Catalysis Letters (2021) 151:2408–2419

https://doi.org/10.1007/s10562-020-03468-6

Construction of Amorphous CoS/CdS Nanoparticles Heterojunctions

for Visible–Light–Driven Photocatalytic ­H2 Evolution
Xuanhao Li1 · Jing Xu1,2,3,4 · Lingjiao Li1 · Sheng Zhao1 · Min Mao1 · Zeying Liu1 · Yanru Li1

Received: 30 July 2020 / Accepted: 16 November 2020 / Published online: 3 January 2021
© Springer Science+Business Media, LLC, part of Springer Nature 2021

Abstract
Due to the poor photocatalytic hydrogen evolution ability of pure CdS, we need to develop a photocatalytic hydrogen evo-
lution catalyst with high activity and no precious metal doping. Therefore, in this article, we used a simple hydrothermal
synthesis of CdS nanoparticles, using water as a carrier, loading a small amount of amorphous CoS, by changing the loading
ratio of amorphous CoS, synthesized TYPE–II type heterojunction composite catalyst CCS. The successful synthesis of
the composite catalyst CCS was verified by XRD, SEM and other characterization methods. UV–vis, PL and other char-
acterization showed that the supported amorphous CoS could significantly improve the photocatalytic activity of CdS, and
the photochemical detection also showed that the performance of composite catalyst CCS was better than that of pure CdS.
Using ­Na2S and ­Na2SO3 mixed solution as electron sacrificial agent, the hydrogen production performance of CCS com-
posite catalyst was determined through hydrogen evolution experiment and cyclic stability experiment. It was found that the
sacrificial agent had a great promotion effect on the hydrogen production performance of photocatalyst. It was found that the
hydrogen production rate of the composite catalyst could reach 2.01 mmol·g−1·h−1, which was 6.3 times of the pure CdS. This
study offers a novel approach for the design of amorphous–based nanostructures as efficient hydrogen evolution cocatalysts.
Graphic Abstract
First, CdS are excited by light, consuming ­S2− and ­SO32− ions in the sacrificial agent, generating a large number of electrons
and holes. Due to the energy difference between the conducting band (CB) of CdS and amorphous CoS, the electrons are
transferred from the surface of CdS to the conducting band (CB) of amorphous CoS, while the electrons obtained from water
and ­H+ in the sacrificial agent are reduced to ­H2. The amorphous CoS is used as the transfer medium of electron acceptor,
and the synergistic effect between heterojunctions is used to improve the charge separation efficiency and electron transfer
rate. Therefore, the photocatalytic hydrogen production effect of the composite catalyst CCS–7 has been greatly improved.

Supplementary Information The online version contains

supplementary material available at https​://doi.org/10.1007/s1056​
2-020-03468​-6.

Extended author information available on the last page of the article

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Construction of Amorphous CoS/CdS Nanoparticles Heterojunctions for Visible–Light–Driven… 2409

