i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4

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ZnCdS/NiAl hydrotalcite S-scheme heterojunction

for efficient photocatalytic hydrogen evolution

Chaoyue Zheng, Guoping Jiang**, Zhiliang Jin*

School of Chemistry and Chemical Engineering, Ningxia Key Laboratory of Solar Chemical Conversion Technology,
Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs Commission, North Minzu University,
Yinchuan, 750021, PR China

highlights

An S-scheme heterojunction composed of ZnCdS and NiAl LDH was formed.

The recombination of photoinduced electron-hole pairs was inhibited.

Highly improved photocatalytic hydrogen evolution activity was obtained.

Hydrogen evolution performance is 7 times the of ZnCdS and 130 times the of NiAl LDH, respectively.

article info abstract

Article history: ZnCdS/NiAl hydrotalcite S-scheme heterojunction with highly effective photocatalytic
Received 6 July 2021 hydrogen evolution activity was devised and prepared by a simple solution-based mixing
Received in revised form way. Layered double hydroxide (LDH), also called hydrotalcite-like compound, is composed
3 October 2021 of adjustable metal cations and exchangeable anions between layers. The hydrogen evo-
Accepted 5 October 2021 lution performance of ZnCdS/NiAl LDH is about 7 times that of ZnCdS and 130 times that of
Available online 28 October 2021 NiAl LDH. Because the rod-shaped ZnCdS and the layered NiAl LDH can construct close
interface contact. This interface contact helps to accelerate charge transfer, thereby
Keywords: achieving more effective photocatalytic hydrogen evolution. The S-scheme ZnCdS/NiAl
ZnCdS LDH heterojunction catalyst shows excellent hydrogen evolution and good stability, which
NiAl LDH not only gets benefits from the prominent performances of the cob-like ZnCdS and the
Heterojunction layered NiAl LDH but also the matching bandgap structure for them. The configuration of
H2 evolution the S-scheme ZnCdS/NiAl LDH heterojunction catalyst accelerates the rapid charge
Photocatalysis movement and inhibits the recombination of charge carriers, thereby greatly enhancing
visible-light-driven water splitting, which is corroborated by the PL spectrum, I-T, LSV, EIS,
MottSchottky and UVevis DRS studies, etc.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
** Corresponding author.
E-mail addresses: 2008028@nun.edu.cn (G. Jiang), zl-jin@nun.edu.cn (Z. Jin).
https://doi.org/10.1016/j.ijhydene.2021.10.032
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4
Introduction
With the development of society and economy, fossil energy
resources such as coal and oil are increasingly depleted, and
the problem of the energy crisis has become more serious
[1e3]. To solve this important problem, we urgently need to
find a sustainable, pollution-free energy source. Hydrogen
energy has attracted much attention as ideal clean energy
[4e6]. Scientists are studying the use of solar energy to drive
semiconductors to split water to produce hydrogen. It is an
important way to solve the energy crisis and reduce carbon
emissions [7,8]. The photocatalysts that have been reported
today are TiO2, g-C3N4, ZnCdS and LDH (Layered Double Hy-
droxide). Among the rest, metal sulfides and LDH as effective
catalysts are diffusely used in the field of photocatalytic
hydrogen evolution [9,10].
ZnCdS solid solution with excellent properties of ZnS and
CdS is a good transition metal semiconductor material
[11e13]. It has a suitable bandgap width and good light ab-
sorption ability, but its development is limited due to its high
light corrosion. Moreover, a single homogeneous catalyst does
not show satisfactory results in the photocatalytic reaction
[14,15]. For this reason, we need to introduce co-catalysts or
other catalysts to build heterojunctions to improve hydrogen
evolution activity [16]. For example, Song's group used WO3 as
a cocatalyst to modify ZnCdS to improve hydrogen evolution
performance [17].
LDH's chemical formula is [M2þ1-xM3þx (OH)2 (An-x/n)]$yH2O.
There are many types of hydrotalcite, such as MgAl LDH, NiAl
LDH, NiCo LDH and CoAl LDH. LDH is diffusely used in the field
of photocatalysis on account of its distinct layered structure
