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Photocatalytic hydrogen production by flower-like

graphene supported ZnS composite photocatalysts

Chi-Jung Chang a,*, Yi-Hung Wei a, Kun-Ping Huang b

a
Department of Chemical Engineering, Feng Chia University, 100, Wenhwa Road, Seatwen, Taichung 40724,
Taiwan, ROC
b
Mechanical and Systems Research Laboratories, Industrial Technology Research Institute, 195, Sec. 4,
Chung Hsing Road, Chutung, Hsin-Chu 31040, Taiwan

article info abstract

Article history: Flower-like graphene (FG) prepared by a transformer coupled plasma enhanced chemical
Received 26 November 2016 vapor deposition method was used as support for the preparation of composite photo-
Received in revised form catalysts. Small ZnS particles were formed on the surface of FG by a hydrothermal process
18 April 2017 with ZnCl2 and Na2S precursors. The surface morphology, surface area, surface chemistry,
Accepted 21 April 2017 crystalline property, optical properties, photogenerated current and photocatalytic
Available online xxx hydrogen production activity of the FG-ZnS photocatalysts were investigated by using the
X-ray diffraction, scanning electron microscope, transmission electron microscopy, X-ray
Keywords: photoelectron spectroscopy, ultraviolet-visible diffuse reflectance spectra, photocurrent
Flower-like response, photoluminescence spectra, electrochemical impedance spectra and photo-
Graphene catalytic hydrogen production tests. The maximum hydrogen production rate of FG-ZnS
ZnS composite photocatalyst ZS-G0.02 was 11600 mmol g
1h
1 under UV light irradiation at a
Photocatalyst graphene/ZnCl2 precursor weight ratio of 0.02. The flower-like structure of FG may help the
Hydrogen production light absorption, adsorption of sacrificing agents in the solution, and separation of pho-
togenerated carriers. In comparison with pristine ZnS photocatalyst, the FG-ZnS nano-
composites exhibits enhanced photocatalytic hydrogen production activity.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

some processes to improve the photocatalytic activity by hy-

Introduction
Semiconductor materials have been developed for some ap-
plications, such as H2 production [1,2], photocatalytic degra-
dation [3,4], and gas sensor [5]. The photocatalyst which has a
more negative conduction band than the reduction potential
of proton will have high photocatalytic water splitting activity
[6,7]. ZnS can generate electron-hole pairs rapidly under light
irradiation and exhibit a relatively high activity for photo-
catalytic H2 production [8e10]. Researchers have reported
bridizing semiconducting photocatalysts with electric
conductive materials which can induce the charge separation
in the photocatalysts, such as fullerene C60 [11], graphene
[12], conducting polyaniline (PANI) [13] and stainless steel wire
mesh substrates [14]. Because of the large specific surface area
and excellent electronic conductivity, graphene with 2D
planar p-conjugation structure can act as a catalyst support
[15,16] Graphene-semiconductor composite photocatalysts
have enhanced photocatalytic H2-production activity by

* Corresponding author.
E-mail address: changcj@fcu.edu.tw (C.-J. Chang).
http://dx.doi.org/10.1016/j.ijhydene.2017.04.219
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Chang C-J, et al., Photocatalytic hydrogen production by flower-like graphene supported ZnS com-
posite photocatalysts, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.219
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9

