CdS-based S-scheme heterojunctions for photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(26)65210-2

Chinese Journal of Catalysis ›› 2026, Vol. 91: 50-67.DOI: 10.1016/S1872-2067(26)65210-2

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CdS-based S-scheme heterojunctions for photocatalytic hydrogen evolution

Haoyu Long^a^,^b, Xinhe Wu^c, Dmitry Selishchev^d^,^*(), Jahan B. Ghasemi^e^,^*(), Jiaguo Yu^a^,^b^,^*(), Huogen Yu^a^,^b^,^*()

^a Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, Hubei, China
^b Inner Mongolia Institute of Technology, China University of geosciences, Ordos 017010, Inner Mongolia, China
^c Hubei Key Laboratory of Pollutant Analysis and Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi 435002, Hubei, China
^d Department of Unconventional Catalytic Processes, Boreskov Institute of Catalysis SB RAS, Novosibirsk 630090, Russia
^e Faculty of Chemistry, School of Sciences, University of Tehran, Tehran 1417614335, Iran

Received:2026-05-25 Accepted:2026-06-22 Online:2026-12-18 Published:2026-10-13
About author:Dmitry Selishchev (Boreskov Institute of Catalysis and Novosibirsk State University, Russia) received his Ph.D. degree in Chemistry from the Boreskov Institute of Catalysis in 2014. He is currently Leader of the Photo- and Electrocatalysis Research Group and Head of the Laboratory of Electrochemical Technologies. His research interests focus on heterogeneous photocatalysis, photoelectrochemistry, semiconductor heterostructures, environmental purification, water splitting, CO₂ reduction, and H₂O₂ production.
Jahan B. Ghasemi (University of Tehran, Iran) is a Professor of Analytical Chemistry in the Chemistry Department at the University of Tehran. Prof. Ghasemi received his B.Sc. degree from the University of Tehran (Iran) in 1988, and his M.Sc. and Ph.D. degrees in Analytical Chemistry from Shiraz University (Iran) under Prof. M. Shamsipur in 1991 and 1995, respectively. He carried out postdoctoral research at Chalmers University of Technology (Sweden) with Professor Mikael Kubista in 2002, and later held a sabbatical position at the University of Delaware (USA) with Prof. S. D. Brown in 2006. Over his career he has held several leadership positions, including Head of the Chemistry Department at K. N. Toosi University of Technology (2011-2013) and at Razi University, as well as Deputy of Research Affairs at K. N. Toosi University of Technology. He currently serves on the editorial boards of BMC Chemistry (Springer Nature, since 2023) and Eureka: Physics and Engineering (since 2022). He is a Distinguished Professor of the University of Tehran (2024) and of the Faculty of Sciences, University of Tehran (2025). His research interests mainly focus on computational and computer-assisted drug design, molecular modeling, photocatalysts, chemometrics, and analytical and environmental applications of nanomaterials. He has published more than 470 peer-reviewed papers.
Jiaguo Yu (China University of Geosciences (Wuhan)) received his BS and MS in chemistry from the Central China Normal University and Xi’an Jiaotong University, respectively, and PhD in materials science from the Wuhan University of Technology (WUT). His research interests include semiconductor photocatalysis, photocatalytic hydrogen production, CO2 reduction, perovskite solar cells, and electrocatalysis. He is a Foreign Member of Academia Europaea (2020) and a Foreign Fellow of the European Academy of Sciences (2020). He obtained the 35th Khwarizmi International Award (2022). His name was also on the list of Highly Cited Researchers from Clarivate Analytics (previously Thomson Reuters) from 2014-2024.
Huogen Yu (China University of Geosciences (Wuhan)) was invited as invited as a young member of the 5th, a member of 6th and 7th Editorial Board of Chin. J. Catal. Prof. Huogen Yu received his PhD from Wuhan University of Technology (WHUT) in 2007. He then worked as a postdoctoral fellow at the University of Tokyo from 2008 to 2010. Upon returning to WHUT, he was promoted to full professor in the same year. Since January 2023, he has held a professorship at the China University of Geosciences (Wuhan). His research primarily focuses on high-performance photocatalytic materials for water splitting and environmental purification. To date, he has published more than 200 SCI-indexed papers in internationally renowned journals, including Nature Communications, Angewandte Chemie International Edition, Advanced Materials, and JACS, which have garnered over 20000 citations. Based on the Scopus database from Elsevier, he has been recognized as one of the Most Cited Chinese Researchers from 2014 to 2025.
Supported by:
National Natural Science Foundation of China(22678545);National Natural Science Foundation of China(U23A20102);National Natural Science Foundation of China(U24A2071);National Natural Science Foundation of China(22361142704);National Natural Science Foundation of China(W2512051);National Natural Science Foundation of China(22302061);the Natural Science Foundation of Hubei Province(2025AFB018)