and large specific surface area [18e20]. For example, Yan's
group grows Ni2P on NiAl LDH for photocatalytic hydrogen
evolution [21].
The construction of heterojunction is the essential way to
increase hydrogen evolution performance [22e24]. There are
many types of heterojunctions. For example, there are type-II,
p-n, Z-scheme and S-scheme heterojunctions [25]. Yu's group
proposed the S-Scheme heterojunction, which can effectively
inhibit the recombination of carriers, promote charge trans-
fer, and have high-efficiency hydrogen evolution performance
[26e30]. In this paper, ZnCdS and NiAl LDH are used to
construct the S-scheme heterojunction to promote electron
delivery and improve the hydrogen evolution capability of the
catalyst [31].
Experiment
Preparation of NiAl LDH
0.28 g Ni(NO3)2$6H2O, 0.12 g Al(NO3)3$9H2O, 0.095 g NH4F,
0.384 g CO(NH2)2 were added into 80 mL pure water and
treated by using an ultrasonic instrument until the mixture
solution was completely dissolved, next it was stirred for 4 h
at ambient temperature. The mixed system was turned into
the PTFE autoclave and kept at 120  C for 12 h. After the re-
action, it was centrifuged and washed with ethanol three
times and dried at 70  C for 8 h [32].
293
Synthesis of ZnCdS
0.379 g Zn(NO3)2$6H2O, 0.617 g Cd(NO3)3$4H2O, 0.984 g CH4N2S
and 20 mL pure water were added into 100 mL of the beaker
and stirred with ultrasonic until it was completely dissolved.
The mixed system was turned into the PTFE autoclave then
kept at 160  C for 5 h. After the reaction, it was washed three
times with ethanol and deionized water by centrifugation,
dried at 120  C for 12 h.
Synthesis of ZnCdS/NiAl LDH
Add 100 mg ZnCdS and 50 mg NiAl LDH into 50 mL ethanol,
then, it was sonicated for 30 min and stirred for 4 h. Subse-
quently, the beaker was placed in a 60  C water bath to make
the piece dry and finally dried at 60  C for 10 h and collected.
Adjust the ratio of ZnCdS nd and NiAl LDH to prepare com-
posite catalyst (see Table 1).
Instruments and meters
XRD (X-ray diffractometer) used the Rigaku RINT-2000 dif-
fractometers with Cu Ka radiation and was operated at 40 kV
and 30 mA, the step size for 0.01 and the scan rate of 8 /min.
Samples were scanned with 2q range from 10 to 60 . The in-
struments used for SEM (Search Engine Marketing) and TEM
(Transmission Electron Microscope) images are German ZEISS
SIGMA 500 and Tecnai-G2-F30, respectively. The equipment
used for the XPS (X-ray photoelectron spectroscopy) image
and BET image are ESCALAB-250Xi and ASAP2020 M, respec-
tively. The UVevis diffuse reflectance spectra (DRS) of the
catalyst were performed on a UV-2550 (Shimadzu) spectrom-
eter. The BaSO4 was used as a reference for baseline correc-
tion. PL (photoluminescence spectroscopy) was acquired by a
FLUOROMAX-4 spectrophotometer at room temperature.
Photoelectric tests (VersaStat4-400, AMETEK) were performed
used an electrochemical workstation with 0.2 mol/L Na2SO4 as
the electrolyte solution. The apparent quantum efficiency
(AQE) under the 300 W Xe lamps and different wavelengths
are measured. The output intensity is obtained by taking the
PL-MW2000 photo-radiometer. The TG and DTG curves of the
catalyst were measured on an asynchronous thermal analyzer
(DSC/DTA-TG STA 449 F5 Jupiter®).
Photocatalytic H2 evolution experiments
Take 30 mL of sacrificial reagent (0.35 mol/L Na2SO3 and
0.25 mol/L Na2S) and 10 mg of material into a 64 mL glass bottle,
Table 1 e The content of ZnCdS and NiAl LDH in
composite photocatalyst.
Materials ZnCdS (mg) NiAl LDH (mg)
ZCNA-1 100 10
ZCNA-2 100 20
ZCNA-3 100 30
ZCNA-4 100 40
ZCNA-5 100 50
ZCNA-6 100 60
294 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4
sonicate uniformly, and remove air with nitrogen to maintain
an anaerobic environment. In the nine-channel reaction sys-
tem (Perfect Light PCX50A Discover), 5 W LED lights are used as
the light source, the wavelength range of the light source was
>420 nm. The integrated intensity was 100 mW/cm2 and the
temperature of the reaction system was kept at about 10  C.
The distance between the light source and the sample is about
3 cm. Put the glass bottle in the reactor, the evolutive hydrogen
