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An amorphous nickel boride-modified ZnxCd1−xS

Cite this: DOI: 10.1039/c9dt04311j
solid solution for enhanced photocatalytic
hydrogen evolution
Yue Cao,a,b,c Guorong Wang, *a,b,c Qingxiang Ma*d and Zhiliang Jin *a,b,c,d

Received 7th November 2019,
Accepted 12th December 2019
DOI: 10.1039/c9dt04311j
rsc.li/dalton
In this work, the rational design of amorphous NixB as a co-catalyst for the modification of ZnxCd1−xS was
achieved. First, NixB was prepared by the redox method and ZnxCd1−xS was synthesized by the hydro-
thermal method. Then, the electrostatic self-assembly method was used to complete the coupling of
NixB and ZnxCd1−xS. The experimental results of H2 production showed that when the mass ratio (wt%) of
NixB in NixB/ZnxCd1−xS was 7 wt%, it had the highest activity, and the hydrogen production could reach
1521 μmol under irradiation with light for 5 h. The hydrogen production activity of the composite catalyst
was 4.75 times higher than that of pure ZnxCd1−xS. The improvement in the photocatalytic activity can be
attributed to the following aspects: (i) UV-vis DRS showed that the addition of NixB increased the absorp-
tion of visible light; (ii) the PL, TRPL, IT, EIS and LSV experiments further proved that the composite catalyst
had excellent photoelectrochemical properties; (iii) the zeta potential results indicated that the electro-
static attraction between NixB and ZnxCd1−xS provided favorable conditions for the rapid transfer of elec-
trons. This work shows that amorphous NixB has a prominent effect on the modification of ZnxCd1−xS,
which provides more ways for the study of photocatalytic H2 evolution.

1. Introduction talysts. At present, transition metal sulfides have been proven

Energy is necessary for the survival of humans. At present,
mankind is facing great challenges because of the serious
environmental pollution and the gradual decline in fossil
energy.1–4 Solar and hydrogen energies are widely studied by
scientists as clean energies. Photocatalysis for hydrogen evol-
ution from water splitting is a promising way to efficiently
utilize solar energy.5–8 A series of catalysts have been reported
to achieve hydrogen production such as TiO2,9,10 CdS,11,12
g-C3N4,13,14 MoS215 and ZnCdS.16–18 However, a common
problem is the fast recombination of photogenerated carriers
and the low light absorption capacity. Therefore, it is vital to
develop efficient, cheap and clean catalysts.
The preparation of suitable catalysts is difficult because of
the stringent requirements on catalysts. Researchers have
made many efforts to improve the catalytic activity of photoca-
a still exist such as a high electron–hole recombination rate and
School of Chemistry and Chemical Engineering, North Minzu University,
Yinchuan 750021, P.R.China
b
Ningxia Key Laboratory of Solar Chemical Conversion Technology,
North Minzu University, Yinchuan 750021, P.R.China
c
Key Laboratory for Chemical Engineering and Technology, State Ethnic Affairs
Commission, North Minzu University, Yinchuan 750021, P.R.China
d solid solution. In addition, surface defects can promote the
State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical
Engineering, Ningxia University, Yinchuan,750021, PR China.
E-mail: zl-jin@nun.edu.cn, maqx@nxu.edu.cn
by many studies to be promising catalysts. CdS has been
widely reported because of its suitable band gap and appropri-
ate visible light response;19 however, high toxicity and suscep-
tibility to photocorrosion are adverse factors for the photo-
catalytic performance of CdS. In addition, ZnS can quickly
generate electron–hole pairs and has excellent catalytic activity
under ultraviolet light. However, its wide band gap (3.6–3.8 eV)
is the main factor hindering its photocatalytic performance.20
Recently, ZnCdS, a solid solution in which some Cd species
are replaced by Zn, has attracted the attention of researchers
because it has unique advantages as compared with single
metallic sulfides. First, the addition of a zinc source causes
the formation of a unique band structure, which increases the
absorption capacity of light and reduces the toxicity of CdS.21
Second, there are strong interactions between the Zn2+ and
Cd2+ ions because the ionic radius of Zn2+ (0.074 nm) is
smaller than that of Cd2+ (0.097 nm).22 Although the perform-
ance of the ZnCdS solid solution has been improved, problems
small surface area. Therefore, the ZnCdS solid solution has
been modified by constructing heterojunctions and surface
defects. The presence of surface defects leads to a narrow
band gap and a wide light absorption range for the ZnCdS
transfer of photoinduced charge between the body and the
surface of ZnCdS.23 It is reported that researchers have modi-

