Research Article

Received: 16 February 2021 Revised: 22 April 2021 Accepted article published: 28 April 2021 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.6768

In situ deposition of CdS on MoS2/rGO-based

nanocomposites for highly efficient
photocatalytic H2 evolution reaction with
visible light
Bi-yu Tan,a Xiao-jie Songa,b and Shi Xian-yanga*

Abstract
BACKGROUND: The development of advanced and inexpensive photocatalytic systems exhibiting high efficiency is highly
desired for hydrogen (H2) production. In this work, a hydrothermal and in situ growth method was employed for the construc-
tion of CdS/MoS2/rGO nanocomposites by coupling MoS2/rGO with CdS to produce H2. The stability and photocatalytic
properties of the nanocomposites for H2 evolution at different CdS content were investigated.
RESULTS: It was found that CdS/MoS2/rGO nanocomposites with 0.35 wt% CdS displayed the highest H2 evolution rate of
11 331.65 ∼mol h−1 g−1. This corresponded to the apparent quantum efficiency of 10.4% at 420 nm, which was approximately
46 times higher than that of pure CdS. The CdS/MoS2/rGO nanocomposites showed excellent stability in 6-run recycling
experiments. Additionally, a plausible H2 production mechanism was proposed.
CONCLUSION: The remarkable photocatalytic activity was attributed to the high electron–hole pair separation efficiency upon
the introduction of MoS2/rGO. This work provides new insights for enhancing the photocatalytic H2 evolution activity.
© 2021 Society of Chemical Industry (SCI).

Supporting information may be found in the online version of this article.

Keywords: CdS/MoS2/rGO nanocomposites; photocatalysis; H2 evolution reaction; visible light

INTRODUCTION hinder their widespread application. Consequently, the develop-

H2 is considered one of the most promising, renewable, and ideal
alternative energy to fossil fuels.1 To alleviate the environmental
concerns and solve the energy crisis, photocatalytic water split-
ting has been proposed as an attractive approach for the genera-
tion of H2.2,3 The key to effective photocatalytic H2 evolution is the
development of an inexpensive, highly efficient, and visible light-
driven photocatalyst.4 In the last few decades, various photocata-
lytic materials have been exploited as potential candidates for the
photocatalytic H2 evolution reaction (HER). For instance, CdS is a
typical semiconductor photocatalyst, which exhibits a narrow
band gap and can effectively absorb visible light.5,6 The photo-
generated electrons produced by CdS show strong reducing
capacity, which can be used for HER. Nevertheless, the photocar-
riers of CdS are easily to recombine.7,8 Moreover, the occurrence
of photocorrosion following light exposure results in low catalyst
activity for HER.9,10 Thus, cocatalysts, including noble metals,
semiconductors, and carbon allotropes, have been widely utilized
to separate and capture photogenerated charge carriers as well as
to enhance the catalytic activity and stability of CdS. Noble metals
such as Pd and Pt, have been demonstrated as particularly excel-
lent cocatalysts. Loading of Pd or Pt on the surface of CdS
enhanced its photocatalytic activity for H2 evolution.11,12 How-
ever, the scarcity and high cost of noble metals considerably
ment of cocatalysts using non-noble metals is important.13
MoS2 is an emerging cocatalyst material, which has been used
as an alternative to noble metal cocatalyst.14–17 It has been deter-
mined that during catalytic HER, the presence of MoS2
nanosheets not only effectively prevents photocorrosion of CdS,
but also provides a large number of reactive sites for HER.18 The
2H phase of MoS2 promotes the separation of photogenerated
electron–hole pairs, while the S atom can easily reduce H+ in
water to H2, increasing the number of catalytic active sites.19
Nonetheless, the poor electrical conductivity of MoS2 limits its
application in photocatalytic HER.20,21 The combination of gra-
phene oxide (GO) with MoS2 has been shown to significantly
improve the electrical conductivity and photocatalytic activity.22
*
Correspondence to: S Xian-yang, Anhui Province Key Laboratory of Wetland
Ecosystem Protection and Restoration, School of Resource and Environmental
Engineering, Anhui University, Hefei 230601. E-mail: shixi381@163.com
a Anhui Province Key Laboratory of Wetland Ecosystem Protection and Restora-
tion, School of Resource and Environmental Engineering, Anhui University,
Hefei, China
b School of Materials and Chemical Engineering, Anhui Jianzhu University, Hefei,
China
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GO has the advantages of high electrical conductivity, large sur-
face area (2630 m2 g−1), and good visible light response.23,24 In
addition, the reduced graphene oxide (rGO) loaded on CdS nanor-
ods has demonstrated good photocatalytic performance for
HER.25 Both rGO and MoS2 have been confirmed as excellent sup-
porting matrices for semiconductor photocatalysts.26 CdS was
previously loaded on the surface of rGO and MoS2, so that they
could receive and transmit photoelectrons generated from the
semiconductor under light irradiation.27 Notably, MoS2/rGO pro-
vides a large contact interface and guarantees intimately interfa-
cial contact between nanocomposites. As an electron transport
medium, rGO facilitates the transfer of the interface charge from
CdS to MoS2, considerably hindering charge recombination.28
Hence, the efficiency of HER could be significantly improved.
