CdS基S型异质结光催化析氢研究进展

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

催化学报 ›› 2026, Vol. 91: 50-67.DOI: 10.1016/S1872-2067(26)65210-2

CdS基S型异质结光催化析氢研究进展

龙浩宇^a^,^b, 吴新鹤^c, Dmitry Selishchev^d^,^*(), Jahan B. Ghasemi^e^,^*(), 余家国^a^,^b^,^*(), 余火根^a^,^b^,^*()

^a 中国地质大学(武汉)材料科学与化学学院, 太阳能燃料实验室, 湖北武汉 430078, 中国
^b 中国地质大学内蒙古研究院, 内蒙古鄂尔多斯 017010, 中国
^c 湖北师范大学化学化工学院, 污染物分析与再利用技术湖北省重点实验室, 湖北黄石 435002, 中国
^d 俄罗斯科学院西伯利亚分院博列斯科夫催化研究所, 非常规催化过程系, 新西伯利亚, 俄罗斯
^e 德黑兰大学理学院化学系, 德黑兰, 伊朗

收稿日期:2026-05-25 接受日期:2026-06-22 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: selishev@catalysis.ru (D. Selishchev),
jahan.ghasemi@ut.ac.ir (J. B. Ghasemi),
yujiaguo@cug.edu.cn (余家国),
yuhuogen@cug.edu.cn (余火根).
基金资助:
国家自然科学基金(22678545);国家自然科学基金(U23A20102);国家自然科学基金(U24A2071);国家自然科学基金(22361142704);国家自然科学基金(W2512051);国家自然科学基金(22302061);湖北省自然科学基金(2025AFB018)

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)

摘要/Abstract

摘要：

氢能因能量密度高、燃烧产物零碳排放, 被认为是支撑未来低碳能源体系的重要载体. 半导体光催化析氢能够直接将太阳能转化为可储存的氢能化学燃料, 其中硫化镉(CdS)因可见光响应强、带隙约为2.4 eV, 且导带位置较负而受到广泛关注. 然而, 本征CdS仍面临光生载流子快速复合和严重光腐蚀两大瓶颈, 限制了其长期高效应用. S型异质结通过调控界面电荷转移路径, 在保留强还原电子的同时消耗CdS中的腐蚀性空穴, 为提升CdS基光催化析氢活性与稳定性提供了重要思路.
本文围绕CdS基S型异质结光催化析氢, 系统总结了其机理演化、界面设计、实验表征与性能提升规律. 首先, 本文梳理了CdS基异质结由传统II型、液相Z型、全固态Z型和直接Z型向S型机制发展的过程. 与II型异质结中电子和空穴分别迁移至较低还原能力和较低氧化能力能带不同, S型异质结以费米能级匹配为热力学基础: CdS通常作为还原光催化剂, 具有较小功函数和较高费米能级; 与功函数较大的氧化光催化剂接触后, 暗态下自由电子由CdS迁移至对方组分并形成由CdS指向氧化光催化剂的内建电场及相应能带弯曲. 光照时, 该内建电场、能带弯曲和界面库仑作用协同促进低还原能力电子与CdS价带空穴在界面定向复合, 从而保留CdS导带中的强还原电子用于质子还原, 同时减少空穴对晶格S^2-的氧化. 其次, 本文归纳了多种界面构筑策略: CdS量子点可将体相扩散距离缩短至纳米尺度, 并通过量子限域增强还原能力; 2D/2D面接触结构可扩大界面接触面积、降低电荷转移阻力并建立均匀内建电场, 原子级Cd-N, Cd-S, Ti-S和Ni-S等界面化学键则可建立轨道耦合通道. 最后, 本文提出S型机制不能依赖单一证据判断, 而应结合紫外-可见光光谱、紫外光电子能谱、价带谱和Mott-Schottky确定能带结构, 利用原位X射线光电子能谱/X-射线吸收光谱、开尔文探针力显微镜或表面光电压跟踪光照下电子流向, 通过原位电子顺磁共振识别强氧化还原活性物种, 并借助时间分辨光致发光谱和飞秒瞬态吸收光谱揭示载流子寿命与超快转移动力学.
未来CdS基S型异质结仍需面向真实反应环境发展原位表征, 实现载流子迁移的时空双重追踪, 并进一步拓展无牺牲剂串联反应、规模化制备、Cd泄漏控制和长期稳定性研究. 本文建立的界面设计与电荷转移动力学表征方法, 可为高效、稳定、可持续的人工光合作用体系开发提供重要指导.

关键词: 硫化镉, S型异质结, 光催化析氢, 界面工程, 原位表征, 载流子动力学

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

龙浩宇, 吴新鹤, Dmitry Selishchev, Jahan B. Ghasemi, 余家国, 余火根. CdS基S型异质结光催化析氢研究进展[J]. 催化学报, 2026, 91: 50-67.

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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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65210-2

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图/表 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基S型异质结光催化析氢研究进展

CdS-based S-scheme heterojunctions for photocatalytic hydrogen evolution

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