Abstract

Abstract:

Cadmium sulfide (CdS) is a promising visible-light-responsive photocatalyst for solar-driven hydrogen (H₂) production owing to its suitable band structure, yet pristine CdS generally exhibits only moderate photocatalytic activity because of rapid charge-carrier recombination and severe photocorrosion. Step-scheme (S-scheme) heterojunctions offer a structural solution to circumvent these bottlenecks. By driving the directional recombination of less reactive charge carriers at the physical interface, the S-scheme mechanism preserves the charge carriers with the strongest redox potentials. This specific pathway maintains robust H₂ evolution kinetics while transferring oxidizing holes away from CdS, effectively mitigating self-oxidation. This review systematically summarizes recent advancements in CdS based S-scheme heterojunctions. We elucidate the fundamental thermodynamic principles and evaluate rational interfacial design strategies across diverse structural dimensions. Furthermore, we highlight the rigorous experimental evidence required to verify charge transfer pathways using advanced dynamic characterization techniques. Finally, we outline current challenges and future directions toward practical applications.

Key words: Cadmium sulfide, S-scheme heterojunctions, Photocatalytic H₂ evolution, Interfacial engineering, In-situ characterization, Carrier dynamics

Haoyu Long, Xinhe Wu, Dmitry Selishchev, Jahan B. Ghasemi, Jiaguo Yu, Huogen Yu. CdS-based S-scheme heterojunctions for photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 91: 50-67.

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Figures/Tables 10

Fig. 1. Schematic illustration of electron-hole recombination mechanisms, redox potentials, and photocorrosion behaviors in different photocatalytic systems: pristine CdS (a), traditional CdS-based Type-II heterojunction (b), and CdS-based S-scheme heterojunction (c).

Fig. 2. (a,b) Crystal structures of hexagonal and cubic CdS. (c) Representative valence band maximum (VBM) and conduction band minimum (CBM) positions of CdS and representative semiconductors versus NHE at pH=7, where the thermodynamic H+/H2 potential is -0.41 V. (d) Schematic diagram of photocatalytic hydrogen evolution over CdS: (1) electron-hole recombination, (2) surface hydrogen evolution kinetics, and (3) photocorrosion of lattice S2- ions.

Fig. 3. Development history of S-scheme heterojunction photocatalysts. (a) Photogenerated carriers in a single photocatalyst. (b) Type-II heterojunction: electron transfer from CdS (RP) to OP. (c) Liquid-phase Z-scheme: charge transfer via soluble redox mediators. (d) All-solid-state Z-scheme: charge transfer via solid mediators. (e) Direct Z-scheme: direct interfacial carrier recombination. (f) S-scheme: vectorial charge transfer driven by band bending and internal electric field. Note that the arrows in the Z-scheme and S-scheme diagrams represent the recombination pathway of low-redox-potential carriers at the mediator or physical interface, rather than Type-II-like bidirectional charge separation.

Fig. 4. Schematic diagrams of charge transfer behavior in an S-scheme heterojunction. (a) Staggered band structures of CdS (RP) and OP semiconductor before contact. (b) Generation of the IEF at the interface after contact. (c) Transfer pathway of photoinduced electrons and holes under light illumination.