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fied the ZnCdS solid solution by constructing p–n heterojunc-
tions,24 which can promote the rapid transfer of photoinduced
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charge and effectively inhibit the recombination of electrons
and holes. In conclusion, these methods can effectively
improve the photocatalytic performance of the ZnCdS solid
solution. Meanwhile, researchers have reported that the
ZnCdS solid solution can be modified using co-catalysts and
excellent results are obtained. Ran et al. modified the ZnCdS
solid solution by using suitable nickel-based co-catalysts.25 Dai
et al. adopted Ni2P as a co-catalyst for modification of
Zn0.5Cd0.5S.26 Wang et al. modified Zn0.5Cd0.5S with cobalt
phosphide nanowires, which significantly improved the catalytic
activity, and the composite catalyst was 22 times better as com-
pared to the pure Zn0.5Cd0.5S. The excellent catalytic perform-
ance was attributed to the splendid conductivity and nanowire
structure of the co-catalyst CoP.27 There have, so far, been large
many reports on the modification methods of co-catalysts. On
the other hand, cheap and environmentally friendly transition
metal borides have been reported less in the field of photocata-
lysis. NixB as a co-catalyst for the modification of the ZnCdS
solid solution has not yet been reported. Herein, we have modi-
fied ZnCdS solid solution by means of a co-catalyst.
In this work, amorphous the NixB was synthesized by a
simple redox method. The composite catalyst NixB/ZnxCd1−xS
was synthesized by the electrostatic self-assembly method and
it showed significant photocatalytic activity under visible light
(λ > 420 nm). The effect of the modification of the NixB
content on the ZnxCd1−xS will be discussed. The composite
catalyst NixB/ZnxCd1−xS showed the highest catalytic activity
when the content of the NixB was 7 wt%. The hydrogen pro-
duction reached 1521 μmol in 5 h, which was 4.75 times higher
than the hydrogen production of the ZnxCd1−xS. The good cata-
lytic activity was attributed to the high absorption capacity of
light, the wonderful photoelectrochemical properties of the
composite catalyst and the electrostatic attraction between the
NixB and the ZnxCd1−xS. This work provides a new idea for the
modification of the ZnxCd1−xS by co-catalyst.
2. Experimental section
2.1 Sample preparation procedure
2.1.1 Preparation of ZnxCd1−xS. The ZnxCd1−xS solid solu-
tion was prepared by a hydrothermal method. Typically,
Cd(Ac)2·2H2O (5 mmol), Zn(Ac)2·2H2O (5 mmol) and thioaceta-
mide (12.5 mmol) were dissolved in 40 mL deionized water
and were stirred continuously. After mixing well, 10 mL of 4 M
NaOH solution was added to the solution and stirred continu-
ously for 1 h. The mixture was then transferred to a 100 mL
Teflon-lined stainless steel autoclave and kept at a constant
temperature in an oven at 180 °C for 24 hours. The yellow sedi-
ment was collected by centrifugation and washed several times
with water and ethanol.27 Finally, the samples were dried in an
oven at 60 °C and named ZCS.
2.1.2 Synthesis of the NixB/ZnxCd1−xS composite photo-
catalyst. NixB was prepared by a redox method. NiCl2·6H2O
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was used as an oxidant and nickel source, and NaBH4 as a
reducing agent and boron source. Specifically, NiCl2·6H2O
(6 g) was dissolved in deionized water (150 mL) to form NiCl2
solution. After adding NaBH4 (2.84 g) powder to the NiCl2 solu-
tion, a large number of bubbles was generated and the solu-
tion was stirred for 30 minutes after the bubbles disappeared.
The black samples were collected by vacuum filtration and
thoroughly cleaned with water and ethanol several times.
Finally, NixB was obtained after 12 h drying in a vacuum
drying box at 80 °C. Specific amounts of the NixB and the ZCS
powders were added to anhydrous ethanol (20 mL) and stirred
for 1 h, then the mixture was evaporated in a water bath at
80 °C. The specific precursor addition amounts are shown in
Table 1, which were named NBZ-1, NBZ-2, NBZ-3, NBZ-4 and
NBZ-5, respectively.
2.2 Characterization
This article, X-ray diffraction (XRD, Rigaku RINT-2000) was
used to characterize the phase composition of the samples.
The zeta potentials of the ZCS and NixB were obtained on a
Litesizer 500. The surface morphologies and microstructures
of the materials were determined using a field emission scan-
ning electron microscope (SEM: JSM-6701F. JEOL) with an
accelerated voltage of 5 V, and a transmission electron micro-
scope (TEM: FEI Tecnai TF 20) with an accelerated voltage of
300 kV. The surface chemical states and chemical compo-
sitions of the catalysts were studied in ultra-high vacuum
(UHV) by X-ray photoelectron spectroscopy (XPS ESCALAB
250Xi). The UV-vis diffuse reflectance spectra (DRS) of the
