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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Energy Mater. 2012, 2, 4246
Dr. X. W. Wang, Dr. G. Liu, Prof. H.-M. Cheng
Shenyang National Laboratory for Materials Science
Institute of Metal Research
Chinese Academy of Sciences
72# Wenhua Road, Shenyang 110016, P.R. China
E-mail: cheng@imr.ac.cn
Dr. X. W. Wang, Prof. L. Z. Wang, Dr. Z.-G. Chen, Prof. G. Q. (Max) Lu
ARC Centre of Excellence for Functional Nanomaterials
Australian Institute of Bioengineering and Nanotechnology
School of Chemical Engineering
School of Mechanical & Mining Engineering
The University of Queensland
QLD 4072, Australia
E-mail: maxlu@uq.edu.au
DOI: 10.1002/aenm.201100528
Photocatalytic hydrogen generation from water on semicon-
ductors has attracted increasing attention in the past four dec-
ades.
[15]
Among the photocatalysts developed for hydrogen
evolution, multicomponent photocatalysts with extended light
absorption and improved photoreactivity as a result of the com-
bined properties of each component are more attractive than
single-phase photocatalysts.
[69]
However, transport processes
of photoexcited charge carriers become more complex in such
a heterostructure, where the transport occurs not only in the
bulk and on the surface of each component
[1013]
but also at
the interfaces. The latter actually plays a key role in improving
photocatalytic activity.
[8,9,14,15]
Pt-loaded CdS for photocatalytic
hydrogen evolution has been widely studied since the 1980s,
[16
18]
ZnOCdS heterostructures with enhanced photocatalytic
hydrogen evolution have been developed via a direct Z-scheme
mechanism,
[8]
where the recombination of photo excited
electrons from the ZnO conduction band and holes from
the CdS valence band occurs at the interface.
[8,19]
Therefore, a
good effective charge carrier transport at the interface is nec-
essary. However, the photoexcited carrier transport process at
the interface between ZnO and CdS is poor because of surface
relaxation and recombination of charge carriers within each
component. Therefore, design of a new structure with some
pathways for charge carriers to be transported quickly at the
interface is highly desired.
Due to the excellent electronic conductivity of metals,
semiconductormetal systems have been widely attempted to
improve the efciency of photocatalytic reactions by the transfer
of photoexcited charge carriers from the semiconductor to the
metal.
[2023]
Compared to metals deposited on semiconductors
that suffer from corrosion and oxidation during the photocata-
lytic reaction,
[20,21]
a metal core enclosed by a semiconductor
shell can have a high stability for retaining the charge-carrier
separation over a long time.
[2224]
Therefore, a high efciency
charge-carrier transport can be achieved by introducing a metal
at the interface of two semiconductors. For example, Tada et
al.
[14]
demonstrated the important role of a nanosized Au core
located in a TiO
2
AuCdS semiconductormetalsemicon-
ductor heterostructure in promoting the recombination of pho-
toexcited electrons from TiO
2
with holes from CdS.
In this study, we develop a new type of heterostructure by
introducing a metal Cd core to improve photoexcited carrier
transport at the interface of a ZnOCdS heterostructure. The
ZnOCdS@Cd structure consists of a metal Cd core and a
ZnOCdS shell, where the CdS shell is directly grown on a Cd
core and ZnO nanoparticles as islands are embedded in the
CdS shell. The Pt nanoparticle loaded ZnOCdS@Cd exhibits a
photocatalytic hydrogen evolution rate as high as 1.92 mmol h
1

(100 mg), which is 5.1 times that of a Pt-loaded ZnOCdS het-
erostructure (0.38 mmol h
1
).
The preparation process of ZnOCdS@Cd heterostructure
involves two main steps: the formation of Cd in the core, and
CdS growth on the surface, as shown schematically in Figure 1.