Although photocatalytic HER using CdS/rGO/MoS2 nanocompo-
sites has been described in several reports, the effect of CdS con-
tent in MoS2/rGO-based nanocomposites on the photocatalytic
activity remain largely unknown.
In this study, MoS2 and rGO were selected as the cocatalysts to
enhance the activity of CdS. CdS nanoparticles (CdS NPs) were
prepared in situ on the surface of MoS2/rGO which was synthe-
sized using a hydrothermal approach. Non-noble ternary nano-
composites exhibiting different CdS content were optimized,
and the HER activity of the prepared CdS/MoS2/rGO nanocompo-
sites was evaluated under visible light irradiation (⊗ >420 nm)
using lactic acid and Na2S-Na2SO3. The stability of the catalysts
was examined and the H2 production mechanism was elucidated.
MATERIALS AND METHODS
Materials
GO dispersion, sodium molybdate dihydrate (Na2MoO4·2H2O),
absolute ethanol (C2H5OH), and thiourea (H2NCSNH2) were pur-
chased from the China National Pharmaceutical Reagent Co., Ltd
(Shanghai, China). Cadmium chloride (CdCl2·2.5H2O) and sodium
sulfide (Na2S·9H2O) were obtained from the Nanjing Huajian
Chemical Co., Ltd (China). Polyvinylpyrrolidone (PVP) was acquired
from the Shanghai Qifuqing Material Technology Co., Ltd (China).
All chemicals used in this study were of analytical grade.
Synthesis of MoS2/rGO nanosheets
Na2MoO4·2H2O of 0.242 g (1 mmol) and H2NCSNH2 of 0.38 g
(5 mmol) were dissolved in 60 mL deionized water. The solution
was stirred for 1 h prior to the addition of 13.5 mL GO
solution (1 mg mL−1). The reaction mixture was subsequently
placed into a 100 mL Teflon-lined stainless steel autoclave and
maintained at 210 °C for 24 h. After cooling to room temperature,
the collected black precipitates were washed three times with
deionized water and absolute ethanol, and then dried under vac-
uum at 80 °C for 12 h. In this process, H2NCSNH2 was used as a
reducing agent and sulfur source to form MoS2 nanosheets on
rGO.29 MoS2 was synthesized employing a similar method without
the addition of GO.
Preparation of CdS/MoS2/rGO nanocomposites
Pure CdS was synthesized by slowly adding a certain amount of
Na2S into a solution of CdCl2·2.5H2O and stirring overnight. To
fabricate CdS/MoS2/rGO nanocomposites, a certain amount of
MoS2/rGO (40 mg) was dispersed in 100 mL of deionized water
by ultrasound. Subsequently, CdCl2·2.5H2O and PVP (200 mg)
were added into the MoS2/rGO dispersion. The Na2S solution
was added dropwise to the mixture under continuous stirring at
2
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B-y Tan, X-j Song, S Xian-yang
room temperature. The reaction mixture was then continuously
stirred for 24 h to ensure complete fixation and crystallization of
CdS NPs. Finally, the products were centrifuged and washed with
deionized water and absolute ethanol to obtain the final samples.
Following drying in an oven at 60 °C for 24 h, the CdS/MoS2/rGO
nanocomposites were ground in an agate mortar for further use.
CdS/MoS2/rGO nanocomposites exhibiting different ratios of
MoS2 and CdS were prepared by varying the amount of the Cd
source. The samples with different CdS mass fractions were
denoted as CdS (0.1 wt%)/MG, CdS (0.2 wt%)/MG, CdS (0.3 wt
%)/MG, CdS (0.35 wt%)/MG, CdS (0.4 wt%)/MG, and CdS
(0.5 wt%)/MG.
