Applied Catalysis A, General 588 (2019) 117281

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Applied Catalysis A, General

journal homepage: www.elsevier.com/locate/apcata

CdS nanorods anchored with CoS2 nanoparticles for enhanced T

photocatalytic hydrogen production
Jie Tanga,1, Bin Gaoa,1, Jinbo Pana,1, Lang Chena,⁎, Zihao Zhaoa, Sheng Shena, Jun-Kang Guoa,⁎,
Chak-Tong Aub, Shuang-Feng Yina,⁎
a
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Provincial Hunan Key Laboratory for Cost-effective
Utilization of Fossil Fuel Aimed at Reducing Carbon-dioxide Emissions, Hunan University, Changsha, 410082, Hunan, People’s Republic of China
b
College of Chemistry and Chemical Engineering, Hunan Institute of Engineering, Xiangtan, 411104, Hunan, People’s Republic of China

A R T I C LE I N FO A B S T R A C T

Keywords: Herein, we report the use of cobalt sulfide (CoS2) as efficient and inexpensive co-catalyst of CdS nanorods for
CoS2/CdS composites photocatalytic water splitting. The aim is to explore the use of earth-abundant cobalt species to replace precious
Photocatalysis metals for the photocatalytic reactions. The results of first-principles DFT simulation and planar-averaged dif-
DFT calculation ferential charge density calculation reveal that at the CoS2/CdS interface, CoS2 has zero band gap which is a class
H2 production
nature of precious metals, and functions as electron trap to enhance the transfer of hot electrons from CdS to
CoS2. Owing to the merits of efficient charge separation, high exposure of active sites as well as large surface
area, the CoS2/CdS composites exhibit outstanding photocatalytic activity in H2 production under visible light
(˜58 mmol·g−1 h−1), which is about 19 times that of CdS nanorods alone and 3 times that of 1 wt%Pt/CdS under
the same conditions.

1. Introduction
With the ever increasing demand of energy, the burning of fossil
fuels is inevitable and environmental pollution is a global concern.
Extensive studies have been conducted in search of energy resources
that are environment-friendly and renewable [1–4]. In this aspect,
hydrogen is the most commendable. The photocatalytic generation of
hydrogen from water splitting using inexhaustible solar energy is a
state-of-the-art strategy, and the use of an efficient photocatalyst is
critical [5–7]. Many attempts have been made to develop high-effi-
ciency photocatalysts, such as phase and morphology adjustment [8],
doping with metal and non-metal elements [9,10], fabrication of het-
erojunctions [11,12] and the use of co-catalysts [13–16]. Among them,
the introduction of a co-catalyst can not only suppress the recombina-
tion of charge carriers through electron trapping but also provide active
sites for proton reduction. Noble metals such as Pt, Pd, Au and Ag have
been widely used as efficient co-catalysts for hydrogen production due
to their low Fermi levels [17–21]. However, the high price and rela-
tively rare resource of precious metals hampers their usage. Therefore,
it is extremely urgent to explore alternatives that are economically
commendable.
Co-catalysts that are based on earth abundant materials are much
cheaper [4], such as transition-metal sulfides (e.g., WS2 [22], MoS2
[23–25], NiS [26,27], CoxSy [28,29], MnS [30]), and many have
showed excellent performance in a majority of photocatalytic systems.
In our previous works, WS2 and MoS2 nanoplates were anchored on CdS
nanorods, and there was great improvement in hydrogen production
under visible light irradiation [31–33]. Recently, there were reports on
the coupling of cobalt sulfide (e.g., CoS [34], CoS2 [35], Co3S4 [36],
Co9S8 [28,29]) with semiconductors to enhance the separation of
charge carriers for the promotion of photocatalytic activity. For ex-
ample, through rational design of Z-scheme system, Tan et al. devel-
oped hierarchical CdS-supported Co9S8 nanoparticles that displayed
high activity and stability in photocatalytic hydrogrn evolution (PHE).
Furthermore, over CdS nanorods modified by cobalt-based co-catalysts
(Co(OH)2, Co3O4, CoS, CoO), Lang et al. observed high photocatalytic
activity and reported that the cobalt-containing species play a sig-
nificant role in the trapping and transport of hot electrons. According to
these photocatalytic systems, cobalt sulfide as a co-catalyst can
strengthen the absorption of solar light, accelerate the separation of
photogenerated charge carriers, and offer ample active sites for reac-
tions [37]. Hou and coworkers reported a hydrogen production effi-
ciency of 1232 μmol·h−1 g−1 over CoS2/g-C3N4 hybrid composites [35].
