可见光驱动的CdS/CuWO4 S型异质结析氢体系: 界面电荷转移与光热活化的双重协同增强

doi:10.1016/S1872-2067(25)64868-6

催化学报 ›› 2026, Vol. 81: 299-309.DOI: 10.1016/S1872-2067(25)64868-6

可见光驱动的CdS/CuWO₄ S型异质结析氢体系: 界面电荷转移与光热活化的双重协同增强

刘青桦^a, 蔡培庆^b, 李恒帅^c, 冀学洋^a(), 张大凤^a(), 蒲锡鹏^a()

^a 聊城大学材料科学与工程学院, 山东省化学储能与新型电池技术重点实验室, 山东聊城 252000
^b 中国计量大学光学与电子技术学院, 浙江杭州 310018
^c 聊城大学物理科学与信息工程学院, 山东省光通信科学与技术重点实验室, 山东聊城 252000

收稿日期:2025-07-10 接受日期:2025-08-22 出版日期:2026-02-18 发布日期:2025-12-26
通讯作者: *电子信箱: jixy0422@126.com (冀学洋),dafengzh@hotmail.com (张大凤),xipengpu@hotmail.com (蒲锡鹏).
基金资助:
山东省自然科学基金(ZR2022ME179);山东省自然科学基金(ZR2024QB228);聊城大学博士项目研究基金(318052350)

Visible-light-driven hydrogen evolution over CdS/CuWO₄ S-Scheme heterojunctions: Dual synergistic enhancement via interfacial charge transfer and photothermal activation

Qinghua Liu^a, Peiqing Cai^b, Hengshuai Li^c, Xue-Yang Ji^a(), Dafeng Zhang^a(), Xipeng Pu^a()

^a School of Materials Science and Engineering, Shandong Provincial Key Laboratory of Chemical Energy Storage and Novel Cell Technology, Liaocheng University, Liaocheng 252000, Shandong, China
^b College of Optical and Electronic Technology, China Jiliang University, Hangzhou 310018, Zhejiang, China
^c School of Physics Science and Information Technology, Shandong Key Laboratory of Optical Communication Science and Technology, Liaocheng University, Liaocheng 252000, Shandong, China

Received:2025-07-10 Accepted:2025-08-22 Online:2026-02-18 Published:2025-12-26
Contact: *E-mail: jixy0422@126.com (X.-Y. Ji),dafengzh@hotmail.com (D. Zhang),xipengpu@hotmail.com (X. Pu).
Supported by:
Shandong Province Natural Science Foundation(ZR2022ME179);Shandong Province Natural Science Foundation(ZR2024QB228);Doctoral Program of Liaocheng University(318052350)

摘要/Abstract

摘要：

氢能因其清洁、高效的特性, 被视为实现“双碳”目标的终极能源载体. 其中, 利用太阳能驱动光催化裂解水制氢, 因其零碳排放和可持续性被认为是最具发展前景的制氢途径之一. 在各类光催化材料中, 硫化镉(CdS)凭借其适宜的带隙宽度和良好的可见光响应能力而受到广泛关注. 然而, 其存在光生载流子复合率高和光腐蚀现象严重等问题, 严重制约了其实际应用. 为克服上述限制, 研究者们提出了S型异质结概念. 该体系可实现光生载流子的高效空间分离并保持强氧化还原能力. 尽管如此, 如何精准调控界面电荷传输路径, 并协同利用物理效应提升催化反应动力学, 仍然是该领域面临的关键挑战.

针对上述问题, 本研究提出了一种“电荷-热”双通道协同增强机制, 即将具有光热效应的CuWO₄纳米颗粒负载在CdS上, 构建具有光热效应的CdS/CuWO₄ S型异质结. 该策略不仅通过S型异质结电荷转移机制实现了光生电子从CdS向CuWO₄的高效迁移, 显著提升了光生载流子分离效率. 还利用CuWO₄的光热效应实现对反应微环境的局域升温, 有效降低了反应活化能, 从而形成了“电荷-热”双通道协同增强机制. 性能测试结果表明, 在可见光照射下, 优化后的CdS/CW-10% S型异质结产氢速率达到2725.91 μmol g^-1 h^-1, 是纯CdS的10.1倍. 此外, 在实验结果和密度泛函理论的双重支持下, 提出并模拟了CdS与CuWO₄界面处内建电场和能带弯曲的形成, 并揭示了CdS向CuWO₄的S型异质结的电荷转移机制. 同时, 界面处形成的S-O-W键合通道可作为电子的快速传输路径, 进一步促进了光生载流子的分离. 光电化学进一步证明了复合材料的电荷转移阻抗显著降低, 这从实验上印证了理论计算结果. 另一方面, CuWO₄的光热效应使催化剂表面的局域温度升高, 从而提升了催化反应动力学, 显著提升了光催化活性.