was detected per 1 h (0.5 mL). The evolved H2 gas is detected by
taking a Tianmei GC7900 gas chromatograph (TCD, 13Xcolumn,
N2 as carrier) per 1 h and the peak area of H2.
Results and discussion
XRD analysis
In-depth research of the catalyst crystals was carried out by
using XRD. In Fig. 1a, there are six apparent feature peaks of the
ZnCdS located at 24.71 , 26.38 , 28.04 , 43.65 , 47.72 and 51.87 ,
respectively. These peaks correspond to (100), (002), (002), (002),
(101), (110), (103), and (201) plane of ZnCdS phase (PDF#49-1302),
which proves the successful composite of the ZnCdS. The
seven diffraction peaks of NiAl LDH are located at 11.51 , 23.22 ,
34.85 , 39.25 , 46.56 , 60.75 and 62.01 , corresponding to (003),
(006), (012) (015), (018), (110) and (113) plane of NiAl LDH
(PDF#15-0087). This result indicates that NiAl LDH was suc-
cessfully prepared. NiAl LDH shows sharp diffraction peaks
indicating higher crystallinity. The diffraction peak of NiAl LDH
shifts toward lower angles, which may be related to the content
of Ni and Al and the layered structure. In the ZCNA-5 sample,
the characteristic peaks of both ZnCdS and NiAl LDH can be
observed, proving the successful construction of the ZnCdS/
NiAl LDH photocatalyst. Fig. 1b is a phase diagram of ZCNA
samples, one can see that the intensity of diffraction peaks at
11.51 , 23.22 , and 34.85 becomes stronger with the increase of
NiAl LDH content, which also further proves the successful
structure of the ZnCdS/NiAl LDH catalysts.
SEM and TEM analysis
The microstructure of the catalyst was studied by TEM and
SEM. A small number of samples were ultrasonically
Fig. 1 e XRD diagrams of (a) Pure NiAl LDH, original ZnCdS and compound ZCNA-5, (b) different percentages of compounds.
dispersed in anhydrous ethanol, and a small amount of so-
lution was coated on the silicon wafer to dry, the test starts. It
can be observed from Fig. 2a that ZnCdS shows a corn-cob-like
structure with an uneven surface, which provides a larger
contact interface for an effective photocatalytic hydrogen
evolution reaction. In Fig. 2b, NiAl LDH exhibits a nano-flower
structure stacked by many rough nanosheets. In Fig. 2c, the
rod-shaped ZnCdS is loaded on the NiAl LDH nano-flower to
form close contact, and a part of the nano-flower-shaped NiAl
LDH is broken into irregular nanosheets contacted closely
with the ZnCdS. Fig. 2dee are TEM images of ZCNA-5. ZnCdS
and NiAl form an immediate connection, which is beneficial to
the rapid transmission of electrons. The lattice spacing of
0.19 nm and 0.26 nm is the (018) and (101) crystal planes of
NiAl LDH. And the (101) crystal plane of ZnCdSis reflected in
the lattice spacing of 0.31 nm. The EDX pattern in Fig. 2f shows
the existences of Ni, Al, Zn, Cd and S elements in ZNCA-5. In
Fig. 2g, the presence of Ni, Al, Zn, Cd, and S in the CNC-5%
catalyst, which further illustrates the successful preparation
of the ZCNA-5 catalyst.
XPS analysis
The chemical states of the elements in ZnCdS, NiAl LDH and
ZCNA-5 samples were also further studied through XPS
photoelectron energy spectroscopy. Take a small amount of
solid sample, put it on the conductive adhesive, and then
place it on the sample table, the test starts. Fig. 3a shows the
full spectrum of binding energies of all elements in the three
catalysts. The sample of ZCNA-5 is composed of Ni, Zn, Al, Cd,
O, S, and C, persistent with the consequence of EDX. In the XPS
spectrum of Zn 2p (Fig. 3b), the Zn 2p3/2 energy level has a peak
at 1021.91 eV, and the Zn 2p1/2 energy level has a peak at
1044.81 eV. In Fig. 3c, Cd has two peaks at 404.80 eV and
411.56 eV, respectively corresponding to the 3d5/2 and 3d3/2
orbitals of Cd. The S 2p3/2 energy level has a peak at 161.15 eV,
and the S 2p3/2 energy level has a peak at 162.35 eV (Fig. 3d). It
is noteworthy that the XPS peaks of Zn, Cd and S of ZCNA-5
move towards lower binding energies compared with ZnCdS,
which indicates electron transfer from NiAl LDH to ZnCdS. In
the Ni 2p energy spectrum (Fig. 3e), the two peaks at 856.23 eV
and 873.96 eV are Ni 2p3/2 and Ni 2p1/2 orbitals, respectively.
The spin energy is 17.73 eV, indicating the Ni element
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4 295