The morphology of the precursor Zn powder is spherical with
a diameter less than 10 m as shown in Figure 2a,b. Several
minor X-ray diffraction (XRD) peaks in Figure 2c, in addition
to the dominant peaks of Zn powder, can be assigned to hex-
agonal ZnO because of a ZnO shell formed by the oxidation of
the exposed Zn surface. To further demonstrate the existence
of the ZnO shell on the Zn core, the spheres were irradiated
with a focused electron beam. As shown in Figure 2d,e, metal
Zn can be easily evaporated from the interior and a ZnO thin
shell remained. The thin and loose ZnO shell does not prohibit
the penetration of Cd
2+
ions to react with Zn atoms in the core.
Finally, a Cd core was formed as shown in Figure 3. Further-
more, with a strong ultrasonic treatment, the replacing process
becomes easier and more complete. After full treatment, Zn
spheres were replaced (shown in Figure 1 and Figure 3a,b). An
XRD pattern (Supporting Information (SI), Figure S1) of the
product conrms that these rods consist of dominant Cd and
minor ZnO phases. The ZnO shell was broken and became
nanoparticles with metal Cd growth in the replacement process.
From both the Energy Disperse X-ray spectroscopy (EDX) pro-
les of Zn and O elements in Figure 3e and XRD patterns of
CdZnO rods in SI, Figure S1, we conclude that ZnO nanoparti-
cles are distributed on the surface of the Cd rods (Figure 3b). Fur-
thermore, a high-resolution transmission electron microscope
(TEM) image of a ZnO nanoparticle on the Cd rod surface is
shown in SI, Figure S2c. The EDX signal intensity for elemental
Zn changes at different points (SI, Figure S2df), indicating that
Xuewen Wang, Gang Liu, Lianzhou Wang, Zhi-Gang Chen, Gao Qing (Max) Lu,*
and Hui-Ming Cheng*
ZnOCdS@Cd Heterostructure for Effective Photocatalytic
Hydrogen Generation
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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Energy Mater. 2012, 2, 4246
The intimate contact between the shell and the core is con-
rmed in a magnied image of the interface in the ZnOCdS@
Cd heterostructure (Figure 4d). Based on the above results, it is
concluded that the heterostructure consists of a metal Cd core
and a CdS shell with dispersed, embedded ZnO nanoparticles.
The absorption range of the rodlike ZnOCdS@Cd heter-
ostructures after the sulfurization in a Na
2
S aqueous solution
for 24 h is extended from 390 to 570 nm compared to those
of the Zn powder and CdZnO rods as a result of the forma-
tion of a CdS shell on the Cd surface (SI, Figure S4). The thick-
ness of the CdS shell gradually increases with the increase in
sulfurization time until the shell becomes completely compact.
The photocatalytic hydrogen evolution rates of ZnOCdS@Cd
heterostructures with different sulfurization-time are given in
the ZnO nanoparticles are distributed as isolated islands instead
of a continuous shell. This is also in good accordance with the
scanning electron microscope (SEM) and TEM results.
The rodlike ZnOCdS@Cd heterostructure is formed by sul-
furization of the CdZnO heterostructures in a Na
2
S aqueous
solution. The effective formation of CdS in the heterostructures
is validated by the appearance of CdS diffraction peaks in the
XRD patterns (SI, Figure S3) and the elemental sulphur signal
in the EDX prole (See in Figure 3f). TEM images of the ZnO
CdS@Cd heterostructure are shown in Figure 4. Some nanopil-
lars with a diameter of less than 10 nm are distributed on the
coarse surfaces (Figure 4b). Seen from the obvious contrast
change between the ZnOCdS shell and the Cd core in Figure 4c,
the average thickness of the ZnOCdS shell is around 15 nm.
Figure 2. a) Low- and b) high-magnication SEM images of the Zn spheres used; c) XRD pattern and d) TEM image of the Zn spheres; e) TEM image
of the Zn spheres after bombardment with a focused electron beam in the microscope.
Figure 1. Scheme of the preparation process of a ZnOCdS@Cd heterostructure with two steps: replacement and sulfurization reactions.
