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Nickel nanoparticles modified CdS e A potential

photocatalyst for hydrogen production through
water splitting under visible light irradiation

Hui Wang a, Wei Chen a, Jing Zhang a, Cunping Huang b, Liqun Mao a,*
a
Lab of Fine Chemistry and Industry, Henan University, Kaifeng 475004, PR China
b
Florida Solar Energy Center, University of Central Florida, FL 32922-5703, USA

article info abstract

Article history: Ni nanoparticles were prepared via chemical reduction of aqueous NiCl2$6H2O by
Received 21 July 2014 N2H4$H2O, and loaded on the surface of CdS by photo-induced electrons as water splitting
Received in revised form reaction was occurring. Resultant CdS modified with Ni nanoparticles (denoted as Ni/CdS)
28 October 2014 was characterized by transmission electron microscopy, X-ray diffraction, UVevis diffuse
Accepted 2 November 2014 reflectance spectrometry, and photoluminescence spectrometry, and its photocatalytic
Available online 22 November 2014 performance for water splitting under visible light irradiation producing hydrogen was
evaluated with a 300 W Xe lamp as the light source (l
420 nm). It was found that as-
Keywords: obtained Ni nanoparticles with an average size of about 10 nm have face centered cubic
CdS structure, and they are preferentially deposited on the (100), (002), and (101) crystal planes
Ni nanoparticles of CdS nanorods to afford Ni/CdS photocatalyst. Besides, as-prepared Ni/CdS photocatalyst
Photocatalyst has a surface area of 28.8 m2/g (determined by BET method), higher than that of CdS
Water splitting nanorods, which indicates that Ni nanoparticles is beneficial to increasing the surface area
Hydrogen production of CdS nanorods. Moreover, as-prepared Ni/CdS photocatalyst shows absorption traits in
Photocatalytic activity the visible light region, and its photoluminescence peak intensity is lower than that of CdS,
which means that Ni nanoparticles function as the trappers of photo-generated electrons
to quench the photoluminescence of CdS. More importantly, although pristine CdS exhibits
no activity for hydrogen production from water splitting under visible light irradiation, Ni/
CdS photocatalyst with a Ni content of 4% (mass fraction) provides a hydrogen production
rate of 25.848 mmol/(h g) (QE ¼ 26.8%, l ¼ 420 nm) from water splitting of (NH4)2SO3
aqueous solution under the same testing condition and it retains a high stability and ac-
tivity even after 20 h of water splitting. This demonstrates that Ni/CdS could be a promising
candidate photocatalyst for visible light water splitting yielding hydrogen.
Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

* Corresponding author. Tel.: þ86 13513781969; fax: þ86 371 2388 1589.
E-mail address: mlq@henu.edu.cn (L. Mao).
http://dx.doi.org/10.1016/j.ijhydene.2014.11.005
0360-3199/Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
 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 4 0 ( 2 0 1 5 ) 3 4 0 e3 4 5
Introduction
Noble metal co-catalysts such as Pt, Pd, and Rh on CdS and
TiO2 matrix can trap light-induced electrons and act as the
active sites for H2 production [1,2]. However, the high cost of
noble metals seriously limits their practical application in
hydrogen evolution through water splitting, which can well
explain why Ni compounds such as NiO, NiS, Ni(OH)2, and
Ni@C/CdS are of particular significance as co-catalysts for
production of hydrogen and oxygen through water splitting
or for degradation of organic pollutants in water and air
[3e11]. With the assistance of these Ni compounds as co-
catalysts, researchers have successfully developed various
TiO2 & CdS based photocatalysts possessing visible light
catalytic activity, such as NiO/TiO2, NiS/CdS, Ni(OH)2/CdS,
and Ni@C/CdS [3,6,7,9e11]. These modified photocatalysts
are valuable, since they can efficiently promote water split-
ting under visible light irradiation and provide high hydrogen
production rates.
Usually, the high activity of NiS/CdS is attributed to the
formation of p-n junctions at the interface of NiS and CdS, and
it is the p-n junctions that effectively suppress the recombi-
nation rates of photogenerated carriers, and thereby largely
enhances hydrogen production rate [3,6,7,9]. The photo-
catalytic H2-production activity of the Ni(OH)2/CdS [10] in
Na2SO3 and Na2S aqueous solutions under visible light irra-
diation improves significantly (146 times) compared with pure
CdS, Ran et al. ascribed it to the proper potential of Ni2þ/Ni,
i.e.,the potential (E0 ¼ 0.23 V) is less negative than the con-
duction band of CdS (E0 ¼ 0.7 V) and more negative than the
potential of Hþ/H (E0 ¼ 0 V), which will favor the transfer of
photogenerated electrons from the conduction band of CdS to
Ni(OH)2 and thus accelerating the rate of photocatalytic H2-
production. Peng et al. [11] synthesized a Ni@C/CdS photo-
catalyst with a hydrogen production rate of 3.328 mmol/(h$g)
under a 300 W Xe-lamp (l
420 nm) in aqueous solution of
Na2SO3 and Na2S, they suggested that the high activity is
governed by the metallic Ni co-catalyst in Ni@C photocatalyst.