Fig. 2 e SEM images of (a) ZnCdS, (b) NiAl LDH and (c) ZCNA-5, (d) and (e) TEM images of ZCNA-5, (f) EDX of ZCNA-5 sample,
(g) the element mapping of ZCNA-5.
296 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4

Fig. 3 e XPS spectra of (a) survey, (b) Zn 2p, (c) Cd 3d, (d) S 2p, (e) Ni 2p, Al 2p for the ZnCdS, NiAl LDH and ZCNA-5 samples.

occupies the Ni2þ oxidation state. Satellite peaks of Ni are

located at 862.42 eV and 880.33 eV. In the Al 2p energy spec-
trum (Fig. 3f), the peak at 74.28 eV belongs to Al3þ in Al(OH)3.
The peak at 68.33 eV may belong to AlN. Compared with NiAl
LDH, XPS peaks of the Ni and Al in ZCNA-5 move to the higher
binding energy position, exhibiting also the charge migration
mechanism between ZnCdS and NiAl LDH [33]. These changes
in binding energy can confirm the direction of electron
transfer and further verify the strong interaction between the
contact surface between ZnCdS and NiAl LDH.

UVevis DRS analysis

The photosensitivity of the three materials was studied by

ultravioletevisible diffuse reflectance spectroscopy (UVevis
DRS). In Fig. 4a, NiAl LDH shows three absorption bands
located at 200e300 nm, 300e500 nm and 600e800 nm. The
region is 200e300 nm owing to ligand-to-metal charge trans- Fig. 4 e (a) UVevis DRS spectra of pristine ZnCdS, NiAl LDH
mit (O 2p /Ni 3d t2g) [34]. The region is 300e800 nm owing to and ZCNA-5% samples.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4
the d-d transition of Ni2þ in the octahedral geometry [35].
ZCNA-5 exhibits the best light absorption intensity among the
three materials, and the bandgap absorption edge is about
600 nm, which is beneficial to improving photocatalytic
hydrogen evolution.
BET analysis
Fig. 5 is the N2 adsorption isotherms of ZnCdS, NiAl LDH and
ZCNA-5, respectively. By measuring the size distribution of
nitrogen adsorption-desorption, the effect of NiAl LDH doping
on the porosity and specific surface area of ZnCdS was stud-
ied, and the change of pore size and specific surface area when
NiAl LDH was coupled with ZnCdS was analyzed. In Fig. 5, all
materials exhibit H4 hysteresis loops and type IV isotherms.
The average pore sizes of ZnCdS, NiAl LDH and ZCNA-5 is 12,
22, and 19 nm showing that all prepared catalysts are meso-
porous materials (see Table 2). The specific surface area of
ZnCdS, NiAl LDH and ZCNA-5 are 5, 62 and 56 m2/g, respec-
tively, and their pore volume is 0.15, 0.35 and 0.11 cm3/g,
respectively. Compared with ZnCdS, both the average pore
size and specific surface area are increased due to the doping
of NiAl LDH, which may supply more active sites for
enhancing hydrogen evolution reaction under visible-light-
driven.
Photocatalytic hydrogen evolution
Under visible light irradiation, 0.35 mol/L Na2SO3 and
0.25 mol/L Na2S were used as the sacrificial reagent to eval-
uate the hydrogen production performance of the synthesized
photocatalysts. In Fig. 6a, the hydrogen production amount of
NiAl LDH and ZnCdS is 0.58 and 9.77 mmol after reaction for
5 h, respectively. It is noteworthy that the hydrogen produc-