inhibiting the recombination of photogenerated electron-hole

pairs in the photocatalysts [17e19].
However, the van der Waals forces between adjacent gra-
phene layers may result in the aggregation of graphene sheets
which lead to a decrease of the specific surface area [20]. A
large surface area is very important for the use of graphene in
some applications such as supercapacitor, sensor and fuel
cell, because it can provide more sites for adsorption and
catalytic reaction [21,22]. In order to solve this problem, many
researchers have devoted to synthesize three dimensional
(3D) porous graphene materials with large specific surface
area and interconnected pore structure by different methods
[23e25].
Some surface morphology, such as nanorod array and pore
array, exhibits light trapping effects [26] which may help to
increase photocatalytic activity [27e31]. Yang et al. reported
that the light-trapping effect by the nanowire arrays enhances
light absorption and improves the photocatalytic activity of
SiNW arrays [32]. Kim et al. [33] found that the surface-
textured TiO2 inverse opal maximized the photon-trapping
effects and improves the photoelectrochemical hydrogen
generation performance. The light-trapping effect can be
confirmed by the decrease in the transmittance and reflec- Scheme 1 e Schematic diagram of the TCP CVD system.
tance spectra of the sample [34]. We believe that the flower
like graphene can exhibit the light-trapping effect and help to 100 mL Teflon-lined autoclave and maintained at 130  C for
improve the photocatalytic activity. 12 h. The final products with different weight ratios of FG were
Recently, some researchers reported the use of flower-like washed several times by distilled water and ethanol, and dried
graphene or carbon for application in supercapacitors [35,36], at 60  C for 10 h.
and methanol oxidation [37]. Inspired by the previous works,
the flower-like graphene (FG) with 3D porous structure was Photocatalytic H2 production
used as conductive photocatalyst support which can enhance
the separation of photogenerated electron-hole pairs in this The photocatalytic hydrogen production reaction was carried
study. The FG remarkably enhances the photocatalytic H2 out in a 100 mL Quartz cell. A 300 W high-pressure mercury
production activity of ZnS nanoparticles compared to the ZnS lamp was used as the UV light source. The photocatalysts is
catalysts. This work demonstrates the feasibility of using 3D placed into the quartz cell filled with 100 mL sacrificial
porous FG supports for the development of highly efficient aqueous solution. The sacrificial aqueous solution was made
ZnS-FG photocatalysts. up of 0.1 M Na2S$9H2O, 0.040 M Na2SO3 and 3 M NaCl. The
solution was continuously stirred throughout the UV light
irradiation procedures. A gas chromatography (TCD, Argon as
Experimental carrier gas, Stainless Steel packed column with 5 mm inner
diameter, Molecular Sieve 5 A as stationary phase) was used to
Preparation of ZnS-FG composites measure the amount of hydrogen production in order to
determine the photocatalytic activity.
The flower-like graphene (FG) was synthesized by means of
the transformer coupled plasma enhanced chemical vapor Nomenclature
deposition (TCP CVD) in the reaction chamber [38]. A sche-
matic diagram of the TCP CVD system for the present exper- The ZnS-FG photocatalysts were denoted as ZS-Gx photo-
iment is illustrated in Scheme 1. Methane was introduced and catalysts. x means the weight ratio of graphene/ZnCl2. For
mixed with argon to grow FG in the reaction chamber. The gas example, the graphene/ZnCl2 weight ratio of ZS-G0.02 is 0.02.
was excited with plasma (medium frequency 250 kHz) in the
TCP system. The flow rates of argon and methane gases were Characterization
kept at 3 and 0.2 slm (standard liter per minute) by the mass
flow controller (MFC), respectively. The medium frequency X-ray Diffraction (XRD) patterns were measured by a MAC
power was set 6000 W for 30 min. The gas pressure was kept at SCIENCE MXP3 diffractometer to investigate the crystal phase
7 Torr during the process. of the photocatalysts. The surface morphologies and energy
Then, 0.2 g ZnCl2 and FG were dispersed in the distilled dispersive X-ray (EDX) were analyzed by a field-emission
water (50 ml), and this solution was heated to 70  C in an oil scanning electron microscope (FE-SEM, HITACHI S-4800).
bath with continuous stirring for 2 h. Subsequently, 0.1 M The microstructures were monitored by transmission elec-
Na2Sƃ9H2O (20 ml) solution was added dropwisely and kept tron microscopy (TEM, JEOLJEM-2100). X-ray photoelectron
stirring for 4 h. Then, the suspension was transferred to a spectroscopy (XPS) was measured by a VG ESCA scientific