Material characterization
The microstructure of CdS/MoS2/rGO nanocomposites was ana-
lyzed using a transmission electron microscope (TEM, JEM-2100,
Japan) and scanning electron microscope (SEM, S-4800, China).
Energy dispersive X-ray spectroscopy (EDS) configured by SEM
was used to investigate the elemental composition of the pre-
pared materials. The changes in the crystallinity and surface func-
tional groups of the catalysts were analyzed by X-ray diffraction
(XRD, SmartLab 9KW, Japan) and Fourier transform infrared spec-
troscopy (FTIR, Vertex80 + Hyperion2000, China). The vibrational
and structural properties of the CdS/MoS2/rGO nanocomposites
were evaluated employing a confocal laser micro-Raman spec-
trometer (Raman, InVia-Reflex, UK) under the excitation wave-
length of 532 nm. UV–visible (UV–vis) absorption spectra were
recorded using a UV–visible spectrophotometer (U-4100, China).
X-ray photoelectron spectroscopy (XPS, ESCALAB 250Xi, USA)
was conducted to detect the valence states of various elements.
The transient PL spectra of the CdS and CdS/MoS2/rGO nanocom-
posites were recorded using a Horiba FluoroMax Plus spectrofluo-
rometer. N2 adsorption isotherms were measured using a porosity
analyzer (ASAP2460, China).
Photocatalytic H2 evolution
The photocatalytic activity of the prepared CdS/MoS2/rGO nano-
composites was investigated using an online photocatalytic H2
production system (MC SCO2II-AG, China). The as-prepared cata-
lysts were placed in a Pyrex glass reactor containing 60 mL of an
aqueous solution of lactic acid or Na2S-Na2SO3 as the sacrificial
electron donor. A 300 W Xe lamp with a 420 nm cut-off filter
was used as the visible light source to trigger the photocatalytic
reaction. Prior to irradiation, Ar gas was passed through the sus-
pension for 30 min to ensure anaerobic conditions in the reaction
system. Quartz agitators were employed in the experiment to
ensure uniformity of the suspension. The reaction solution was
maintained at a low temperature using a circulating water system.
The evolved H2 was analyzed employing an online gas chromato-
graph (GC 9790, MS-5A column, Fuli). The apparent quantum effi-
ciency (AQE) of the catalysts for HER was calculated according to
the following equations30:
ne− 2nH2
AQE ð%Þ = ×100 = ×100 ð1Þ
np np
⊔ I×t×S
np = = ð2Þ
hv hv
where ne− refers to the number of reacted electrons, np is the num-
ber of incident photos, nH2 indicates the number of evolved H2
molecules, ⊔ (J) denotes the total energy of incident photos,
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In situ deposition of CdS on MoS2/rGO-based nanocomposites
h (J s−1) is the Planck constant, v (Hz) is the light frequency,
I (W m−2) refers to the illumination intensity, t (s) is the irradiation
time, and S (m2) indicates the irradiation area.
Photoelectrochemical measurements
An electrochemical workstation (BAS 100B) was used to assess the
electrochemical performance of the CdS/MoS2/rGO nanocompo-
sites. A mixed slurry of each sample was coated onto a fluorine-
doped tin oxide (FTO) glass plate (1 × 1 cm2), and the obtained
electrode was dried at 60 °C overnight. A 0.5-M aqueous solution
of Na2SO4 was used as the electrolyte. The standard three-
electrode system was composed of platinum mesh, saturated cal-
omel electrode, and FTO glass coated with the samples.
RESULTS AND DISCUSSION
Structure and morphology of CdS/MoS2/rGO
nanocomposites
The CdS/MoS2/rGO nanocomposites were synthesized via a
hydrothermal and in situ growth method (Fig. 1(a)). The functional
groups in the samples were identified by FTIR spectroscopy. As
shown in Fig. 1(b), the peaks of the CdS at 3300 cm−1 were
assigned to the adsorbed hydroxyl group (-OH), and the spectrum
of primary GO exhibited two characteristic vibration peaks at
1630 cm−1 and 1392 cm−1, which corresponded to the C O
and O H stretching bands, respectively. The signal at
1085 cm−1 was attributed to the C O group. Notably, the inten-
sity of the above peaks in the spectra of the CdS/MoS2/rGO nano-
composites was significantly reduced. The signals ascribed to the
oxygen-containing functional groups in the spectra of GO nearly
disappeared in the spectra of the CdS/MoS2/rGO nanocompo-
sites, indicating that GO was successfully reduced to rGO follow-
ing hydrothermal treatment.31 According to the Raman spectra
Figure 1. (a) Schematic of the synthesis of CdS/MoS2/rGO nanocomposites. (b) FT-IR spectra of GO, MoS2/rGO, CdS, CdS/MoS2/rGO nanocomposites.