tion activity of ZCNA-5 is 75.60 mmol under the same condi-
tions, which indicates that the adulterate of layered NiAl LDH
greatly improved the photocatalytic hydrogen performance.
And the results of the control experiment show that the
hydrogen production performance of ZCNA-5 is about 7 times
that of ZnCdS and 130 times that of NiAl LDH. Compared with
ZnCdS and NiAl LDH, the hydrogen evolution performance of
ZCNA-5 has been dramatically improved, which means that
the forming of S-scheme heterojunction between ZnCdS and
NiAl LDH accelerated rapid electron migration for improved
the hydrogen evolution activity. In Fig. 6b, based on the
distinct quality ratios of ZnCdS and NiAl LDH, they were
Fig. 5 e The N2 adsorption and desorption isotherms and the pore size distribution curves (inset) of ZnCdS, NiAl LDH and
ZCNA-5 samples.
297
Table 2 e Various performance parameters of physical
adsorption.
Sample SBET/(m2/g) Pore Average pore
volume/(cm3/g) size/nm
ZnCdS 5 0.15 12
NiAl LDH 62 0.35 22
ZCNA-5 26 0.11 19
divided into six groups for hydrogen production experiments.
It may be seen that the composite catalyst exhibits the best
hydrogen evolution performance when the mass ratio of
ZnCdS and NiAl LDH is 2:1. Thus, ZCNA-5 has the best
hydrogen evolution efficiency, which is proving that the ratio
of ZnCdS and NiAl LDH plays a vital role in boosting more
effective hydrogen evolution. The percentage of ZnCdS and
NiAl LDH is of great significance for forming a good space
electric field to promote electron transport.
A continuous 20 h hydrogen production experiment was
performed on ZCNA-5 to test the stability of the catalyst
(Fig. 6c). From the first to the fourth cycle system, the activity
of the ZCNA-5 catalyst showed a downhill tendency, which
may be due to the reduction of Na2S and Na2SO3 in the reac-
tion system [36]. In the first circulation system, the hydrogen
production of ZCNA-5 was 75.60 mmol. The hydrogen pro-
duction in the last cycle system is 64.18 mmol, which is 15%
lower than the first cycle system. It shows that the ZCNA-5
material has good stability in the photocatalytic reaction.
Additionally, the TON is calculated to be 9.13 for 5 h over
ZCNA-5, whereas, the TON for pure NiAl LDH is only 0.07
(Fig. 6d). The enhanced photocatalytic activity can be attrib-
uted to the synergistic effect of the 0D/3D p-n heterostructure
and the quantum confinement effect of Co3O4 QDs that
confined the holes, which significantly promoted the separa-
tion efficiency of photo-generated electrons and holes. Its
enhanced photocatalytic activity is attributed to the con-
struction of a heterojunction between the two, which signifi-
cantly improves the separation efficiency of electrons and
holes. Additionally, the wavelength dependent apparent
quantum efficiency (AQE) of hydrogen evolution is given in
Fig. 6d, the highest AQE of 2.11% is obtained at 470 nm. And
AQE calculated according to the following equation:
the number of evolved H2 molecules
AQE ¼
the number of incident photon
298 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4

