nosaka et al. investigated the
influence of different noble metal co-catalysts on the photo-
catalytic activities of CdS powders, and demonstrated that
Rh- and Pt-loaded CdS particles showed higher activities.156
Reber and co-workers reported a series of good hydrogen
production efficiencies of about 16%, 25% and 34% at 60 1C
in Na2S, S2/SO32 and S2/H2PO2 aqueous solutions respec-
tively.47 Borgarello et al. deposited very small quantities of
RuO2 on CdS, which resulted in the quantum yield of H2
formation reaching 35% after loading, and they attributed
this high efficiency to the catalysis of hole transfer from the
valence band of CdS to sulphide solution.151 Pt-like tungsten
carbide was also reported to act as an excellent co-catalyst
for CdS in photocatalytic H2 production under visible light
irradiation.35 Recently, transition metal compounds, especially
metal sulphides, were found to be excellent co-catalysts for
photocatalytic hydrogen production by CdS.33,157–159 Zong
and co-workers investigated the effect of MoS2 loading on
the photocatalytic activity of CdS. They found that the activity
of MoS2/CdS was even higher than those of CdS loaded
with different noble metals, and the junction formed between
MoS2 and CdS as well as the excellent H2 activation energy
of MoS2 were supposed to be responsible for this enhanced
activity.33,159 Zhang et al. synthesized a novel highly active
NiS/CdS photocatalyst by a simple hydrothermal loading
method, and a high quantum efficiency of 51.3% was measured
at 420 nm in lactic acid sacrificial solution.158 Furthermore,
the most encouraging achievement was made by H. J. Yan
and C. Li, who reported an extremely high quantum efficiency
of 93% at 420 nm approaching the level of natural photo-
synthesis, while Pt and PdS were simultaneously deposited
on the surface of CdS particles to act as reduction and
oxidation co-catalysts respectively (Fig. 8).24,25 This effective
strategy to achieve high quantum yield by co-loading suit-
able dual co-catalysts will be of considerable importance in
the design and preparation of highly active photocatalysts
in the future.
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Fig. 8 (a) Apparent quantum yield at 420 nm of CdS, Pt/CdS, PdS/CdS and
Pt/PdS/CdS. (b) Charge transmission mechanism on Pt/PdS/CdS during photo-
catalytic reaction. Reprinted from ref. 24. Copyright (2009), with permission from
Elsevier.
All the above studies focus on the development of highly
efficient co-catalysts for the CdS photocatalyst, however, the
influences of crystal structure, crystallinity, defects and nano-
structure on the photocatalytic performance of CdS are also
worth unremittingly investigating. Matsumura et al. system-
atically studied the photocatalytic activities of CdS with
different crystal structures. Pt-loaded CdS powder having a
hexagonal crystal structure was found to be much more effi-
cient than that having a cubic crystal structure.26 Bao and
co-workers successfully tuned the crystal structure of CdS by a
simple cadmium–thiourea complex thermolysis route, and
further confirmed the superiority of hexagonal CdS in the
photocatalytic process.39 CdS photocatalysts with different
morphology, such as nanocrystals, nanowires and nanorods, were
also reported for the photocatalytic hydrogen production.36,38,43,160
The most interesting discovery was that CdS with special surface
nanosteps, synthesized through a novel thermal sulfuration
method by L. J. Guo and D. W. Jing, exhibited an apparent
quantum efficiency as high as 25% at 420 nm, and the nanostep
structure was found to be crucial for the remarkable enhance-
ment of photocatalytic hydrogen production, as the reaction
sites were successfully separated by this special structure
(Fig. 9).41 Then CdS powder with porous nanostructure, including
nanosheets and hollow nanorods, was prepared via a two-step
aqueous route by Bao et al. (Fig. 10). After 10 wt% Pt loading,
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Catalysis Science & Technology
Fig. 9 (a) SEM micrographs of CdS with surface nanostep structure. (b) Photo-
catalytic activities of as-prepared CdS photocatalysts. CdS-S-400 and CdS-S-300
were samples prepared by the thermal sulfuration method at different tempera-
tures. CdS-C was synthesized by a precipitation method, and CdS-N-400 repre-
sented CdS-C after thermal treatment at 400 1C under a N2 atmosphere. Reprinted
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D
with permission from ref. 41. Copyright 2006 American Chemical Society.
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Fig. 10 Photocatalytic activity of CdS with porous nanosturcture composed of
nanorods and nanosheets (a and b) and their formation mechanism (c). Reprinted
with permission from ref. 44. Copyright 2008 American Chemical Society.
a high quantum yield of about 60% was measured at 420 nm.
They attributed its high efficiency to the efficient charge
separation, fast transport of the photo-generated carriers, and
fast photochemical reaction at the CdS/electrolyte interface.44
Although CdS is the most often investigated sulphide photo-
catalyst for hydrogen production, there are still some existing
shortcomings such as photocorrosion and the need for noble
metal cocatalysts. Meanwhile, ZnS is a good candidate for photo-
catalytic water splitting, but its large band gap limits the range of
light response. Therefore, considering the similar crystal structures
of CdS and ZnS, much attention has been focused on making
Cd1xZnxS solid solutions in order to overcome the above
disadvantages.97,100,104,105,108,161,162 The important achieve-
ments in this subject will be mentioned in Section 7.