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posite photocatalysts, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.219
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
theta probe. The UVevis diffuse reflection spectra of the
photocatalysts were analyzed by the spectrophotometer
(JASCO V-650). The photoluminescence spectra were recorded
by a photoluminescence spectrometer (Hitachi F-7000). The
photoinduced currents of the photocatalyst were investigated
by PC controlled PEC-SECM (photoelectrochemical scanning
electrochemical microscopy, CHI model 900C, CHI In-
struments). The Pt electrode and Ag/AgCl electrode were used
as the counter and reference electrodes, respectively. The
photocatalyst coated ITO glass acted as the working electrode
(irradiation area of 2.25 cm2). BET surface area measurements
were performed by N2 adsorption at 77 K on a Micromeritics
ASAP2000 instrument.
Results and discussion
XRD
The XRD patterns of FG, pure ZnS and the resulting nano-
composites of FG-ZnS are shown in Fig. 1. The XRD patterns of
FG-ZnS nanocomposites with different weight ratios of FG are
similar to that of ZnS. The photocatalyst exhibits peaks of
(111), (220), and (311) crystal planes of the face centered cubic
ZnS at 2q values of 28.5, 47.5, and 56.3 (JCPDS No.05-0566). No
diffraction peaks for FG was observed in the FG-ZnS com-
posite photocatalysts, which might result from the low
amount and relatively low diffraction intensity of FG.
SEM
The morphologies and microstructures of the flower-like
graphene and ZnS decorated flower-like graphene (ZS-G0.02)
samples were observed by field-emission scanning electron
microscopy (FESEM). Fig. 2a and b presents the morphology of
the FG. The graphene framework has uniformly distributed
flower-like structure with a lot of folds. Each fold width is
about 200 nm. The FG exhibits porous architectures, which
may be a good support material of photocatalysts. From Fig. 2c
and d, the ZS-G0.02 nanocomposite had a rough morphology.
Fig. 1 e XRD patterns of FG and ZS-Gx photocatalysts with
different FG contents.
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posite photocatalysts, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.219
3
The surface of the graphene petals was decorated with ZnS
nanoparticles.
The rough surface of FG in Fig. 2c and d indicates the
presence of ZnS nanoparticles. Fig. 3aed shows the FESEM
image of ZnS-FG nanoparticle and the mapping of Zn, C and S
elements, respectively. The dots of Zn and S indicated the
distribution of ZnS nanoparticles. The well distributed Zn, S
and C dots on the photocatalyst indicates the formation of ZnS
nanoparticles on the FG. Peaks of atomic Zn, S and C was
observed by SEM EDX analysis of the ZS-G0.02 sample (Fig. 3d).
It reveals the ZnS nanoparticles decorated flower-like gra-
phene structure of the composite photocatalyst.
TEM
The microstructures of the ZS-G0.02 samples were examined
by TEM. Some small ZnS particles were observed on the
flower-like graphene (Fig. 4a). The result confirms the com-
bination of FG and ZnS particles, which is consistent with that
found in the FESEM image (Fig. 2d). The TEM image (Fig. 4a)
indicates that the size of the ZnS particles in ZS-G0.02 is about
10-20 nm. The high-resolution TEM (HR-TEM) image (Fig. 4(b))
presents that the detail of the lattice fringe of the individual
ZnS nanocrystals. The interplanar spacing is about 0.31 nm,
corresponding to the (111) lattice plane of cubic ZnS. The TEM
image reveals the formation of a good interfacial contact be-
tween the flower-like graphene and ZnS nanoparticles.
Because of the high carrier mobility on the graphene surface,
formation of ZnS nanoparticles/FG interface can enhance the
transfer of photo-induced charge from ZnS to graphene.
Effective separation of photogenerated charge carriers can
elevate the photocatalytic activity of the composite
photocatalyst.
X-ray photoelectron spectroscopy (XPS)
The functionalization of flower-like graphene was character-
ized by XPS. Fig. 5a and b shows the C1s XPS spectra of FG and
FG/ZnS composite (ZS-G0.02), respectively. The asymmetrical
and broad C1s XPS peaks reveal the existence of C species. A
deconvolution of signal by Gaussian curve fitting reveals the
existence of different C species in the photocatalyst. The XPS
spectrum of C1s from FG (Fig. 5a) can be deconvoluted into two
smaller peaks, which can be related to some functional
groups: sp2 bonded carbon (C]CeC, 284.8 eV), and carbonyls
(C]O, 287.8 eV). The element species and chemical states of
the photocatalyst surface were determined by XPS. To inves-
tigate the surface chemistry of ZS-G0.02 composite photo-
catalyst, XPS spectrum was depicted in Fig. 5b. The C 1s peak
of ZS-G0.02 can be deconvoluted into three peaks at 284.8 (sp2
carbon, C]CeC bonds), 286.5 (CeO bonds), and 289.4 eV
(carboxyl OeC]O bonds), respectively [39e41], revealing the
existence of oxygen-containing functional groups. The hy-
drophilic (oxygen-containing) groups on the surface of gra-
phene, including CeO bond and carboxyl groups, can help the
dispersion of flower-like graphene in water, enhancing the H2
generation process in aqueous solution.
Fig. 5c and d shows the XPS Zn 2p3 and S 2p spectra of ZS-
G0.02 composite photocatalyst, respectively. The peaks
observed at 1045.0 and 1022.1 eV are ascribed to Zn 2p1/2 and Zn
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9

Fig. 2 e FESEM images of (a) FG (b) enlarged image of FG and (c) ZS-G0.02 (d) enlarged image of ZS-G0.02 composite
photocatalyst.

