Journal of Alloys and Compounds 960 (2023) 170382

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Mn-doped CdS/Cu2O: An S-scheme heterojunction for photocatalytic

hydrogen production ]]
]]]]]]
]]

⁎ ⁎ ⁎
Lufang Fan a, Jiahui Han b, , Kai Wei a, , Changchang Ma a, Sheng Feng a, , Yun Zhou a,
Xiaojun Dai a, Zhiwei Ye a, Yang Wang a
a
School of Environmental Science and Engineering, Changzhou University, Jiangsu 213164, China
b
Chinese Society for Environmental Sciences, Beijing 100082, China

a r t i cl e i nfo a bstr ac t

Article history: This study aimed to regulate the band structure and enhance the reduction ability of CdS by substituting it
Received 26 January 2023 with Mn2+. Subsequently, this nano MnCdS solid solution was anchored on the surface of truncated octa­
Received in revised form 26 April 2023 hedral Cu2O through a simple hydrothermal process, forming an S-scheme heterojunction at the interface
Accepted 30 April 2023
between MnCdS and Cu2O. Equilibrating the Fermi level at the MnCdS/Cu2O heterojunction led to spon­
Available online 3 May 2023
taneous diffusion of electrons in MnCdS to Cu2O, generating an internal electric field that drove the re­
combination of electrons in the conduction band (CB) of Cu2O and holes in the valence band (VB) of MnCdS.
Keywords:
S-scheme heterojunction Consequently, this process preserved the powerful photogenerated electrons in the CB of MnCdS, facilitating
Hydrogen evolution robust photocatalytic hydrogen evolution. The MnCdS/Cu2O exhibited a photocatalytic hydrogen evolution
Cu2O rate of 66.3 mmol g−1 h−1, which was 3.4- and 54.3-times higher than that of MnCdS (19.4 mmol g−1 h−1) and
Mn-Cd-S Cu2O (1.2 mmol g−1 h−1), respectively. This study elucidates advanced S-scheme heterojunction catalyst
Photocatalytic architectures for photocatalytic hydrogen production.
© 2023 Elsevier B.V. All rights reserved.

1. Introduction sufficiently negative CB position, thus generating a stronger driving

Utilising solar energy for photocatalytic hydrogen production is a
promising alternative to achieve the carbon neutrality [1–3]. Semi­
conductor-based photocatalytic water splitting is considered the
most favourable method producing H2 [4,5]. However, the devel­
opment of single-component photocatalytic systems for H2 pro­
duction is limited by the thermodynamic contradiction between
redox potentials and optical absorption [6]. Recently, S-scheme ar­
tificial photocatalytic systems consisting of two different photo­
catalysts have demonstrated promising potential for efficient H2
production [7,8]. According to this concept, photoinduced electrons
and holes accumulate in a semiconductor with a more negative CB
position, while in other semiconductors, they accumulate in the VB
position, which is relatively positive [9]. A crucial prerequisite for
designing S-scheme H2 production systems is the use of a semi­
conductor that can accumulate photoinduced electrons with a
⁎
Corresponding authors.
E-mail addresses: flf1558@163.com (L. Fan), hanjia-jiahan@163.com (J. Han),
18070505489@163.com (K. Wei), machang719@163.com (C. Ma),
shfeng@cczu.edu.cn (S. Feng), 550584586@qq.com (Y. Zhou),
563239323@qq.com (X. Dai), 923777017@qq.com (Z. Ye),
1206842181@qq.com (Y. Wang).
force for proton reduction (H+→H2) [10–12].
Various semiconductors have been developed for the construc­
tion of S-scheme photocatalytic systems, such as TiO2, CdS, g-C3N4,
etc [13–18]. Among them, CdS has received significant attention for
photocatalytic H2 production because of its wide visible-light cap­
ture range (band gap: 2.1–2.5 eV) and high electron mobility per­
formance (approximately 350 cm2 V–1 s–1) [19,20]. However, CdS
catalysts bear a low efficiency of solar to H2 conversion owing to
their insufficient electron-hole separation performance and low CB
position (−0.41 V vs normal hydrogen electrode (NHE), pH = 7)
[21,22]. S-scheme heterojunction formation is capable of boosting
photoinduced carrier separation; however, it is unable to increase
the reduction ability by upshifting the CB position of CdS [23]. Pre­
vious studies have indicated that in CdS, the CB is mainly derived
from Cd 3d orbitals, whereas the VB is primarily derived from S 2p
orbitals [24,25]. Recently, a transition-metal-substituted solid solu­
tion (MnxCd1−xS) was developed to enhance the photocatalytic H2
evolution performance of CdS [26–28]. Theoretically, the d electronic
states of doped metal ions can strongly hybridise with the electronic
states of the host CdS, thereby shifting the CB position [29–31].
Herein, we propose that the use of transition metals as dopants
might realise a CB upshift in CdS.