Fu et al. improved the light harvesting ability of carbon quantum dots

⁎
Corresponding authors.
E-mail addresses: huagong042cl@163.com (L. Chen), jkguozd@126.com (J.-K. Guo), sf_yin@hnu.edu.cn (S.-F. Yin).
1
The authors contributed equally to this work.

https://doi.org/10.1016/j.apcata.2019.117281
Received 21 August 2019; Received in revised form 29 September 2019; Accepted 3 October 2019
Available online 08 October 2019
0926-860X/ © 2019 Elsevier B.V. All rights reserved.
J. Tang, et al.
(CDs) by adding CoMo-S in the photocatalytic system [38]. Reddy and
coworkers also used C@CoS2 as co-catalyst to enhance the PHE activity
of CdS nanorods [37]. It is hence envisaged that similar to noble metals,
cobalt sulfides may facilitate the transfer of photogenerated charge
carriers at the heterojunctions.
It was reported that cobalt disulfide (CoS2) with intrinsic metallic
conductivity (6.7 × 103 S cm−1 at 300 K) displayed remarkable elec-
trocatalytic and photoelectrocatalytic activities [39]. Using metallic
cobalt pyrite CoS2 (micro- and nanostructure) as catalysts, Matthew
et al. observed good electrocatalytic performance for hydrogen evolu-
tion reaction (HER) [40]. Using Si microwires surrounded by cobalt
disulfide as photocathode for solar hydrogen evolution, Chen and
coworkers found that CoS2 not only served as protective layer, but also
as a co-catalyst to reduce the recombination of charge carriers [41]. In
other words, CoS2 can promote the migration and separation efficiency
of photoelectrons. Despite the presence of cobalt sulfide is known to be
beneficial for electron transfer from semiconductors, the exact nature of
charge separation at the composite interfaces is always neglected.
In this work, we facilely anchored CoS2 nanoparticles on CdS na-
norods by an in-situ solvothermal method, and analyzed the band gap
as well as the shift direction of interfacial electrons at the CoS2/CdS
heterojunction by DFT calculations. Owing to large surface area, high
exposure of active sites, and effective transfer of photogenerated elec-
trons from CdS to CoS2, the CoS2/CdS composite gave a H2 production
rate of ˜58 mmol·g−1 h−1 (λ ≥ 400 nm), much higher than that of CdS
or Pt/CdS.
2. Experimental section
2.1. Preparation
2.1.1. Synthesis of CdS nanorods
CdS nanorods were prepared according to the solvothermal method
described by Jiang et al. [42]. Typically, 20.23 mmol of CdCl2·2.5H2O
and 60.69 mmol of CH4N2S were dissolved in ethanediamine (60 mL).
Then the solution was transferred to a polyphenylene-lined autoclave of
100 mL and heated at 160 °C for 50 h. The yellow product was collected
by filtration, washed with de-ionized water and ethanol for three times,
and dried at 80 °C for 12 h.
2.1.2. Synthesis of CoS2/CdS composites
The synthetic process of CoS2/CdS composites is illustrated in
Scheme 1. Briefly, 1 mmol of Co(NO3)2·6H2O and 2 mmol of thiourea
were dissolved in 80 mL of ethylene glycol, and the mixture was stirred
for 10 min to form a pink solution. Then a certain amount of the as-
prepared CdS nanorods was added with stirring in a period of 10 min.
The mixture was then subject to ultrasonic treatment with stirring for
60 min. The as-generated yellow solution was transferred into a poly-
phenylene-lined autoclave of 100 mL and heated at 180 °C for 24 h. The
final product was collected by filtration, washed with deionized water
Scheme 1. Synthetic procedure of CoS2/CdS composites.
2
Applied Catalysis A, General 588 (2019) 117281
and ethanol for three times, and dried at 80 °C overnight. Altogether
seven CoS2/CdS composites with Co:Cd molar ratio of 1:0.5, 1:1, 1:2,
1:3, 1:4, 1:5, and 1:6 were synthesized, and are herein denoted as
CC0.5, CC1, CC2, CC3, CC4, CC5, and CC6, respectively. The pure CoS2
catalyst was synthesized following the above steps but without the
addition of CdS.