Keywords CdS · Amorphous CoS · Heterojunction · Photocatalytic

1 Introduction 2 Experimental

With the global energy crisis and environmental pollution 2.1 Materials and Methods
becoming more and more serious, it is urgent to develop
sustainable and clean energy to replace fossil fuels [1–4]. The chemicals used in this work were of analytical reagent
Hydrogen energy has attracted great attention because of grade. Cadmium nitrate tetrahydrate (Cd(NO3)2·4H2O),
its reproducibility and environmental friendliness [5, 6]. sodium sulphide hydrate (NaS·9H2O), cobalt nitrate hex-
The utilization of solar energy to decompose water to pro- ahydrate (Co(NO 3) 2·6H 2O), Sodium sulfite anhydrous
duce hydrogen is a long–term and high return strategic ­(Na2SO3).
research topic [7]. Among many semiconductors [8–11],
sulfide is one of the new photocatalysts for visible light
semiconductors that have been developed. Among them, 2.2 Preparation of CdS Nanoparticles
metal sulfide semiconductor material CdS has a strong
photoelectric effect on visible light, has excellent charge Preparation of CdS nanoparticles by hydrothermal method
transfer performance, suitable conduction band position, [41]. 10 mmol Cd(NO3)2·4H2O and 50 mmol NaS·9H2O
narrow band gap and high electron mobility, and is consid- were dissolved in 25 mL deionized water and stirred to form
ered as one of the most promising photocatalytic materi- the slurry at room temperature. After stirring for 60 min, the
als [12–15]. Supporting cocatalyst on CdS semiconductor orange slurry was transferred to the stainless steel high tem-
photocatalyst can effectively promote the separation of perature reaction kettle at 200 ℃ for 20 h. After the stainless
photogenic electrons and holes, so as to further improve steel high temperature reactor was cooled to room tempera-
the catalytic activity of photocatalyst [16]. Up to now, ture, the resulting precipitate was washed with deionized
various methods have been carried out for modifications water and ethanol multiple times, and finally the CdS nano-
of pure CdS photocatalyst, such as hollow nanorods [17], particles are obtained by vacuum drying at 60 ℃ overnight.
flowers [18], nanowires [19, 20], nanospheres [21] and
nanocubes [22]. But their disadvantages are obvious, such
as having faster electron–hole recombination rates and 2.3 Preparation of Amorphous CoS
photoetching [23–29]. Precious metals such as Pt, Ru, Pd,
Rh and Ag are the most effective catalysts for photocata- Co(NO3)2·6H2O and NaS·9H2O were placed in 60 mL of
lytic hydrogen evolution. Whereas, the high price of pre- deionized water at a molar ratio of 1:1. After stirring with a
cious metals hinders their practical application [30–33]. constant magnetic stirrer for 10 h at room temperature, the
Therefore, it is of great significance to study the mineral precipitate was filtered with a vacuum circulation pump. The
rich and cheap catalysts for photocatalytic decomposition precipitate was washed several times with deionized water
of water to produce hydrogen. and ethanol, and dried under vacuum at 60 ℃ overnight to
In the field of photocatalysis, amorphous materials obtain amorphous CoS.
sometimes have higher catalytic activity and selectivity
than crystalline materials [34–38]. Moreover, the large
density of active sites is observed on the amorphous sur- 2.4 Synthesis of CCS Composites
faces compared to the crystalline surfaces due to their
no preferred oriented bonds. Thus, amorphous materials The 100 mg CdS nanoparticles prepared by the above
show a significant enhancement in the adsorption of reac- method were put into 60 mL deionized water and stirred for
tants leading to higher activity than that on the crystalline 6 h to make them evenly dispersed. Then add appropriate
ones [39]. In recent years, the preparation method of high amount of Co(NO3)2·6H2O and NaS·9H2O, the molar ratio
specific surface area amorphous catalysts has been devel- is 1:1. After stirring them for 10 h, the precipitate was fil-
oped. In this paper, an amorphous CoS–supported CdS tered with a vacuum circulation pump. The precipitate was
catalyst was prepared by chemical precipitation to improve washed with deionized water and ethanol, and dried under
the efficiency of hydrogen production [40]. However, this vacuum at 60 ℃ overnight to to obtain the composite cata-
method can not successfully prepare amorphous materials lyst CoS/CdS. According to different Co(NO3)2·6H2O and
with uniform size and controllable size, so it needs to be NaS·9H2O content, composite catalysts CCS–X (X = 6%,
improved. 7%, 8%, 9%) with different mass ratios of amorphous CoS
and CdS were obtained.

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2.5 Characterization of the Instrument

The gas chromatographic model is SP–2100 with a 13X

molecular sieve column (5m × 4mm), the gas velocity
of 40 mL ­min−1. The program is N2000 online chroma-
tographic workstation. X–ray DIFFRACTION (XRD)
was measured using SmartlabSE03030502, SEM (SSX-
5503040700), TEM (JEM 2100F), XPS (Vario EL Cube
03,030,402), BET (ASAP 2020), UV–VIS (Lambda 750S),
and PL (Fluoro Max-43030105).