samples were tested on the UV WinLab V6 (Lambda750)
spectrometer (with BaSO4 as the reference background). N2
adsorption–desorption isotherms of samples were obtained
using an ASAP 2020M (Micromeritics) at 77 K.
Photoluminescence (PL) spectra were obtained using a
FluoroMax-4 spectrometer. Time-resolved photoluminescence
(TRPL) spectra were obtained using a Horiba instrument
(France). The electrochemical testing of samples was con-
ducted on an electrochemical workstation (VersaSTAT4-400,
AMETEK) with a standard three-electrode cell. Typically, 5 mg
of catalyst was uniformly dispersed in 100 μL mixed solution
(Nafion : ethanol = 1 : 9). The dispersed catalyst was coated in
f-doped tin oxide (FTO) glass (1 × 1 cm2) as the working elec-
trode. A platinum sheet was used as the counter electrode. A satu-
rated calomel electrode (SCE) was employed as a reference elec-
trode and Na2SO4 (0.5 M, pH = 0.68) aqueous solution was the
electrolyte. The transient photocurrent response of the samples
was tested with a 300 W xenon lamp as the light source.
Table 1 Addition amount of each precursor
Samples ZnxCd1−xS (mg) NixB (mg)
NBZ-1 200 6
NBZ-2 200 10
NBZ-3 200 14
NBZ-4 200 18
NBZ-5 200 24
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2.3 Photocatalytic hydrogen evolution experiments
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All samples were tested with 30 mL lactic acid solution (10
vol%), which was used as a sacrificial reagent in a 62 mL
quartz reactor. The catalyst (10 mg) was dissolved in the lactic
acid solution, and the solution was homogenized by ultrasonic
treatment. Air was removed from the bottle and replaced with
N2. A 5 W xenon lamp (PLS-SXE 300C) was used as the
light source, and a gas chromatograph equipped with a
thermal conductivity detector (TCD) (Tianmi GC7900, TCD,
13× column, N2 as the carrier) was used for analysis.
Hydrogen production was measured by sampling 0.5 mL per
hour for a total of 5 h. To tested the stability of the catalyst.
Five cycles were recorded, and H2 was completely removed
from the bottle with N2 at the end of each cycle. A 300 W
xenon lamp was used to test the apparent quantum efficiency
(AQE), obtaining different light origins by transforming filter
slices (420 nm, 450 nm, 475 nm, 500 nm, 520 nm and
550 nm). The quantum efficiency of the composite catalyst
NBZ-3 was tested by using a 10 mg catalyst in the lactic acid
system (10 vol%). The filter plate was transformed every hour
and the hydrogen production was recorded. The calculation of
Fig. 1 Zeta potential of pure ZCS and NixB.
Fig. 2 XRD patterns of (A) pure ZnxCd1−xS and the standard card, (B) pure NixB and NixB/ZnxCd1−xS.
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the apparent quantum efficiency at different wavelengths is
shown in eqn (1).
2  the number of evolved hydrogen molecules
AQE ¼  100%
the number of incident photon
ð1Þ
3. Results and discussion
3.1 Zeta potential
The zeta potentials of the pure NixB and ZCS are shown in Fig. 1.
It can be seen that the zeta potential of the NixB and ZCS are
26.18 mV and −11.37 mV, respectively. Because the NixB and ZCS
have opposite zeta potentials, there is a strong electrostatic attrac-
tion between them, which promotes the charge transfer between
them.28,29 In addition, due to electrostatic adsorption, the contact
between ZCS and NixB is closer,30 which improves the hydrogen
production performance of the NBZ-3 composite catalyst.
3.2 Structure and morphology analysis
3.2.1 XRD analysis. The crystal phases of all samples were
measured by X-ray diffraction (XRD). In Fig. 2A, the ZnxCd1−xS
sample has six obvious characteristic peaks (2θ = 26.87°, 28.30°,
44.60°, 47.19°, 52.80°, 56.10°), which move towards high and low
angles as compared to the CdS (PDF# 89-440) and ZnS (PDF# 65-
5476), respectively. The results show that the ZnxCd1−xS is not a
mixture of the CdS and ZnS; it is a solid solution of the
ZnxCd1−xS.21 In addition, the ZnxCd1−xS samples have good crys-
tallinity because the diffraction peaks are very strong. In Fig. 2B,
the NixB has a typical amorphous feature with a wide peak at 2θ =
45°, which is consistent with the results in the literature.31,32,39
The characteristic peak of NixB does not appear in the NBZ-n (n =
1, 2, 3, 4, 5) composite because of the amorphous state and the
low load. These results prove the formation of the ZnxCd1−xS
solid solution and the NixB. The formation of the NBZ-n compo-
site material was further proved using TEM and XPS.
3.2.2 SEM and TEM analysis. The morphologies of the
samples were tested by scanning electron microscopy (SEM).
In Fig. 3A, the single ZCS exhibited a surface with a smooth and
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Fig. 3 SEM images of (A) pure ZCS, (B) NixB, (C) NBZ-3; TEM images of (D) NBZ-3; (E) HRTEM images of NBZ-3 and (F) EDX images of NBZ-3. (G)
The element mapping of NBZ-3.