Namely, the Ni nanoparticle functions as co-catalyst and the
graphite-like carbon acts as the support of CdS nanoparticles
and electron acceptor simultaneously, they jointly work to
result in efficient charge separation and enhanced photo-
activity and stability thereby providing enhanced H2 produc-
tion under visible-light irradiation.
In our previous work, we have found that CdS loading with
2.5% (mass fraction; the same hereafter) Ni nanoparticles with
a size of 2e4 nm can well catalyze water splitting under visible
light irradiation (l
420 nm) and provide a hydrogen pro-
duction rate of up to 9.050 mmol/(h$g) [12]. Anticipating that
the crystallization behavior and crystallinity of Ni nanocrystal
may have significant influences on the photocatalytic perfor-
mance of Ni-modified CdS, in the present research we prepare
Ni nanocrystal-loaded cadmium sulfide (denoted as Ni/CdS)
and evaluate its catalytic performance for water splitting-
hydrogen evolution under visible light irradiation. This
paper highlights the structural characterization of as-
prepared Ni/CdS photocatalyst and evaluation of its surpris-
ingly high catalytic activity (the hydrogen production rate is as
much as 25.848 mmol/(h$g), QE ¼ 26.8%, l ¼ 420 nm) for water
341
splitting in (NH4)2SO3 aqueous solution generating hydrogen
under visible light irradiation.
Experimental sections
Reagents
Cd(NO3)2$4H2O, NH2CSNH2, NiCl2$6H2O, N2H4$H2O (80%) and
NaOH were purchased from Kermel Chemical Reagent Co. Ltd
(Tianjin, China). NaBH4 and polyvinlylpyrolidone (PVP, K-30)
were commercially obtained from Sinopharm Chemical Re-
agent Co. Ltd (Shanghai, China) and BASF (Shanghai, China),
respectively. Absolute ethanol was provided by Ante Biotech
Co. Ltd (Tianjin, China). All the chemical reagents are of
analytical grade and were used as received. Doubly distilled
water was used as the solvent and for washing and rinsing as
well.
Preparation of Ni/CdS photocatalyst
Nanorod-like cadmium sulfide was prepared by solvothermal
method. Briefly, 48 mL of 1,2-ethylenediamine (en), 3.0753 g of
Cd(NO3)2$4H2O and 2.2766 g of NH2CSNH2 were added to a
beaker and allowed to react at room temperature for 30 min
under stirring. Then the reaction solution was transferred into
a sealed teflon-lined autoclave and kept at 433 K for 48 h. Upon
completion of the reaction, the solution was filtered to afford
crude yellow product. The as-obtained crude product was
sequentially washed with distilled water and absolute
ethanol, followed by drying for 24 h at 313 K in a vacuum
furnace and grinding with a pestle to provide the desired CdS
nanorods. Prior to preparing Ni/CdS photocatalyst, as-
obtained CdS nanorods were stored in an airtight vial.
Ni nanocrystal was prepared with NiCl2$6H2O as the pre-
cursor. Briefly, 2.377 g (0.0118 mol) of NiCl2$6H2O and 6 mL of
N2H4$H2O (80%) were sequentially dissolved in 50 mL water
under stirring. Then 1.0 mol/L NaOH was dropped into the
resultant solution in order to adjust the pH value to be around
10. Afterward the reaction solution was heated at 343 K for 1 h
to speed up the reduction reaction of Ni2þ. The as-obtained Ni
nanoparticles precipitate was separated and collected by
filtration, followed by washing with distilled water and abso-
lute ethanol and drying at 313 K for 24 h under vacuum to form
Ni nanocrystal.
The as-obtained Ni nanocrystal was mixed with 0.1 g of
CdS nanorods under stirring for water splitting-hydrogen
generation reaction. During the water splitting reaction pro-
cess, Ni nanocrystal was deposited on CdS surface with the
assistance of photo-induced electrons.