4. IIB–IIIA–VIA sulphide photocatalysts
ZnIn2S4, which is the most popular IIB–IIIA–VIA sulphide
semiconductor, always exhibits two distinct polymorphs based
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Fig. 11 Schematic diagram of hexagonal and cubic crystal structure ZnIn2S4.168
on cubic and hexagonal lattices as shown in Fig. 11. The
structure of cubic ZnIn2S4 can be described by an ABC stacking
of sulphur atoms, with Zn atoms tetrahedrally coordinated and
In atoms octahedrally coordinated by S atoms. The hexagonal
polymorph of ZnIn2S4 exhibits several different polytypes. The
structure of these polytypes is essentially based on stacking of
packets of S–Zn–S–In–S–In–S layers. Each packet could have an
ABCA stacking of sulphur atoms or an ABAB stacking of
sulphur atoms. In each packet containing zinc, indium and
sulphur, the zinc atoms are tetrahedrally coordinated by sulphur
atoms, the indium atoms of one layer are tetrahedrally coordi-
nated and those of the other layer are octahedrally coordinated
by sulphur atoms. The stacking of these packets also generates
a layer of vacancies between two weakly bonded sulphur
layers.120,163–165 Thus the solution coordination model (SCM)
was always proposed to explain the formation mechanism of
ZnIn2S4 with different crystal structures, since the coordination
of the ions formed in solution can serve as a template to retain
the same coordination mode in the solid.164,166,167
ZnIn2S4 possesses many distinct optical and photoelectrical
properties, and has attracted widespread attention since the
first report on its application in photocatalysis,111 due to the
suitable band gap in the visible region and substantial
chemical stability.124 Gou et al. synthesized ZnIn2S4 with
various morphologies including nanotubes, nanoribbons,
nanowires and microspheres by hydrothermal/solvothermal
methods, but they did not evaluate the photocatalytic
activities.167 Chen et al. synthesized flower-like ZnIn2S4 micro-
spheres with different crystal structures via a facile hydro-
thermal method by simply changing the metal precursors.
Both hexagonal and cubic ZnIn2S4 exhibited photocatalytic
activities for the degradation of MO, but the photocatalytic
performances over them were different.166 Then they per-
formed photocatalytic degradation of RhB and MO over hexa-
gonal ZnIn2S4 microspheres and cubic ZnIn2S4 nanoparticles.
Hexagonal ZnIn2S4 microspheres exhibited a higher photo-
catalytic activity in the degradation of RhB as compared to
cubic ZnIn2S4 nanoparticles, while a reverse phenomenon was
observed in the degradation of MO. It was concluded that the
exposed negative (0001) S plane which is composed of the
hexagonal ZnIn2S4 microspheres played an important role in
the adsorption of cationic dyes and accumulation of photo-
generated holes.169 Lei reported hydrothermal synthesis of
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ZnIn2S4 nanoparticles and examined the photocatalytic water
reduction performance under visible-light irradiation.111 Shen
and co-workers synthesized cubic and rhombohedral ZnIn2S4
by thermal sulfuration of a Zn–In mixed oxide precursor
at different temperatures. It was found that ZnIn2S4 with
rhombohedral structure photocatalyzed H2 evolution from
sacrificial agent solution efficiently, whereas cubic ZnIn2S4
was not active for this reaction.168 Thus the photocatalytic
activity for H2 evolution of ZnIn2S4 with cubic crystal structure
was rarely reported, whereas hexagonal ZnIn2S4, especially with
flower-like microsphere morphologies, has been intensively
studied in recent years. Guo’s group synthesized ZnIn2S4 micro-
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spheres via hydrothermal/solvothermal processes and investi-
gated their visible-light-driven photocatalytic H2 evolution
performances, and a proportional relationship between the
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d(006) space and quantum yields of the photocatalysts was
discovered (Fig. 12).114,116,118 Peng et al. reported that the
hydrothermal temperature and pH value had important effects
on the crystal structures, morphologies, optical properties and
photocatalytic activities of the ZnIn2S4 micropheres. Photo-
catalysts prepared at 160 1C and pH = 1.00 showed the highest
photocatalytic H2 production with an apparent quantum yield
of up to 34.3% at 420 nm.113
The ZnS–In2S3 system, which is reported to exist in various
modifications with the general formulation of ZnmIn2S3+m
(m = 1–5), is also a good candidate for photocatalytic hydrogen
production.120,163 ZnmIn2S3+m are formed by m layers of ZnS4
tetrahedra and a constant structural unit consisting of one layer
of indium atoms in octahedral voids, another layer of indium
atoms in tetrahedral voids, and a layer which is not occupied by
cations. Shen et al. synthesized ZnmIn2S3+m photocatalysts with
different m values by a simple hydrothermal method. The
morphology of ZnmIn2S3+m greatly depended on the atomic
ratio of Zn/In, while the absorption edges of ZnmIn2S3+m shifted
to a shorter wavelength as the atomic ratio of Zn/In in the
synthetic solution was increased (i.e. m increased from 1 to 5).