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granular appearance. In Fig. 3B, the morphology of the pure
NixB is similar to that of lamellar aggregates. In Fig. 3C, the
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granular ZCS and irregular sheet NixB are clearly observed.
To study the nanostructure of the samples, the NBZ-3 was
investigated using transmission electron microscopy (TEM)
and high-resolution transmission electron microscopy
(HRTEM). In Fig. 3D, the NBZ-3 composite catalyst shows a
similar granular morphology, which is consistent with SEM
characterization results, but it could not distinguish between
ZCS and NixB. Therefore, a further study was conducted on the
NBZ-3 by HRTEM. In Fig. 3E, the lattice with interplanar spa-
cings of 0.33 nm and 0.35 nm in the ZCS can be clearly
observed, which corresponds to the (002) and (100) crystal
planes, respectively. The results are consistent with those
reported in the literature.33 In addition, the amorphous NixB
Fig. 4 (A) XPS survey spectra of NBZ-3, (B–F) high-resolution XPS spectra of Zn 2p, Cd 3d, S 2p, Ni 2p and B 1s.
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was observed in the circle. In particular, the close contact
between the ZCS and NixB promotes charge transfer, which
improves hydrogen production performance.34 In Fig. 3F, the
NBZ-3 composite samples were investigated using energy-dis-
persive X-ray spectroscopy (EDX). The data show that the
NBZ-3 contains Zn, Cd, S, Ni and B. Finally, Fig. 3(G) shows
the element mapping of NBZ-3, including the mapping images
of Zn, Cd, S, Ni and B, respectively. The Zn, Cd, S, Ni and B
elements are evenly distributed. The analysis further demon-
strated the successful synthesis of the amorphous NixB and
NBZ-3 composites.
3.2.3 XPS analysis. X-ray photoelectron spectroscopy (XPS)
was used to determine the chemical state of elements in the
NBZ-3 composite catalyst. As shown in Fig. 4A, Zn, Cd, S, Ni
and B can be clearly observed, which is consistent with EDX.
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In Fig. 4B, the peaks located at binding energies of 1022.05 eV
and 1045.06 eV belong to Zn 2p3/2 and Zn 2p1/2, respectively,
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proving the presence of Zn2+ in the NBZ-3 composite catalyst.35
In Fig. 4C, the high-resolution Cd 3d spectrum displays peaks
at 405.49 eV and 412.24 eV, which correspond to Cd 3d5/2 and
Cd 3d3/2, revealing the presence of Cd2+ species originating
from the NBZ-3 composite catalyst.36 In Fig. 4D, the two peaks
corresponding to S 2p3/2 and S 2p1/2 appear at 162.11 eV and
163.18 eV, respectively.37 In Fig. 4E, there are two main decon-
voluted peaks at 856.31 eV and 874 eV, which are ascribed to
Ni 2p3/2 and Ni 2p1/2. In addition, the peaks at the binding
energies of 862.28 eV and 880.22 eV can be attributed to the
oscillating satellite peaks of Ni2+.38 In Fig. 4F, there is just one
predominant peak of B 1s. The peaks located at 191.85 eV
reflect the binding energy of boron oxide.39 The binding ener-
gies of the elements in the composite sample are consistent
with the reported literature, which further indicates that the
NBZ-3 composite catalyst was successfully synthesized.
3.2.4 BET analysis. The BET specific surface area (SBET)
and pore size distribution of the ZCS, NixB and NBZ-3 samples