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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Energy Mater. 2012, 2, 4246
(100 mg) when the sulfurization time is over 24 h, which is much
higher than that of CdS (0.012 mmol h
1
) prepared by a solution
method. Based on the analysis by inductively coupled plasma
(ICP), the composition ratio in the ZnOCdS@Cd heterostruc-
ture sulfurized for 24 h is n
Cd
:n
CdS
:n
ZnO
= 83.81:10.55:5.64.
Sulfurization in a Na
2
S aqueous solution does not cause the
CdS shell to grow continuously with increasing time. There-
fore, H
2
S gas as a sulfur source, which can rapidly and com-
pletely convert Cd to CdS, was used to sulfurize the Cd surface
to form a CdS shell. The ZnOCdS@Cd heterostructure with
a thick CdS shell sulfurized by a H
2
S for a long time exhibits
much lower photocatalytic hydrogen evolution rate compared to
that of the aforementioned ZnOCdS@Cd prepared in a Na
2
S
aqueous solution. The co-operation between ZnO and CdS
acting as oxidation and reduction sites in a ZnOCdS heter-
ostructural shell, will disappear due to the fact that ZnO nano-
particles on the Cd rod are buried in the thick CdS shell during
the H
2
S sulfurization process.
Cocatalysts can effectively collect photoexcited electrons/
holes as reduction/oxidation sites to promote the separation
of photoexcited electrons and holes.
[2527]
The noble metal Pt
widely used on sulde compounds
[10,11,27]
is also suitable for
ZnOCdS heterostructures.
[8]
The photocatalytic hydrogen
evolution rates on the ZnOCdS@Cd heterostructures can
be remarkably improved by loading with a Pt cocatalyst as
shown in Table 2. The optimal load content of 3 wt% leads to a
Table 1. It is clear that the hydrogen evolution increases slightly
with increasing sulfurization time from 0.5 to 24 h. The highest
photocatalytic hydrogen evolution rate is around 0.6 mmol h
1

Table 2. Photocatalytic hydrogen evolution rate of the ZnOCdS@Cd
heterostructures loaded by different contents of Pt nanoparticles.
Serial Number Samples Pt Co-catalyst Hydrogen Evolution
[mmol h
1
]
a)
(a) ZnOCdS@Cd 0 0.61
(b) ZnOCdS@Cd 1 wt% 1.18
(c) ZnOCdS@Cd 2 wt% 1.31
(d) ZnOCdS@Cd 3 wt% 1.92
(e) ZnOCdS@Cd 5 wt% 1.42
(f ) ZnOCdS@Cd 8 wt% 1.17
a)
Photocatalytic hydrogen evolution conditions: 100 mg sample; 300 W Xe lamp;
300 mL aqueous solution containing 0.1 M Na
2
S and 0.1 M Na
2
SO
3
.
Figure 3. a,b) SEM images of CdZnO rods via replacing the Zn atoms of
ZnO spheres with Cd
2+
ions; c,d), SEM images of the ZnOCdS@Cd het-
erostructure after sulfurization in a Na
2
S aqueous solution for 24 h; e,f )
EDX proles of the CdZnO rods and ZnOCdS@Cd heterostructure.
Figure 4. a) TEM image of the ZnOCdS@Cd heterostructure rods;
b) TEM image of a localized region of a rod; c,d) high-resolution TEM
images of the interface between the Cd core and the ZnOCdS shell of
the ZnOCdS@Cd heterostructure.
Table 1. Photocatalytic hydrogen evolution rate of the ZnOCdS@Cd
heterostructures treated in a Na
2
S aqueous solution for different time.
Serial Number Samples Sulfurization Time
[h]
Hydrogen Evolution
[mmol h
1
]
a)
(a) ZnOCdS@Cd 0.5 0.52
(b) ZnOCdS@Cd 1 0.52
(c) ZnOCdS@Cd 5 0.56
(d) ZnOCdS@Cd 10 0.58
(e) ZnOCdS@Cd 24 0.61
(f ) ZnOCdS@Cd 48 0.60
a)
Photocatalytic hydrogen evolution conditions: 100 mg sample; 300 W Xe lamp;
300 mL aqueous solution containing 0.1 M Na
2
S and 0.1 M Na
2
SO
3
.