2.6 Photocatalytic Hydrogen Evolution

This experiment was conducted in a dark environment with

a 250 mL photochemical reactor [42]. The experiment is
equipped with a magnetic stirrer and condensate circulation
device to ensure that the solution fully reacts, controls the
temperature and reduces the changes in the external con- Fig. 1  XRD patterns of amorphous CoS, CdS, CCS–X (X = 6, 7, 8, 9)
ditions of the experiment. Dispersed 20 mg of catalyst in
100 mL of 0.35 M ­Na2S and 0.25 M ­Na2SO3 solution [36],
after ultrasonic dispersion for 30 min, transfer to a 250 mL CdS nanoparticles is consistent with the standard card
photochemical reactor. Nitrogen is injected into the reactor PDF#41–1049. The diffraction peak is very clear and there
by a vacuum pump for gas replacement, so that the reac- is no clutter, indicating that the sample has high purity, good
tor contains only nitrogen.The reactor was irradiated with synthesis effect and good crystallinity. Different diffraction
a 300 W xenon lamp (CEL–HXF300), which was paired angles can accurately correspond to (1 0 0), (0 0 2), (1 0 1),
with a 420 nm cut–off filter to simulate visible light. Hydro- (1 0 2), (1 1 0), (1 0 3) and (1 1 2) crystal faces of CdS. No
gen production was measured using a gas chromatograph diffraction peak was detected in the CoS sample, indicating
SP–2100. that the CoS sample exists in an amorphous form. The dif-
fraction peaks of composite catalyst CCS and CdS nanopar-
2.7 Electrochemical Measurements ticles are almost the same, indicating that the introduction
of amorphous CoS has not changed the crystal structure of
In this experiment, standard three–electrode battery was CdS. After loading amorphous CoS, the position of its dif-
used for photochemical measurement on ChenHua660D fraction peak did not change significantly, indicating that
[43]. The working electrode was prepared by physical dep- loading amorphous CoS did not change the crystal struc-
osition method. A small amount of catalyst was dispersed ture of CdS. As the load of amorphous CoS continued to
in ethanol solution and ground to form a slurry, then apply increase, the diffraction peak strength of composite catalyst
them evenly to the surface of ITO conductive glass. ITO CCS decreased slightly, indicating that the excess amor-
working electrode was prepared after drying at 60 ℃ for 8 h. phous CoS was attached to the surface of CdS, affecting the
In this experiment, Pt sheet electrode was used as the con- detection results.
trast electrode and saturated calomel electrode was used as
the reference electrode. The carrier electrolyte was ­Na2SO4
(0.2 M) aqueous solution. The immersion area of the catalyst 3.1.1 Morphology of Photocatalysts
in ­Na2SO4 solution was about 1 cm2. The light source was
300 W xenon lamp with 420 nm cut–off filter. In order to study the structure and morphology of the cata-
lyst, SEM, TEM and element mapping were carried out on
the catalyst. Figure 2a is the SEM image of CdS, which
3 Results and Discussion shows that CdS exists in the form of irregular granular
agglomeration. The diameter of the agglomerated CdS par-
3.1 Structure and Morphology ticles is about 1.5–6 μm. The unaggregated CdS particles
adhere to the surface of the agglomerated CdS particles. Fig-
The crystal structure and corresponding diffraction phe- ure 2b is the SEM image of the composite catalyst CCS–7.
nomenon of the sample were analyzed by XRD detec- It can be seen that compared with the pure CdS, the par-
tion. As can be seen from Fig. 1, the diffraction peak of ticles on the surface are clearer. At the same time, some

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Construction of Amorphous CoS/CdS Nanoparticles Heterojunctions for Visible–Light–Driven… 2411

Fig. 2  (a) SEM image of C

­ dS, (b) SEM image of CSS–7

amorphous CoS are filled into the uneven surface of CdS,

making the surface of CdS smoother.
Figure 3 is the TEM image of the composite catalyst
CCS–7. From Fig. 3 we can clearly see the lattice fringes
in different directions of CdS. The two lattice fringes with
lattice spacings of 3.3599 nm and 3.5861 nm correspond to
the crystal plane (1 0 0) and the crystal plane (0 0 2) of CdS,
respectively. There is no lattice fringes were found around
CCS–7, indicating that amorphous CoS was supported on
the surface of CdS. The results confirmed the existence of
CdS and amorphous CoS. In addition, Fig. 4 is the map-
ping element pattern of the composite catalyst CCS–7. The
mapping element pattern of the composite catalyst CCS–7
shows the uniform dispersion of Cd, Co and S elements in
the composite catalyst CCS–7 [44].