Fig. 12 SEM images of ZnIn2S4 prepared by the hydrothermal method (a and b).
Relationship between d(006) spaces and quantum yields of ZnIn2S4 for different
hydrothermal times (c) and with different CTAB amounts (d).114
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It was found that the Zn2In2S5 product had the highest photo-
catalytic activity under visible light among these ZnmIn2S3+m
photocatalysts, with the quantum yield at 420 nm determined
to be 11.1%.120
5. IB–IIIA–VIA sulphide photocatalysts
IB–IIIA–VIA (IB = Cu, Ag; IIIA = Al, In, Ga; VIA = S) ternary
sulphide semiconductors, with the general formulae of I–III–VI2
and I–III5–VI8, have been receiving considerable research and
industrial interest recently. These ternary semiconductors are
good photo-absorbers for solar cells and photoelectrochemical
cell (PEC) devices, because their energy band gaps lie between
0.8 and 2.0 eV.170–176 Especially, Cu–In–S and Ag–In–S are also
interesting photocatalyst materials, which have attracted much
attention because of their suitable band gaps for solar energy
conversion and capacities for H2 production.172 Fujishima et al.
investigated the photocatalytic activities of CuInS2 and CuIn5S8
for H2 evolution in sulphite aqueous solution almost twenty
years ago. The activity of CuIn5S8 was about twice that of CuInS2
and was improved remarkably by the addition of silver sul-
phide, which was attributed to the improvement of hole trans-
fer in the heterojunction of CuIn5S8 and Ag2S.177 Garskaite and
co-workers prepared transition metal doped CuInS2 films by a
chemical bath method. Sb-doped CuInS2 exhibited the maxi-
mum photocurrent density of 8.58 mA cm2, and the maxi-
mum hydrogen evolution of p-type Zn-doped CuInS2 films was
33.26 mL cm2.178 Xie’s group synthesized monodisperse
CuInS2 with hierarchical microarchitectures by a facile in situ
formed template solvothermal route. They found that a phase
conversion process from binary sulphide (CuS) to ternary
sulphide (CuInS2) played an important role in the formation
of the special morphology, which resulted in a much higher
average hydrogen yield of 59.4 mmol h1.129 Chen and Ye
reported AgIn5S8 as an excellent visible-light response photo-
catalyst in S2/SO32 aqueous solution for the first time, and H2
evolution could be observed even when the wavelength of the
cutoff filter was greater than 640 nm by this photocatalyst.130
Kudo et al. prepared layered metal sulphides AGa2In3S8 (A = Cu
or Ag) by a solid state reaction, both CuGa2In3S8 (1.91 eV) and
AgGa2In3S8 (2.27 eV) gave 15% apparent quantum yields at
560 nm and 460 nm for H2 evolution with the assistance of Rh
cocatalysts, respectively, and Rh/CuGa2In3S8 responded to
680 nm for the photocatalytic H2 evolution.133 They also prepared
visible-light active NaInS2 photocatalysts using a solid state
reaction, and a hydrogen evolution rate of 470 mmol h1 g1
was achieved under visible-light irradiation.179
Ternary semiconductors of the I–III–VI2 group always exist
as a chalcopyrite structure, which is composed of tetrahedral
units with four anions coordinated to a cation. Thus the unit
cell of the chalcopyrite type can approximately be regarded as
two unit cells of a zinc-blende type piled up along the c axis.137
It is known that ZnS with a zinc-blende structure has an
excellent ability to produce H2 under ultraviolet-light irradia-
tion, and is a good host material for the development of visible-
light-driven photocatalysts by making solid solutions with
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Fig. 13 (a) Photocatalytic H2 evolution over Ru/ZnS–AgInS2–CuInS2 solid
solution (black dot) and Pt/CdS (black circle). (b) Action spectrum of H2 evolution
over Ru/ZnS–AgInS2–CuInS2. A.Q.Y. = apparent quantum yield. K–M = diffuse
reflection spectra converted into absorbance by the K–M method. Reprinted with
permission from ref. 23. Copyright 2005 Wiley-VCH.
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other narrow band gap semiconductors.138 Therefore, alloyed
nanocrystals between chalcopyrite sulphide semiconductors
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and ZnS have been intensively investigated recently. Tsuji
et al. demonstrated that I–II–VI2/ZnS photocatalysts inherit an
outstanding capacity in hydrogen generation from aqueous
solutions containing sacrificial reagents under visible light
irradiation (Fig. 13).22,23,137–139 These solid solution photo-
catalysts showed high activities for H2 evolution, and the
highest H2 production rate was reported to be 8.2 L h1 m2.