Fig. 5. Schematic illustration of rational interface designs for CdS-based S-scheme heterojunctions: (a) conventional random contacts, (b) low-dimensional architectures, (c) face-to-face coupling, (d) hierarchical architectures, and (e) advanced atomic-level chemical bonding.

Fig. 6. (a) High-magnification TEM images of CdS quantum dots (CdS QDs) and their particle-size histogram (inset). (b) Schematic diagram of CdS QDs/C-NiO1-x catalyst preparation. (c) Schematic of the synthesis of 2D/2D Ni-MOF/CdS nanosheets (NCx) composites. (d) Preparation route of CdS/RF composite, where RF denotes resorcinol-formaldehyde resin. (e) Band structure of CdS and RF. (f) Illustration of multiple reflections within CdS/Co3S4 double-shelled nanoboxes. (g) Schematic morphology and TEM images of CdS/Co3S4 double-shelled nanoboxes. (a) Reprinted with permission from Ref. [154]. Copyright 2023, Elsevier. (b) Reprinted with permission from Ref. [55]. Copyright 2025, Elsevier. (c) Reprinted with permission from Ref. [76]. Copyright 2025, Elsevier. (d,e) Reprinted with permission from Ref. [181]. Copyright 2023, Elsevier. (f,g) Reprinted with permission from Ref. [168]. Copyright 2025, Wiley-VCH GmbH.

Fig. 7. (a,b) Partial COHP analysis of Cd-S and Cd-N bonds in PyTdCOF/CdS, where PyTdCOF denotes a pyrene-thienothiophene-based covalent organic framework. (c) ELF mapping of the PyTdCOF/CdS. (d) NBO analysis in PyTdCOF/CdS heterojunction (Isovalue=0.05). (e) Charge carrier dynamics in CSTNi, where CSTNi denotes a TiO2/CdS/Ni photocatalyst. (f) Charge carrier transfer channel in CdS/TiO2 and CdS/Ni interfaces. (a-d) Reprinted with permission from Ref. [187]. Copyright 2025, Wiley-VCH GmbH. (e,f) Reprinted with permission from Ref. [185]. Copyright 2025, Wiley-VCH GmbH.

Fig. 8. Characterization roadmap for S-scheme heterojunction photocatalysts, including the determination of S-scheme configuration, the observation of interfacial charge transfer, active sites and redox active species tracking, and the ultrafast carrier dynamics.

Fig. 9. (a) High-resolution XPS spectra of C 1s, Cd 3d, and S 2p in the samples. (b) N K-edge and Cd M-edge absorption signals of PyTdCOF and PyTdCdS5 (PyTdCOF denotes a pyrene-thienothiophene-based covalent organic framework), and N K-edge and Cd M-edge absorption signals of PyTdCdS5 under in-situ UV irradiation (at 365 nm). (c) AFM image, VCPD (under dark and light), height value, and the SPV of CdS/BiOBr S-scheme photocatalyst. (a) Reprinted with permission from Ref. [225]. Copyright 2021, Wiley-VCH GmbH. (b) Reprinted with permission from Ref. [187]. Copyright 2025, Wiley-VCH GmbH. (c) Reprinted with permission from Ref. [228]. Copyright 2025, Wiley-VCH GmbH.

Fig. 10. (a) EPR spectra for the photocatalytic systems with or without light irradiation. (b) Photocatalytic oxidation pathway on CPDB composite (where CPDB denotes a CdS/PDB composite and PDB denotes pyrene-alt-difluorinated benzothiadiazole). 2D mapping (c) and TA spectral signals (d) of pure CdS and CPDB5. (e) Normalized decay kinetic curves of CdS and CPDB5 at 510 nm. (f) The decay pathways of photogenerated electrons in the CdS and CPDB composite. (a-f) Reprinted with permission from Ref. [229]. Copyright 2022, Wiley-VCH GmbH.

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CdS-based S-scheme heterojunctions for photocatalytic hydrogen evolution

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