Fig. 3  TEM image of CCS–7

Fig. 4  The mapping element pattern of Cd, Co, S

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2412 X. Li et al.

3.1.2 XPS Analysis of the Composite Photocatalyst CdS, CCS–7 has a slight red shift, indicating the addition of
amorphous CoS After that, the composite catalyst CCS–7
We used x–ray photoelectron spectroscopy (XPS) to analyze has a larger visible light absorption range than pure CdS.
the surface chemical composition of the composite catalyst It is further proved that the composite catalyst CCS–7 has
CCS–7 [45], as shown in Fig. 5. Figure 5a is the general pic- excellent photocatalytic performance. Figure 7b and c are
ture of XPS analysis, indicating that the composite catalyst the band gaps of CdS and amorphous CoS. The correspond-
CCS–7 is composed of Cd, Co and O elements. Figure 5b ing band gap energies can be calculated by the Tauc equa-
shows that the peaks of Co 2­ p3/2 are located at 778.1 eV and tion: αhv = A(hv–Eg) 1/2 for the direct band gap material,
the satellite peak at 781.3 eV, while those of Co ­2p1/2 are based on the tangent lines of (αhν)2 to hν plots (where α is
located at 793.1 eV and 797.2 eV. However, the diffraction the absorption coeffiffifficient and hν is the photon energy)
peak of S in the amorphous CoS is located at 168.8 eV and [46]. The band gap of CdS is 2.22 eV and that of amorphous
the satellite peak at 162.3 eV in Fig. 5c, which fully illus- CoS is 2.6 eV.
trates the synthesis of amorphous CoS. The diffraction peak Figure S1 shows the AQY of CCS–7 under monochro-
of O 1 s in the composite catalyst CCS–7 is at 531.3 eV, matic light in different wavelength bands. Under the mono-
as Fig. 5d shows. Figure 5e shows two multiple splitting chromatic light of 420 nm, CCS–7 shows the highest AQY
peaks of 404.8 eV and 411.6 eV, which can be attributed to which is 3.86%. The change in AQY is similar to the visible
Cd ­3d5/2 and Cd ­3d3/2, respectively. The results showed that light absorption range of CCS–7, indicating that the main
Cd ions existed in the catalyst in the form of + 2. The peaks activity of the catalyst comes from CdS.
of ­S2− in CdS are 161.5 eV and 162.3 eV, corresponding
to S ­2p3/2 and S ­2p1/2, respectively. It shows the successful 3.2 Photoluminescence (PL) Experiment
synthesis of CdS.
The efficiency of electron and hole separation of the pho-
3.1.3 Analysis of ­SBET and BJH Pore Size Distribution tocatalyst was measured by fluorescence spectroscopy. As
of the Photocatalysts can be seen from Fig. 8, the excitation peaks of CdS and
CCS–7 can be seen at 535 nm. However, under the excita-
The ASAP 2020 physical adsorption instrument was used tion wavelength of 400 nm, amorphous CoS has no obvi-
to determine the pore volume, pore size and specific surface ous fluorescence response between 480 nm and 700 nm. At
area of all samples. Figure 6a shows the adsorption–desorp- the same time, the fluorescence quenching intensity of the
tion curves of amorphous CoS, CdS and CCS–7. The CdS composite catalyst CCS–7 is significantly lower than that of
and composite catalyst CCS–7 is a typical type IV isotherm CdS, indicating that with the addition of amorphous CoS,
with H3 type hysteresis ring. Amorphous Cos is a type III the electron transfer rate of the composite catalyst CCS–7
isotherm with H3 type hysteresis loop. It means that the is higher than CdS, that is, the composite catalyst CCS–7
force between the amorphous CoS and ­N2 is very weak. Fig- has a low electron–hole recombination rate, and can more
ure 6b shows the pore size distribution curve of the catalyst. effectively carry out charge separation.
Among them, the amorphous CoS is the mesoporous mate- Figure S2 describes the transient PL spectrum of different
rial, while CoS and CCS–7 are composed of a large number samples. It represents the dynamic charge transfer effect of
of mesoporous and a small number of large holes. As can different samples. After CoS is loaded, the fluorescence life
be seen from Table 1, the specific surface areas of amor- of the composite catalyst CCS–7 is enhanced, which indi-
phous CoS, CdS and CCS–7 are 23.21 m2g−1, 26.62 m2g−1, cates that the separation efficiency of photogenic carriers is
40.24 m2g−1, respectively. With the addition of amorphous improved, thus improving the hydrogen production effect.
CoS, the composite catalyst CCS–7 has a larger specific Meanwhile, the decrease of τ2 value in Table S1 is also con-
surface area than the amorphous CoS and CdS. The larger sidered as a marker of electron energy transfer.
specific surface area indicates that there are more active
sites to improve the electron transfer efficiency and hence 3.3 Photoluminescence and Photoelectrochemical
the photocatalytic performance. Measurement