Theory band structure calculation and the photophysical
analysis revealed that the visible-light-response should be
attributed to the contribution of Cu 3d and Ag 4d orbitals to
the valence band and that of In 5s5p orbitals to the conduction
band. Especially, the Zn 4s4p orbitals played an important role
in maintaining the conduction band energy level high enough
to reduce H2O.144
However, the synthesis method of I–II–VI2/ZnS photo-
catalysts was obviously not cost-effective and environmentally
friendly due to the use of H2S gas and thermal treatment at
high temperature. Thus, considerable efforts have been made
to develop a novel synthesis method for I–III–VI2/ZnS photo-
catalysts.140,180,181 Guo et al. reported the preparation of
(CuIn)xZn2(1x)S2 type solid solutions for all 0.01 o x o 0.5
values using a facile hydrothermal route with CTAB as a
surfactant. Particles obtained showed a spherical super-
structural morphology, and the CTAB helps to increase the
specific surface of the photocatalysts. After 1.5 wt% Ru-loading,
the photocatalyst presented the best activity for photocatalytic
H2 evolution with an energy conversion efficiency of 0.9% and
an apparent quantum yield of 15.45% at 420 nm.182 Chen’s
group achieved an extremely high photocatalytic activity on a
novel nanoporous ZnS–In2S3–Ag2S photocatalyst which was
prepared by a simple template-free hydrothermal method, even
in the absence of co-catalysts (Fig. 14).183,184 The apparent
quantum yield of ZnIn0.23Ag2xS1.345+x (x = 0.02 and 0.035)
nanostructures at 420 nm is 19.8% and 19.6%, respectively,
amongst the highest reported yields for semiconductor photo-
catalysts under visible light. Then they synthesized hierarchical
ZnS–In2S3–CuS nanospheres with nanoporous structure by a
similar method. An especially high photocatalytic activity
(an apparent yield of 22.6% at 420 nm) is achieved by unloaded
ZnIn0.25Cu0.02S1.395 because of its high crystallinity, large pore
volume and the special microstructure.185
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Fig. 14 (a) TEM images and EDX elemental mappings of novel nanoporous
ZnS–In2S3–Ag2S photocatalysts. (b) Photocatalytic activity of nanoporous ZnS–
In2S3–Ag2S without noble co-catalysts under visible-light. Reprinted with permis-
sion from ref. 183. Copyright 2009 The Royal Society of Chemistry.
6. IB–IIB–IVA–VIA sulphide photocatalysts
Stannite-type I2–II–IV–VI4 (I = Cu and Ag, II = Zn, IV = Sn and
Ge, VI = S) compounds are quaternary complex sulphides whose
crystal structures are similar to a zinc-blende structure of ZnS
and a chalcopyrite structure of CuInS2. Each metal cation is
tetrahedrally coordinated by four sulfur anions. The structures
of Cu2ZnSnS4 and Cu2ZnGeS4 containing Cu as a monovalent
ion have been investigated in detail. There are alternating
cation layers of mixed Zn and IVA atoms, which are separated
from each other by layers of Cu atoms.186 These semiconductors
can be obtained by replacing half of the In atoms in CuInS2
with Zn, and by replacing the other half with Sn or Ge. Since the
abundance of Zn and Sn is much larger than that of In, this
compound has been studied extensively as one of the most
promising alternatives for an absorber of thin film solar cells,
and recently conversion efficiency of the Cu2ZnSnS4-based solar
cell has reached over 6.7%.187 Kudo’s group has aimed at these
quaternary complex sulphides as new visible-light-driven
photocatalysts, because the constituting elements such as Cu,
Ag and Zn could contribute to the valence and conduction band
formation (Fig. 15).144 They synthesized quaternary stannite-
type complex sulphides by a solid state reaction method similar
to the preparation of ZnS–AgInS2–CuInS2, and Ru cocatalyst-
loaded Cu2ZnGeS4, Ag2ZnGeS4 and Ag2ZnSnS4 showed high
activities for photocatalytic H2 evolution from an aqueous
Na2S–K2SO3 solution under visible-light irradiation. Especially
the CuAgZnSnS4 photocatalyst possessed a band gap of about
Fig. 15 Band structure of stannite-type I2–II–IV–VI4 (I = Cu and Ag, II = Zn, IV =
Sn and Ge, VI = S) compounds. Reprinted with permission from ref. 144. Copy-
right 2010 The Royal Society of Chemistry.
Catal. Sci. Technol.