Fig. 3 e (a) C (b) Zn (c) S element mapping images (d) EDX spectrum of ZS-G0.02 composite photocatalyst.

2p3/2 of the ZnS nanoparticles, respectively. The peak at
162.3 eV corresponds to the binding energies of S 2p3/2 of the
ZnS nanoparticles. The binding energies values for Zn 2p and S
2p peaks are consistent with data reported in the literature [42].
Photocatalytic hydrogen production
The photocatalytic H2 production activity of the FG-ZnS
nanocomposites from a solution containing 0.1 M Na2S,
0.04 M Na2SO3 and 3 M NaCl under UV-light irradiation is
shown in Fig. 6. The sacrificial reagent can hinder the recom-
bination of holeeelectron pairs and increase the number of
active electrons. ZnS photocatalyst shows some photocatalytic
H2-production activity, the rate of H2 evolution is
1500 mmol h
1 g
1. The content of FG has a great influence to-
wards the photocatalytic activity of ZnS. The activity of the ZGx
photocatalyst is enhanced by introducing graphene. The rate
of H2 evolution over ZS-G0.01 reaches 8820 mmol h
1 g
1. The H2

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9 5

Fig. 4 e (a) TEM image (b) high-resolution TEM image of ZS-G0.02 photocatalyst.

Fig. 5 e XPS (a) C1s spectra of FG and (b) C1s (c) Zn 2p3 (d) S 2p spectra of ZS-G0.02 composite photocatalyst.

production rate increases with increasing of FG content,
reaching a maximum of 11600 mmol h
1 g
1 at the FG content of
2 wt% (ZS-G0.02), which is 7.7 times of that of ZnS photo-
catalyst. In comparison with ZnS photocatalyst, the ZS-G0.02
photocatalyst provides more active sites for photocatalytic
reaction. FG can act as an electron collector and transporter
which can suppress the charge recombination. More reactive
species formed, leading to high photocatalytic H2-production
rate. When graphene content is higher than 2 wt%, a further
increase in FG content results in a decreased photocatalytic H2
production activity. The H2-production activity of ZS-G0.05
becomes 5900 mmol h
1 g
1. Introducing a large amount of
black flower-like graphene decreased the intensity of incident
light through the reaction solution, preventing the photo-
generated electrons. Besides, incorporating excessive amount
of FG may cover the active sites on the photocatalyst surface
and hinder the contact between the sacrificial agents and the
photocatalyst. Adding an appropriate amount of FG in the
composite photocatalysts is important for optimizing the
photocatalytic H2 production activity of photocatalysts.
BET surface area
The nitrogen adsorptionedesorption isotherms of pristine ZnS
nanoparticles, flower-like graphene, and FG-ZnS photocatalyst
ZS-G0.02 were shown in Fig. 7. The adsorption and desorption
isotherms of the ZnS, flower-like graphene, and FG-ZnS pho-
tocatalyst ZS-G0.02 exhibit hysteresis loops. The shapes of
hysteresis loops often reveal the types of pore structures [43]. In
Fig. 7a, the pristine ZnS displays the type H1 hysteresis loop.

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6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9

Fig. 6 e H2 production of ZnS and FG-ZnS photocatalysts

with different FG content.