综上, 本研究通过“电荷-热”双通道协同增强机制, 成功实现了光生载流子的快速分离与局域升温, 显著提升了光催化裂解水析氢的性能. 该策略克服了单一调控方式的局限, 为设计高效、稳定的光催化体系提供了理论依据和实验参考.

关键词: S型异质结, 硫化镉, 钨酸铜, 光热, 光催化, 析氢

Abstract:

S-scheme heterojunctions can offer an effective strategy for spatially separating photogenerated charge carriers, thereby sigFnificantly enhancing photocatalytic performance. In this study, cadmium sulfide (CdS)/copper tungstate (CFuWO₄) (CdS/CW) S-scheme heterojunction photocatalysts with adjustable components were fabricated by decorating CdS nanorods with CuWO₄ nanoparticles. The optimal hydrogen evolution rate (2725.91 μmol g^-1 h^-1) of CdS/CW-10% with excellent cycling stability under visible light is 10.1-fold higher than pure CdS. Density functional theory calculations and photoelectrochemical analyses confirmed that the S-scheme charge-transfer mechanism from CdS to CuWO₄ is responsible for the enhanced photocatalytic performance by promoting charge separation. Additionally, the photothermal effect of CuWO₄ increased the local temperature of the photocatalyst, further accelerating the reaction kinetics. This study highlights a dual-enhancement approach based on interfacial charge modulation by constructing an S-scheme heterojunction and photothermal activation, providing valuable insights into the design of high-efficiency S-scheme photocatalysts for solar-driven hydrogen production.

Key words: S-Scheme heterojunction, CdS, CuWO₄, Photothermal, Photocatalyst, Hydrogen evolution

刘青桦, 蔡培庆, 李恒帅, 冀学洋, 张大凤, 蒲锡鹏. 可见光驱动的CdS/CuWO₄ S型异质结析氢体系: 界面电荷转移与光热活化的双重协同增强[J]. 催化学报, 2026, 81: 299-309.

Qinghua Liu, Peiqing Cai, Hengshuai Li, Xue-Yang Ji, Dafeng Zhang, Xipeng Pu. Visible-light-driven hydrogen evolution over CdS/CuWO₄ S-Scheme heterojunctions: Dual synergistic enhancement via interfacial charge transfer and photothermal activation[J]. Chinese Journal of Catalysis, 2026, 81: 299-309.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64868-6

https://www.cjcatal.com/CN/Y2026/V81/I2/299

图/表 6

Fig. 1. (a) CdS/CW preparation process. (b) XRD patterns of samples. (c) XPS survey spectra. High-resolution XPS spectra of Cd 3d (d), S 2p (e), W 4f (f), and O 1s (g) of samples.

Fig. 2. SEM images (a-c), elemental mapping (d), TEM (e), and high-resolution TEM (f) images of samples.

Fig. 3. (a) DRS. (b, c) Tauc plots. (d, e) Mott-Schottky plots. (f) Photocurrent responses. (g) Electrochemical impedance spectroscopy Nyquist plots. (h) Transient PL spectroscopy emission spectra. (i) Transient PL spectra of samples.

Fig. 4. Photocatalytic (a) activities and (b) H2 evolution rates of samples. (c) Recycling stability of CdS and CdS/CW-10%. (d) AQE curves against CdS/CW-10 wavelength. (e) comparison of photocatalytic hydrogen evolution performance of CdS/CW-10 with previously reported CdS-based photocatalysts. (f) XRD patterns of CdS/CW-10% before and after photocatalysis. (g) Timeline with photothermal mapping images of CdS, CW, and CdS/CW-10% under visible light.