were calculated to adapt to N2 adsorption–desorption iso-
therms, as shown in Table 2. In Fig. 5A, all samples exhibit type
IV adsorption isotherms and type H3 hysteresis loops. In
Fig. 5B, all samples pores are concentrated between 2–50 nm,
further proving that the material has a mesoporous structure.40
The adsorption isotherm in the figure is represented by eqn (2).
Va cðp=p*Þ
¼ ð2Þ
a
Vm ð1  p=p*Þ½1 þ ðc  1Þp=p*
Va, amount adsorbed under pressure, P; Vam, saturation adsorp-
tion amount of the monolayer; P*, saturated vapor pressure of
Table 2 Parameters of physical adsorption
Pore volume Average pore
Samples SBET (m2 g−1) (cm3 g−1) size (nm)
ZCS 38.17 0.33 35.63
NixB 42.84 0.15 14.86
NBZ-3 35.99 0.27 30.98
Fig. 5 (A) N2 adsorption–desorption isotherms and (B) pore size distribution curves of ZCS, NixB and NBZ-3.
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the liquid adsorbed at the adsorption temperature; C, adsorp-
tion constant that is related to the adsorption heat.
The analysis is based on the results in Table 2. The specific
surface area of the ZCS (38.17 m2 g−1) is obviously larger than
that of the NBZ-3 (35.99 m2 g−1) introduced with the NixB. It is
worth noting that the pore size of NixB (14.86 nm) is about
half of the ZCS (35.63 nm), and the pore volume of NixB
(0.15 cm3 g−1) is also about half of the ZCS (0.33 cm3 g−1).
Therefore, it was further inferred that the NixB particles were
embedded in the porous structure of the ZCS. Based on the
above analysis, it can be concluded that the increase in the
hydrogen production activity of the NBZ-3 is not directly
related to the specific surface area.
3.3 Photocatalytic H2 production activity
In Fig. 6A, the NBZ-3 composite catalyst shows significant
hydrogen production activity as compared to the single ZCS.
After 5 h of light, the NBZ-3 produced 1521 μmol of hydrogen
and the ZCS produced only 320 μmol. The catalytic perform-
ance of NBZ-3 improved 4.75 times as compared with that of
the ZCS. The low hydrogen production of the ZCS is attributed
to the fast recombination of photoexcited electrons and holes,
which leads to the reduction of electrons transferred to the
surface of the ZCS and the reduced ability to reduce hydrogen
ions. In Fig. 6B, as the content of NixB loaded on the ZCS gradu-
ally increases, similar to the volcano diagram, it shows that the
hydrogen production performance first increases and then
decreases. When the content of the NixB increased from 3 wt%
(NBZ-1) to 7 wt% (NBZ-3), the hydrogen production was on the
rise because the addition of the NixB increased the electron
transfer rate of the ZCS conduction band and provided more
active sites. Hydrogen production declined when the NixB
increased to 15 wt% (NBZ-5). Therefore, it is the optimum load
for the ZCS when the NixB content reached 7 wt% (NBZ-3). The
catalyst stability tests are shown in Fig. 6C. The NBZ-3 showed a
small decrease after five cycles of testing but showed almost the
same catalytic activity in the first four cycles. The small decrease
in the hydrogen production of NBZ-3 in the last cycle may be
due to the consumption of lactic acid. The results show that
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Fig. 6 (A and B) H2 production activity of ZCS and NixB and NBZ-n (n = 1, 2, 3, 4, 5). (C) Stability test of the NBZ-3 sample; (D) AQE of NBZ-3 at
different wavelengths (420–550 nm).