2.1.3. Synthesis of physically mixed CoS2-CdS composite
For comparison purpose, a sample of CoS2-CdS composite was
prepared by physical mixing (Co:Cd = 1:4, denoted as CC4(P)). Briefly,
1 mmol of as-prepared CoS2 powder and 4 mmol of CdS nanorods were
thoroughly ground in an agate mortar for 30 min, and the collected
powder was dried at 80 °C overnight.
2.1.4. Synthesis of Pt/CdS composite
The Pt/CdS composite was prepared by loading 1 wt% of Pt on CdS
according to the photoreduction method reported by Zhang et al. [43].
First, 50 mL of H2PtCl6·6H2O solution containing 2 mg of Pt was pre-
pared. Then 200 mg of CdS nanorods was added to the solution, and the
mixture was allowed to stand at 25 °C for 2 h. The solution was then
illuminated using a 300 W Xe lamp (with a cut-off filter to remove light
with λ < 400 nm) for 2 h with stirring. Finally the yellow powder was
collected, washed with deionized water and absolute ethyl alcohol for
three times, and dried at 80 °C overnight.
2.2. Characterization
Powder X-ray diffraction (XRD, D/MAX-2000/PC, λ = 0.15406 nm,
Rigaku Corporation) was employed for the characterization of crystal
structure. The morphology and elemental mapping analyses were
conducted over a field emission scanning electron microscope (FE-SEM)
(Hitachi S-4800) and a transmission electron microscope (TEM, accel-
erating voltage: 100 kV, Tecnai G2 F20). The element contents of
samples were calculated according to the results of ICP-OES analysis
(Varian 720). The surface composition and chemical states of elements
was analyzed by means of X-ray photoelectron spectroscopy (XPS,
Thermo SCIENTIFIC K-Alpha). The specific surface area (BET) of sam-
ples was obtained by using a Gemini VII 2390 instrument
(Micromeritics Instrument Corp.). UV–vis diffuse reflectance spectra of
samples were recorded using a spectrophotometer (Cary 100, Agilent).
Photoluminescence (PL) measurement was performed on a fluorescence
spectrophotometer (excitation light: 350 nm). An electrochemical ana-
lyzer (CHI660D, Shanghai Chenhua) was employed to record photo-
electrochemical activity, using Ag/AgCl (3 M KCl) as reference elec-
trode, Pt wire as counter electrode, prepared sample (20 mg powder,
0.5 mL Nafion, 1.5 mL alcohol, and dried at 80 °C for 2 h) as working
electrode, and sodium sulfate (Na2SO4, 0.2 M) as electrolyte. The data
for the plotting of M-S curves were measured using sodium sulfate
electrolyte solution (0.2 M, pH = 7), and the amplitude voltage was
5 mV at a selected frequency. The final potentials vs. Ag/AgCl were
J. Tang, et al.
translated into the standard hydrogen electrode using the below
equation [44]:
ENHE = EAg/AgCl + 0.197
We carried out the density functional theory (DFT) calculations with
the Perdew-Burke-Ernzerhof (PBE) exchange-correlation fuctional in
the Vienna ab initio simulation package (VASP) and employed the
empirical correction method proposed by Grimme (DFT-D2) to describe
the van deer Waals (vdW) interaction. The Heyd-Scuseria-Ernzerhof
(HSE06) hybrid functional was adopted to investigate the band gap due
to the underestimation of PBE. The energy cutoff for plane-wave basis
set and the Monkhorst-Pack k-point grid were set as 350 eV and 3 × 3
× 1, respectively. A vacuum space of over 15 Å along the c axis was
constructed to minimize the interaction between adjacent layers. The
geometric structure was optimized until the convergence standard of
total energy was 1.0 × 10–5 eV and the force on per atom was smaller
than 0.05 eV∙Å–1.