Fig. 5. PDOS of CdS (a) and CW (b). Wf values of CdS (202) (c) and CW (-133) (d). (e) Calculated free energy of HER intermediates at zero potential. (f) Calculated H2O adsorption energy. 3D electron differential density structure (g), ELF patterns (h), and corresponding profile plot (i) at CdS/CW heterojunction interface.

Fig. 6. XPS spectra with in-situ irradiation of Cd 3d (a), S 2p (b), Cu 2p (c), and W 4f (d) in CdS/CW-10%. EPR spectra of DMPO-?O2- (e) and DMPO-?OH (f) for CdS, CW, and CdS/CW-10%. (g) Mechanism of visible-light-induced CdS/CW photocatalytic hydrogen evolution.

参考文献

[1]	J.-D. Xiao, R. Li, H.-L. Jiang, Small Methods, 2023, 7, 2201258.
[2]	L. Zhang, J. Zhang, J. Yu, H. García, Nat. Rev. Chem., 2025, 9, 328-342.
[3]	S. K. Wang, D. F. Zhang, P. Su, X. T. Yao, J. C. Liu, X. P. Pu, H. S. Li, P. Q. Cai, J. Colloid Interface Sci., 2023, 650, 825-835.
[4]	Y. Wang, X. Hao, L. Zhang, Y. Li, Z. Jin, Energy Fuels, 2020, 34, 2599-2611.
[5]	B. Chong, H. Li, B. Xu, G. Yang, Catal. Today, 2022, 405, 227-234.
[6]	M. M. Kandy, V. G. Gaikar, Renew. Energy, 2019, 139, 915-923.
[7]	M.-H. Sun, M.-Y. Qi, C.-L. Tan, Z.-R. Tang, Y.-J. Xu, Chin. Chem. Lett., 2023, 34, 108022.
[8]	B. Zhang, F. Liu, B. Sun, T. Gao, G. Zhou, Chin. J. Catal., 2024, 59, 334-345.
[9]	W. Wang, X. Li, F. Deng, J. Liu, X. Gao, J. Huang, J. Xu, Z. Feng, Z. Chen, L. Han, Chin. Chem. Lett., 2022, 33, 5200-5207.
[10]	J. Cai, C. Cheng, B. Liu, J. Zhang, C. Jiang, B. Cheng, Acta Phys.-Chim. Sin., 2025, 41, 100084.
[11]	H. Ran, X. Liu, J. Fan, Y. Yang, L. Zhang, Q. Guo, B. Zhu, Q. Xu, J. Materiomics, 2025, 11, 100918.
[12]	L. Zhang, J. Zhang, H. Yu, J. Yu, Adv. Mater., 2022, 34, 2107668.
[13]	M. Wei, X. Zhou, C. Cheng, J. Zhang, C. Jiang, B. Cheng, J. Mater. Sci. Technol., 2025, 232, 302-312.
[14]	M. Gu, J. Zhang, I. V. Kurganskii, A. S. Poryvaev, M. V. Fedin, B. Cheng, J. Yu, L. Zhang, Adv. Mater., 2025, 37, 2414803.
[15]	J. Zhang, G. Yu, C. Yang, S. Li, Curr. Opin. Chem. Eng., 2024, 45, 101040.
[16]	A. H. Raza, S. Farhan, Z. Yu, Y. Wu, Acta Phys.-Chim. Sin., 2024, 40, 2406020.
[17]	X. Jin, X. Li, L. Dong, B. Zhang, D. Liu, S. Hou, Y. Zhang, F.-M. Zhang, B. Song, Nano Energy, 2024, 123, 109341.