The two branches are almost vertical and nearly parallel at high
relative pressure (P/Po) between 0.8 and 1.0. The type H1 hys-
teresis loop is often related to porous materials consisting of
agglomerates of approximately uniform spheres. The BET sur-
face area of the pristine ZnS sample calculated from the linear
part of the BET plot is 90.1 m2 g
1. The BET surface area of the
flower-like graphene reaches 179.9 m2 g
1. The flower-like
graphene exhibits the type H3 hysteresis loop (Fig. 7b). The
Type H3 hysteresis loop is observed with aggregates of plate-
like nanostructures with slit-shaped pores. It agrees with the
FESEM images shown in Fig. 2a and b. The flower-like graphene
with a lot of petals exhibits large surface area. The BET surface
area of the FG-ZnS photocatalyst ZS-G0.02 is 151.9 m2 g
1,
which is close to that of the flower-like graphene. Formation of
the flower-like graphene (FG) can prevent the stacking of
adjacent graphene microstructure. Meanwhile, the large sur-
face area can also contribute to the superior photocatalytic
activity of the FG-ZnS photocatalyst. In Fig. 7c, the pristine ZnS
displays the type H2 hysteresis loop. Type H2 loop is related to
'ink bottle' pores (pores with narrow necks and wide bodies).
Fig. 2c and d revealed that a rough morphology formed with ZnS
nanoparticles decorated on the graphene petal surface of the
FG-ZnS photocatalyst ZS-G0.02. The H2 loop indicated that “ink
bottle” pores formed when ZnS nanoparticles were decorated
on the flower-like graphene.

Photocurrent
Fig. 7 e Nitrogen adsorptionedesorption isotherms of (a)
Photoelectrochemical experiments were then performed to
ZnS (b) flower-like graphene (c) FG-ZnS photocatalyst ZS-
investigate the electronic interaction between ZnS and flower-
G0.02.
like graphene. The chopped photocurrent-time transient re-
sponses of pure ZnS and ZS-G0.02 were investigated for two
on
off cycles of irradiation. (Fig. 8). The reproducible on
off photoexcited electron-hole pairs of the composite photo-
cycles of the photocurrent appears for all samples under light catalyst ZS-G0.02, allowing more charge carriers to form
illumination. The ZS-G0.02 composite photocatalyst exhibited reactive species.
higher photocurrent than pure ZnS. The photocurrent of the
ZS-G0.02 is about 4.4 times that of ZnS photocatalyst. Gra- Diffuse reflectance spectra (DRS)
phene with two dimensional p-conjugation structure is an
excellent electron-acceptor. Flower-like graphene can act as Fig. 9 shows the UVevis absorption spectra of the ZS-Gx
an electron acceptor and decreases the recombination of the photocatalysts (x ¼ 0, 0.1, 0.2, 0.5). There is a broad

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 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9 7

Fig. 8 e The chopped current-time transient photocurrent

response of ZnS and ZS-G0.02 photocatalyst. Fig. 10 e Photoluminescent spectra of ZnS and ZnS-G0.02
excited at 230 nm.

Fig. 9 e Diffuse reflectance spectra of ZnS and FG-ZnS

based photocatalysts.

background absorption in the visible-light region

(500e800 nm) for the composite samples. Such absorption
gradually increases by increasing the FG content. The color of
the photocatalyst changed from white to gray. The presence of
FG in the composite photocatalysts reduces the reflection of
incident light and enhances the light absorption. Besides, the
composite samples exhibit nearly the same absorption edge
as that of the pristine ZnS, indicating FG is not incorporated
into the lattice of ZnS.

Photoluminescence spectra
The photoluminescence (PL) emission results from the
recombination of charge carriers [44]. Therefore, PL is a useful
tool for investigating the charge carrier trapping and recom-
bination efficiency of the photocatalyst. As shown in Fig. 10,
photoluminescence measurements were carried out to
investigate the interaction between flower-like graphene and
ZnS in the ZnS-G0.02 photocatalyst. The PL spectrum of the
FG/ZnS composite ZnS-G0.02 is similar to that of pure ZnS. For
Fig. 11 e EIS Nyquist plots of (a) ZnS (b)ZS-G0.02
photocatalysts.
the ZnS-G0.02 photocatalyst, the peak ranging from 350 to
425 nm results from the emission of band gap transition with
the energy of light equal to the band gap of ZnS. The shoulder
ranging from 425 to 525 nm can be attributed to excitonic PL,
resulting from surface defects. The ZnS-G0.02 photocatalyst
exhibits lower fluorescence intensities than ZnS, indicating