2.3. Photocatalytic hydrogen generation
Photocatalytic hydrogen production experiments were carried out
in a sealed quartz reactor (250 mL) equipped with pumping facility. The
reactor top was illuminated with a 300 W Xe lamp (HSX-F300,
Perfectlight, Beijing) with a cut-off filter (λ ≥ 400 nm). First, 20 mg of
photocatalyst was put in the reactor lumen together with an aqueous
solution containing lactic acid or Na2S/Na2SO3 (50 mL, 20 vol%). Then
the gases were removed using a vacuum pump, and the reaction system
was kept in the dark with constant stirring for 30 min to establish ad-
sorption-and-desorption equilibrium. The production of hydrogen was
hourly monitored using a gas chromatograph (Agilent, 7820A, 5A
molecular sieve column) equipped with a thermal conductivity de-
tector. The apparent quantum yield (A.Q.Y.) was measured upon
monochromatic light irradiation according to the method reported in
our previous work [31] using the following equations:
number of reacted electrons
A.Q. Y. = × 100%
number of incident photons
2 × (number of evolved hydrogen molecules)
= × 100%
number of incident photons
3. Results and discussion
The XRD patterns of CdS, CoS2 and CoS2/CdS samples are compiled
in Fig. 1a. The peaks of CdS nanorods match well with those of hex-
agonal phase CdS (JCPDS 41-1049) [42], while the main peaks of CoS2
nanoparticles are assignable to those of cubic CoS2 (JCPDS 41-1471)
[45], suggesting that pure CdS and CoS2 were successfully prepared. As
for the CoS2/CdS composites, the characteristic peaks of CdS can be
detected but those of CoS2 cannot. The absence of CoS2 signal could be
due to its high dispersion, low content, and/or poor crystallinity. Si-
milar phenomena were reported in the works of Chen et al. [13] and
Jiang et al. [42]. It is worth pointing out that the relative intensity of
the (100) peak (2θ = 24.807°) of CdS as well as that of the composites
are much higher than that of standard CdS (in the PDF card), indicating
the high exposure of the CdS (100) plane. Similarly, the XRD pattern of
CoS2 indicates the high exposure of the (200) plane. Furthermore, the
actual composition of the CoS2/CdS composites was verified by ICP-
OES analysis (Table S1, supporting information, SI†), and the genuine
Co:Cd molar ratios are quite in agreement with the nominal ones.
Overall, the results of XRD and ICP analyses evidence the successful
fabrication of the CoS2/CdS composites. Furthermore, because there is
no detection of impurity phases, it is deduced that the coupling of CoS2
with CdS has little effect on the crystallinity and phase structure of CdS.
We performed XPS analysis to investigate the chemical states and
composition of surface elements. The survey spectra of CdS, CoS2 and
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Applied Catalysis A, General 588 (2019) 117281
CoS2/CdS samples are displayed in Fig. 1b, which indicates the pre-
sence of Cd and S on CdS, Co and S on CoS2, and Co, Cd, S on the CoS2/
CdS composites. The Co 2p spectrum of CoS2 shows deconvoluted peaks
at 797.6, 793.9, 781.5, and 778.7 eV as well as two shake-up satellite
peaks (Fig. 1c). The peaks at 797.6 eV and 781.5 eV are Co 2p1/2 and
2p3/2 signals of CoS2, while those at 793.9 eV and 778.7 eV are Co 2p1/2
and 2p3/2 signals of cobalt oxide [46,47]. As for CdS, it shows Cd 3d
peaks at 410.8 eV and 404.1 eV (Fig. 1d), and S 2p peaks at 161.5 eV
and 160.4 eV (Fig. 1e), in agreement with literature data [31,42].
Compared with the S 2p spectrum of CdS, that of CoS2 is more com-
plicated (Fig. 1e). The CoS2 peaks at 163.2 eV and 161.9 eV are as-
cribable to the S 2p1/2 and 2p3/2 signals of CoS2, which overlap strongly
with those of SeC species. As for the peak at 168.9 eV, it is attributable
to the S 2p1/2 and 2p3/2 signals of SeO entities [38,47,48]. The XPS
spectra of the hybrid CoS2/CdS samples (i.e. CC2, CC4 and CC6) are
rather similar (Fig. 1f,g,h). The Cd 3d3/2 and Cd 3d5/2 peaks are at
411.6 eV and 404.8 eV, respectively (Fig. 1d), which are consistent with
the Cd2+ signals of CdS in literature [13,31]. The Co 2p signals at
796.6 eV and 780.6 eV are assignable to Co-S of CoS2, while those at
794.0 eV and 778.9 eV) to Co-O of cobalt oxide, and the two peaks in
purple color are attributed to shake-up satellites [45,47]. In Fig. 1h, the
peaks at 161.1 eV and 163.0 eV are ascribed to the S 2p3/2 and 2p1/2 of
Co-S bond, and the signals at 168.8 eV was caused by SeO bond, which
is in agreement with previous reports [29,43]. Compared to CdS, CC4
exhibits positive shift (˜0.8 eV) in Cd 3d and S 2p binding energy, while
compared to CoS2, there is negative shift (˜0.8 eV) of Co 2p and S 2p
binding energy, which indicate electron transfer from CdS to CoS2
[28,49,50]. Based on the XPS results, it is deduced that there are close
interaction between CdS and CoS2, forming interfaces in CC2, CC4 and
CC6 that act as ‘electron bridges’ to accelerate charge transfer.