(c) Raman spectra of GO, MoS2/rGO, CdS, CdS/MoS2/rGO nanocomposites.
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of the catalysts in Fig. 1(c), the D and G bands of GO were detected
at 1347 cm−1 and 1580 cm−1. These bands corresponded to the
defect of the graphene edge and in-plane stretching vibration
of the C atom sp2 hybridization, respectively. Moreover, the sig-
nals at 380 and 405 cm−1 in the spectrum of MoS2/rGO were
attributed to the typical E12g and A1g orbital vibrations of MoS2,
correspondingly. The D and G peeks of GO in the spectra of the
CdS/MoS2/rGO nanocomposites disappeared upon the addition
of CdS. Compared with pure CdS, the vibration modes of the
CdS/MoS2/rGO nanocomposites were blue shifted (1LO from
297.2 cm−1 to 302 cm−1 and 2LO from 600.91 cm−1 to
602.5 cm−1). The CdS (0.35 wt%)/MG nanocomposites exhibited
a similar peak to those of pure CdS. This is because the Raman
peaks of MoS2/rGO displayed low intensity, and imperfections of
rGO were covered by the CdS NPs signals.32 The 2LO/1LO value
of the CdS/MoS2/rGO nanocomposites (0.52) was higher than that
of pure CdS NPs (0.48). We speculated that the presence of rGO
increased the transmission of electrons between MoS2 and CdS.33
XRD was used to evaluate the crystallinity of the MoS2/rGO and
CdS/MoS2/rGO nanocomposites. As demonstrated in Fig. 2, the
diffraction peaks of the CdS/MoS2/rGO nanocomposites corre-
sponded to the standard spectrum of MoS2 (JCPDS card No. 37–
1492) and CdS (JCPDS card No. 41–1049). No other diffraction
peaks were detected. The XRD pattern of the CdS (0.3 wt%)/MG
nanocomposites (Fig. 2(a)) exhibited strong diffraction peaks at
2⊔ = 13.8°, 33.5°, 39.3°, and 59°, which were attributed to (002),
(101), (103), and (110) planes of MoS2, respectively. The diffraction
peaks of the CdS (0.3 wt%)/MG nanocomposites resembled those
of the MoS2. Additionally, all characteristic peaks of CdS were
found. In Fig. 2(b), CdS (0.35 wt%)/MG nanocomposites displayed
the same diffraction peaks as pure CdS, suggesting that the exis-
tence of MoS2/rGO did not significantly affect the structure of CdS
NPs. The three main diffraction peaks of the CdS (0.35 wt%)/MG
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Figure 2. XRD patterns of MoS2/rGO and CdS/MoS2/rGO nanocomposites.

Figure 3. Microscopic characterization of the catalyst materials: (a) SEM image of the CdS/MoS2/rGO nanocomposites, (b) and (c) TEM images of the
CdS/MoS2/rGO nanocomposites, (d) and (e) HR-TEM images of the CdS/MoS2/rGO nanocomposites, and (f) EDS analysis of the CdS/MoS2/rGO
nanocomposites.

nanocomposites at 2⊔ of 26.5°, 43.8°, and 51.9° corresponded to the more obvious. No typical diffraction peaks of MoS2 and rGO were
(002), (110), and (112) crystal planes of CdS, respectively. As the mass detected because of the low content and weak diffraction intensity
fraction of CdS increased, the typical peaks ascribed to CdS become of rGO and MoS2.26
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Figure 4. XPS spectra for the CdS (0.35 wt%)/MG nanocomposites: (a) survey, high resolution spectra of (b) C 1 s, (c) S 2p, (d) Mo 3d, and (e) Cd 3d.