Characterization
The structure and size of Ni nanocrystal were determined by
powder X-ray diffraction (XRD; Bruker D8 Advance, Germany;
Cu Ka radiation) at an applied current of 40 mA and a voltage
of 40 kV. The XRD data were collected in a 2q range of 10e90 at
a scan rate of 0.5 per step. The grain size and microstructure
of Ni/CdS were analyzed with a transmission electron mi-
croscope (TEM; JEM-2010, Jeol Company, Japan). The
342 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 4 0 ( 2 0 1 5 ) 3 4 0 e3 4 5
Fig. 1 e XRD spectra of Ni, CdS nanorods and Ni/CdS.
absorption characteristics of Ni/CdS samples with different Ni
dosages were measured with an ultravioletevisible light
spectrophotometer (UVevis; UV-2450, Shimadzu, Japan) and
an X-ray fluorescence spectrometer (X-FS; F7000, Hitachi
Company Limited, Japan) under 80 nm excitation. A Bru-
nauereEmmetteTeller surface analyzer (BET; Quanta Chrome
NOVA1000, USA) was performed to determine the BET surface
area and porosity of CdS samples based on N2 adsorption at
77 K. Prior to the measurements of BET surface area and
porosity, the samples were degassed at 573 K for 24 h to
remove any moisture or adsorbed contaminants on the
surface.
Evaluation of photocatalytic activity
A water-jacketed stainless vessel (diameter 12.5 cm, height
14.0 cm) fitted with a quartz window (diameter 6.4 cm,
exposed area 32 cm2) was used as the photoreactor. The
photolyte temperature was maintained at 298 ± 0.1 K by
circulating isothermal water in the water jacket of the pho-
toreactor. A 300 W Xe lamp (Beijing Perfectlight Company;
Beijing, China) equipped with a cut-off filter (l > 420 nm) was
used as the light source. Before photocatalytic reaction was
commenced, 0.1 g of Ni/CdS photocatalyst was added to 50 mL
of 1 M (NH4)2SO3 solution and transferred into the photo-
reactor which was purged with highly pure N2 flow.
Fig. 2 e TEM images of CdS nanorods modified with Ni.
Results and discussion
Characterization of Ni/CdS photocatalyst
Fig. 1 shows the XRD pattern of as-prepared Ni nanoparticles.
The diffraction peaks at 2q ¼ 44.53 , 51.76 , 76.27 , 92.97 and
98.4 correspond to metallic Ni with face centered cubic
structure (fcc; JCPDS card No. 04-0850, a ¼ 3.524 Ǻ); and these
XRD peaks are strong and sharp, which indicates that as-
synthesized Ni nanocrystal exhibits a high extent of crystal-
lization [13].
Fig. 1 also shows the XRD pattern of as-synthesized CdS
and Ni/CdS after photoecatalytic reaction, respectively. All
the diffraction peaks can be indexed to hexagonal CdS phase
with the lattice constants a ¼ 4.14 Å and c ¼ 6.72 Å (space
group: P63mc; JCPDS card No. 41-1049); and no peaks of im-
purities are detected, which means that as-synthesized CdS
and Ni/CdS consist of highly pure single phase [14]. Besides, as
compared with the standard card, as-synthesized CdS ex-
hibits relatively strong diffraction peaks of (100) and (110)
planes but weak diffraction peak of (002) plane, which sug-
gests that CdS nanorods might prefer to grow along the c-axis
direction [14,15]. Moreover, CdS and Ni/CdS show differences
in the relative peak intensity of each crystal plane. Namely, as
compared with CdS, Ni/CdS exhibits weaker peak intensity of
crystal planes (100), (002), and (101) but much stronger peak
intensity of crystal planes (110), (103), (200), (112) and (201).
This reveals that, under visible light irradiation, Ni nano-
particles tend to preferentially deposit on the crystal planes
(100), (002) and (101) of CdS nanorods thereby reducing the
opportunity for these crystal planes to be exposed and
decreasing the intensity of corresponding XRD peaks. Such an
orientated deposition of Ni nanoparticles on CdS surface
might be related to the transfer mechanism of photo-induced
carriers inside the semiconductor. The relationship between
the electron transfer and the structure of semiconductor
photocatalyst awaits further investigations.
Fig. 2 displays the low and high magnification TEM images
of Ni/CdS after photocatalytic hydrogen generation reaction,
and the inset in the upper left corner of Fig. 2a is the electron
diffraction (ED) pattern. It can be seen that Ni/CdS consists of
single crystal CdS nanorods with an average diameter of about
 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 4 0 ( 2 0 1 5 ) 3 4 0 e3 4 5 343

Table 1 e XRD analyses of nano-Ni/CdS photocatalyst and Table 2 e BET testing results of CdS and Ni/CdS.