Fig. 6 e (a) H2 production of pure ZnCdS, NiAl LDH and ZCNA-5, (b) H2 evolution comparison of samples in different
proportions, (c) stability of hydrogen production performance of ZCNA-5, (d) the TON of hydrogen evolution over ZCNA-5
and NiAl LDH, (e) AQE of hydrogen evolution over ZCNA-5.

The turnover number (TON) of monodisperse ZCNA-5 for
H2 generation is calculated by using the following equation:
moles of evolved H2
TON ¼
moles of NiAl LDH on photocatalyst
Photoluminescence (PL) spectroscopy results
The steady-state and transient spectra were performed to
research further the internal mechanism of electron delivery
in ZnCdS/NiAl LDH S-scheme heterojunction. A 5 mg sample
was taken and put into a 25 mL fluorescent flask for volume
measurement. The excitation wavelength is 380 nm and the
slit width is 3 nm. In Fig. 7a, ZnCdS has the highest PL emis-
sion intensity, indicating the fast recombination of photo-
generated electrons and holes. When NiAl LDH was doped
into ZnCdS, the PL emission intensity of ZnCdS/NiAl LDH S-
scheme heterojunction catalyst decreases, which is due to the
structure of S-scheme heterojunction between ZnCdS and
NiAl LDH restrain the recombination of electrons and holes
and promotes hydrogen evolution reaction [37,38]. Fig. 7b is
the transient fluorescence spectrum. In Table 3, the average
charge lifetimes of ZnCdS and ZCNA-5 are 2.98 and 2.92 ns,
respectively. There is no significant change in the average life
of the two, which shows that the average life does not effect
on the efficiency of the catalyst.
Photoelectrochemical studies
To further research the photocatalytic hydrogen evolution
performance of the obtained catalysts, a large number of
electrochemical characterization tests were carried out.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4
Fig. 7 e (a) PL spectra excited at 380 nm and (b) Time-resolved PL spectra of as-prepared ZnCdS and ZCNA-5 samples.
Photoelectric tests (VersaStat4-400, AMETEK) were per-
formed used an electrochemical workstation with 0.2 mol/L
Na2SO4 as the electrolyte solution, 300w xenon lamp as the
light source (BL-GHX-Xe-300). Weigh 5 mg of the sample and
disperse it in 10 mL nafion of the solution. After 30 min of
ultrasound, apply it evenly on 1 cm2 conductive glass. After
the sample on the conductive glass is dried, the test starts.
Fig. 8a is a transient photocurrent reply curve used to study
the photoelectrochemical capability of the material surface
[39]. The photocurrent curves of the catalysts during the five
switching cycles are relatively stable. Under illumination,
when the energy of the incident ray is batter than the
bandgap of the trigger, the electrons and holes are
separated, generating a photocurrent response. ZnCdS and
ZCNA-5 show cathodic photocurrent peaks afterward the
commence of light exposure, which is because the photo-
generated electron pairs are separated at the electrode/
electrolyte interface. Compared with ZnCdS and NiAl LDH,
the photocurrent density of ZCNA-5 is significantly increased
at a bias voltage of 0.4 V because the photogenerated holes
and electrons of ZCNA-5 are well separated. Fig. 8b is LSV
(Linear Sweep Voltammetry) image to research the hydrogen
production performance of the catalyst. The cathode current