https://doi.org/10.1016/j.jallcom.2023.170382
0925-8388/© 2023 Elsevier B.V. All rights reserved.
L. Fan, J. Han, K. Wei et al.
Based on this hypothesis, we regulated the band structure of CdS
with Mn2+ substitution. Given the possible bandgap changes during
the MnxCd1−xS (MCS) solid-solution formation, Cu2O with a narrow
bandgap (approximately 2.0 eV) was chosen as an alternative to
build an S-scheme system to guarantee optical absorption.
Experimentally, MCS was deposited on the surface of truncated oc­
tahedral Cu2O via a simple hydrothermal process. The band structure
and Fermi level of MCS and Cu2O and the S-scheme charge-transfer
route of MCS/Cu2O (MCSCO) were systematically investigated.
Expectedly, the S-scheme MCSCO heterojunction photocatalyst de­
monstrated excellent performance in photocatalytic hydrogen pro­
duction by facilitating water reduction. The hydrogen production
rate of MCSCO was 3.4 and 55.3 times that of MCS and Cu2O, re­
spectively.
2. Experimental methods
2.1. Chemicals materials
Manganese acetate tetrahydrate (Mn(CH3COO)2∙4H2O), cadmium
acetate dihydrate Cd(CH3COO)2∙2H2O, thioacetamide (C2H5NS),
Cupric sulfate pentahydrate (CuSO4∙5H2O), sodium carbonate
(Na2CO3), glucose (C6H12O6) were purchased from Sinopharm
Chemical Regent Co., Ltd. Sodium citrate Sodium citrate
(Na3C6H5O7∙2H2O), polyvinyl pyrrolidone (PVP) were purchased
from Aladdin. All the reagents were not purified in any way.
2.2. Synthesis of MCS, Cu2O and MCS/Cu2O
A simple hydrothermal approach was used to fabricate the Mn-
Cd-S solid-solution photocatalysts. First, 1 mmol Mn
(CH3COO)2∙4H2O, 1 mmol Cd(CH3COO)2∙2H2O, and 6 mmol thioace­
tamide were added to 35 mL deionised water and stirred for 30 min.
The liquid was then placed in a 50 mL Teflon-lined autoclave and
held at 180 °C for 24 h. After naturally cooling to ambient tempera­
ture, the samples were washed multiple times with ethanol and
deionised water, and left to dry at 60 ℃. Pure CdS were prepared
using the aforementioned procedures, without the inclusion of Mn
(CH3COO)2∙4H2O. The MCSCO was also prepared with the same
procedure (Fig. S1). During stirring, 35 mL of an aqueous solution
was prepared and different amounts of Cu2O (0.025 g, 0.05 g, and
0.075 g) were dispersed in it; herein, the composite samples are
referred to as MCSCO-1, MCSCO-2, and MCSCO-3, respectively. The
Cu2O was prepared according to a previous report [32]. Unless
otherwise stated, the MCSCO used in this study was MCSCO-2.
2.3. Photocatalytic activity experiments
This part is present in the Text S1.
2.4. Characterization
This part is present in the Text S2.
3. Results and discussion
3.1. Characterization of MCSCO
The irregularly shaped nanoparticles in Fig.1a were MCS, with a
diameter range of 100–300 nm. Meanwhile, the Cu2O had a trun­
cated octahedral structure, with a smooth surface and average dia­
meter of 1.5 nm (Fig. 1b). Interestingly, Cu2O featured a 3D structure
with holes which enhanced light capture via light scattering and
reflection effects. The MCS nanoparticles were uniformly anchored
on the surface of truncated octahedral Cu2O through a simple hy­
drothermal process. Obviously, Cu2O could inhibit the aggregation of
2
Journal of Alloys and Compounds 960 (2023) 170382
MCS, providing more active sites for photocatalytic hydrogen evo­
lution. The microstructure of the MCSCO was characterised using
TEM, suggesting that MCS was compactly attached to the surface of
Cu2O (Fig. 1c). The SAED patterns showed five obvious diffraction
rings corresponding to the (100), (110), (112) plane of MCS and the
(220), (311) plane of Cu2O (Fig. 1d), which proved the successful
recombination of the two phases. High-resolution TEM presented
two different fringes spacing of 0.207 and 0.301 nm, which were
respectively assigned to the (110) lattice plane of MCS and the (110)
lattice plane of Cu2O (Fig. 1e), further verifying the formation of
heterojunction. In the base plane of MCS and Cu2O, the lattice spa­
cing can be determined according to the atomic intensity distribu­
tion respectively. High-angle annular dark field-scanning TEM
(HAADF-STEM) of MCSCO and corresponding elements distribution
result offered further evidence for the successful fabrication of
MCSCO with a uniform distribution of Mn, Cd, S, Cu, and O, with no
presence of foreign elements contaminate MCSCO (Figs. 1f-1m).
Furthermore, the 3D structural assembly of MCSCO significantly
increased its BET specific surface area and pore volume (Fig. S2 and
Table1), thus providing more reactive sites for light capture and H+
reduction.
The crystal structures and phase compositions of the as-prepared
materials were further evaluated using XRD (Fig. 1n). The diffraction
peaks at 24.8°, 26.5°, 28.2°, 43.7°, and 51.8° in MCS corresponded to
the (100), (002), (101), (110), and (112) planes, respectively, of hex­
agonal CdS (PDF#41-1049) [33]. The (110), (111), (200), (220), and
(311) crystal planes of Cu2O (PDF#77-0199) were identified from the
diffraction peaks of 29.6°, 36.5°, 42.4°, 61.6° and 73.7°, respectively
[34]. Diffraction peaks of both CdS and Cu2O were observed in the
MCSCO, suggesting successful fabrication of MCSCO via the hydro­
thermal process with MCS and Cu2O as precursors. The blue shift
observed in the diffraction peaks of MCS resulted from the sub­
stitution of Mn2+ for Cd2+, where the covalent radius of Mn was
0.46 Å (6 coordinated), was smaller than that of Cd 0.97 Å (6 co­
ordinated radius) (Fig. 1o) [35–39]. Mn2+ substituted Cd2+ from CdS
would lead to lattice shrinkage phenomenon, being reflected as blue
shift in XRD patterns, confirming the formation of MCS solid solu­
tion. ICP-OES results disclosed that 14 % of the Cd was substituted by
Mn in the MCS (Fig. 1p).
Infrared spectroscopy was used to further characterise the
MCSCO structure (Fig. 2a). The peak at 1380 cm−1 was responsible for
the C-N bond, which was caused by the addition of thioacetamide
during the preparation process [40]. Meanwhile, the peaks at
505 cm−1 and 629 cm−1 were assigned to the stretching vibrations of
Cu(I)-O in Cu2O. Interestingly, the Cu(I)-O peaks in MCSCO shifted
from 505 cm−1 to 536 cm−1 and from 629 cm−1 to 695 cm−1, respec­
tively. Notably, the close interfacial contact between MCS and Cu2O
changed the dipole moment of Cu(I)-O in Cu2O, suggesting a deep
hybridisation of MCS and Cu2O, rather than just a physical mixture,
which may facilitate electron transfer in the MCSCO heterojunction.
X-ray photoelectron spectroscopy (XPS) was conducted to
monitor electrons migration in MCSCO. The full survey spectrum of
MCSCO indicated the presence of Cd, Mn, S, Cu, and O (Fig. S3a). In
the XPS spectra of Cd 3d in MCS, two peaks corresponding to the Cd
3d5/2 and Cd 3d3/2 of Cd2+ were observed 405.04 and 411.78 eV,
which could be associated with the Cd 3d5/2 and Cd 3d3/2 of Cd2+,
respectively (Fig. 2b) [41]. After the formation of MCSCO, the binding
energies of Cd 3d5/2 and Cd 3d3/2 shifted positively to 405.33 and
412.08 eV, respectively. The same trend was observed for the binding
energies of Mn 2p3/2 and 2p1/2, which shifted from 640.54 to
641.04 eV and from 651.54 to 651.98 eV, respectively (Fig. S3b) [39].
In contrast, the binding energies of Cu 2p3/2 and 2p1/2 shifted ne­
gatively from 932.17 (Cu2O) to 931.96 eV (MCSCO) and from 952.08
(Cu2O) to 951.73 eV (MCSCO) (Fig. 2c), respectively, evidencing that
the electron flow from the Cd and Mn in MCS to the Cu in Cu2O
during the formation of MCSCO heterojunction [42]. Cu LMM Auger
L. Fan, J. Han, K. Wei et al. Journal of Alloys and Compounds 960 (2023) 170382