According to the XRD results, the most exposed surfaces of the
CoS2/CdS composites are those of the CoS2 (200) and CdS (001) planes
(Fig. 1a). We hence conducted the first-principles DFT simulation
(Fig. 2a and b) based on the structures of CoS2 (200) and CdS (001)
surfaces: cubic phase with Pa-3 space group for CoS2 and hexagonal
phase with P63mc space group for CdS. The geometric structure of
CoS2/CdS is illustrated in Fig. 2c, and the lattice mismatch is no more
than 2.53%. The calculated binding energy of CoS2/CdS is less than
zero, which indicates that CoS2 and CdS can form a heterostructure that
is thermodynamically stable. We performed first-principle calculation
to explore the innate characteristics of charge transfer and separation.
The Fermi levels (EF) of the exposed CdS (001) and CoS2 (200) surfaces
are estimated as follows:
Φ = E vac − EF
Where Φ is the work function, which is calculated to be 5.17 eV and
5.23 eV, respectively, for CdS (001) and CoS2 (200) surfaces
(Fig. 2d − e), and Evac is the energy of a stationary electron at the va-
cuum level (assumed to be 0 eV). Accordingly, the EF of CdS (001) and
CoS2 (200) surfaces can be calculated to be -5.17 and -5.23 eV, re-
spectively. The results are consistent with the work of Xu et al., which
revealed that the work function (vs. vacuum level) of CdS and CoS2 was
5.18 eV and 5.49 eV, respectively [51]. It is obvious that the EF of CoS2
(200) surface is more negative than that of CdS (001) surface. Thus,
when the CdS (001) and CoS2 (200) surfaces are in contact, electrons
tend to migrate from CdS to CoS2 for potential equilibrium, restraining
the recombination of charge carriers as a result. To further demonstrate
the charge transfer at the CoS2/CdS interface, the planar-averaged
differential charge density was calculated and the result is shown in Fig.
S1 (SI†). The positive value represents charge accumulation, while the
negative value indicates charge depletion. It is apparent that at the
CoS2/CdS interface, electrons primarily transfer from the CdS layer to
the CoS2 layer.
As shown in Fig. 3a and b, the SEM images of pure CdS clearly show
nanorods with an average length of 800 nm. The surface of the na-
norods is smooth, showing no impurity or pores [44]. On the other
J. Tang, et al.
Fig. 1. (a) XRD patterns, (b) XPS survey spectra, and high-resolution XPS spectra of samples: (c) (f) Cd 3d, (d) (g) S 2p, (e) (h) Co 2p.
hands, pure CoS2 exists as microparticles approximately 1.5 μm in size
(Fig. 3c and d), which are assemblies of nanoparticles. The morphology
of CoS2/CdS heterostructure is displayed in Fig. 3e and f. It is clear that
the CoS2 nanoparticles (about 15 nm in size) are evenly distributed on
the CdS nanorods with no sight of aggregation, and hence could not be
detected in XRD analysis. Furthermore, the BET surface area of CdS and
CC4 is 32.7 m2 g−1 and 34.7 m2 g−1, respectively (Fig. S2, SI†). Despite
the difference in specific surface area is not apparent, there are much
more active sites on the latter due to the presence of CoS2.
The TEM and HRTEM images of pristine CdS nanorods and CC4 are
displayed in Fig. 4. In consistent with the SEM results, the TEM image of
Fig. 4a clearly shows that the surface of CdS nanorods is smooth. The
HRTEM image (Fig. 4b) reveals crystal lattice fringes of 0.36 nm which
is assignable to the (100) lattice plane of CdS [52]. The images of CC4
in Figs. 4c and d exhibit the presence of particles approximately 15 nm
in size on the CdS nanorod, and their presence does not alter the
structure of the CdS nanorod. The lattice spacings of 0.25 nm and
4
Applied Catalysis A, General 588 (2019) 117281
0.24 nm are attributed to the (210) plane of CoS2 and (102) plane of
CdS, respectively. The results are in line with those of previous reports
[13,53,54]. The elemental mapping (Fig. 4e − h) and EDX analysis
results (Fig. S3, SI†) of CC4 further disclose homogeneous distribution
of Cd, S and Co elements which confirms the high dispersion of CoS2
nanoparticles on CdS.