3.1.4 Optical Properties of Photocatalysts In order to explore the electron transport mechanism of

the catalyst, we tested the photoelectric properties of the
In order to analyze the light absorption characteristics of dif- prepared catalyst. Figure 9a shows the transient photocur-
ferent samples, UV–visible diffuse reflection tests were per- rent–time curves of amorphous CoS, CdS and CCS–7. It can
formed on different catalysts. As can be seen from Fig. 7a, be clearly seen that the photocurrent response of the amor-
the ultraviolet absorption edges of pure CdS and composite phous CoS is the weakest, and the photocurrent response
catalyst CCS–7 are 548 nm and 570 nm, compared with intensity of the composite catalyst CCS–7 is the highest.

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Construction of Amorphous CoS/CdS Nanoparticles Heterojunctions for Visible–Light–Driven… 2413

Fig. 5  (a) XPS survey spectrum of CCS–7, (b–e) high–resolution XPS spectras of Co 2p, S 2p, O1s, Cd 3d

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2414 X. Li et al.

Fig. 6  (a) ­N2 isothermal adsorption curves of CoS, CdS and CCS–7. (b) BJH adsorption average pore diameter of CoS, CdS and CCS–7

Table 1  Parameters of different samples obtained from the analysis of In addition, in order to prove that the improvement of pho-
­N2 adsorption isotherms tocatalytic performance of the composite catalyst CCS–7 is
Samples SBET(m2g−1)1 Pore volume Average due to the synergistic effect of amorphous CoS and CdS, we
­(cm3g−1)2 pore size made linear sweep voltammetry (LSV) for all samples, and
(nm)3 the results are shown in the Fig. 9b. Obviously, compared
CoS 23.21 0.0667 11.0062 with the composite catalyst CCS–7, both amorphous CoS
CdS 26.62 0.1821 26.5387 and CdS showed weaker photocurrent density. To sum up,
CCS–7 40.24 0.2025 18.4944 the composite catalyst CCS–7 has a high electron transfer
rate, which provides important support for the explanation of
1
BET specific surface area the excellent photocatalytic activity of the composite catalyst
2
BJH adsorption cumulative volume of pores CCS–7.
3
BJH adsorption average pore diameter The Mott-Schottky measurements (Fig. S3) were car-
ried out to evaluate the flat band position of the samples
and thus to clarify the possible photocatalytic mechanism.
This fully shows that the addition of amorphous CoS can As shown in Fig. 7, all samples show positive slopes,
accelerate the electron transfer rate of CdS, thereby improv- reflecting the typical characterization of the n–type sem-
ing the performance of photocatalytic hydrogen production. iconductor. Where, the bottom of the conduction band