Fig. 1. SEM images of (a) MCS and (b) Cu2O. (c) TEM and (d) SEAD pattern for MCSCO. (e) HR-TEM image of MCSCO and intensity profiles along the dashed lines in panel. (f)
HAADF-STEM image and elemental mappings of (g) total, (h) O, (i) Cu, (j) Mn, (k) Cd, (l) S and (m) total distribution result. (n) XRD spectra of MCSCO, MCS, Cu2O and (o) enlarged
XRD spectra of CdS, MCS. (p) ICP elements content of MCS and CdS.

Table 1 This highlighted the dominant contribution of heterojunction con­

Parameters of physical adsorption. struction to the enhanced H2 generation performance. The reusa­
Samples Surface area Pore volume Average pore bility of photocatalysts was a critical concern. Notably, the MCSCO
(m2 g−1) (cm3 g−1) size (nm) heterojunction retained more than 95 % of its intrinsic H2 production
Cu2O 3.3043 0.003517 4.2574 reactivity after six cycles. Moreover, the H2 production performance
MCS 4.4462 0.005672 5.1030 of the MCSCO heterojunction outperformed those of previously re­
MCO-2 11.2354 0.016318 5.8094 ported working catalysts (Table 2), demonstrating the synergetic
effect between band regulation and heterojunction architecture.
spectrum (Fig. 2d) was used to further determine the valence state of
Cu, a peak at 916.9 eV belonging to the Cu+ species was observed.
3.3. Photocatalytic H2 generation mechanism of MCSCO
Meanwhile, these spectral results indicated that Cu+ was well pre­
served in the composite material [43,44]. The XPS spectra of S 2p
The H2 production performance of MCSCO was determined based
and O 1s, which showed a positive shift in S 2p and a negative shift
on the interfacial charge-transfer process between MCS and Cu2O,
of O 1s, is consistent with the above. (Fig. S3c and S3d).
which was related to the band structure and Fermi level. The band
gap can be calculated using the following equation: (αhυ)n = A(hυ -
3.2. Photocatalytic hydrogen production performance of MCSCO Eg), where α is the absorption coefficient, hυ is the photon energy, A
is a constant, and n is 2 [56]. As shown in Fig. 4a, Mn2+ substitution
The photocatalytic hydrogen production of the samples was reduced the band gap of CdS from 2.21 eV to 2.19 eV, facilitating light
evaluated using visible light irradiation simulations (Fig. 3a). As capture. The band gap of Cu2O was 1.86 eV, indicating excellent light
shown in Fig. 3b, CdS exhibited moderate H2 generation perfor­ absorption. The band structures and Fermi levels of CdS, MCS, and
mance. The H2 evolved rate of CdS was 2.2 mmol g−1 h−1. The MCS Cu2O were investigated using ultraviolet photoelectron spectroscopy
solid solution significantly enhanced the H2 generation performance, (UPS) (Fig. 4b). The work function (Φ) of CdS and Cu2O was 4.53 eV
increasing the H2 evolved rate was up to 19.4 mmol g−1 h−1. H2 and 5.13 eV, respectively. Notably, Mn2+ substitution significantly
evolved rate of optimised MCSCO was 66.3 mmol g−1 h−1 (Fig. S4), increased the Φ of CdS to 4.99 eV. The valence bands of the semi­
which was 3.4 and 54.2 times that of MCS and Cu2O, respectively. conductor at vacuum energy levels and standard hydrogen

3
L. Fan, J. Han, K. Wei et al. Journal of Alloys and Compounds 960 (2023) 170382

Fig. 2. (a) The FT-IR of MCS, Cu2O and MCSCO. The XPS of (b) Cd 3d and (c) Cu 2p in MCS and MCSCO. (d) Cu LMM Auger spectra of Cu2O and MCSCO.

electrodes can be calculated using the following equations: Evb=Wf
+Eoneset and ENHE= -EAVS-4.5 [57,58]. According to the band gaps and
Φ, the VB and CB of CdS, MCS and Cu2O were calculated and are
displayed in Fig. 4c. As expected, the Mn2+ substitution negatively
shifted the VB and CB of CdS. The shift of CB from − 0.93 eV to
− 1.36 eV could significantly enhance the driving force for proton
reduction (Tab. S1).
Based on the band and Fermi level positions, we speculate that
the interfacial charge-transfer process followed the S-scheme me­
chanism (Fig. 4d). Upon close contact between CdS or MCS and Cu2O,
the free electrons in CdS or MCS were spontaneously transferred to
Cu2O across the interface until their Fermi levels were aligned. At
equilibrium, free electrons accumulate on the interface of Cu2O and
the electron density on the CdS or MCS interface simultaneously
decreases, resulting in downward band bending on CdS or MCS and
upward band bending on Cu2O. Hence, a built-in electric field was
established at the interface, with the direction pointing from CdS or
MCS to Cu2O. The difference between the Fermi level of CdS and
Cu2O was 0.6 eV, while that between MCS and Cu2O was 0.14 eV. The
downward band bending on CdS weakened the reduction capacity of

Fig. 3. (a) Time-yield plots of the CdS, MCS, Cu2O and MCSCO samples. (b) H2 production rate of CdS, MCS, Cu2O and MCSCO samples. (c) Cycle performance of MCSCO.
Experimental condition: 10 mg catalyst, 50 mL Na2S (0.25 mol/L) solution and 50 mL of Na2S (0.35 mol/L) solution used as the sacrificial agent.

4
L. Fan, J. Han, K. Wei et al. Journal of Alloys and Compounds 960 (2023) 170382

Table 2
Comparison of photocatalytic H2 production rate reported in the literature with Cu2O/MnCdS.