of the three materials is between 0.7 ~ 0.2 V, which be-
longs to the hydrogen production reaction. Because of the
drop in the overpotential, the powerful hydrogen production
performance of the material is exhibited [40]. The potential
of ZnCdS and NiAl LDH is 0.577 V and 0.586 V, respec-
tively. ZCNA-5 has a low overpotential of 0.566 V, which
proves beneficial to hydrogen evolution reaction. The elec-
trochemical impedance test is used to study the trans-
mission efficiency of electrons (Fig. 8c). All catalysts have a
resistance curve response. The smaller the arc radius of the
curve, the smaller impedance of the material and the higher
the electron transmission efficiency. ZCNA-5 has the small-
est arc radius, showing that it has the lowest electron
migration resistance and excellent electrical conductivity.
Table 3 e The dynamics parameters of photocatalysts internal reaction.
Samples t1 [ns] t2 [ns]
ZnCdS 5.71 (31.79%) 155 (39.69%)
ZCNA-5 5.56 (31.60%) 153 (40.31%)
299
Since the structure of S-scheme heterojunction between
ZnCdS and NiAl LDH, the resistance of ZCNA-5 tends to
decrease. The n-type semiconductors character of ZnCdS and
NiAl LDH could be proved by the positive tangent slopes in
Mott-Schottky graphs (Fig. 8dee). Relative to SCE, the Efb of
the pure NiAl LDH and ZnCdS catalysts are 0.68 V and
0.79 V. The conduction band (ECB) of the n-type semi-
conductor and its EFB are minus 0.1 or 0.2 V. Therefore, the ECB
estimates for NiAl LDH and ZnCdS are 0.88 V and 0.99 V
versus SCE, or 0.64 V and 0.75 V versus normal hydrogen
electrode (ENHE) of.
Stability experiment
Through SEM, XRD, TGA (thermogravimetric analysis) and
XPS tests, further study the stability of the catalyst. Fig. 9a is
the SEM image of ZCNA-5 (After) (ZCNA-5 catalyst after the
hydrogen evolution test is completed). There is no significant
change in the morphology between it and ZCNA-5, and it still
exhibits the original morphology and structure. In Fig. 9b, the
peak intensity of ZCNA-5 before and after the reaction slightly
changed, but the position of the characteristic peak did not
change, which can prove the stability of the photocatalyst
ZCNA-5. Fig. 9c and d are the TG and DTG comparison curves
of ZCNA-5 and ZCNA-5 (After) at 900  C, respectively. The
combustion trend of ZCNA-5 and ZCNA-5 (After) in the curve
of Fig. 9c is basically similar, and the thermal weight loss rate
of ZCNA-5 is lower than that of ZCNA-5 (After). The weight
loss rate of ZCNA-5 at 834  C is 5.62%/min, and the weight
loss rate of ZCNA-5 (After) at 839  C is 4.75%/min. The tem-
perature corresponding to the maximum weight loss rate of
ZCNA-5 (After) has a slight drop, which also verifies that the
performance of ZCNA-5 in the hydrogen evolution cycle test
decreases slightly with the increase of reaction time, but it is
not very obvious. Fig. 9e shows the full spectrum of binding
energies of all elements in the catalysts. The sample of ZCNA-
5 (After) is composed of Ni, Zn, Al, Cd, O, S, and C. In Fig. 9fej,
t3 [ns] c2 tav [ns]
1.03 (28.52%) 1.58 2.98
0.99 (28.09%) 1.58 2.92
300 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4

Fig. 8 e (a) Transient photocurrent response, (b) EIS, (c) LSV curves of ZnCdS, NiAl LDH, and ZCNA-5; (dee) Mott-Schottky of
ZnCdS and NiAl LDH.