The absorption coefficient of the composites is determined ac-
cording to the following equation:
1
α (ω) = ( 2 ) ω [ ε1 (ω)2 + ε2 (ω)2 − ε1 (ω)] 2
Where ε1 (ω) and ε2 (ω) are the real and imaginary parts of dielectric
function, respectively, and ω is defined as the function of optical fre-
quency. As shown in Fig. 5a, CdS has poor optical absorption and needs
improvement in the 1.6 − 3.1 eV region for visible light absorption,
while the absorption coefficient of CoS2 is higher than that of CdS.
Upon coupling of CdS and CoS2, there is significant enhancement of
light absorption. In order to disclose the energy band structure of CdS
J. Tang, et al.
Fig. 2. Side and top views of (a) CoS2, (b) CdS and (c) CoS2/CdS; calculated electrostatic potentials along z direction of (d) CdS and (e) CoS2.
and CoS2, we carried out calculation using density functional theory
(DFT). The electronic band structure of CoS2 and CdS are shown in
Fig. 5b and c. It is clear that the band gap of CoS2 is 0 eV, which is in
consistent with the result of Chen et al. [55]. Meanwhile, the band gap
of CdS is 1.52 eV, in agreement with the calculation result of Garg et al.
that planar CdS is a semiconductor with a band gap of 1.60 eV [56]. The
agreement indicates that our calculation adopting the PBE approach is
appropriate. The outcomes (Fig. 5) predict that CoS2 has good light-
harvesting ability and good photoelectron conductivity (Eg = 0 eV at
the CoS2/CdS interface) at the CoS2/CdS heterojunction. It is hence
theoretically confirmed that the metallic property of CoS2 is crucial in
the transfer and separation of photoelectrons for photocatalytic evolu-
tion of hydrogen in water splitting.
The UV–vis diffuse reflectance spectra of the as-prepared samples
are depicted in Fig. 6a. Pure CdS nanorods show obvious absorption in
the region of 400–530 nm as previously reported [15,42], and CoS2
exhibits absorption that covers almost the entire visible light region
[45]. As for the composites, they show light absorption pattern similar
to that of CdS but with enhanced absorption in the 530–700 nm region,
in agreement with the DFT calculation results (Fig. 5a). The phenom-
enon could be ascribed to the strong absorption capacity of CoS2 in
visible light region and the interfacial interaction between CdS and
CoS2. In addition, the band gaps of the CoS2/CdS samples can be ob-
tained using the following equation [15]:
αhv = A(hv-Eg)n/2
where α, h, v, A and Eg stand for the absorption coefficient, Planck’s
constant, light frequency, proportionality constant, band gap, respec-
tively; and n is dependent on the type of semiconductor. According to
the Kubelka–Munk plots in Fig. 6b, the band gap values of CdS and CC4
are 2.38 eV and 2.37 eV, respectively, which are larger than the theo-
retical value (1.52 eV). It is plausibly because the former are experi-
mental values based on bulk samples while the latter is calculated value
based on a small model of layered CdS at the CoS2/CdS interface. The
5
Applied Catalysis A, General 588 (2019) 117281
Mott–Schottky curves were plotted to qualitatively analyze the p–n
junctions in the absence of illumination as illustrated in Fig. S4 (SI†).
The C−2/F−2-E plot of CdS displays a positive slope, which is char-
acteristic of n-type semiconductor. By obtaining the X intercept by
means of extrapolation of Mott-Schottky plots (in supporting informa-
tion), the flat-band potential (Vfb) vs. NHE of CdS at pH = 7.0 is
roughly -0.719 V. Using the band gap of CdS (2.38 eV) estimated from
the UV–vis DRS graph, the valence band of CdS is found to be +1.661 V
vs. NHE at pH = 7.0. With built-in electric field at the CoS2/CdS het-
erojunction, the photoelectrons quickly transfer from CdS to CoS2,
leading to enhanced H2 production under visible light irradiation.