Photocatalyst Light Source Production rate Sacrificial reagent Refs

−1 −1
Cu2O/MnCdS 300 W Xe lamp 66.3 mmol g h Na2S (0.35 mol/L)/Na2SO3(0.25 mol/L This study
CoWO4/Mn0.47Cd0.53S 300 W Xe lamp 41.5 mmol g−1 h−1 Na2S (0.25 mol/L)/Na2SO3(0.35 mol/L) [28]
Mn0.5Cd0.5S/Cu3P 300 W Xe lamp 19.6 mmol g−1 h−1 Na2S (0.35 mol/L)/Na2SO3(0.25 mol/L) [45]
Mn0.2Cd0.8S/CeO2 5 W Xe lamp 8.7 mmol g−1 h−1 Na2S (0.35 mol/L)/Na2SO3(0.25 mol/L) [46]
Mn0.5Cd0.5S/CuCo2S4 λ > 420 nm 15.7 mmol g−1 h−1 Na2S (0.35 mol/L)/Na2SO3(0.25 mol/L) [47]
Mn0.2Cd0.8S@CoAl LDH 300 W Xe lamp 23.5 mmol g−1 h−1 Na2S (0.35 mol/L)/Na2SO3(0.25 mol/L) [48]
Cu2O/Cu7S4 300 W Xe lamp 1.60 mmol g−1 h−1 Na2SO3 (0.5 mol/L) [49]
Cu2O/g-C3N4 300 W Xe lamp 33.2 μmol h−1 g−1 20 mL TEOA [50]
Cu@TiO2-Cu2O 300 W Xe lamp 1.2 mmol g−1 h−1 20 vol% methanol [51]
Cu2ZnSnS4/Cu2O 300 W Xe lamp 17.9 mmol g−1 h−1 10 mL Methanol [52]
CdS/CoP 300 W Xe lamp 15.7 mmol g−1 h−1 Na2S (0.1 mol/L)/Na2SO3 (0.1 mol/L) [53]
CdS/WO3 300 W Xe lamp 35.4 μmol g−1 h−1 Na2S (0.1 mol/L)/Na2SO3 (0.35 mol/L) [54]
CdS/MoO2/MoS2 300 W Xe lamp 1.3 mmol g−1 h−1 0.1 vol% LA [55]

CdS more than that of MCS, further highlighting the contribution of
Mn2+ substitution to enhancing the H2 production performance
during heterojunction construction.
XPS provided the first evidence of the S-scheme interfacial
charge-transfer mechanism in MCSCO with free-electron flow from
MCS to Cu2O (Figs. 2b-c, S2). Furthermore, under irradiation, the
electrons in MCS and Cu2O jumped from the VB to the CB upon
excitation. The built-in electric field at the interface were able to
drive the photogenerated electrons of Cu2O to consume the photo­
generated holes of MCS, leaving behind the holes and electrons in
the VB of Cu2O and the CB of MCS [59]. To confirm this mechanism,
and to rule out a type-II process (Fig. S5), the reduction capacities of
the MCSCO heterojunctions were determined. Expectedly, Cu2O, CdS,
alone could not effectively reduce NP to p-aminophenol (AP) (NP/AP,
−0.77 V), whereas MCS significantly decreased the concentration of
NP under simulated solar light (Fig. 4e) [60]. MCSCO exhibited the
highest NP reduction performance, confirming that the charge-
transfer path of MCSCO is the S-scheme route. The strong reduction
ability of the CB electrons in the MCS was preserved, thus providing
a strong driving force for proton reduction. Moreover, CdS/Cu2O
(CSCO) did not reduce the NP to AP, indicating the importance of
Mn2+ substitution to the enhanced reduction ability of MCSCO.
3.4. Optical property and spatial charge separation ability
The S-scheme heterojunction architecture widened the light
absorption range (Fig. 5a). The efficient charge separation in MCSCO
was attributed to the built-in electric-field-mediated S-scheme
charge-transfer process, which can be investigated by analysing
carrier recombination [61]. Fig. 5b showed the photoluminescence
(PL) spectra of the prepared samples. MCSCO exhibited the lowest PL
intensity, corresponding to the highest photogenerated carrier se­
paration performance [23]. Compared to the transient photocurrent
responses of MCS and Cu2O, MCSCO exhibited the highest photo­
current intensity (Fig. 5c). This was further supported by the sig­
nificantly smaller arc radius observed in the electrochemical
impedance spectroscopy (EIS) Nyquist plots of MCSCO compared to
those of MCS and Cu2O (Fig. 5d) [62]. A low overpotential for hy­
drogen evolution corresponded to a low energy barrier for the H+
reduction reaction. The structural properties of MCSCO significantly

Fig. 4. (a) DRS Tauc plots of CdS, MCS, and Cu2O. (b) UPS spectras of CdS, MCS, and Cu2O. (c) The band structures of CdS, MCS and Cu2O. (d) Schematic illustration of S-scheme
charges transfer process of MCSCO. (e) optical absorption spectra of p-nitrophenol (NP) solution at the initial state and after 30 min reaction with different photocatalysts under
simulating visible light irradiation. Experimental conditions: 20 mL NP (0.01 mol/L) solution, 10 mg catalyst, methanoic acid (10 vol%) and KIO3 (0.01 mol/L) used as hole and
electron acceptors, respectively.