Figure 5. (a) UV–vis absorption spectrum of CdS, CdS/MoS2/rGO nanocomposites, and (b) (Ahv)2versus hv plots of CdS and CdS/MoS2/rGO
nanocomposites.

TEM and SEM images were used to evaluate the morphology
and microstructure of the CdS/MoS2/rGO nanocomposites. As
shown in Fig. 3(a), the synthesized CdS (0.35 wt%)/MG nanocom-
posites exhibited a flower-like morphology. CdS was evenly dis-
persed on the flower-like MoS2/rGO. Based on the acquired TEM
images (Fig. 3(b) and (c)), there was close contact between rGO
and MoS2, which was conducive to the transfer of electrons
between the two phases, leading to a shorter transport distance
for photogenerated electrons.34 Moreover, the MoS2/rGO
nanosheets acted as carrier for CdS NPs with a diameter of
4–10 nm. The coexistence and uniform distribution of CdS
enabled the material to absorb visible light more effectively. The
HR-TEM image (Fig. 3(d)) reveals that the interlayer distance of
MoS2 was 0.62 nm, which corresponded to the (002) peak of
MoS2. The HR-TEM images evidently demonstrated that the lattice
distance of CdS attached to the MoS2/rGO nanosheets was
0.35 nm in Fig. 3(e). In addition, the CdS lattice fringe image was
consistent with the crystal plane (002) in the XRD pattern, indicating
that the CdS/MoS2/rGO nanocomposites displayed excellent crys-
tallinicity. The EDS analysis confirmed the presence of only the
peaks attributed to C, S, Mo, and Cd in the obtained products
(Fig. 3(f)), suggesting that the CdS/MoS2/rGO nanocomposites
exhibited high purity. Notably, all of the above analyses proved that
the CdS/MoS2/rGO nanocomposites were successfully synthesized.
The surface chemical states and composition of the CdS/MoS2/
rGO nanocomposites were examined using XPS. Four peaks
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(i.e., C 1s, S 2p, Mo 3d, Cd 3d) were observed in the XPS survey spec-
trum (Fig. 4(a)). Importantly, the composition of the elements is
consistent with the target component. Figure 4(b) shows that C
1s of the CdS (0.35 wt%)/MG nanocomposites contained three
peaks at 284.6, 286.26, and 288.64 eV, which were attributed to
the C C, C O and C O functional groups, respectively.35 There
was a significant decrease in the signals corresponding to the
oxygen-containing functional groups, which was in agreement with
the FTIR spectra. This implied that following hydrothermal treatment,
GO was successfully reduced to rGO.36 The distinct peaks at 162.25
and 163.3 eV (Fig. 4(c)) were ascribed to the binding energy of S
2p3/2 and S 2p1/2.37 Furthermore, the doublet peaks at 229.41 and
232.64 eV (Fig. 4(d)) were attributed to Mo 3d5/2 and Mo 3d3/2 and
are characteristic of Mo4+.38 As shown in Fig. 4(e), Cd 3d was further
separated into Cd 3d5/2 (405.95 eV) and Cd 3d3/2 (412.67 eV), dem-
onstrating that Cd was in the form of Cd2+.39
We subsequently assessed the light absorption capacity of the
MoS2/rGO-based nanocomposites by UV–vis. The UV–vis absorption
spectrum of pure CdS NPs was also evaluated in Fig. 5(a) for compar-
ison. As a classic visible light photocatalyst, CdS displays a good vis-
ible light absorption capacity, showing a strong absorption edge in
the 475–560 nm wavelength range. This corresponds to the band
edge of the CdS nanostructure.40 CdS/MoS2/rGO nanocomposites
exhibited stronger light absorption capacity in the visible light region
(⊗ > 560 nm). The obtained spectrum showed that the introduction
of the MoS2/rGO cocatalysts could extend the wavelength of visible
light to 560–780 nm; therefore, visible light could be used for HER
more effectively. The forbidden band width (Eg) diagram of the
above samples is illustrated in Fig. 5(b). The following formula was
used41,42:
Figure 6. (a) N2 adsorption–desorption curves, (b) pore distribution, (c) transient photocurrent response, and (d) EIS spectra of the CdS and CdS/MoS2/
rGO nanocomposites.