Fig. 7  (a) UV–vis DRS of CoS, CdS and CCS–7. The band gap width of CdS (b), CoS (c)

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3.4 Photocatalytic Activity of Catalyst

In order to prove that adding amorphous CoS can improve

the photocatalytic activity of CdS, we conducted hydrogen
production experiments on amorphous CoS, CdS and com-
posite catalyst CCS–7 loaded with different proportions of
amorphous CoS. The results are shown in Fig. 10. It can be
clearly seen from the figure that pure CdS and amorphous
CoS have poor hydrogen production performance. The
hydrogen production is 6.38 μmol·h−1 and 1.29 μmol·h−1,
respectively. With the loading of amorphous CoS, the com-
posite catalyst CCS showed higher hydrogen production per-
formance. When the loading ratio of amorphous CoS was
7%, the hydrogen production could reach 40.13 μmol·h−1.
This is about 6.3 times higher than pure CdS. When the load
ratio of amorphous CoS exceeds 7%, the hydrogen produc-
tion effect of composite catalyst CCS decreases significantly,
Fig. 8  Steady–state fluorescence spectra of different samples in ­H2O which may be due to the additional amorphous CoS attached
solution to the surface of CdS, covering the active sites of CdS and
inhibiting electron transfer.
At the same time, in order to compare the advantages
(CB) of CdS is close to −0.65 eV, and since the Eg of CdS of hydrogen production performance in this experiment,
is 2.22 eV, the calculated valence band (VB) position of we compared the hydrogen production performance of the
CoS is 1.57 eV. Similarly, CB and VB of CoS are 0.38 eV reported CdS heterojunction catalyst, and the results are
and 2.98 eV respectively. shown in Table 2. Although some experimental conditions
In order to measure charge transfer rates of different are different, such as light source, sacrificial reagent and
samples, electrochemical impedance spectroscopy was CdS amounts, the ­H2 evolution amount of 1 g of CdS pho-
used, as shown in Fig. S4.The composite catalyst CCS–7 tocatalysts per hour is used to compare. The catalyst FeP/
has the smallest radius of curvature, indicating that the CdS of the minimum amount of hydrogen production, only
charge transfer rate is the largest, which is beneficial to 278 μmol ­g−1·h−1 [48]. Even compared with typical catalyst
improve the photocatalytic hydrogen production rate. CdS/TiO2 [49], the hydrogen production performance of
catalyst CCS–7 is slightly better than that the photocata-
lyst CdS/TiO2. The above results are also apply to catalyst
CdS/SrTiO3 [50]. The hydrogen production performance

Fig. 9  (a) Photocurrent response curves of different samples with ITO. (b) LSV curves of different samples with ITO

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2416 X. Li et al.

oxidized to N­ a2SO4, which will not damage the photocata-

lyst. Therefore, N
­ a2S@Na2SO3 solution plays an important
role in the high efficiency hydrogen production result of
CCS–7 over the composite catalyst.
Figure S8 shows the photocatalytic performance of the
same photocatalyst CCS–7 when ­Na2S@Na2SO3 mixed
solutions with different concentrations were used as electron
sacrificial agents.The results showed that changing the ratio
of electron sacrifice agent at different concentrations did not
have a great effect on the hydrogen production of the com-
posite catalyst CCS–7, which may be due to the absence of
­S2− and ­SO3−, which led to the decrease of the cavity elimi-
nation rate.When the mixed solution with a concentration
of 0.35 M N ­ [email protected] M ­Na2SO3 was used as the electron
sacrificial agent, the composite catalyst CCS–7 had the best
photocatalytic activity.