The photoluminescence (PL) spectra of CoS2/CdS composites are
shown in Fig. 6c. That of CdS shows an apparent peak at about 537 nm
due to the direct recombination of photogenerated charge carriers. A
lower PL signal means higher separation efficiency of photo-excited
charge carriers. Apparently, the loading of CoS2 nanoparticles on the
CdS nanorods results in lowering of PL intensity. Among the CoS2/CdS
composites, CC4 shows the lowest PL intensity and hence is the most
efficient in preventing the recombination of charge carriers. To further
confirm the mobility of photogenerated charge carriers in the CoS2/CdS
samples, transient photocurrent was recorded and analyzed using
electrodes coated with the samples under visible light irradiation
(Fig. 6d). It is clear that photocurrent could only be obtained upon light
irradiation. Specifically, pure CdS nanorods is the lowest in photo-
current intensity while CC4 the highest, giving an intensity order of
CdS < CC2 < CC6 < CC4. Again, the results demonstrate that the
loading of CoS2 nanoparticles on CdS nanorods can efficiently enhance
the transfer and separation of photoexcited electrons and holes.
Photocatalytic hydrogen evolution under visible light illumination
was used to assess the photocatalytic performance of the CoS2/CdS
composites. As illustrated in Fig. 7a, there is no detection of H2 over
CoS2 nanoparticles owing to its class nature of precious metals, while
the activity of CdS is limited (3.1 mmol·g−1 h−1 after an irradiation of
3 h). Gratifyingly, all the CoS2/CdS composites show activity higher
J. Tang, et al. Applied Catalysis A, General 588 (2019) 117281

Fig. 3. SEM images of (a) (b) CdS nanorods, (c) (d) CoS2 and (e) (f) CC4.

Fig. 4. TEM images of (a) (b) CdS nanorods, (c) (d) CC4 and (e)–(h) the relevant EDX mappings of Cd, S, Co.

6
J. Tang, et al.
than that of CdS (Fig. 7b). Among the prepared catalysts, CC4 is the
most efficient, giving a H2 production rate of 58.1 mmol·g−1 h−1,
which is ca. 19 times that of CdS nanorods, four times that of CC4(P)
prepared by physical mixing (14.7 mmol·g−1 h−1), and three times that
of 1 wt%Pt/CdS (19.8 mmol·g−1 h−1). The results reveal that CoS2 can
replace noble metals as an effective co-catalyst for photocatalytic gen-
eration of hydrogen in water splitting. Among the CdS-based photo-
catalysts using Co-containing compounds as co-catalysts for H2 pro-
duction under visible light irradiation, CC4 is moderate in activity.
However, among the reported CdS photocatalysts modified by cobalt
sulfides, CC4 is the highest in activity as well as apparent quantum yield
(A.Q.Y., 39.6% at 400 nm) (Table S2, SI†).
To evaluate the reusability of CC4, recycling experiments were
performed (Fig. S5a, SI†). When lactic acid is used as sacrificial agent,
Fig. 6. (a) UV–vis diffuse reflectance spectra (DRS), (b) the corresponding (αhv)2 versus hv curves, (c) photoluminescence spectra (excitation light: 350 nm), and (d)
transient photocurrent response in 0.5 M Na2SO4 aqueous solution under visible light (λ > 400 nm) of pure CdS and CoS2/CdS composites.
7
Applied Catalysis A, General 588 (2019) 117281
Fig. 5. (a) The optical absorption spectra of
CoS2, CdS and CoS2/CdS; electronic band
structures of (b) CoS2 and (c) CdS calculated by
PBE functional. The Fermi level is placed at zero
and marked by horizontal green dotted lines.
The vertical red dash lines G, M and K represent
the high-symmetry k points: (0, 0, 0), (0, 1/2, 0)
and (-1/3, 2/3, 0), respectively. (For inter-
pretation of the references to colour in this
figure legend, the reader is referred to the web
version of this article).
there is apparent decrease in H2 production across the four cycles.