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B-y Tan, X-j Song, S Xian-yang
Ahv=Kðhv−EgÞ1=2 ð3Þ
where A, h, and v are the absorption coefficient, Planck con-
stant (J s−1), and light frequency (Hz), respectively. K is a con-
stant, while Eg indicates the optical band gap energy. The
band gap of CdS is 2.2 eV. However, the addition of MoS2/rGO
resulted in the reduction of the band gap width of the
CdS/MoS2/rGO nanocomposites. The decrease in the band
gap of the CdS/MoS2/rGO nanocomposites from 2.1 to
1.85 eV might contribute to the interaction between CdS and
MoS2/rGO, thus considerably increasing the response range of
the catalysts to visible light. The transient PL spectra of CdS
and CdS/MoS2/rGO were recorded (Fig. S1), where low PL inten-
sities indicated a faster separation efficiency of electron–hole
pairs. The CdS/MoS2/rGO nanocomposites showed lower
intensity compared to CdS, indicating their higher separation
efficiency of electron–hole pairs.
The N2 adsorption–desorption isotherms were utilized to assess
the effects of the MoS2/rGO on the specific surface area of
CdS/MoS2/rGO nanocomposites. As shown in Fig. 6(a), compared
with CdS, the specific surface area for CdS/MoS2/rGO nanocompo-
sites increased significantly from 7.15 to 96.75 m2 g−1, indicating
that the MoS2/rGO nanosheets exhibited efficient adsorption
and transport of charge carriers. We hypothesized that the large
specific surface area and pore volume (Fig. 6(b)) might result in
a greater number of reaction sites promoting H2 evolution during
photocatalytic reactions.
Figure 6(c) demonstrates the transient photocurrent mea-
surements of CdS and the CdS/MoS2/rGO nanocomposites.
The transient photocurrent response of MoS2/rGO and MoS2
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In situ deposition of CdS on MoS2/rGO-based nanocomposites
Figure 7. (a) and (b) Photocatalytic H2 evolution rate over MoS2/rGO, CdS, CdS/MoS2/rGO nanocomposites, (c) CdS (0.35 wt%)/MG nanocomposites
under different catalyst dosage, (d) stability tests for the photocatalytic H2 evolution over CdS and CdS (0.35 wt%)/MG nanocomposites.
was determined at 0.2 and 2 μA cm−2, respectively. The photo-
current density of the CdS/MoS2/rGO nanocomposites was
approximately 5 times higher than that of pure of CdS, implying
a higher separation efficiency of the photogenerated electron–
hole pairs. This could be attributed to the coupling effects and
chemical interactions between CdS and the MoS2/rGO
nanosheets, which extended the lifetime of the electron–hole
pairs.43 Moreover, to further understand electron-transport
abilities of CdS and the CdS/MoS2/rGO nanocomposites, we
prepared EIS Nyquist plots. In general, Nyquist curves with
smaller radius display larger surface electrode responses.44 As
shown in Fig. 6(d), the arc radius of the CdS/MoS2/rGO nano-
composites was smaller than that of pure CdS, which sug-
gested a decrease in the interface layer resistance and
charge-transfer resistance on the surface. These outcomes fur-
ther confirmed the enhancement of conductivity and charge
separation ability upon the addition of MoS2/rGO.45,46
Visible light-driven photocatalytic H2 evolution
The photocatalytic H2 production activity of the optimized photo-
catalysts was explored with lactic acid (10 vol%) as a sacrificial
electron donor. As shown in Fig. 7(a), no H2 signal was detected
for MoS2/rGO, indicating that the material showed no activity for
HER. The CdS NPs exhibited low photocatalytic activity due to
the rapid recombination of charge carriers in the absence of
cocatalysts. Notably, the H2 evolution rate of the CdS/MoS2/rGO
nanocomposites significantly increased, suggesting that non-
noble metal MoS2/rGO was crucial for enhancing the photocataly-
tic water splitting. We subsequently examined the effects of the
CdS mass fractions in the CdS/MoS2/rGO nanocomposites on
the photocatalytic H2 production activity in more detail. As the
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CdS mass fractions increased from 1 to 5, the H2 evolution rate
of the CdS/MoS2/rGO nanocomposites first increased and then
decreased. The maximum H2 release rate reached 38.13 μmol h−1
at the CdS mass fractions of 3, which was 23 times higher than
that of pure CdS (0.45 wt%) NPs (1.67 μmol h−1).