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1.4 eV which could utilize a wide range of visible light. As the
crystal structures of the stannite-type complex sulphides are
similar to those of photocatalysts with zinc-blende-type and
wurtzite-type structures, such as CdS, ZnS and ZnS–AgInS2–
CuInS2, they have also tried to make solid solutions of
Cu2ZnSnS4, Ag2ZnSnS4 and ZnS. The incorporation of ZnS
samples gave an upward shift of conduction band edges,
whereas the presence of Ag2ZnSnS4 in the solid solution might
make them possess n-type conductivity, leading to efficient
migration of photogenerated electrons to the surface to induce
water reduction into H2.143
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7. Highly efficient Cd1xZnxS photocatalysts
As is known, the ultimate goal of photocatalytic water splitting
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is to meet the practical energy demand of human beings, the
key issue of which is to develop highly efficient and low cost
photocatalysts with excellent sunlight responses. Cd1xZnxS,
which is the solid solution of CdS and ZnS, has attracted lots of
attention in recent years, due to the controllable band structure
and excellent performance in photocatalytic hydrogen produc-
tion under visible light irradiation, especially in the absence of
noble metal co-catalysts. Systematic investigation of the devel-
opment of highly efficient Cd1xZnxS should be highly evalu-
ated from the standpoints of both theoretical research and
industrial application. However, the photocatalytic activity of
the Cd1xZnxS photocatalyst is still far from the fundamental
requirement of practical application. Thus in order to signifi-
cantly improve the photocatalytic efficiency, development of
novel approaches for the modification of the Cd1xZnxS photo-
catalyst is highly desired.
7.1. Seeking for novel synthesis methods
Many methods have been explored to fabricate Cd1xZnxS solid
solution, such as coprecipitation,92 micro-emulsion,188 hydro-
thermal/solvothermal,91,189 and decomposition of molecular
precursors.190 Recently, Xing et al. synthesized Cd1xZnxS solid
solutions via simple co-precipitation followed by heat treat-
ment under a N2 atmosphere, and a quantum efficiency of
2.17% and 0.60% was obtained using Cd0.62Zn0.16S under
ultraviolet and visible light irradiation, respectively.88 Villoria
and co-workers systematically investigated the influence of
thermal treatment on the photocatalytic activity of Cd1xZnxS.
They found that elemental losses upon heat treatment caused
the change in the composition and the appearance of defects
in the crystalline structure of the Cd1xZnxS solid solutions,
thus intensively affecting the photocatalytic performance for
hydrogen production.191 Guo’s group applied a novel thermal
sulfuration method for the preparation of Cd1xZnxS for the
first time, Cd0.8Zn0.2S exhibited the highest photocatalytic
activity and a high apparent quantum yield of 10.23% at
420 nm without needing the deposition of noble metal cocata-
lysts, which was also the highest efficiency of non-loaded
photocatalysts at that time. Comparative studies showed
that the sulphide photocatalyst prepared by thermal sulfura-
tion has a much higher activity than that prepared by
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conventional methods, which is attributed in part to its
better crystallinity and more importantly to the existence of a
charge gradient due to the uneven distribution of anionic S2,
which promotes the charge separation of e–h+ pairs and
avoids their recombination in the bulk of the semiconductor,
leading to significantly improved photocatalytic hydrogen
production.90
7.2. Transition or alkaline metal ions doping
7.2.1. Transition metal doping. Although Cd1xZnxS can
successfully overcome the shortcomings of photocorrosion
from CdS and a wide band gap of ZnS, the band gap of this
solid solution is still larger than the ideal value (1.8 eV), which
thus limits the utilization of the solar spectrum for hydrogen
evolution. Therefore doping of Cd1xZnxS solid solution with
various metal ions has been intensively studied recently, such
as Cu,94 Ni192,193 and Sn194, which can enhance the visible light
response by forming impurity levels in the forbidden band. Liu
et al. synthesized a Cu doped Cd0.1Zn0.9S photocatalyst by a
coprecipitation method, and an apparent quantum yield of
about 9.6% at 420 nm was achieved by the Cd0.1Cu0.01Zn0.89S
photocatalyst without cocatalysts.195,196 Xu and co-workers
reported a novel solid solution of Zn0.95Cu0.05S and CdS with
a cubic structure, as shown in Fig. 16. The solid solution
sample (Zn0.95Cu0.05)1xCdxS with x = 0.33 gave the highest
H2 production rate, and the apparent quantum efficiencies
obtained were 15.7% and 31.8% for the samples without and
with Pt, respectively. It was concluded that the Zn and Cd
contributed to obtain a proper band gap while maintaining a
relatively high conduction band potential, and Cu2+ impurity
levels in the forbidden band could accommodate the photo-
generated charge carriers and thus increased the photocatalytic
activity.197 Recently, they synthesized Cu–Cd–Zn sulphide
nanospheres with controlled copper locations by a two-step
solvothermal method. It was found that the activity of the
sample with copper only on the surface shell is about two times
of that with copper only in the core, but the highest hydrogen
production rate was obtained on the nanosphere sample with
copper both in the core and on the surface shell.198
7.2.2. Alkaline metals doping. However, although transi-
tion metal ions doping significantly enhances the visible light
Fig. 16 (a) UV-vis absorption spectra of (Zn0.95Cu0.05)1xCdxS. (a–g) represent
samples with different x values (0, 0.17, 0.27, 0.33, 0.50, 0.67, 1). (b) Band
structures of CdS, Zn0.95Cu0.05S and (Zn0.95Cu0.05)1xCdxS. Reprinted with permis-
sion from ref. 197. Copyright 2009 American Chemical Society.
