Zn0.5Cd0.5S中金属‒硫键的极化率调控及其可见光驱动光催化完全分解水研究

doi:10.1016/S1872-2067(26)65099-1

催化学报 ›› 2026, Vol. 87: 217-229.DOI: 10.1016/S1872-2067(26)65099-1

Zn_0.5Cd_0.5S中金属‒硫键的极化率调控及其可见光驱动光催化完全分解水研究

王臣^a, 张悦^a^,^b, 罗皓霖^a, 黄火帅^a, 苏千翔^a, 叶朕^a, 江治^a, 朱勇^c, 陈铭夏^a, 韦之栋^a^,^b^,^*(), 上官文峰^a^,^*()

^a 上海交通大学燃烧与环境技术研究中心, 上海 200240
^b 上海交通大学智慧能源创新学院, 上海 200240
^c 华东理工大学机械与动力工程学院, 上海 200237

收稿日期:2026-01-17 接受日期:2026-03-12 出版日期:2026-08-18 发布日期:2026-06-24
通讯作者: ^*电子信箱: weizhidong1013@sjtu.edu.cn (韦之栋),
shangguan@sjtu.edu.cn (上官文峰).
基金资助:
国家自然科学基金(22102095);上海交通大学“双一流”建设项目(WH220545009)

Regulation of Metal‒Sulfur bond polarizability in Zn_0.5Cd_0.5S for visible-light-driven photocatalytic overall water splitting

Chen Wang^a, Yue Zhang^a^,^b, Haolin Luo^a, Huoshuai Huang^a, Qianxiang Su^a, Zhen Ye^a, Zhi Jiang^a, Yong Zhu^c, Mingxia Chen^a, Zhidong Wei^a^,^b^,^*(), Wenfeng Shangguan^a^,^*()

^a Research Center for Combustion and Environmental Technology, Shanghai Jiao Tong University, Shanghai 200240, China
^b College of Smart Energy, Shanghai Jiao Tong University, Shanghai 200240, China
^c School of Mechanical and Power Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2026-01-17 Accepted:2026-03-12 Online:2026-08-18 Published:2026-06-24
Supported by:
National Natural Science Foundation of China(22102095);Shanghai Jiao Tong University “Double First-Class” Construction(WH220545009)

摘要/Abstract

摘要：

太阳能驱动光催化全分解水被视为实现可持续氢能制取的重要途径. 相较于单一光催化剂全分解水体系, Z型全分解水体系具有可见光吸收、氧化还原位点分离等方面的优势, 而被视为实现光催化全分解水的理想策略之一. 其中, 硫化物催化剂具有可见光吸收能力较强、析氢还原性能优异等方面的特点, 是Z型体系中析氢端催化剂的理想选择之一. 然而, 在反应过程中, 硫化物催化剂会与K₃[Fe(CN)₆]/K₄[Fe(CN)₆]等氧化还原介体发生副反应, 所生成的中间衍生物可能会覆盖反应位点进而产生空间位阻效应, 显著降低光催化活性及稳定性. 因此, 抑制中间衍生物等副产物的空间位阻效应, 对于构建高效稳定的Z型全分解水体系而言极具挑战.

近年来, 由于催化剂极化率的调控可以优化界面电子结构、调控电荷转移路径, 为光催化剂的设计提供了新的思路. 本文构建了Ni掺杂的Zn_0.5Cd_0.5S催化剂, 成功实现了金属‒硫键(M‒S; M = Cd, Zn)极化率的调控, 显著提升了Z型全分解水体系的稳定性. 该策略成功的关键在于, 热处理有效的调控了S-M键的极化率, 并驱动电荷重排, 使Ni原子成为电子富集中心. 这一电子结构的变化既能促进析氢反应的进行, 又能减弱析氢端催化剂对[Fe(CN)₆]^3‒的吸附能力. 结果表明, 在可见光(λ ≥ 420 nm)照射下, 产氢和产氧速率分别达到109.04和52.04 μmol·h^‒1, 氢氧化学计量比为2.09:1, 420 nm处表观量子效率达4.06%, 40 h循环测试后仍保持初始活性的86.7%, 显著提高了其稳定性. 相关密度泛函理论计算证明, Ni位点的电子富集使析氢端催化剂对[Fe(CN)₆]^3‒的吸附能从‒5.79降至‒5.35 eV, 吸附能的减弱有效抑制了竞争还原反应和副产物的产生. 基于此, 本文提出了可能的反应机理: 金属‒硫键的极化率调控诱导了电子在Ni位点富集, 不仅增强了催化剂对H⁺的亲和力, 降低了析氢反应能垒; 而且减弱了对[Fe(CN)₆]^3‒的吸附, 有效抑制了普鲁士蓝衍生物的生成, 降低其空间位阻效应, 从而实现了“促进主反应”与“抑制副反应”的协同优化.