To further enhance the photocatalytic performance of the as-
prepared photocatalysts for HER, it was essential to further design
CdS/MoS2/rGO nanocomposites with different mass fractions of
CdS (Fig. 7(b)). When the CdS content increased from 0.2 wt% to
0.35 wt%, the photocatalytic efficiency of the CdS/MoS2/rGO
nanocomposites was considerably enhanced. The maximum H2
evolution rate reached 83.33 μmol h−1(10 mg catalyst), which
was approximately 46 times higher than that of pure CdS (0.6 wt
%) NPs (1.82 μmol h−1). The improved photocatalytic activity for
HER with increasing CdS content could be attributed to with the
fact that the photogenerated electrons of CdS were effectively
trapped by the MoS2/rGO cocatalysts. Nevertheless, a further
increase in the CdS content to 0.4 wt% resulted in a decrease in
the photocatalytic activity (63.67 μmol h−1) due to the shielding
effect caused by excess CdS. Hence, the photogenerated elec-
trons of CdS could not be effectively trapped and utilized because
the low amount of MoS2/rGO might hinder the transfer of elec-
trons between MoS2/rGO and CdS.47 These outcomes clearly indi-
cated that careful consideration of the CdS content in the
CdS/MoS2/rGO nanocomposites was essential for enhanced effi-
ciency of photocatalytic HER.
As it can be seen in Fig. 7(c), the lower the amount of the catalyst
(5–20 mg), the higher the efficiency of the photocatalytic H2 evo-
lution per unit time. This is because lower the amount of the cat-
alyst, the better the dispersion and the easier it is for the catalyst
to receive light.33 The average photocatalytic H2 production
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Figure 8. Photocatalytic H2 evolution rate of CdS (0.35 wt%)/MG nanocomposites in (a) lactic acid solution and (b) Na2S-Na2SO3 solution.
Figure 9. Schematic illustration of the photocatalytic H2 evolution in the
presence of the CdS/MoS2/rGO nanocomposites.
efficiency of 5 mg of the CdS (0.35 wt%)/MG nanocomposites was
determined at 11331.65 μmol h−1 g−1, which corresponded to an
AQE of 10.4% at 420 nm. The performance of the CdS/MoS2/rGO
nanocomposites was compared with previously reported systems
consisting of MoS2 cocatalysts (Table S1). It is noteworthy that the
H2 evolution rate of the CdS (0.35 wt%)/MG nanocomposites was
considerably higher than that of other nanocomposites, demon-
strating its remarkable potential as a photocatalyst.48 Generally,
chemical stability is regarded as an important indicator of effec-
tive photocatalysts. To assess the chemical stability of the CdS
(0.35 wt%)/MG nanocomposites, a series of experiments were
conducted under the same conditions. As shown in Fig. 7(d), after
6 cycle tests, the H2 evolution rate of pure CdS
significantly decreased every 5 h, which could be attributed to
photocorrosion.49 Nonetheless, the activity of the CdS/MoS2/rGO
nanocomposites remained nearly unchanged, and the recovery
rate was up to 91%. This implied that MoS2/rGO prevented the
photocorrosion of CdS NPs and improved the stability and recov-
ery rate for HER.
It is known that surface-bound protons are related to the gener-
ation of H2 in aqueous solutions and that the photocatalytic per-
formance depends on the concentration of the sacrificial
donor.50 To evaluate the importance of the sacrificial donor and
concentration on the H2 evolution rate, the photocatalytic tests
were conducted under different operating conditions. As shown
in Fig. 8(a) and (b), in the presence of 10 vol% lactic acid, the
CdS (0.35 wt%)/MG nanocomposites exhibited the highest H2
8
wileyonlinelibrary.com/jctb © 2021 Society of Chemical Industry (SCI).
B-y Tan, X-j Song, S Xian-yang
evolution rate, which was approximately 2.7 times higher than
that in 0.1 M Na2S-0.5 M Na2SO3 (41.72 μmol h−1). This implied
that the unsaturated active S atoms on the exposed edge of
MoS2 could capture the abundance of H+ in the lactic acid solu-
tion easier than in the Na2S-Na2SO3 solution, facilitating H2 pro-
duction.51 The outcomes obtained herein also demonstrated
that the H2 evolution rate decreased with an increase in the sac-
rificial donor concentration. This could be ascribed to the fact
that higher concentrations of the sacrificial donor could not
effectively inhibit the recombination of the electron–hole pairs,
leading to a slower transfer of the photogenerated carriers. Con-
sequently, under light illumination, the CdS/MoS2/rGO nano-
composites generated more carriers at low concentrations of
the sacrificial donor, which resulted in the involvement of more
electrons for HER.