CdS.
Sample BET surface Pore volume Pore
2q/ Lattice plane I INi/CdS/ICdS area (m2/g) (cm3/g) size (Å)
Ni/CdS CdS CdS 23.8 0.09 78
Ni/CdS 28.8 0.18 124
25.16 (100) 458.9 521.9 0.88
26.41 (002) 1060.4 1290.7 0.82
28.04 (101) 1680.8 1991.5 0.84
36.82 (102) 587.3 519.7 1.13 Fig. 5 shows the photoluminescence (PL) spectra of as-
43.98 (110) 765.8 706.5 1.08 synthesized CdS nanorods and Ni/CdS measured at room
47.89 (103) 1436.3 1383.5 1.04 temperature at an excitation wavelength of 380 nm. As-
50.23 (200) 232.3 207.2 1.12 synthesized CdS exhibits three emission peaks at 440 nm,
51.08 (112) 425.9 405.3 1.05
520 nm and 600 nm, respectively. The PL behavior of CdS
52.94 (201) 642.1 600.1 1.07
nanostructured materials has been studied intensively
[17e20]. According to previous studies, CdS nanostructures
generally have two PL emissions: band-edge emission and
20e30 nm and Ni nanoparticles with a size of about 10 nm; surface-defect emission. On the one hand, due to the quan-
and CdS nanorods are evenly decorated with Ni nanoparticles tum confinement effect, the PL peak position of the band-edge
(Table 1). emission of nanostructures is strongly size-dependent, and
Fig. 3a shows the nitrogen adsorptionedesorption iso- that of CdS nanostructure is usually located in the wavelength
therms of CdS nanorods at 77 K. The hysteresis loop in the range of 420e500 nm [19e22]. On the other hand, the surface-
relative pressure (P/P0) range between 0.8 and 0.9 reveals the defect emission is caused by surface states such as sulphur
microporous structure of the as-prepared CdS nanorods. In vacancies or/and sulphur dangling bonds; and the PL peak
addition, Ni/CdS composite photocatalysts feature an in- position of the surface-defect emissions is usually located in
crease in the BET surface area, which might attribute to the the wavelength range of 530e680 nm [17,18,23]. However, as
loading of Ni nanocrystallines on the surface of CdS Ni nano-crystallines were deposited on as-prepared CdS sur-
nanorods. The data such as BET surface area, pore volume, face (Fig. 5), the intensity of the peak at 440 nm decreased
and average pore size are calculated and given in Table 2. significantly. Ni nano-crystallines loading on CdS surface
Compared with pure CdS nanorods, Ni/CdS exhibits more function as the trapper of the electrons, and thus the light-
distinctive microporous structure [15]. induced electrons could transfer from the conduction band
of CdS to Ni, which results in the fluorescence quenching of
Absorption properties CdS nanorods [24]. According to the results, the intensity of
other two peaks (520 nm and 600 nm) don't change a lot, while
UVeVis diffuse reflectance spectra of CdS nanorods and Ni/ the two peaks correspond to the surface-defect emissions of
CdS after photoecatalytic reaction are shown in Fig. 4. The CdS. So we assume that the Ni nanoparticles doesn't be loaded
absorption threshold of pure CdS nanorods is at about 530 nm, on the site of the surface-defect of CdS nanorod, this is in
and the corresponding band gap of the sample is 2.4 eV, which accordance with the XRD analysis which reveals the prefer-
should be assigned to the intrinsic band gap absorption of entially deposit on the (100), (002) and (101) crystal planes of
CdS. Furthermore, in comparison to CdS, the absorption edge CdS nanorods.
of the Ni/CdS has no obvious change, implying that Ni was not
incorporated into the lattice of CdS but highly dispersed on its Photo-catalytic properties of Ni/CdS photocatalyst
surface [16]. However, the Ni/CdS shows a small enhanced
absorption in the visible-light region (530e850 nm), which Fig. 6 shows the H2 evolution rates over Ni/CdS photocatalysts
may be due to the absorption of grayish black metallic Ni with different loadings of Ni nanoparticles. When hydrogen
nanoparticles. evolution reaction is performed with CdS nanorods catalyst

Fig. 3 e N2 adsorptionedesorption properties of (a) CdS nanorods and (b) Ni/CdS.