This journal is c The Royal Society of Chemistry 2013

Catalysis Science & Technology
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D
Fig. 17 Dependence of photocatalytic activity for H2 evolution and PL emission
intensity over Sr-doped CdS–ZnS solid solutions. The Zn atomic ratios were
Downloaded by University of Queensland on 24/04/2013 07:43:45.
(a) 20%, (b) 33%, and (c) 80%. The movement trend of the photoluminescence
intensity was almost opposite to that of photocatalytic activity.109
response of photocatalysts with wide band gaps, this modifica-
tion strategy seems to be not suitable for Cd1xZnxS with
narrow band gaps. Alkaline metal ions doping has been proved
to be a good modification strategy for oxide semiconductor
photocatalysts with no influence on their band structure,199–202
but there are still no reports on the influences of alkaline metal
ions doping on the photocatalytic properties of sulphide photo-
catalysts. Guo’s group has performed alkaline metal ions
doping for the modification of Cd1xZnxS (Fig. 17). They found
that Sr atoms could not be incorporated into the bulk phase by
the coprecipitation method due to their bigger atomic size,
and preferred to exist on the surface or near the surface of
Cd1xZnxS nanocrystals, which efficiently suppressed the
recombination of photogenerated electrons and holes and
dramatically enhanced the photocatalytic activities of these
photocatalysts. It was suggested that Sr atoms existing on the
surface of Cd1xZnxS photocatalysts could act as trapping
centers for photo-induced electrons and holes, thus efficiently
improving the separation and migration of carriers and
resulting in higher photocatalytic activities.109 In order to
further improve the photocatalytic activity of Cd0.8Zn0.2S photo-
catalysts, they tried to combine alkaline metal doping with the
thermal sulfuration method, which were both proved to be
beneficial for sulphide modification (Fig. 18). Due to the bigger
atomic size of Ba than Cd and Zn, surface Ba doping resulted in
a significant change in metal element space distribution. It was
suggested that the decrease of Zn concentration from the bulk
phase to the surface could provide a favorable driving force for
the migration of electrons, and be beneficial for the photo-
catalytic reaction. Although Ba doping would not influence the
light absorption property, it could induce transition of band
structure from the direct to the indirect type and a significant
increase in density of states at the top of the valence band,
which were favorable for the migration of photo-induced
carriers. As a result, Ba-doped Cd0.8Zn0.2S photocatalysts exhi-
bited much more improved photocatalytic activities, and the
This journal is c The Royal Society of Chemistry 2013
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Minireview
Fig. 18 Schematic illustration of the charge separation mechanism for Ba(x)–
Cd0.8Zn0.2S. The decrease of Zn concentration from the bulk phase to the surface
provides a favorable driving force for the migration of electrons, and surface Ba
doping is also favorable for the migration of photo-induced carriers.110
highest photocatalytic activity was about 1.1 times higher than
that of Cd0.8Zn0.2S, with an apparent quantum yield of 17.4% at
425 nm and an energy conversion efficiency of 0.54% in the
range of 420–760 nm.110 Alkaline metal ions doping is expected
to provide guidelines for the exploration of new active sulphide
photocatalysts.
7.3. Constructing special nano-structure
As is known, point defects in semiconductors, such as vacan-
cies and interstitial atoms, always act as recombination centres
for photogenerated electrons and holes in photocatalytic water
splitting. However, the role of planar defects in photocatalysis
has been rarely reported up to now. II–VI group semiconductors
have been extensively reported to exist as zinc-blende or
wurtzite crystal structure (Fig. 5). The zinc-blende structure
can be pictured as two interpenetrating cubic-close-packed
lattices, one of which has been translated in the [111] direction
pffiffiffi
through a distance 3ac =4, where ac is the cubic lattice
constant. Wurtzite is composed of two interpenetrating hexa-
gonal-close-packed lattices, one of which has been translated in
the [0001] direction through a distance 3c/8, where c is the
height of the hexagonal unit cell.145,203 Obviously, zinc blende
and wurtzite will match perfectly in the [111-0001] direction if
pffiffiffi
the value of c is equal to 2 3ac =3. Thus it is reasonable that ZnS
and CdS show many polytypes consisting of periodically
arranged WZ and ZB layers along the [111-0001] direction.
Especially, single crystals of ZnS or CdS sometimes show planar
defects, such as stacking faults and twinning, with the WZ/ZB
interface along the [111-0001] direction.204
Consequently, Liu et al. introduced nano-twin structure into
Cd1xZnxS for the first time by a one pot precipitation–
hydrothermal method. These as-prepared samples exhibited
superior photocatalytic activities for H2 evolution from water
under visible light irradiation without noble metal co-catalysts,
especially Cd0.5Zn0.5S nanocrystals show the highest activity for
hydrogen evolution with an extremely high apparent quantum
yield (AQY = 43%) at 425 nm, achieving a hydrogen evolution
rate of 1.79 mmol h1 without noble metals.89 It was suggested
that the ‘‘back to back’’ potential formed by parallel nano-twins
Catal. Sci. Technol.