5
L. Fan, J. Han, K. Wei et al.
Fig. 5. (a) UV–Vis absorption spectra, (b) PL spectra, (c) I-t plots, (d) Nyquist plots, (e) LSV curves, (f) Tafel slopes of MCS, Cu2O, MCSCO.
Scheme 1. Schematic illustration of the H2 evolution mechanism of MCSCO.
decreased the overpotential of H2 evolution, as evidenced by the
linear sweep voltammogram (LSV) curves in Fig. 5e [63,64]. The Tafel
slope further confirmed the highest H2 evolution performance of
MCSCO with a minimum value (89 mV dec−1), which was lower than
those of MCS (108 mV dec−1) and Cu2O (140 mV dec−1), indicating
faster photogenerated electron transferred from the inside to the
outside of the as-prepared material (Fig. 5f) [65].
4. Conclusion
In this study, we substituted Cd2+ with Mn2+ to downshift the
Fermi level and upshift the band position of CdS, effectively en­
hancing its reduction ability (Scheme 1). Using a simple hydro­
thermal process, the MnCdS solid solution was anchored to the
surface of truncated octahedral Cu2O. The interfacial charge-transfer
mechanism of MnCdS/Cu2O followed an S-scheme route. The in­
ternal electric field formed during the Fermi level equilibrium be­
tween MnCdS and Cu2O drove the recombination of electrons in the
CB of Cu2O and holes in the VB of MnCdS, leading to the preservation
of the CB of MnCdS for proton reduction. The optimised MnCdS/Cu2O
exhibited a wider light capture range and higher reduction potential,
6
Journal of Alloys and Compounds 960 (2023) 170382
resulting in a remarkable H2 evolution rate of 66.3 mmol g−1 h−1,
which was 3.4 and 54.3 times those of MnCdS (19.4 mmol g−1 h−1)
and Cu2O (1.2 mmol g−1 h−1), respectively. This study demonstrated a
strategy for regulating the Fermi level and band position of semi­
conductors, enabling the design and construction of highly efficient
S-scheme heterojunctions.
CRediT authorship contribution statement
Lufang Fan: Conceptualization, Methodology, Validation,
Investigation, Data curation, Formal analysis, Writing – original
draft. Jiahui Han: Investigation, Data curation, Formal analysis,
Writing – original draft. Kai Wei: Writing – review & editing, su­
pervision. Changchang Ma: Data curation, Formal analysis. Sheng
Feng: Resources, Validation, Supervision. Yun Zhou: Resources,
Supervision. Xiaojun Dai: Formal analysis. Zhiwei Ye: Data curation.
Yang Wang: Data curation.
Data Availability
Data will be made available on request.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported by National Natural Science Foundation
of China (No.22075032 and No.22278043).
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.jallcom.2023.170382.
L. Fan, J. Han, K. Wei et al.
References
[1] J. Chen, X. Tao, L. Tao, H. Li, C. Li, X. Wang, C. Li, R. Li, Q. Yang, Novel conjugated
organic polymers as candidates for visible-light-driven photocatalytic hydrogen
production, Appl. Catal. B 241 (2019) 461–470, https://doi.org/10.1016/j.apcatb.
2018.09.011
[2] Y. Wang, X. Fang, J. Zeng, S. Li, X. Wang, B. Zhang, 0D/2D/3D ternary Au/Ti3C2/
TiO2 photocatalyst based on accelerating charge transfer and enhanced stability
for efficiently hydrogen production, Appl. Surf. Sci. 615 (2023) 156397, https://
doi.org/10.1016/j.apsusc.2023.156397
[3] B. Xia, Y. Yang, Y. Zhang, Y. Xia, M. Jaroniec, J. Yu, J. Ran, S.-Z. Qiao, Metal–organic
framework with atomically dispersed Ni–N4 sites for greatly-raised visible-light
photocatalytic H2 production, Chem. Eng. J. 431 (2022) 133944, https://doi.org/
10.1016/j.cej.2021.133944
[4] Y. Liu, X. Zhou, Y. Zhou, G. Chen, Construction of Ag decorated 2D rGO/SnS2
nanostructure towards synergistically enabling overall water splitting, Chem.
Eng. J. 433 (2022) 133198, https://doi.org/10.1016/j.cej.2021.133198
[5] L. Wu, F. Su, T. Liu, G.-Q. Liu, Y. Li, T. Ma, Y. Wang, C. Zhang, Y. Yang, S.-H. Yu,
Phosphorus-doped single-crystalline quaternary sulfide nanobelts enable effi­
cient visible-light photocatalytic hydrogen evolution, J. Am. Chem. Soc. 144
(2022) 20620–20629, https://doi.org/10.1021/jacs.2c07313
[6] S. Ouyang, J. Ye, β-AgAl1−xGaxO2 solid-solution photocatalysts: continuous
modulation of electronic structure toward high-performance visible-light pho­
toactivity, J. Am. Chem. Soc. 133 (2011) 7757–7763, https://doi.org/10.1021/
ja110691t
[7] Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu, S-Scheme heterojunction photocatalyst,
Chem 6 (2020) 1543–1559, https://doi.org/10.1016/j.chempr.2020.06.010
[8] L. Zhang, J. Zhang, H. Yu, J. Yu, Emerging S-scheme photocatalyst, Adv. Mater. 34
(2022) 2107668, https://doi.org/10.1002/adma.202107668
[9] H. Hamad, M.M. Elsenety, W. Sadik, A.-G. El-Demerdash, A. Nashed, A. Mostafa,
S. Elyamny, The superior photocatalytic performance and DFT insights of S-
scheme CuO@TiO2 heterojunction composites for simultaneous degradation of
organics, Sci. Rep. 12 (2022) 2217, https://doi.org/10.1038/s41598-022-05981-7
[10] J. Liu, J. Wan, L. Liu, W. Yang, J. Low, X. Gao, F. Fu, Synergistic effect of oxygen
defect and doping engineering on S-scheme O-ZnIn2S4/TiO2−x heterojunction for