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8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
the recombination of the photogenerated electrons and holes
was effectively inhibited by incorporating graphene in the
ZnS-G0.02 photocatalyst. The electrons are excited from the
valence band to the conduction band of ZnS and then trans-
ferred to FG, preventing the recombination of photogenerated
electrons and holes.
Electrochemical impedance spectra (EIS)
EIS Nyquist plots of bare ZnS and ZS-G0.02 photocatalysts are
shown in Fig. 11. The arc radius of the EIS Nyquist plot of ZS-
G0.02 is much smaller than that of bare ZnS. In general, the arc
radius of EIS spectra denotes the interface layer resistance
occurring at the surface of the electrode. The smaller arc
radius indicates a higher transfer rate of interfacial charge and
improved separation of photoinduced charge carriers over ZS-
G0.02 photocatalyst. To further investigate the transfer pro-
cess of photoexcited charge carriers, PL spectra of ZnS and ZS-
G0.02 are measured. The emission spectra of bare ZnS and ZS-
G0.02. The PL intensity obtained over ZS-G0.02 is about one-
third of pristine ZnS. The improved interfacial charge trans-
fer between ZnS and FG leads to the fluorescence quenching.
The results of the photocurrent response and EIS analysis are
consistent. Improved interfacial charge transfer leads to the
enhanced photocatalytic activity of hydrogen production [45].
Conclusion
Photocatalysts with flower-like hierarchical graphene-ZnS
structure consisting of graphene-nanosheet clusters and
decorated ZnS nanoparticles were prepared. Due to their
three-dimensional macroporous structure and high acces-
sible surface area, the composite photocatalysts display
outstanding photocatalytic H2 production activity (up to
11600 mmol h
1 g
1). The results of electrochemical impedance
spectra, photoluminescent spectra, and the chopped current-
time transient photocurrent response confirm the enhanced
electronehole separation efficiency. The diffuse reflectance
spectra revealed the improved adsorption capability. The
increased light absorption, electronehole separation effi-
ciency, and adsorption capability of flower-like composite
photocatalysts can contribute to the remarkable H2 produc-
tion performance.
Acknowledgments
The authors would like to thank the financial support from the
Ministry of Science and Technology under the contract of
MOST 104-2221-E-035-075. The authors appreciate the Preci-
sion Instrument Support Center of Feng Chia University in
providing the measurement facilities.
references
[1] Zhang K, Jing D, Xing C, Guo L. Significantly improved
photocatalytic hydrogen production activity over Cd1-xZnxS
Please cite this article in press as: Chang C-J, et al., Photocatalytic hydrogen production by flower-like graphene supported ZnS com-
posite photocatalysts, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.219
photocatalysts prepared by a novel thermal sulfuration
method. Int J Hydrogen Energy 2007;32:4685e91.
[2] Anbuvannan M, Ramesh M, Viruthagiri G, Shanmugam N,
Kannadasan N. Synthesis, characterization and
photocatalytic activity of ZnO nanoparticles prepared by
biological method. Spectrochim Acta A 2015;143:304e8.
[3] Chang CJ, Hsu MH, Weng YC, Tsay CY, Lin CK. Hierarchical
ZnO nanorod-array films with enhanced photocatalytic
performance. Thin Solid Films 2013;528:167e74.
[4] Li J, Zhou SL, Hong GB, Chang CT. Hydrothermal preparation of
P25egraphene composite with enhanced adsorption and
photocatalytic degradation of dyes. Chem Eng J 2013;219:486e91.
[5] Hung ST, Chang CJ, Hsu CH, Chu BH, Lo CF, Hsu CC, et al.
SnO2 functionalized AlGaN/GaN high electron mobility
transistor for hydrogen sensing applications. Int J Hydrogen
Energy 2012;37:13783e8.
[6] Li Q, Guo B, Yu J, Ran J, Zhang B, Yan H, et al. Highly efficient