[18]	X. T. Yao, X. Jiang, D. F. Zhang, S. Y. Lu, M. Y. Wang, S. H. Pan, X. P. Pu, J. C. Liu, P. Q. Cai, J. Colloid Interface Sci., 2023, 644, 95-106.
[19]	Z. Liu, Y. Bian, G. Dawson, J. Zhu, K. Dai, Chin. Chem. Lett., 2025, 36, 111272.
[20]	X. Liu, S. Wang, J. Cao, J. Yu, J. Dong, Y. Zhao, F. Zhao, D. Zhang, X. Pu, J. Colloid Interface Sci., 2024, 673, 463-474.
[21]	M. H. Elsayed, M. Abdellah, A. Z. Alhakemy, I. M. A. Mekhemer, A. E. A. Aboubakr, B.-H. Chen, A. Sabbah, K.-H. Lin, W.-S. Chiu, S.-J. Lin, C.-Y. Chu, C.-H. Lu, S.-D. Yang, M. G. Mohamed, S.-W. Kuo, C.-H. Hung, L.-C. Chen, K.-H. Chen, H.-H. Chou, Nat. Commun., 2024, 15, 707.
[22]	Y. Tang, Y. Zhang, L. Kong, Y. Zhu, X. Zhao, J. Liaocheng Univ. (Nat. Sci. Ed.), 2025, 38, 587-595.
[23]	S. K. Pilli, T. G. Deutsch, T. E. Furtak, L. D. Brown, J. A. Turner, A. M. Herring, Phys. Chem. Chem. Phys., 2013, 15, 3273.
[24]	Z. Lu, Z. Wang, Mater. Sci. Semicond. Process., 2023, 153, 107177.
[25]	N. Jatav, J. Kuntail, D. Khan, A. Kumar De, I. Sinha, J. Colloid Interface Sci., 2021, 599, 717-729.
[26]	G. Wang, C. Xu, W. Tang, S.-D. Guo, J. Duan, D. Hu, C. Yu, Y. Chen, B. Wang, W. Zhang, H. Yuan, Phys. Scr., 2024, 99, 105937.
[27]	H. Chen, X. Xiong, L. Hao, X. Zhang, Y. Xu, Appl. Surf. Sci., 2016, 389, 491-495.
[28]	Y. N. Lu, X. L. Zou, L. Wang, Y. L. Geng, J. Liaocheng Univ. (Nat. Sci. Ed.), 2023, 36(6), 57-64.
[29]	X. Jiang, M. Wang, B. Luo, Z. Yang, W. Li, D. Zhang, X. Pu, P. Cai, J. Alloys Compd., 2022, 926, 166878.
[30]	G. Kim, H. Mohan, G. H. Ha, H. R. Lee, T. Shin, J. Ind. Eng. Chem., 2025, 145, 534-542.
[31]	K. Wu, L. Mao, X. Gu, X. Cai, Y. Zhao, Chin. Chem. Lett., 2022, 33, 926-929.
[32]	F. Liu, B. Sun, Z. Liu, Y. Wei, T. Gao, G. Zhou, Chin. J. Catal., 2024, 64, 152-165.
[33]	J. H. Yu, X. T. Yao, P. Su, S. K. Wang, D. F. Zhang, B. Ge, X. P. Pu, J. Liaocheng Univ. (Nat. Sci. Ed.), 2024, 37(1), 52-61.
[34]	D. B. Pal, A. K. Rathoure, A. Singh, Int. J. Hydrogen Energy, 2021, 46, 26757-26769.
[35]	V. S. Perera, H. Liu, Z. Wang, S. D. Huang, Chem. Mater., 2013, 25, 4703-4709.
[36]	Y. Zhou, H. Deng, Z. Li, Y. Wang, T. Ma, Catal. Lett., 2023, 153, 2319-2330.
[37]	D. Ma, Q. Xue, Y. Liu, F. Liang, W. Li, T. Liu, C. Zhuang, Z. Zhao, S. Li, J. Mater. Sci. Technol., 2026, 243, 265-274.
[38]	J. Ren, Q. Ma, X. Sun, S. Wang, G. Liu, H. Yang, J. Colloid Interface Sci., 2025, 691, 137452.