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Fig. 19 The migration of free charges over nano-twin Cd0.5Zn0.5S–PH crystals.
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D
Reprinted with permission from ref. 89. Copyright 2011 The Royal Society of
Chemistry.
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in the Cd1xZnxS crystals can significantly improve the separation
of the photogenerated electrons–holes (preventing their recombi-
nation) thus enhancing the photocatalytic activity (Fig. 19).
Noble metals were selectively photo-deposited at central regions
between the twin boundaries, which further confirmed such a
mechanism.
Recently, we developed a novel two step synthesis method
for sulphide photocatalysts, which consisted of ultrasonic
assisted co-precipitation and solvothermal processes. ZnS and
Cd1xZnxS were present in the form of separated nano-particles
in composite photocatalysts, and there were lots of defects in
Cd1xZnxS nano-particles, especially repetitive stacking faults.
The highest apparent quantum yield was calculated to be 48.7%
at 425 nm, which was much higher than the other non-loaded
photocatalysts reported up to now. Comparative studies suggested
that there was no synergistic effect between ZnS and Cd1xZnxS,
and the efficient photocatalytic activity was due to the efficient
separation and migration of photo-induced electrons and holes in
Cd1xZnxS nanoparticles, which originated from the special
stacking faults. We suggest that the anomalous photovoltaic
effect plays an important role in the photocatalytic process. The
changes in structure from cubic to hexagonal induced by
stacking faults lead to a significant difference in electrostatic
potential around the structure interface, and efficiently separate
the photo-induced electrons and holes, thus resulting in the
extremely high photocatalytic activity.205–208 These interesting
findings will be published in international journals later.
Apparently, the efficient charge separation ability of planar
defects (stacking faults and twinning) provides a novel modi-
fication idea for semiconductor development. If we could
manually control the distribution of stacking faults and twinning
in the future, photocatalysts with a much higher photocatalytic
efficiency might be obtained.
7.4. Development of low-cost co-catalysts
Noble metal loading has been widely used to enhance the
separation of photogenerated charges in photocatalytic water
splitting. However, it is not acceptable to use these noble
metals of quite high cost from the viewpoint of practical
application, and therefore development of novel low-cost
Catal. Sci. Technol.
View Article Online
Catalysis Science & Technology
Fig. 20 Schematic illustration of charge transfer and separation in the RGO–
Zn0.8Cd0.2S. Reprinted with permission from ref. 102. Copyright 2012 American
Chemical Society.
co-catalysts is also a key issue in the present stage. Thus lots
of efforts have been made to design novel co-catalysts to further
improve the photocatalytic efficiency of Cd1xZnxS.101,209
Carbon materials, such as carbon nanotubes (CNT) and
graphene, have attracted considerable attention because of
their special structure, large specific area, extraordinary mecha-
nical and unique electronic properties and their wide range of
potential applications. In particular, they have a large electron-
storage capacity, and exhibit metallic conductivity similar to
metals.210,211 Thus it is believed that carbon nanotubes and
graphene could be excellent cocatalysts for semiconductor
photocatalysts. Yu and co-workers have systematically investi-
gated the influences of carbon nanotubes and reduced graphene
oxide (RGO) on the photocatalytic activities of Cd1xZnxS solid
solutions (Fig. 20).98,102 They found that CNT content had a
great influence on the photocatalytic activity, and an optimum
amount of CNT was determined to be ca. 0.25 wt%, at which the
CNT–Cd0.1Zn0.9S displayed the highest photocatalytic activity
under visible light, giving an H2-production rate of 78.2 mmol h1
with an apparent quantum efficiency (QE) of 7.9% at 420 nm.
Moreover, the optimized RGO–Zn0.8Cd0.2S photocatalyst has a
high H2-production rate of 1824 mmol h1 g1 at the RGO
content of 0.25 wt% and the apparent quantum efficiency of
23.4% at 420 nm (the energy conversion efficiency is ca. 0.36%
at simulated one-sun (AM 1.5 G) illumination). These results
exhibit significantly improved photocatalytic hydrogen produc-
tion, and are better than that of the optimized Pt–Zn0.8Cd0.2S
under the same reaction conditions. The enhanced photo-
catalytic activity was due to CNT and RGO as excellent electron
acceptors and transporters, thus reducing the recombination of
charge carriers and enhancing the photocatalytic activity.
Furthermore, the prepared samples were photostable and no
photocorrosion was observed after photocatalytic recycling.
These studies show not only the possibility of utilizing low cost
carbon materials as a substitute for noble metals (such as Pt) in
the photocatalytic H2-production but also a significant enhance-
ment in the H2-production activity using metal-free carbon
materials as effective co-catalysts.