Fig. 7 (A) UV-vis diffuse reflectance spectra of ZCS, NixB, NBZ-3. (B) The plot of (ahv)1/2 versus energy for the band gap energy of ZCS.

NBZ-3 has reliable stability. In Fig. 6D, the AQE of NBZ-3 was
analyzed at different monochromatic wavelengths. Two higher
values appear in the wavelength range from 420 nm to 550 nm.
The AQE is 5.8% at the wavelength of 475 nm, and almost
nothing at a wavelength of 550 nm. The maximum quantum
efficiency of the NBZ-3 sample is 6.9% at 420 nm.
3.4 Optical properties of the photocatalysts
3.4.1 UV-vis DRS analysis. UV-vis diffuse reflectance spec-
trometry (UV-vis DRS) is a necessary method for studying the
optical properties of semiconductors. In Fig. 7A, it can be
clearly seen that the absorption band edge of a single ZCS is
located near 530 nm, with low absorption between 530–800 nm.
We found that the absorption of the NBZ-3 showed a significant
increase as compared to the ZCS in the 500–800 nm range when
the NixB was introduced. The macroscopic phenomenon is that
the sample changes from pale yellow to dark green. It is undeni-
able that the substantial increase in light absorption by NBZ-3
is an important factor for the improvement of the hydrogen pro-
duction performance. The electron band gap of the ZCS was