Photocatalytic H2 production mechanism
Based on the above analysis, we proposed a tentative photocata-
lytic mechanism of the CdS/MoS2/rGO nanocomposites (Fig. 9).
Under visible light irradiation, CdS generated a large number of
electron–hole pairs at the conduction band (CB) and valence
band (VB), respectively.52 The holes on the CdS were quickly con-
sumed by the sacrificial agent (i.e., lactic acid), and the lactic acid
was oxidized to produce pyruvic acid.53 The good electrical con-
ductivity and electron mobility of rGO were conducive to charge
separation and electron transport.54 Then the photogenerated
electrons of CdS were then directionally migrated from the CB
of the CdS to MoS2 along charge transfer channel of rGO.27,28 Fur-
thermore, some of electrons could be transferred directly to MoS2
due to the low CB of the MoS2 nanosheets.55 This effectively pre-
vented the direct recombination of electron–hole pairs and pro-
longed the lifetime of charge carriers. In an aqueous solution,
the unsaturated active S atoms in MoS2 could accept electrons,
while the transferred electrons easily reduced H+ in H2O to pro-
duce H2, increasing the number of active sites for HER.56 MoS2/
rGO acted as a bridge between the intermediate transport
charges in the CdS/MoS2/rGO nanocomposites, which not only
offered intimate interfacial contact for promoting the separation
and transfer of the electron–hole pairs, but also provided highly
reactive sites for H2 production.9,57 The photocatalytic decompo-
sition of water on the CdS/MoS2/rGO nanocomposites to produce
H2 involved the absorption of photons, photogenerated electrons
accumulation and H+ reduction in the aqueous solution.58 The
described reactions are summarized below:
J Chem Technol Biotechnol 2021
In situ deposition of CdS on MoS2/rGO-based nanocomposites
2H + +2e− →H2 ð4Þ
It is well understood that the H2 evolution activity depends on two
processes, i.e., the ability to absorb visible light as well as the
capacity to hinder the recombination of captured photogener-
ated carriers and facilitate the electron transfer processes on the
surface.59 CdS NPs absorbed light and electron–hole pairs were
excited. Notably, the presence of rGO and MoS2 contributed sig-
nificantly to the absorption of visible light and effectively limited
the recombination of electron–hole pairs, which extended life-
time of the photogenerated electrons and made more electrons
participate in the evolution of H2. We concluded that MoS2/rGO
appeared to be a key factor to enhance photocatalytic perfor-
mance.60 Thus, these kinds of structural CdS/MoS2/rGO nanocom-
posites could achieve high H2 evolution rates and played an
important role in improving the activity for HER.
CONCLUSIONS
In summary, a novel CdS/MoS2/rGO photocatalyst was effectively syn-
thesized by loading CdS on the surface of MoS2/rGO via an in situ
growth method. The photocatalytic H2 evolution activity of the
CdS/MoS2/rGO nanocomposites was evaluated under visible light irra-
diation using lactic acid or Na2S-Na2SO3 as the sacrificial electron
donor. The highest H2 evolution rate of 11 331.65 μmol h−1 g−1 was
achieved in a lactic acid solution at an optimal CdS content of
0.35 wt%. This corresponded to an AQE of 10.4% at 420 nm, which
was more than 46 times higher than that of CdS. The high photocata-
lytic H2 production activity was predominantly attributed to the addi-
tion of the MoS2/rGO cocatalysts, which promoted the charge transfer
and suppressed the recombination of photogenerated electron–hole
pairs. In addition, the CdS/MoS2/rGO nanocomposites exhibited high
stability, with no significant decrease in activity after 6 cycles. This indi-
cated that the ternary system enhanced the stability of the catalysts
and inhibited the photocorrosion of the CdS NPs. The present study
demonstrates that the non-noble metal CdS/MoS2/rGO nanocompo-
sites display high H2 evolution activity and great potential for the
production and transformation of sustainable energy.
ACKNOWLEDGEMENTS
The authors acknowledge the National Natural Science Founda-
tion of China (51278001), and Anhui Province Major Science and
Technology Projects (202003a0702014) for supporting this work.
SUPPORTING INFORMATION
Supporting information may be found in the online version of this
article.
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