Fig. 10  H2 evolution amount of different catalyst samples (20 mg 3.5 Cyclic Stability of Catalyst
catalyst, 5 h)

In order to explore the photocatalytic stability of the catalyst,

of catalyst CCS–7 is only slightly weaker than that of the we conducted a photocatalytic cycle experiment on the com-
catalyst CdS/Ni–MOF [47], this is because the structure of posite catalyst CCS–7, that is, without changing the amount
the catalyst CdS/Ni–MOF is superior to the catalyst CCS–7, of catalyst, the hydrogen production experiment of 20 mg of
which is the direction we need to explore and improve in the composite catalyst CCS–7 was continuously carried out
the future. for 4 cycles. The results are shown in the Fig. 11. As can be
In order to prove the role of N ­ a2S@Na2SO3 sacrificial seen from the figure, the composite catalyst CCS–7 showed
agent in the experiment, we used water instead of N ­ a2S@ good photocatalytic stability, and the best hydrogen produc-
Na2SO3 solution to conduct hydrogen generation experiment tion in the fourth cycle could reach 178.56 μmol. Even when
for five hours, and the results were shown in Fig. S7. As can the catalyst was soaked for 20 h and exposed to 20 h of light,
be seen from the figure, the hydrogen production value of the hydrogen production in the fourth cycle was only 11%
CCS–7 without N ­ a2S@Na2SO3 solution is extremely low, lower than that in the first cycle. Therefore, the composite
with the hydrogen production rate reaching only 0.4 mol·h−1. catalyst CCS–7 shows excellent photocorrosion resistance
In addition, when N ­ a2S@Na2SO3 was used as the electron and good photocatalytic stability.
sacrificial agent, the ­S2− and S­ O32− in the photocatalyst
could effectively eliminate the holes in the photocatalyst, 3.6 Photocatalytic Mechanism
which inhibited the electron–hole compound in the catalyst,
thus improving the photocatalytic hydrogen production per- The CB and VB positions of the individual semiconductors
formance. At the same time, the electron sacrificial agent is are calculated from empirical formulas [53–55]:

Table 2  This experiment is compared with the hydrogen production of the previously reported CdS heterojunction
Photoanode Light and intensity H2 production rate Sacrifice agent References

CdS/Ni-MOF λ > 420 nm 300 W Xe lamp 2.508 mmol ­g−1·h−1 60 mL of a mixed aqueous solution containing 6% [47]
lactic acid
−1 −1
FeP/CdS λ > 420 nm 300 W Xe lamp 278 μmol ­g ·h 80 mL solution containing 10 vol% of lactic acid [48]
CdS/TiO2 λ > 420 nm 1.776 mmol ­g−1·h−1 0.1 M ­Na2S + 0.1 M ­Na2SO3 [49]
Xe-lamp (Perfect Light PLS-SXE 300)
CdS/SrTiO3 300 W Xe lamp 1.332 mmol ­g−1·h−1 80 mL of water solution containing 8 mL methanol [50]
CdS/Cu7S4 300 W Xe lamp 27.8 mmol ­g−1·h−1 0.25 M ­Na2S + 0.25 M ­Na2SO3 [51]
MoS2/CdS λ > 420 nm 300 W Xe lamp 3.125 mmol ­g−1·h−1 80 mL solution containing 10 vol% of lactic acid [10]
Ni2S/CdS 350 W Xe lamp 18.96 mmol ­g−1·h−1 0.25 M ­Na2S + 0.25 M ­Na2SO3 [52]
CCS–7 λ > 420 nm 300 W Xe lamp 2.01 mmol ­g−1·h−1 0.35 M ­Na2S + 0.25 M ­Na2SO3 This work

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Construction of Amorphous CoS/CdS Nanoparticles Heterojunctions for Visible–Light–Driven… 2417

Fig. 12  Photocatalytic mechanism of composite catalyst CCS–7 in

visible light

Fig. 11  H2 evolution stability test for CCS–7 (20 mg catalyst, each
efficiency and electron transfer rate. Therefore, the pho-
cycle lasts for 5 h)
tocatalytic hydrogen production effect of the composite
catalyst CCS–7 has been greatly improved.
ECB = X − EC − 0.5Eg