Nonetheless, when Na2S/Na2SO3 (0.35 M Na2S/0.25 M Na2SO3) is used,
there is no apparent loss, confirming the high stability of CC4 in alka-
line solution. We employed the XRD, TEM and XPS techniques to
analyze CC4 before and after reaction using either lactic acid or Na2S/
Na2SO3 as sacrificial agent. The XRD patterns suggest no change of
phase structures after reaction (Fig. S6, SI†). There is no change in the
Cd 3d spectra neither after reaction (Fig S7, SI†). Hence the XRD and
XPS results confirm the stability of CdS nanorods. However, there is
obvious loss of Co 2p signal after recycling in lactic acid solution (Fig.
S7, SI†), and the depletion of Co species may result in the loss of
photocatalytic activity. The loss of CoS2 nanopartices in lactic acid
solution was further confirmed by the TEM images (Fig. S8a and b, SI†).
In the case of using Na2S/Na2SO3 as sacrificial agent, Co 2p signal
J. Tang, et al.
Fig. 7. (a) Extent of photocatalytic H2 evolution, and (b) photocatalytic H2 evolution rate over the as-prepared samples under visible light irradiation. Reaction
conditions: 100 mL (10 vol% LA) aqueous solution, 20 mg catalyst, 300 W Xe-lamp (λ ≥ 400 nm) for 3 h.
Fig. 8. Possible mechanism of visible-light-driven H2 production over CdS na-
norods modified with CoS2 nanoparticles using hole scavenger.
similar to that of fresh CC4 can still be observed after use (Fig. S7, SI†).
Also, uniform dispersion of CoS2 nanoparticles on CdS can be found in
the TEM image of CC4 after 4 cycles of use (Fig. S8c and d, SI†). The
results indicate the stability of CC4 when Na2S/Na2SO3 is adopted as
sacrificial agent.
Overall, CdS nanorods exhibit low activity in photocatalytic hy-
drogen production due to poor separation efficiency of photogenerated
charge carriers. When CoS2 nanoparticles are used as co-catalyst, the
modified CdS nanorods exhibit higher hydrogen production efficiency
under visible light irradiation. It is because CoS2 nanoparticles can
strengthen the absorption of visible light and enhance the separation
efficiency of photogenerated charge carriers. Furthermore, the loading
of CoS2 nanoparticles with class nature of precious metals can enrich
the CdS surface with sites for proton reduction. Based on the above
results, a possible mechanism is proposed for HER under visible light as
illustrated in Fig. 8. Upon visible light illumination, electrons and holes
are generated on the surface of CdS nanorods. Then the photoexcited
charge carriers are subject to immediate separation and/or transition
under the influence of internal electric field. Part of the photogenerated
electrons in the CdS valence band (VB) transfer to the CdS conduction
band (CB) and ulteriorly migrate to the catalyst surface, leaving holes in
the VB of CdS. Finally, lactic acid molecules (or Na2S/Na2SO3) are
oxidized by the VB holes and water molecules are reduced to hydrogen
by the CB electrons. The presence of CoS2 nanoparticles on CdS can
lower the migration resistance of photogenerated electrons for facile
transit to CoS2 nanoparticles, consequently enhancing the separation of
charge carriers and promoting the photocatalytic performance of CdS
8
Applied Catalysis A, General 588 (2019) 117281
for visible-light-driven water splitting.
4. Conclusion
In summary, CoS2 nanoparticles were successfully loaded on the
surface of CdS nanorods using a simple in-situ solvothermal method.
With the deposition of an optimal amount CoS2 nanoparticles, CdS
nanorods exhibit high apparent quantum yield (39.6%, λ = 400 nm)
and outstanding efficiency for H2 production (˜58.1 mmol·g−1 h−1)
under visible light, much higher than that of CdS nanorods deposited
with 1 wt%Pt (19.8 mmol·g−1 h−1). Based on the results of DFT cal-
culation and characterization, it is deduced that with class nature of
precious metals, cobalt disulfide acts as an effective co-catalyst that can
not only efficiently enhance the separation and migration of photo-
generated charge carriers but also offer ample surface sites for proton
reduction. This article demonstrates that CoS2 is a commendable al-
ternative to noble metals as co-catalyst for the enhancement of photo-
catalytic H2 production under visible light irradiation. Moreover, the
findings provide a new synthetic route for the coupling of zero di-
mensional nanoparticles with two dimensional semiconductors.
Acknowledgements
This project was financially supported by the NSFC
(Grants21725602, 21776064, and21671062), and Innovative Research
Groups of Hunan Province (Grant 2019JJ10001). C. T. Au thanks HNU
for an adjunct professorship.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.apcata.2019.117281.
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