ZCNA-5 has no change in the set of elements before and after
the reaction. The above characterization proves that the
photocatalyst ZCNA-5 has good stability.
Hydrogen evolution mechanism
Fig. 10a and b are the valence band spectra of NiAl LDH and
ZnCdS, respectively. The valence bands of NiAl LDH and
ZnCdS are 1.73 eV and 1.44 eV, respectively. According to
Mott Schottky, the conduction band positions of the two
materials are obtained, and the bandgap diagrams of the two
materials are drawn (Fig. 10c). According to the bandgap di-
agram, the possible Type-II heterojunction and S-Scheme
mechanism are proposed (Fig. 10d). Type-II heterojunction
principle, ZnCdS and NiAl LDH are in close contact under the
action of coulomb force. Under light, the electrons gain
energy and are excited, the electrons transition from the VB
to the CB, and the electrons of ZnCdS migrate from the CB to
the CB of NiAl LDH to undergo hydrogen evolution reaction.
Since the energy spectrum of XPS shows that the binding
energy of Zn, Cd and S elements shifts to a low direction, the
electron density increases, so electrons are transferred from
NiAL LDH to ZnCdS. Therefore, the theory of Type-II heter-
ojunction is not valid and the mechanism of S-Scheme het-
erojunction is proposed. ZnCdS and NiAl LDH establish a
close contact relationship under the action of coulomb force,
forming a built-in electric field. When illuminated by visible
light, the electrons in the catalyst gain energy and are
excited, and the electrons transition from the VB to the CB
position. The electrons of NiAl LDH CB recombine with the
holes of ZnCdS VB, the electrons with the most potent
reducing ability of ZnCdS CB are retained to partake in
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4 301

Fig. 9 e (a) SEM images of ZCNA-5 (After), (b) XRD diagrams of Pure ZCNA-5 and ZCNA-5 (After), (c) TG curves of ZCNA-5 and
ZCNA-5 (After), (d) DTG curves of ZCNA-5 and ZCNA-5 (After), XPS spectra of (e) survey, (f) Ni 2p, (g) Al 2p, (h) Cd 3d, (i) S 2p, (j)
Zn 2p for the ZCNA-5 and ZCNA-5 (After).
302 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4

Fig. 10 e (a) The EVB of NiAl LDH, (b) the EVB of ZnCdS, (c) bandgap diagram of ZnCdS and NiAl LDH, (d) Charge transfer
mechanisms over S-scheme heterojunction of ZCNA-5 under visible light irradiation.

hydrogen evolution response, and the holes with the most
potent oxidizing ability of NiAl LDH VB are depleted by the
sacrificial reagent, which improves the hydrogen evolution
performance of the catalyst.
Conclusion
In summary, a new s-scheme heterojunction catalyst ZCNA-5
was constructed by a simple solution-based mixing method
of ZnCdS and NiAl LDH. This paper mainly studies the
performance of ZnCdS and NiAl LDH photocatalytic water
splitting and their synergistic effects. Compared with ZnCdS,
the introduction of NiAl LDH effectively prevents the aggre-
gation of ZnCdS from reducing active sites, improves the light
absorption intensity, increases the separation efficiency of
electrons and holes, and reduces the transfer resistance of
electrons. Due to the introduction of NiAl LDH, ZCNA-5 ex-
hibits excellent photocatalytic performance in the water-
splitting reaction. The hydrogen evolution kinetic experi-
ment results show that the hydrogen production perfor-
mance of ZCNA-5 is about 7 times that of ZnCdS and 130
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 9 2 e3 0 4
times that of NiAl LDH. A continuous 20 h hydrogen pro-
duction experiment was carried out on ZCNA-5, and its effi-
ciency is still about 85%. The characterization of the reacted
catalyst further proves that ZCNA-5 has good stability. This
experimental work provides unique insights into the design
of S-scheme heterojunction photocatalysts.
Author contributions
Chaoyue Zheng and Guoping Jiang design the experiments;
Zhiliang Jin contributed materials and test equipment;
Chaoyue Zheng wrote the paper.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
This work was financially supported by the Natural Science
Foundation of Ningxia Province (2020AAC02026).
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