visible-light-driven photocatalytic hydrogen production of
CdS-cluster-decorated graphene nanosheets. J Am Chem Soc
2011;133:10878e84.
[7] Jin J, Yu J, Liu G, Wong PK. Single crystal CdS nanowires with
high visible-light photocatalytic H2-production performance.
J Mater Chem A 2013;1:10927e34.
[8] Zhang J, Yu J, Zhang Y, Li Q, Gong JR. Visible light
photocatalytic H2-production activity of CuS/ZnS porous
nanosheets based on photoinduced interfacial charge
transfer. Nano Lett 2011;11:4774e9.
[9] Wang F, Zheng M, Zhu C, Zhang B, Chen W, Ma L, et al.
Visible light photocatalytic H2-production activity of wide
band gap ZnS nanoparticles based on the photosensitization
of graphene. Nanotechnology 2015;26. 345402.
[10] Hu JS, Ren LL, Guo YG, Liang HP, Cao AM, Wan LJ, et al. Mass
production and high photocatalytic activity of ZnS nanoporous
nanoparticles. Angew Chem Int Ed 2005;117:1295e9.
[11] Fu H, Xu T, Zhu S, Zhu Y. Photocorrosion inhibition and
enhancement of photocatalytic activity for ZnO via
hybridization with C60. Environ Sci Technol 2008;42:8064e9.
[12] Zhang H, Lv X, Li Y, Wang Y, Li J. P25-graphene composite as
a high performance photocatalyst. ACS Nano 2009;4:380e6.
[13] Li X, Wang D, Cheng G, Luo Q, An J, Wang Y. Preparation of
polyaniline-modified TiO2 nanoparticles and their
photocatalytic activity under visible light illumination. Appl
Catal, B 2008;81:267e73.
[14] Chang CJ, Lee Z, Wang CF. Photocatalytic hydrogen
production by stainless Steel@ZnS core-shell wire mesh
photocatalyst from saltwater. Int J Hydrogen Energy
2014;39:20754e63.
[15] Lightcap IV, Kosel TH, Kamat PV. Anchoring semiconductor
and metal nanoparticles on a two-dimensional catalyst mat.
Storing and shuttling electrons with reduced graphene
oxide. Nano Lett 2010;10:577e83.
[16] Xiang QJ, Yu JG, Jaroniec M. Graphene-based semiconductor
photocatalysts. Chem Soc Rev 2012;41:782e96.
[17] Li Q, Guo BD, Yu JG, Ran JR, Zhang BH, Yan HJ, et al. Highly
efficient visible-light-driven photocatalytic hydrogen
production of CdS-cluster-decorated graphene nanosheets.
J Am Chem Soc 2011;133:10878e84.
[18] Wang F, Zheng M, Zhu C, Zhang B, Chen W, Ma L, et al.
Visible light photocatalytic H2-production activity of wide
band gap ZnS nanoparticles based on the photosensitization
of graphene. Nanotechnology 2015;26. 345402.
[19] Mukherji A, Seger B, Lu GQ, Wang L. Nitrogen doped Sr2Ta2O7
coupled with graphene sheets as photocatalysts for
increased photocatalytic hydrogen production. ACS Nano
2011;5:3483e92.
[20] Guo S, Dong S. Graphene nanosheet: synthesis, molecular
engineering, thin film, hybrids, and energy and analytical
applications. Chem Soc Rev 2011;40:2644e72.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e9
[21] Yao Z, Zhu M, Jiang F, Du Y, Wang C, Yang P. Highly efficient
electrocatalytic performance based on Pt nanoflowers
modified reduced graphene oxide/carbon cloth electrode.
J Mater Chem 2012;22:13707e13.
[22] Sheng ZM, Guo CX, Li CM. Nitrogen-doping templated
nanoporous graphitic nanocage and its supported catalyst
towards efficient methanol oxidation. Electrochem Commun
2012;19:77e80.
[23] Fan D, Liu Y, He J, Zhou Y, Yang Y. Porous graphene-based
materials by thermolytic cracking. J Mater Chem
2012;22:1396e402.
[24] Worsley MA, Pauzauskie PJ, Olson TY, Biener J, Satcher Jr JH,
Baumann TF. Synthesis of graphene aerogel with high
electrical conductivity. J Am Chem Soc 2010;132:14067e9.
[25] Cong HP, Ren XC, Wang P, Yu SH. Macroscopic
multifunctional graphene-based hydrogels and aerogels by a
metal ion induced self-assembly process. ACS Nano
2012;6:2693e703.
[26] Chang CJ, Kuo EH. Light-trapping effects and dye adsorption
of ZnO hemisphere-array surface containing growth-
hindered nanorods. Colloid Surf A 2010;363:22e9.
[27] Wei Y, Ke L, Kong J, Liu H, Jiao Z, Lu X, et al. Enhanced
photoelectrochemical water-splitting effect with a bent ZnO