4 Conclusion
EVB = ECB + Eg

In the above formulas, X is the absolute electroneg- In summary, XRD, SEM, TEM and other structural charac-
ativity of the semiconductor, and the value of which is terization methods show that we successfully synthesized
equivalent to the geometric mean of the absolute elec- a composite catalyst CCS–7 with granular agglomeration.
tronegativity of its constituent atoms; E
­ CB and E
­ VB are the Further experimental analysis shows that the loading of dif-
conduction band and valence band potential (VS.NHE) of ferent proportions of amorphous CoS has a great influence
the corresponding semiconductor, respectively; ­Ec is the on the hydrogen production rate of the composite catalyst
diference between the standard hydrogen electrode and CCS. When the mass ratio of supported amorphous CoS
the vacuum level (about 4.5 eV); E ­ g is the band gap of is 7%, the composite catalyst CCS can reach the optimal
the semiconductor. From the Fig. 7 results, the bandgap hydrogen production rate, and the hydrogen production rate
of CdS is 2.22 eV and that of amorphous CoS is 2.60 eV. can reach 2.01 mmol·h−1, which is 6.3 times that of pure
which is consistent with the previous reports. Respectively, CdS. The composite catalyst not only has an efficient pho-
the valence band potentials of CdS and CoS calculated tocatalytic hydrogen production effect, but also has good
via the above formulas are 1.57 eV and 2.98 eV, respec- photocatalytic stability. Under the condition of alkaline sac-
tively, and the conduction band potentials are − 0.65 eV rificial agent, the composite catalyst CCS can still maintain
and 0.38 eV, respectively. a high photocatalytic activity under continuous illumination
We have made a brief analysis on the hydrogen produc- for 20 h. Through the electrochemical and fluorescence spec-
tion mechanism of the composite catalyst CCS–7, and the trum characterization methods, it was shown that with the
results are shown in the Fig. 12. First, CdS are excited addition of amorphous CoS, the charge separation efficiency
by light, consuming ­S2− and S ­ O32− ions in the sacrificial and electron transfer efficiency of CdS were significantly
agent, generating a large number of electrons and holes. improved, promoting the formation of unsaturated active
Due to the energy difference between the conducting band sites. It has a good application prospect and provides new
(CB) of CdS and amorphous CoS, the electrons are trans- ideas and methods for the design and development of simple
ferred from the surface of CdS to the conducting band new amorphous composite catalysts.
(CB) of amorphous CoS, while the electrons obtained
Acknowledgements This work was supported by the Natural Science
from water and ­H+ in the sacrificial agent are reduced to Foundation of Ningxia Province (NZ17262).
­H2. The amorphous CoS is used as the transfer medium
of electron acceptor, and the synergistic effect between Funding This work was financially supported by the Open Project of
heterojunctions is used to improve the charge separation State Key Laboratory of High–efficiency Utilization of Coal and Green
Chemical Engineering, Ningxia University (2019-KF-36).

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2418 X. Li et al.

Compliance with Ethical Standards 16. Gai Q, Zheng X, Liu W, Dong Q, Wang Y, Gao R, Ren S (2019)
2D–2D heterostructured CdS–CoP photocatalysts for efficient
­H2 evolution under visible light irradiation. Int J Hydrog Energ
Conflict of Interest All authors have no conflict of interest with respect
44(50):27412–27420
to this manuscript.
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Affiliations

Xuanhao Li1 · Jing Xu1,2,3,4 · Lingjiao Li1 · Sheng Zhao1 · Min Mao1 · Zeying Liu1 · Yanru Li1

3
* Jing Xu Ningxia Key Laboratory of Solar Chemical Conversion
[email protected] Technology, North Minzu University, Yinchuan 750021,
People’s Republic of China
1
School of Chemistry and Chemical Engineering, 4
Key Laboratory for Chemical Engineering and Technology,
North Minzu University, Yinchuan 750021,
State Ethnic Affairs Commission, North Minzu University,
People’s Republic of China
Yinchuan 750021, People’s Republic of China
2
State Key Laboratory of High‑Efficiency Utilization of Coal
and Green Chemical Engineering, Ningxia University,
Yinchuan 750021, People’s Republic of China

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