[39]	J. Zhang, J. Fu, Z. Wang, B. Cheng, K. Dai, W. Ho, J. Alloys Compd., 2018, 766, 841-850.
[40]	X. Li, W. Sun, Q. Ming, G. Liao, H. Wang, J. Jiang, J. Liaocheng Univ. (Nat. Sci. Ed.), 2024, 37(1), 70-75.
[41]	Z. Du, D. Wang, X. Zhang, Z. Yi, J. Tang, P. Yang, R. Cai, S. Yi, J. Rao, Y. Zhang, Int. J. Mol. Sci., 2023, 24, 504.
[42]	Y. Wu, Y. Yang, M. Gu, C. Bie, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 53, 123-133.
[43]	L. Chen, Y. Luo, Z.-P. Yu, Y.-K. Cheng, Y. Zheng, L. He, J.-H. Xiong, W.-W. Kong, Tungsten, 2024, 6, 859-868.
[44]	R.-H. Xu, H.-Y. Jiang, D.-D. Cui, K.-R. Du, H.-R. Zhang, S.-J. Xu, Y.-Q. Li, Z.-Z. Ren, L. Wang, W.-C. Hao, Y. Du, Tungsten, 2025, 7, 71-79.
[45]	R. R. Atram, V. M. Bhuse, R. G. Atram, C.-M. Wu, P. Koinkar, S. B. Kondawar, Mater. Chem. Phys., 2021, 262, 124253.
[46]	S. Wang, X. Su, W. Han, G. Xu, D. Zhang, C. Su, X. Pu, P. Cai, Int. J. Hydrogen Energy, 2023, 48, 21712-21722.
[47]	T. Ma, Z. Li, G. Wang, J. Zhang, Z. Wang, Catalysts, 2022, 12, 1527.
[48]	W. Yang, F. Zhou, N. Sun, J. Wu, Y. Qi, Y. Zhang, J. Song, Y. Sun, Q. Liu, X. Wang, J. Mi, M. Li, J. Colloid Interface Sci., 2024, 662, 695-706.
[49]	Y. Bi, K. Xu, Y. Wang, X. Li, X. Zhang, J. Wang, Y. Zhang, Q. Liu, Q. Fang, J. Colloid Interface Sci., 2024, 661, 501-511.
[50]	G. Wang, Y. Quan, K. Yang, Z. Jin, J. Mater. Sci. Technol., 2022, 121, 28-39.
[51]	M. Dai, Z. He, P. Zhang, X. Li, S. Wang, J. Mater. Sci. Technol., 2022, 122, 231-242.
[52]	Z. Li, X. Meng, Z. Zhang, J. Colloid Interface Sci., 2019, 537, 345-357.
[53]	N. Jatav, A. Shrivastava, A. Kumar De, I. Sinha, J. Environ. Chem. Eng., 2022, 10, 107975.
[54]	R. Mann, D. Khushalani, ACS Appl. Mater. Interfaces, 2023, 15, 1219-1226.
[55]	W. Chen, X.-Q. Qiao, G. Hui, B. Sun, D. Hou, M. Wang, X. Wu, T. Wu, D.-S. Li, J. Energy Chem., 2025, 100, 710-720.
[56]	H. He, Z. Wang, J. Zhang, S. Mamatkulov, O. Ruzimuradov, K. Dai, J. Low, Y. Li, Energy Environ. Sci., 2025, 18, 6191-6201.
[57]	K. Wang, S. Li, Y. Li, Y. Li, G. Wang, Z. Jin, Int. J. Hydrogen Energy, 2022, 47, 23618-23631.
[58]	J. Zhang, L. Zhang, W. Wang, J. Yu, J. Phys. Chem. Lett., 2022, 13, 8462-8469.
[59]	X. Sun, T. Xian, C. Sun, J. Zhang, G. Liu, H. Yang, J. Mater. Sci. Technol., 2025, 228, 256-268.