344 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 4 0 ( 2 0 1 5 ) 3 4 0 e3 4 5
Fig. 4 e UVeVis diffuse reflectance spectra of CdS nanorods
and Ni/CdS.
alone at room pressure, almost no H2 is detected. Contrary to
the above, loading a small amount of Ni leads to a significant
increase in the catalytic activity of CdS for H2 evolution, which
means that Ni nanocrystal endows CdS nanorods with cata-
lytic activity for water splitting generating hydrogen. As
argued in the PL testing, Ni nano-crystallines loading on CdS
surface could trap the light-induced electrons of CdS, and thus
accelerate the hydrogen evolution rate.
However, since as-prepared Ni nanocrystal cannot be well
dispersed in the reaction solution, a poor contact is realized
between Ni nanocrystal and CdS nanorods. In other words,
there is still a small part of free Ni nanocrystal in the aqueous
solution, which makes it infeasible to accurately determine
the optimal dosage of Ni nanocrystal in as-prepared NieCdS
photocatalyst for photo-reduction generating hydrogen. Ac-
cording to the present research, the nominal optimal dosage
of Ni crystal in as-prepared NieCdS photocatalyst is suggested
as 4%, and a maximum hydrogen production rate of
25.848 mmol/(h$g) is acquired at this dosage of Ni
nanocrystals.
Fig. 7 shows the time course of photocatalytic H2 produc-
tion over Ni/CdS (Ni: 2.5%, 4%) photocatalyst. It can be seen
that Ni/CdS photocatalyst exhibits good durability and retains
a high photocatalytic activity even after 20 h of photocatalytic
reaction. Namely, at the beginning of photocatalytic reaction,
Fig. 5 e PL spectra of CdS nanorods and Ni/CdS.
Fig. 6 e Hydrogen evolution rate on Ni/CdS. Ni loading
content (wt%): 1.5, 3.0, 4.0, 6.0, and 7.0. Reaction
conditions: 0.1 g Ni/CdS, 50 mL aqueous solution
containing 1 M (NH4)2SO3; 300 W Xe lamp (l ≥ 420 nm).
the hydrogen evolution rate tends to increase with extending
reaction time, possibly due to enrichment of photo-induced Ni
nanoparticles on CdS surface therewith. After 2 h of photo-
catalytic reaction, the hydrogen evolution rate of 4.0%Ni/CdS
photocatalyst tends to stabilize around 22.539 mmol/(h$g),
and in follow-up four cycles it remains around 28.902, 29.801,
28.970, and 26.328 mmol/(h$g), respectively. For 2.5% Ni/CdS
photocatalyst, the hydrogen evolution rate in five cycles is
17.789, 19.705, 23.001, 23.287, and 20.658 mmol/(h$g), respec-
tively. This phenomenon indicates Ni/CdS possesses excellent
durability in photocatalytic water splitting reaction [25,26].
Conclusions
Ni nanoparticles with a high degree of crystallization and a
size of about 10 nm are prepared by chemical reduction of
NiCl2$6H2O by N2H4$H2O. As-obtained Ni nanoparticles are
then adopted to improve CdS nanorods prepared through
solvothermal method in order to afford Ni/CdS photocatalyst.
The structure characterizations by TEM, XRD, and UVeVis
Fig. 7 e Time course of photocatalytic hydrogen production
over Ni/CdS (Ni dosage: 2.5% & 4.0%) photocatalyst. In the
darkness, the reaction system is switched to N2 flow to
remove H2.
 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 4 0 ( 2 0 1 5 ) 3 4 0 e3 4 5
indicate that Ni nanoparticles are uniformly loaded on CdS
nanorod surface, and they tend to preferentially deposit on
the (100), (002) and (101) crystal planes of CdS under light-
induced reduction. Moreover, as-prepared nano-Ni/CdS pho-
tocatalyst exhibits good visible light catalytic activity towards
water splitting-hydrogen evolution in (NH4)2SO3 aqueous so-
lution. Particularly, nano-Ni/CdS photocatalyst with a Ni
loading of 4% possesses the best visible-light catalytic activity
for water splitting-hydrogen evolution and provides a
hydrogen production rate of up to 25.848 mmol/(h$g)
(QE ¼ 26.8%, l ¼ 420 nm), while it exhibits stabilized photo-
catalytic activity towards H2 evolution as well, showing
promising potential as a candidate photocatalyst for water
splitting generating hydrogen under visible light irradiation.
Acknowledgments
The authors are grateful for the financial support from Inter-
national Cooperation Program (Science & Technology
Department of Henan Province, grant No. 130602). This
research is also financially supported by Chinese National
Engineering Center of Environmental Photocatalysis. (K-
092001).
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