nanorod photoanode decorated with Ag nanoparticles.
Nanotechnology 2012;23. 235401.
[28] Chen X, Jun YS, Takanabe K, Maeda K, Domen K, Fu X, et al.
Ordered mesoporous SBA-15 type graphitic carbon nitride: a
semiconductor host structure for photocatalytic hydrogen
evolution with visible light. Chem Mater 2009;21:4093e5.
[29] Wang X, Xiao Y, Zeng D, Xie C. Optimizing the packing
density of TiO2 nanorod arrays for enhanced light harvesting
by a light trapping effect and its photocatalytic
decomposition of gaseous benzene. CrystEngComm
2015;17:1151e8.
[30] Wang X, Xiao Y, Zeng D, Xie C. Optimizing the packing
density of TiO2 nanorod arrays for enhanced light harvesting
by a light trapping effect and its photocatalytic
decomposition of gaseous benzene. CrystEngComm
2015;17:1151e8.
[31] Hsu MH, Chang CJ. S-doped ZnO nanorods on stainless-steel
mesh as immobilized hierarchical photocatalysts for
photocatalytic H2 production. Int J Hydrogen Energy
2014;39:16524e33.
[32] Yang T, Wang H, Ou XM, Lee CS, Zhang XH. Iodine-Doped-
Poly (3, 4-ethylenedioxythiophene)-modified Si nanowire 1D
core-shell arrays as an efficient photocatalyst for solar
hydrogen generation. Adv Mater 2012;24:6199e203.
Please cite this article in press as: Chang C-J, et al., Photocatalytic hydrogen production by flower-like graphene supported ZnS com-
posite photocatalysts, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.219
9
[33] Kim K, Thiyagarajan P, Ahn HJ, Kim SI, Jang JH. Optimization
for visible light photocatalytic water splitting: gold-coated
and surface-textured TiO2 inverse opal nano-networks.
Nanoscale 2013;5:6254e60.
[34] Chang CJ, Hung ST. Electrochemical deposition of ZnO pore-
array structures and photocurrent properties of ZnO/
polymer hybrid films. Thin Solid Films 2008;517:1279e83.
[35] Yue R, Ren F, Wang C, Xu J, Du Y. Facile preparation of
flower-like graphene-nanosheet clusters with the assistance
of copper particles and their application in supercapacitors.
RSC Adv 2014;4:500e4.
[36] Liang J, Chen S, Xie M, Wang Y, Guo X, Guo X, et al.
Expeditious fabrication of flower-like hierarchical
mesoporous carbon superstructures as supercapacitor
electrode materials. J Mater Chem A 2014;2:16884e91.
[37] Zhang Q, Jiang F, Yue R, Du Y. Electrochemically fabricated
flower-like graphene as a highly efficient Pt electrocatalyst
support for methanol oxidation. RSC Adv 2014;4:12105e8.
[38] Huang KP, Chang CC, Kou CS. Method for manufacturing
Graphene flower. 2016. Taiwan Patent TW I539043.
[39] Stankovich S, Piner RD, Chen X, Wu N, Nguyen ST, Ruoff RS.
Stable aqueous dispersions of graphitic nanoplatelets via the
reduction of exfoliated graphite oxide in the presence of poly
(sodium 4-styrenesulfonate). J Mater Chem 2006;16:155e8.
[40] Akhavan O, Ghaderi E. Photocatalytic reduction of graphene
oxide nanosheets on TiO2 thin film for photoinactivation of
bacteria in solar light irradiation. J Phys Chem C
2009;113:20214e20.
[41] Xiang Q, Yu J, Jaroniec M. Preparation and enhanced visible-
light photocatalytic H2-production activity of graphene/C3N4
composites. J Phys Chem C 2011;115:7355e63.
[42] Liu W. Low temperature synthesis of hexagonal phase ZnS
nanocrystals by thermolysis of an air-stable single-source
molecular precursor in air. Mater Lett 2006;60:551e4.
[43] Sing KSW. Reporting physisorption data for gas/solid
systems with special reference to the determination of
surface area and porosity (Provisional). Pure Appl Chem
1982;54:2201e18.
[44] Yu J, Ma T, Liu S. Enhanced photocatalytic activity of
mesoporous TiO2 aggregates by embedding carbon
nanotubes as electron-transfer channel. Phys Chem Chem
Phys 2011;13:3491e501.
[45] Yang J, Wang X, Zhao X, Dai J, Mo S. Synthesis of uniform
Bi2WO6-Reduced graphene oxide nanocomposites with
significantly enhanced photocatalytic reduction activity.
J Phys Chem C 2015;119:3068e78.