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determined through the intersection of the tangent line of the are fitted to a three-exponential attenuation, according to the
curve and the horizontal axis and eqn (3). following equation:
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X
IðtÞ ¼ Bi expðt=τi Þ ð4Þ
ahv ¼ Aðhv  Eg Þ1=2 ð3Þ i¼1;2;3

a, absorption coefficient; h, Planck’s constant; v, light fre-
quency; Eg, band-gap energy; A, constant.
In Fig. 7B, the band gap of the ZCS is 2.35 eV, which
belongs to the range of visible light excitation. In addition, the
small band gap of 2.35 eV is more easily excited by visible
light, which is more favorable for hydrogen production.
3.4.2 The PL and TRPL spectra. Photoluminescence (PL)
spectroscopy can provide more evidence for carrier migration
and recombination.41 The PL spectra of the ZCS, NBZ-1, NBZ-3
and NBZ-5 are shown in Fig. 8A. A semiconductor is excited to
produce electron–hole pairs, some of which are transferred to
the surface of the material and the rest recombine rapidly. The
recombined energy is released in the form of fluorescence.42
The ZCS sample presents a strong fluorescence signal at
500 nm. When the NixB is loaded, the trend of fluorescence
quenching can be seen. The experimental phenomenon shows
that on the addition of co-catalyst, the NixB could improve the
charge migration of the ZCS and inhibit the rapid recombina-
tion of electrons and holes. The NBZ-3 demonstrated excellent
fluorescence quenching; this can be attributed to the success-
ful suppression of carrier recombination by the introduction
of NixB. The rapid separation and migration of electrons and
holes is an important reason for the improvement of the
hydrogen production performance of the NBZ-3.
The kinetics of charge migration was also analyzed. Time-
resolved photoluminescence spectra (TRPL) were obtained for
the samples. In Fig. 8B, the attenuation curves of all samples
I is the normalized emission intensity; t is the time after the
pulsed laser excitation; τi are the respective decay lifetimes; Bi
are the corresponding weight factors.
The parameters of fitting are shown in Table 3. The
NBZ-3 has a faster TRPL decay than other samples. The reason
for this phenomenon is the high charge transfer efficiency.
NixB, as an electron acceptor, can rapidly transfer electrons
from the valence band of ZCS. The EIS test results also con-
firmed the above conclusion.43
X X
hτi ¼ Bi τ i 2 = Bi τ i ð5Þ
i¼1;2;3 i¼1;2;3
〈τ〉 is the average lifetime; τi are the respective decay times; Bi
are the corresponding weight factors.
Eqn (5) was used to calculate the average lifetime of all
samples. The average lifetimes of ZCS and NBZ-3 were 1.46 and
1.13 ns, respectively. From the information given in Table 3, it
can be seen that τ1, τ2, τ3 of the NBZ-3 are all decreased com-
pared with pristine ZCS. The average lifetime of the NBZ-3 is the
shortest as compared with other samples. It was reported that
the shortening of the charge lifetime is related to the increase
in transmission rate.44
1 1
KET ¼  ð6Þ
hτiNBZ‐n hτiZCS
According to eqn (6), KET of the NBZ-1, NBZ-3 and NBZ-5
are 0.12, 0.2 and 0.16, respectively. The improvement of the