effective photocatalytic hydrogen production by water reduction coupled with
oxidative dehydrogenation, Chem. Eng. J. 430 (2022) 133125, https://doi.org/10.
1016/j.cej.2021.133125
[11] C. Cheng, B. He, J. Fan, B. Cheng, S. Cao, J. Yu, An inorganic/organic S-Scheme
heterojunction H2-production photocatalyst and its charge transfer mechanism,
Adv. Mater. 33 (2021) 2100317, https://doi.org/10.1002/adma.202100317
[12] J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu, Ultrathin 2D/2D WO3/g-C3N4 step-scheme H2-
production photocatalyst, Appl. Catal. B 243 (2019) 556–565, https://doi.org/10.
1016/j.apcatb.2018.11.011
[13] W. Huang, W. Xue, X. Hu, J. Fan, C. Tang, Y. Shi, E. Liu, T. Sun, A S-scheme het­
erojunction of Co9S8 decorated TiO2 for enhanced photocatalytic H2 evolution, J.
Alloy. Compd. 930 (2023) 167368, https://doi.org/10.1016/j.jallcom.2022.167368
[14] Y.-P. Zhang, W. Han, Y. Yang, H.-Y. Zhang, Y. Wang, L. Wang, X.-J. Sun, F.-M. Zhang,
S-scheme heterojunction of black TiO2 and covalent-organic framework for
enhanced photocatalytic hydrogen evolution, Chem. Eng. J. 446 (2022) 137213,
https://doi.org/10.1016/j.cej.2022.137213
[15] Y. Xiong, T. Liu, X. Wang, W. Liu, Y. Xue, X. Zhang, C. Xiong, J. Tian, S-scheme
heterostructure based on ultrathin 2D CdS coated W18O49 nanosheets-as­
sembled network for highly-efficient photocatalytic H2 evolution, J. Alloy.
Compd. 918 (2022) 165652, https://doi.org/10.1016/j.jallcom.2022.165652
[16] Y. Liu, J. Sun, X. Zhou, C. Lv, Y. Zhou, B. Cong, G. Chen, An in-plane S-scheme
heterostructure drives H2 production with water and solar energy, Chem. Eng. J.
437 (2022) 135280, https://doi.org/10.1016/j.cej.2022.135280
[17] Y. Shang, C. Wang, C. Yan, F. Jing, M. Roostaeinia, Y. Wang, G. Chen, C. Lv, An efficient
and multifunctional S-scheme heterojunction photocatalyst constructed by tung­
sten oxide and graphitic carbon nitride: design and mechanism study, J. Colloid
Interface Sci. 634 (2023) 195–208, https://doi.org/10.1016/j.jcis.2022.12.039
[18] X. Chen, T. Hu, J. Zhang, C. Yang, K. Dai, C. Pan, Diethylenetriamine synergistic
boosting photocatalytic performance with porous g-C3N4/CdS-diethylene­
triamine 2D/2D S-scheme heterojunction, , J. Alloy. Compd. 863 (2021) 158068,
https://doi.org/10.1016/j.jallcom.2020.158068
[19] I. Vamvasakis, I.T. Papadas, T. Tzanoudakis, C. Drivas, S.A. Choulis, S. Kennou,
G.S. Armatas, Visible-light photocatalytic H2 production activity of β-Ni(OH)2-
modified CdS mesoporous nanoheterojunction networks, ACS Catal. 8 (2018)
8726–8738, https://doi.org/10.1021/acscatal.8b01830
[20] I. Vamvasakis, B. Liu, G.S. Armatas, Size effects of platinum nanoparticles in the
photocatalytic hydrogen production over 3D mesoporous networks of CdS and
Pt nanojunctions, Adv. Funct. Mater. 26 (2016) 8062–8071, https://doi.org/10.
1002/adfm.201603292
[21] Y. Xu, M.A.A. Schoonen, The absolute energy positions of conduction and valence
bands of selected semiconducting minerals, Am. Mineral. 85 (2000) 543–556,
https://doi.org/10.2138/am-2000-0416
[22] X. Xiang, B. Zhu, B. Cheng, J. Yu, H. Lv, Enhanced photocatalytic H2-production
activity of CdS quantum dots using Sn2+ as cocatalyst under visible light irra­
diation, Small 16 (2020) 2001024, https://doi.org/10.1002/smll.202001024
[23] H. Alshaikh, L.A. Al-Hajji, M.H.H. Mahmoud, A.A. Ismail, Visible-light-driven S-
scheme mesoporous Ag3VO4/C3N4 heterojunction with promoted photocatalytic
performances, Sep. Purif. Rev. 272 (2021) 118914, https://doi.org/10.1016/j.
seppur.2021.118914
7
Journal of Alloys and Compounds 960 (2023) 170382
[24] C. Wang, L. Wang, J. Jin, J. Liu, Y. Li, M. Wu, L. Chen, B. Wang, X. Yang, B.-L. Su,
Probing effective photocorrosion inhibition and highly improved photocatalytic
hydrogen production on monodisperse PANI@CdS core-shell nanospheres, Appl.
Catal. B 188 (2016) 351–359, https://doi.org/10.1016/j.apcatb.2016.02.017
[25] Z.-R. Tang, B. Han, C. Han, Y.-J. Xu, One dimensional CdS based materials for
artificial photoredox reactions, J. Mater. Chem. A 5 (2017) 2387–2410, https://
doi.org/10.1039/C6TA06373J
[26] Z. Jin, H. Gong, H. Li, Visible-light-driven two dimensional metal-organic fra­
mework modified manganese cadmium sulfide for efficient photocatalytic hy­
drogen evolution, J. Colloid Interface Sci. 603 (2021) 344–355, https://doi.org/10.
1016/j.jcis.2021.06.111
[27] Q.-Z. Huang, Y. Xiong, Q. Zhang, H.-C. Yao, Z.-J. Li, Noble metal-free MoS2 mod­
ified Mn0.25Cd0.75S for highly efficient visible-light driven photocatalytic H2
evolution, Appl. Catal. B 209 (2017) 514–522, https://doi.org/10.1016/j.apcatb.
2017.03.035
[28] G. Yang, H. Zhang, M. Dou, H. Yang, X. Yin, D. Li, H. Zhao, J. Dou, In situ con­
struction of 0D CoWO4 modified 1D Mn0.47Cd0.53S for boosted visible-light
photocatalytic H2 activity and photostability, J. Colloid Interface Sci. 610 (2022)
1057–1066, https://doi.org/10.1016/j.jcis.2021.11.159
[29] M. Liu, L. Zhang, X. He, B. Zhang, H. Song, S. Li, W. You, l-Cystine-assisted hy­
drothermal synthesis of Mn1−xCdxS solid solutions with hexagonal wurtzite