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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Energy Mater. 2012, 2, 4246
band (VB) of CdS is a key step to prolong the lifetime of the
photoexcited electrons on the CB of CdS and the holes from
the VB of ZnO.
[8]
In the ZnOCdS@Cd heterostructure, the
presence of a metal Cd core as an effective channel is cer-
tainly benecial for such recombination (shown in Figure 6).
Then, photocatalytic reduction and oxidation reactions pro-
ceed on the CdS and ZnO, respectively, which is similar to
that on TiO
2
-Au-CdS.
[14]
2) The thickness of the ZnOCdS heterostructural shell is ca.
15 nm so that the diffusion length of charge-carrier transport
in the ZnOCdS@Cd heterostructure can be greatly short-
ened to reduce bulk combination in the ZnO or CdS.
In summary, a ZnOCdS@Cd heterostructure consisting
of a metal Cd core and a ZnOCdS heterostructural shell was
prepared, where ZnO nanoparticles are embedded in the CdS
shell. The stable photocatalytic hydrogen evolution rate on the
ZnOCdS@Cd heterostructure is 0.61 mmol h
1
(100 mg).
After loading with 3 wt% Pt cocatalyst, the hydrogen evolu-
tion rate reaches 1.92 mmol h
1
. The metal Cd core provides
an efcient charge-carrier transport channel for improving the
recombination of photoexcited electrons from ZnO and holes
from CdS based on the Z-scheme co-operation. The shortened
charge-carrier transport length in the thin ZnOCdS heter-
ostructural shell also contributes to the improvement of photo-
catalytic hydrogen evolution.
Experimental Section
Sample Preparation: Commercial Zn powder with a thin ZnO
shell (100 mg) was added to a aqueous solution (50 mL) containing
CdCl
2
2H
2
O (500 mg). The mixed solution was ultrasonically treated
for 10 min and stirred for 30 min so that Zn atoms were replaced by
Cd ions. The resultant CdZnO deposit after fully washing was then
transferred to aqueous solution (30 mL) with Na
2
S9H
2
O (3 g), and
was stirred for different times (0.5 h, 1 h, 5 h, 12 h, 24 h or 48 h)
to prepare the ZnOCdS@Cd. Prior to drying at 100 C for 24 h, the
deposit was fully washed. To improve the sulfurization of CdS, we
further treated the ZnOCdS@Cd in a H
2
S atmosphere (25 mL min
1
)
at 200 C for 1 h.
Pt Co-catalyst Loading Process: The loading of Pt nanoparticles on
ZnOCdS@Cd heterostructures was conducted by a photodeposition
method. The ZnOCdS@Cd sample (100 mg) was added to the
aqueous solution containing the desired amount of H
2
PtCl
6
6H
2
O (1 mg
Pt mL
1
). The solution was irradiated by a Xe lamp (300 W) for 1 h while
being magnetically stirred.
hydrogen evolution rate increase by a factor of
3.15 with respect to the bare ZnOCdS@Cd
heterostructure. The rate of 1.92 mmol h
1

is also 5.1 times that of the Pt-loaded ZnO
CdS heterostructure
[8]
(a video of the high
volume of hydrogen bubbles due to the
photocatalytic hydrogen evolution on the
ZnOCdS@Cd heterostructure is given in
the SI). EDX proles collected at three dif-
ferent points in the 3 wt% Pt-loaded ZnO
CdS@Cd heterostructure are shown in
SI, Figure S5, where the presence of Pt on
the surface can be conrmed. A recycling
of photo catalytic hydrogen evolution on
the ZnOCdS@Cd heterostructure is esti-
mated for investigating photocatalytic stability during a long-
term photo catalytic reaction (See Figure 5). The respective
total photocatalytic evolutions for 20 h with the bare and the
3 wt% Pt-loaded ZnOCdS@Cd heterostructure was 6.32 and
39.26 mmol (100 mg), where no noticeable degradation after
four cycles of photocatalytic reactions was detected. Further XPS
analysis shows no shift of the binding energy of Zn 2p, Cd 3d,
S 2p, and O 1s in the ZnOCdS@Cd heterostructure except for
the S 2p due to Na
2
SO
3
absorption (SI, Figure S6). There is no
clear change of the coreshell structure in the high-resolution
TEM image of the ZnOCdS@Cd heterostructure after 20 h
reaction compared to that before the reaction (SI, Figure S7).