Fig. 8 (A) PL spectra of ZCS, NBZ-1, NBZ-2, NBZ-3 and NBZ-4. (B) TRPL spectra of ZCS, NBZ-1, NBZ-2, NBZ-3 and NBZ-4.

Table 3 Decay parameters for ZCS, NBZ-1, NBZ-3 and NBZ-5 samples

Samples τ1 [ns] τ2 [ns] τ3 [ns] τave [ns] KET [109 s−1]

ZCS 4.82 (39.99%) 0.62 (37.25%) 114.36 (22.76%) 1.46

NBZ-1 4.64 (39.71%) 0.52 (37.83%) 109.22 (22.46%) 1.24 0.12
NBZ-3 4.58 (38.85%) 0.48 (38.65%) 109.44 (22.50%) 1.13 0.2
NBZ-5 4.60 (37.99%) 0.50 (39.17%) 110.75 (22.83%) 1.19 0.16

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hydrogen production performance of the ZCS is attributed to
the fact that the NBZ-3 composite effectively improved the sep-
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aration and migration of electrons and holes.
3.5 Electrochemical characterization
Photoelectrochemical properties provide an essential index
that can reflect the charge separation and transfer efficiency of
semiconductor photocatalytic materials. The photocurrent
reflects the ability of photogenerated electrons under visible
light;45 therefore, the transient photocurrents of the ZCS,
NBZ-1 and NBZ-3 samples were explored. In Fig. 9A, the
relationship between photocurrent and time was obtained
under the periodic switching of light. Obviously, NBZ-3 has a
very high photocurrent density as compared to the bare ZCS.
This phenomenon further proves that the interface between
the ZCS and NixB has efficient electron transfer-ability and the
increased NixB content could greatly improve the visible light
response. It is worth noting that the photocurrent densities of
the samples present a trend of NBZ-3 > NBZ-1 > ZCS, which is
very similar to the trend of hydrogen production. Furthermore,
the electrical conductivities of the samples were studied
through EIS Nyquist plots. Generally, the smaller radius of the
curve signified the lower impedance value of the sample. In
Fig. 9B, the arc radius of the NBZ-3 is the smallest. The
phenomenon indicates that the NBZ-3 has lower impedance as
compared with bare ZCS, which further provides favorable con-
Fig. 9 (A) Photocurrent response, (B) electrochemical impedance spectroscopy (EIS), (C) linear scan voltammetry (LSV) curves of ZCS, NBZ-1 and
NBZ-3. (D) Mott–Schottky curves of ZCS.
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Paper
ditions for hydrogen production kinetics.46 All the above ana-
lyses are consistent with the results of PL and TRPL. Linear
sweep voltammetry (LSV) was used to demonstrate the electro-
catalytic hydrogen evolution activity of the samples.47 In
Fig. 9C, the polarization curves of all the samples are dis-
played. The cathode current density of the ZCS is very small at
a high applied voltage. Among all test samples, the NBZ-3
composite showed the highest current density and the lowest
overpotential. The experimental phenomenon indicates that
the addition of the NixB can significantly reduce the overpo-
tential of the ZCS and improve the efficiency of charge separ-
ation. These results indicate that NixB can promote the electro-
chemical properties of the ZCS and improve hydrogen pro-
duction activity.
The Mott–Schottky plot provides more evidence for the
band structure of materials. In Fig. 9D, the curve of the ZCS
shows a positive slope, indicating that the ZCS is a typical
n-type semiconductor.48 The flat band potential (Efb) of ZCS is
−0.46 V, relative to SCE. According to literature, the n-type
semiconductor conduction band potential (ECB) is more nega-
tive by 0.1 V or 0.2 V as compared to the corresponding Efb.49
Therefore, the ECB of ZCS is −0.66 V relative to SCE. The other is
expressed as −0.419 V, corresponding to the normal hydrogen
electrode NHE (ENHE = ESCE + 0.241). According to the results of
the UV-vis spectra and Mott–Schottky plot, the valence band
potential (EVB) of the ZCS is 1.931 V (EVB = ECB + Eg).
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Fig. 10 The photocatalytic mechanism for NixB/ZnxCd1−xS.
3.6 Reaction mechanism
The mechanism for the photocatalytic hydrogen production of
the catalyst was proposed through a series of experimental
data and is shown, in Fig. 10. It is well known that valence
electrons enable the valence band to gain enough energy and
transfer it to the conduction band, leaving holes in the valence
band when light excites the semiconductor; however, most of
the electrons and holes quickly recombine. Some of the elec-
trons that migrate to the semiconductor surface undergo a
reduction reaction to form H2. Lactic acid is oxidized by the
holes to pyruvate, which effectively inhibits the recombination
of electrons and holes. The low hydrogen production perform-
ance of the pure ZCS is due to the fact that the electrons in the
valence band cannot transfer too quickly, leading to the fast
recombination rate of electrons and holes. As for the NBZ-3
composite, due to the electrostatic attraction between the ZCS
and NixB, electrons can rapidly transfer from the ZCS to NixB.
The number of electrons participating in the reduction reac-
tion keeps increasing, thus improving the photocatalytic
activity. In addition, the NixB plays an effective role in visible
light capture, enabling the NBZ-3 composite to have a higher
light absorption capacity. Therefore, the NixB plays a vital role
in the photocatalytic reaction system.
4. Conclusion
The amorphous NixB was synthesized by a redox method, and
the NBZ-3 composite catalyst was synthesized by electrostatic
self-assembly. The NBZ-3 catalyst has the highest photo-
catalytic hydrogen production capacity in lactic acid solution.
The hydrogen production capacity is 4.75 times higher than
pure ZCS. It can be seen from the zeta potential that there is
an electrostatic attraction between NixB and ZCS, which pro-
vides favorable conditions for the rapid transfer of electrons.
The results of UV-vis DRS show that the absorption of the
NBZ-3 composite catalyst in the visible light range is high and
the utilization rate of light is improved. Photochemical and
electrochemical experiments further showed that the NBZ-3
Dalton Trans.
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Dalton Transactions
composite catalyst has excellent photoelectrochemical pro-
perties and promotes charge transfer efficiency. This work
reveals that the amorphous NixB has an excellent modification
effect on the ZCS.
Author contributions
Yue Cao and Guorong Wang designed the experiments,
Zhiliang Jin and Qingxiang Ma contributed reagents/materials
and analysis tools; and Yue Cao wrote the paper.
Conflicts of interest
The authors declare that they have no competing interests.
Acknowledgements
This work was financially supported by the Chinese National
Natural Science Foundation (41663012, 21862002), the Open
Project of State Key Laboratory of High-efficiency Utilization of
Coal and Green Chemical Engineering, Ningxia University
(2019-KF-36), the new technology and system for clean energy
catalytic production, major scientific project of North Minzu
University (ZDZX201803) and The Ningxia low-grade resource
high value utilization and environmental chemical integration
technology innovation team project, North Minzu University.
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