structure for efficient photocatalytic hydrogen evolution under visible light ir­
radiation, J. Mater. Chem. A 2 (2014) 4619–4626, https://doi.org/10.1039/
C3TA15342H
[30] Z. Li, X. Wang, X. Wang, Y. Lin, A. Meng, L. Yang, Q. Li, Mn-Cd-S@amorphous-
Ni3S2 hybrid catalyst with enhanced photocatalytic property for hydrogen pro­
duction and electrocatalytic OER, Appl. Surf. Sci. 491 (2019) 799–806, https://
doi.org/10.1016/j.apsusc.2019.05.313
[31] Z. Suo, J. Dai, S. Gao, H. Gao, Effect of transition metals (Sc, Ti, V, Cr and Mn)
doping on electronic structure and optical properties of CdS, Results Phys. 17
(2020) 103058, https://doi.org/10.1016/j.rinp.2020.103058
[32] Y. Zhou, S. Feng, X. Duan, W. Wu, Z. Ye, X. Dai, Y. Wang, X. Cao, Stable self-
assembly Cu2O/ZIF-8 heterojunction as efficient visible light responsive photo­
catalyst for tetracycline degradation and mechanism insight, J. Solid State Chem.
305 (2022) 122628, https://doi.org/10.1016/j.jssc.2021.122628
[33] R.-B. Wei, Z.-L. Huang, G.-H. Gu, Z. Wang, L. Zeng, Y. Chen, Z.-Q. Liu, Dual-co­
catalysts decorated rimous CdS spheres advancing highly-efficient visible-light
photocatalytic hydrogen production, Appl. Catal. B 231 (2018) 101–107, https://
doi.org/10.1016/j.apcatb.2018.03.014
[34] G. Zheng, J. Wang, H. Li, Y. Li, P. Hu, WO3/Cu2O heterojunction for the efficient
photoelectrochemical property without external bias, Appl. Catal. B: Environ.
265 (2020) 118561, https://doi.org/10.1016/j.apcatb.2019.118561
[35] Y. Gui, L. Qian, X. Qian, Hydrothermal synthesis of uniform rock salt (α-) MnS
transformation from wurtzite (γ-) MnS, Mater. Chem. Phys. 125 (2011) 698–703,
https://doi.org/10.1016/j.matchemphys.2010.09.071
[36] M. Xiong, Y. Qin, B. Chai, J. Yan, G. Fan, F. Xu, C. Wang, G. Song, Unveiling the role
of Mn-Cd-S solid solution and MnS in MnxCd1−xS photocatalysts and decorating
with CoP nanoplates for enhanced photocatalytic H2 evolution, Chem. Eng. J. 428
(2022) 131069, https://doi.org/10.1016/j.cej.2021.131069
[37] M. Luo, Y. Liu, J. Hu, H. Liu, J. Li, One-pot synthesis of CdS and Ni-doped CdS
hollow spheres with enhanced photocatalytic activity and durability, ACS Appl.
Mater. Interfaces 4 (2012) 1813–1821, https://doi.org/10.1021/am3000903
[38] Q.-Z. Huang, Z.-J. Tao, L.-Q. Ye, H.-C. Yao, Z.-J. Li, Mn0.2Cd0.8S nanowires modified
by CoP3 nanoparticles for highly efficient photocatalytic H2 evolution under
visible light irradiation, Appl. Catal. B 237 (2018) 689–698, https://doi.org/10.
1016/j.apcatb.2018.06.040
[39] X. Jiang, H. Gong, Q. Liu, M. Song, C. Huang, In situ construction of NiSe/
Mn0.5Cd0.5S composites for enhanced photocatalytic hydrogen production under
visible light, Appl. Catal. B 268 (2020) 118439, https://doi.org/10.1016/j.apcatb.
2019.118439
[40] W. Xu, J. Wang, H. Yu, P. Liu, G.-R. Zhang, H. Huang, D. Mei, Size-dependent
electron injection over sensitized semiconductor heterojunctions for enhanced
photocatalytic hydrogen production, Appl. Catal. B 308 (2022) 121218, https://
doi.org/10.1016/j.apcatb.2022.121218
[41] X. Lin, L. Zhu, B. Li, D. Jiang, H. Du, C. Zhu, Z. Yu, Y. Yuan, Highly soluble Ni-salen
molecules enable boosted photocatalytic hydrogen evolution of polymeric
carbon nitride/CdS heterojunction, J. Alloy. Compd. 915 (2022) 165351, https://
doi.org/10.1016/j.jallcom.2022.165351
[42] R. Nazir, A. Kumar, M. Ali Saleh Saad, S. Ali, Development of CuAg/Cu2O nano­
particles on carbon nitride surface for methanol oxidation and selective con­
version of carbon dioxide into formate, J. Colloid Interface Sci. 578 (2020)
726–737, https://doi.org/10.1016/j.jcis.2020.06.033
[43] Y. Yao, Y. Zhou, X. Liu, Y. Li, D. Wang, X. Chi, X. Wang, R. Zhao, H. Zhang, Y. Sun, Z.-
Y. Yang, Y. Wei, Y.-M. Yan, Restraining lattice oxygen of Cu2O by enhanced Cu–O
hybridization for selective and stable production of ethylene with CO2 electro­
reduction, J. Mater. Chem. A 10 (2022) 20914–20923, https://doi.org/10.1039/
D2TA05565A
[44] S. Guo, Y. Ji, Y. Li, H. Li, P. An, J. Zhang, J. Yan, S. Liu, T. Ma, Amorphous quantum
dots co-catalyst: defect level induced solar-to-hydrogen production, Appl. Catal.
B 330 (2023) 122583, https://doi.org/10.1016/j.apcatb.2023.122583
[45] N. Fang, X. Song, M. Zhang, Y. Chu, Design and fabrication of C–Mn0.5Cd0.5S/Cu3P
ternary heterojunction catalyst for photocatalytic hydrogen evolution, Int. J.
Hydrogen Energy 46 (2021) 30382–30392, https://doi.org/10.1016/j.ijhydene.
2021.06.180
L. Fan, J. Han, K. Wei et al.
[46] Y. Wang, X. Hao, L. Zhang, Y. Li, Z. Jin, Rational design of all-solid-state 0D/2D
Mn0.2Cd0.8S/CeO2 direct Z-scheme for photocatalytic hydrogen evolution, Energy
Fuels 34 (2020) 2599–2611, https://doi.org/10.1021/acs.energyfuels.9b04386
[47] M. Zhang, N. Fang, X. Song, Y. Chu, S. Shu, Y. Liu, p–n heterojunction photo­
catalyst Mn0.5Cd0.5S/CuCo2S4 for highly efficient visible light-driven H2 produc­
tion, ACS Omega 5 (2020) 32715–32723, https://doi.org/10.1021/acsomega.
0c05106
[48] S. Liu, K. Wang, M. Yang, Z. Jin, Rationally designed Mn0.2Cd0.8S@CoAl LDH S-