The improved and stable photocatalytic hydrogen evolution
is mainly attributed to the new structure: the metal core and
ZnOCdS heterostructural shell. The mechanism proposed is
as follows:
1) In a ZnOCdS heterostructure photocatalyst based on the
Z-scheme charge-carrier transport, an effective and rapid
recombination of the photoexcited electrons from the con-
duction band (CB) of ZnO with the holes from the valence
Figure 5. Time-circle photocatalytic hydrogen evolution over the
a) ZnOCdS@Cd heterostructure and b) 3 wt% Pt-loaded one (100 mg)
in 300 mL aqueous solution containing 0.1 M Na
2
S and 0.1 M Na
2
SO
3

under irradiation from a 300 W Xe lamp.
Figure 6. Scheme of the improving mechanism of photoexcited charge-carrier transport in the
ZnOCdS@Cd heterostructure.
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2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Energy Mater. 2012, 2, 4246
Characterization: X-ray diffraction (XRD) patterns were recorded
on Rigaku diffractometer using Cu K irradiation. Scanning electron
microscopy (SEM) images were obtained on a SUPRA SEM 35.
Transmission electron microscope (TEM) images and Energy
Dispersive X-ray spectroscopy (EDX) proles were obtained using a
Tecnai F30 (FEI). The UVvis absorption spectra were measured with a
UVvis spectrophotometer (JACSO-V550). The chemical compositions
of the samples were analyzed using X-ray photoelectron spectroscopy
(Thermo Escalab 250, a monochromatic Al K X-ray source). All
binding energies were referenced to the C 1s peak (284.6 eV)
arising from adventitious carbon. Inductively coupled plasma mass
spectrometry (ICPMS) provided an elemental analysis (Thermo
Electron X-7).
Photocatalytic Hydrogen-Evolution Measurements: Photocatalytic
hydrogen evolution reactions were carried out in a gas-closed
circulation with vacuum. Typically, photocatalyst powder (100 mg) was
dispersed in aqueous solution (300 mL) containing 0.1 M Na
2
S and
0.1 M Na
2
SO
3
. The light source was a Xe lamp (300 W). The amount
of hydrogen evolution was determined using a gas chromatograph
(Shimadzu-2014).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author. It Includes an XRD pattern of the CdZnO rod and
ZnOCdS@Cd heterostructure, TEM images and EDX proles of the
CdZnO rod and Pt-loaded ZnOCdS@Cd heterostructure, UVvis
diffuse spectra of the ZnOCdS@Cd heterostructure, CdZnO rod,
and Zn powder, XPS spectra and TEM images of the ZnOCdS@Cd
heterostructure before and after reaction, and a video of photocatalytic
hydrogen evolution.
Acknowledgements
The nancial support from Major Basic Research Program, Ministry
of Science and Technology China (No. 2009CB220001), NSF of China
(Nos. 50921004, 51002160, 21090343, 51172243), Solar Energy Initiative
(KJCX2-YW-H21-01) of the Chinese Academy of Sciences, MOF Grants
ZDYZ2008-2-A12, Australian Research Council through its Centre
grant and DP0666345 are gratefully acknowledged. GL thanks the IMR
SYNL-T.S. K Research Fellowship.
Received: September 7, 2011
Revised: September 27, 2011
Published online: December 12, 2011
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