8. Conclusion and perspective
We selectively summarize the main achievements of sulphide
semiconductor materials in the field of photocatalytic hydrogen
production in this paper. It is encouraging that the photocatalytic
This journal is c The Royal Society of Chemistry 2013

Catalysis Science & Technology
efficiencies of sulphide photocatalysts have been tremendously
improved during the past several decades, while significant
scientific and technological knowledge has already been accu-
mulated by researchers all around the world. However, there
are still many issues and challenges remaining in this area.
8.1. Enhancement of hydrogen production efficiency
For an ideal photocatalyst suitable for industrial application, high
photocatalytic efficiency in combination with excellent solar spec-
trum response should be achieved. Thus development of excellent
sulphide photocatalysts requires narrowing the band gaps and
enhancing the separation of photogenerated charges simulta-
Published on 19 February 2013 on http://pubs.rsc.org | doi:10.1039/C3CY00018D
neously. Sulphide semiconductors always possess excellent solar
spectrum responses. Moreover, promising strategies such as
doping foreign elements and making solid solution of wide band
Downloaded by University of Queensland on 24/04/2013 07:43:45.
gap and narrow band gap sulphide semiconductors have been
widely applied for the modification of band gaps, and the light
absorption edge of sulphides can be readily extended to nearly
800 nm. Thus at the present stage the key issue of development
of efficient sulphide photocatalysts lies in the enhancement of
hydrogen production efficiency. As is known, the behaviour of
photogenerated electrons and holes is crucial for the photo-
catalytic process, and could be affected by many factors, such as
crystallinity, crystal structure, surface states, defects and morpho-
logy. However, there is still a serious lack of deep and systematic
investigations on these factors as well as their interrelationship.
Thus intensive investigations should be carried out in the future,
in order to provide scientific references for maximizing the
photocatalytic efficiencies of sulphide semiconductors.
8.2. Cost reduction of sulphide photocatalysts
Noble metal loading on the surface of sulphide photocatalysts
as co-catalysts is a useful way to accelerate the separation of
photogenerated charges. For example, Pt and PdS working as
dual-cocatalysts on CdS have been proved to be very effective for
the improvement of photocatalytic activity. However, it is not
desirable to use these noble metals of quite high cost from the
viewpoint of industrial application. Therefore it is necessary to
develop novel photocatalysts with low cost that could efficiently
utilize the solar spectrum (both the ultraviolet region and the
visible light region). Transition metal sulphides have been
reported recently to be excellent co-catalysts for H2 evolution
on sulphide photocatalyst systems, which provides a clue in the
search for novel low cost sulphide photocatalysts. Furthermore,
design of highly efficient sulphide photocatalysts without noble
metal cocatalysts is also highly desired from the standpoint of
practical application. Thus, highly efficient sulphide photo-
catalysts, which exhibit excellent photocatalytic properties with-
out noble metal co-catalysts, have attracted much attention in
recent years, such as Cd1xZnxS, ZnS–In2S3–Ag2S. Especially,
the Cd1xZnxS solid solution photocatalyst has been studied
extensively due to its controllable band structure and excellent
performance in photocatalytic hydrogen production under
visible light irradiation. Many efforts have been made to
improve the photocatalytic activity of Cd1xZnxS, but it is still
far from the requirement of practical application.
This journal is c The Royal Society of Chemistry 2013
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8.3. Strengthening stabilities of sulphide photocatalysts
Sulphide photocatalysts always suffer from photocorrosion during
the photocatalytic process. Therefore sacrificial agents are needed
to prevent the anodic photocorrosion by providing sacrificial
electron donors to consume the photogenerated holes. However,
using sacrificial reagents cannot be the ultimate solution for
the stability enhancement of sulphide photocatalysts. Recently,
incorporating sulphide semiconductors into the interlayers of
oxide materials with layered structure or the mesopores of
molecular sieves has been extensively investigated.42,212 The
composite photocatalysts always result in much more improved
resistance to photocorrosion. Apparently, it reveals a novel
modification strategy for sulphide photocatalysts, but satisfactory
photocatalytic efficiency has not been achieved until now.
8.4. Developing scale-up devices
The lack of extensive studies for a successful scale-up of the
laboratory setup into an industrially relevant scale is another
issue for photocatalytic hydrogen production. To directly utilize
solar light in the open air, a compound parabolic concentrator
(CPC)-based photocatalytic hydrogen production reactor was
recently designed by Jing et al.213–215 Efficient photocatalytic
hydrogen production under direct solar light was accomplished
by coupling a tubular reactor with the CPC concentrator. This
demonstration drew attention for further studies in this pro-
mising direction. Nevertheless, both for material and reactor
design, reduction of cost will have to be given special priority,
before the final utilization for semiconductor-based photo-
catalytic hydrogen generation.
Acknowledgements
The authors gratefully acknowledge the financial support from the
National Natural Science Foundation of China (No. 51121092) and
National Basic Research Program of China (No. 2009CB220000).
The authors also thank Mr Xixi Wang and Dr Dengwei Jing in Xi’an
Jiaotong University for assistance in editing the manuscript.
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