scheme heterojunction for efficient photocatalytic hydrogen production, Acta Phys.
-Chim. Sin. 38 (2021) 2109023, https://doi.org/10.3866/PKU.WHXB202109023
[49] M. Zhang, Z. Chen, Y. Wang, J. Zhang, X. Zheng, D. Rao, X. Han, C. Zhong, W. Hu,
Y. Deng, Enhanced light harvesting and electron-hole separation for efficient
photocatalytic hydrogen evolution over Cu7S4-enwrapped Cu2O nanocubes,
Appl. Catal. B 246 (2019) 202–210, https://doi.org/10.1016/j.apcatb.2019.01.042
[50] C. Ji, S.-N. Yin, S. Sun, S. Yang, An in situ mediator-free route to fabricate Cu2O/g-
C3N4 type-II heterojunctions for enhanced visible-light photocatalytic H2 gen­
eration, Appl. Surf. Sci. 434 (2018) 1224–1231, https://doi.org/10.1016/j.apsusc.
2017.11.233
[51] P. Qiu, J. Xiong, M. Lu, L. Liu, W. Li, Z. Wen, W. Li, R. Chen, G. Cheng, Integrated p-
n/Schottky junctions for efficient photocatalytic hydrogen evolution upon
Cu@TiO2-Cu2O ternary hybrids with steering charge transfer, J. Colloid Interface
Sci. 622 (2022) 924–937, https://doi.org/10.1016/j.jcis.2022.04.107
[52] K. Sun, X. Zhao, Y. Zhang, D. Wu, X. Zhou, F. Xie, Z. Tang, X. Wang, Enhanced
photocarrier separation in novel Z-scheme Cu2ZnSnS4/Cu2O heterojunction for
excellent photocatalyst hydrogen generation, Mater. Chem. Phys. 251 (2020),
https://doi.org/10.1016/j.matchemphys.2020.123172
[53] Y. Zou, C. Guo, X. Cao, L. Zhang, T. Chen, C. Guo, J. Wang, Synthesis of CdS/CoP
hollow nanocages with improved photocatalytic water splitting performance for
hydrogen evolution, J. Environ. Chem. Eng. 9 (2021) 106270, https://doi.org/10.
1016/j.jece.2021.106270
[54] X. Xiong, Y. Jin, H. Wang, P. He, X. Xiang, P. Hu, K. Liu, Q. Wei, B. Wang, Study on
the hydrogen production properties and electron transfer mechanism of CdS/
WO3 composite photocatalyst, Mater. Chem. Phys. 281 (2022), https://doi.org/10.
1016/j.matchemphys.2022.125824
[55] C. Bie, B. Zhu, L. Wang, H. Yu, C. Jiang, T. Chen, J. Yu, A bifunctional CdS/MoO2/
MoS2 catalyst enhances photocatalytic H2 evolution and pyruvic acid synthesis,
Angew. Chem. Int. Ed. 61 (2022) e202212045, https://doi.org/10.1002/anie.
202212045
[56] H. Song, Q. Zhang, D. Hu, Z. Sun, Y. Han, H. Meng, T. Sun, X. Zhang, In-situ partial
cation exchange-derived ZnIn2S4 nanoparticles hybridized 1D MIL-68/In2S3
Journal of Alloys and Compounds 960 (2023) 170382
microtubes for highly efficient visible-light induced photocatalytic H2 produc­
tion, Sep. Purif. Technol. 287 (2022) 120585, https://doi.org/10.1016/j.seppur.
2022.120585
[57] W. Ge, K. Liu, S. Deng, P. Yang, L. Shen, Z-scheme g-C3N4/ZnO heterojunction
decorated by Au nanoparticles for enhanced photocatalytic hydrogen produc­
tion, Appl. Surf. Sci. 607 (2023) 155036, https://doi.org/10.1016/j.apsusc.2022.
155036
[58] Q. Liu, J. Cao, Y. Ji, Y. Liu, C. Liu, G. Che, D. Wang, J. Cao, W. Li, X. Liu, The direct Z-
scheme CdxZn1−xS nanorods-Fe2O3 quantum dots heterojunction/reduced gra­
phene oxide nanocomposites for photocatalytic degradation and photocatalytic
hydrogen evolution, Appl. Surf. Sci. 570 (2021) 151085, https://doi.org/10.1016/j.
apsusc.2021.151085
[59] J. Bai, W. Chen, L. Hao, R. Shen, P. Zhang, N. Li, X. Li, Assembling Ti3C2 MXene into
ZnIn2S4-NiSe2 S-scheme heterojunction with multiple charge transfer channels
for accelerated photocatalytic H2 generation, Chem. Eng. J. 447 (2022) 137488,
https://doi.org/10.1016/j.cej.2022.137488
[60] D. Zhao, Y. Wang, C.-L. Dong, Y.-C. Huang, J. Chen, F. Xue, L. Guo, Boron-doped
nitrogen-deficient carbon nitride-based Z-scheme heterostructures for photo­
catalytic overall water splitting, Nat. Energy 6 (2021), https://doi.org/10.1038/
s41560-021-00795-9
[61] Y. Tang, W. Zhou, Q. Shang, Y. Guo, H. Hu, Z. Li, Y. Zhang, L. Liu, H. Wang, X. Tan,
T. Yu, J. Ye, Discerning the mechanism of expedited interfacial electron trans­
formation boosting photocatalytic hydrogen evolution by metallic 1T-WS2-in­
duced photothermal effect, Appl. Catal. B 310 (2022) 121295, https://doi.org/10.
1016/j.apcatb.2022.121295
[62] Q. Wang, J. Li, L. Xiao, Y. Wang, H. Du, Constructing Z-scheme Fe3N/BiVO4 het­
erojunction via electrostatic self-assembly toward high visible-light photo­
catalytic hydrogen evolution, J. Alloy. Compd. 935 (2023) 168062, https://doi.
org/10.1016/j.jallcom.2022.168062
[63] Y. Chen, H. Zhang, K. Liu, X. Zhu, H. Yuan, C. Wang, Photocatalytic activities of
Bi2O2CO3/g-C3N4@PAN nanofibers in hydrogen production, Appl. Surf. Sci. 599
(2022) 154013, https://doi.org/10.1016/j.apsusc.2022.154013
[64] L. Wang, G. Zhou, Y. Tian, L. Yan, M. Deng, B. Yang, Z. Kang, H. Sun, Hydroxyl
decorated g-C3N4 nanoparticles with narrowed bandgap for high efficient pho­
tocatalyst design, Appl. Catal. B 244 (2019) 262–271, https://doi.org/10.1016/j.
apcatb.2018.11.054
[65] C. Zhang, K. Wang, K. Xie, X. Han, W. Ma, X. Li, G. Teng, Controllable preparation
of hierarchical MnCo bimetallic photocatalyst and the effect of atomic ratio on
its photocatalytic activity, Chem. Eng. J. 446 (2022) 136907, https://doi.org/10.
1016/j.cej.2022.136907