可见光驱动的CdS/CuWO₄ S型异质结析氢体系: 界面电荷转移与光热活化的双重协同增强

Visible-light-driven hydrogen evolution over CdS/CuWO₄ S-Scheme heterojunctions: Dual synergistic enhancement via interfacial charge transfer and photothermal activation

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 6

参考文献

相关文章 15

编辑推荐

Metrics

[1]	陆家平, 林超, 李超, 石泓杰, 刘能益, 邢万东, 汪思波, 张贵刚, 陈藤藤, 陈雄. 联吡啶整合的双恶唑基给体-受体共价有机框架用于增强光催化过氧化氢合成[J]. 催化学报, 2026, 81(2): 185-194.
[2]	胡永盛, 杜史记, 郎集会, 刘恵莲, 李雪飞, 张旗, 鲁铭, 李鑫, 李彬榕, 魏茂彬, 杨丽丽. 构建MXene衍生TiO₂/CoNiO₂双位点S型异质结: 助力C-C偶联以实现高效光催化CO₂转化为C₂H₄[J]. 催化学报, 2026, 81(2): 227-245.
[3]	周港华, 刘杰, 张龙云, 毕传周, 徐航敏, 姜为易, 朱兴旺, 宁欣, 许晖, 王小治. 原子级Mn掺入Co₃O₄用于纯水和稀释CO₂条件下CO₂选择性光还原[J]. 催化学报, 2026, 81(2): 216-226.
[4]	王聪聪, 权永康, 石穗丽, 王国荣, 靳治良. 自组装3D/2D ZnIn₂S₄/CN-NH₄构建S型异质结用于纯水中高效制备过氧化氢[J]. 催化学报, 2026, 81(2): 259-271.
[5]	张哲, 潘桂旭, 朱炜, 张珂瑜, 梁桂杰, 王诗涵, 王宁, 邢艳, 李云锋. 分子间作用力增强聚巴比妥酸全有机异质结界面载流子迁移以实现高效光催化制氢[J]. 催化学报, 2026, 81(2): 284-298.
[6]	王雄, 彭超, 肖永康, 张子烨, 郑慧平, 岳文杰, 田昇, 胡星盛, 邵伟凡, 陈广辉, 王丙昊, 王慧娟, 尹明明, 李锦锌, 李扬, 陈浪, 尹双凤. 通过表面工程提升Bi₂WO_6-_x在选择性C-H键光氧化反应中的催化活性与稳定性[J]. 催化学报, 2026, 81(2): 246-258.
[7]	戚克振, 程蓓, Mahboobeh Setayeshmehr, Alireza Z. Moshfegh. 通过S型光催化与串联羰基化相结合实现太阳光驱动CO₂到化学品转化[J]. 催化学报, 2026, 81(2): 1-4.
[8]	田娜, 袁超凡, 周桐, 于文英, 王莹珲, 张娜, 张以河, 黄洪伟. 缺陷调控氮化碳负载Au纳米颗粒用于高效压电光催化制备H₂O₂[J]. 催化学报, 2026, 81(2): 272-283.
[9]	杨博霖, 靳菲, 靳治良. 非贵金属负载共价有机框架构建异质结高效光催化产氢[J]. 催化学报, 2026, 81(2): 172-184.
[10]	石苗苗, 何月轩, 张宁, 鲍迪, 赵大明, 钟海霞, 鄢俊敏, 蒋青. 室温下直接电化学液氨分解实现现场产氢[J]. 催化学报, 2026, 81(2): 310-318.
[11]	梁舒淇, 肖针, 沈锦妮, 戴文新, 张子重. AgPd-Co₃O₄级联活性位点调节•OH生成促进光催化甲烷制甲醇[J]. 催化学报, 2026, 80(1): 189-199.
[12]	蒋浩朋, 李金河, 于晓慧, 董慧龙, 王伟康, 刘芹芹. β-酮烯胺共价键桥接的S型异质结实现同步光还原CO₂为CO以及茴香醇选择性氧化为茴香醛[J]. 催化学报, 2026, 80(1): 113-122.
[13]	张金鹏, 梁腾, 陈恬, 郭美君, 余乐, 佘萍, 冉景润. 实现塑料光重整与产氢耦合实际应用的关键要素[J]. 催化学报, 2026, 80(1): 20-37.
[14]	徐燕东, 景子慧, 苏雯皓, 徐加乐, 王明亮. B-TiO₂@COF S型双功能光催化剂上过氧化氢生产与糠酸合成的协同耦合效应[J]. 催化学报, 2026, 80(1): 135-145.
[15]	王少单, 杨恒, 薛丽君, 张建军, 欧阳述昕, 温丽丽. 金属掺杂ZnIn₂S₄/TpPa-1 S型异质结: 通过调控氢吸附/脱附和内建电场促进双功能光催化[J]. 催化学报, 2026, 80(1): 159-173.