综上, 本文利用金属‒硫键极化率调控的策略, 实现了可见光(λ ≥ 420 nm)照射下Z型体系中高效稳定的完全分解水, 阐明了极化率调控对抑制中间衍生物等副产物的空间位阻效应的作用机制, 为Z型体系中硫化物基光催化剂的设计和稳定性提升提供了新思路.

关键词: 极化率, Ni掺杂, 普鲁士蓝衍生物

Abstract:

The development of efficient and stable visible-light-driven Z-scheme systems for overall water splitting was crucial for solar hydrogen production. However, performance was often limited by photocorrosion of sulfide-based hydrogen evolution photocatalysts and competing, deactivating side reactions involving the redox shuttle. Herein, we construct a robust Z-scheme system by employing a CoP-modified Ni-doped Zn_0.5Cd_0.5S heterojunction with strong interfacial interaction as the HEP, coupled with BiVO₄ as the oxygen evolution photocatalyst. The optimized system exhibited an apparent quantum yield of 4.06% at 420 nm and enabled sustained co-evolution of hydrogen and oxygen at a near-stoichiometric ratio. It also demonstrated outstanding cycling stability. Crucially, it had been demonstrated that the regulation of the internal polarizability of HEP effectively suppressed the competitive reduction of the redox medium and the formation of passivated Prussian blue derivatives on the catalyst surface. This work provides fundamental insights into mitigating the side effects caused by fusion through polarizability regulation.

Key words: Polarizability, Ni doping, Prussian blue derivative

王臣, 张悦, 罗皓霖, 黄火帅, 苏千翔, 叶朕, 江治, 朱勇, 陈铭夏, 韦之栋, 上官文峰. Zn_0.5Cd_0.5S中金属‒硫键的极化率调控及其可见光驱动光催化完全分解水研究[J]. 催化学报, 2026, 87: 217-229.

Chen Wang, Yue Zhang, Haolin Luo, Huoshuai Huang, Qianxiang Su, Zhen Ye, Zhi Jiang, Yong Zhu, Mingxia Chen, Zhidong Wei, Wenfeng Shangguan. Regulation of Metal‒Sulfur bond polarizability in Zn_0.5Cd_0.5S for visible-light-driven photocatalytic overall water splitting[J]. Chinese Journal of Catalysis, 2026, 87: 217-229.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65099-1

https://www.cjcatal.com/CN/Y2026/V87/I8/217

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Fig. 1. XRD pattern (a,b), Raman spectra (c), high-resolution Zn 2p (d), Cd 3d (e), S 2p (f), Ni 2p (g), Co 2p (h), and P 2p (i) XPS spectra of as-prepared photocatalysts.

Fig. 2. SEM images of ZCS (a), 5NZCS (b), 6CoP-5NZCS (c), 6CNZCS-400 (d). (e-g) TEM images of 6CNZCS-400. (h) Elemental mapping images for Zn, Cd, S, Ni, Co and P with the overlay image of the mapping images.

Fig. 3. (a) Photocurrent transient spectra. (b) TRPL spectra. (c) EIS Nyquist plots. (d) Transient photocurrent responses. CV curves of aqueous solutions without (e) and containing K3[Fe(CN)6] (f). (g) Anodic currents for [Fe(CN)6]3− reduction. (h) Anodic currents for [Fe(CN)6]4− oxidation.

Fig. 4. (a, b) H2 generation rate of different photocatalysts in the lactic acid aqueous solution. (c) O2 generation rate of different photocatalysts in the K3 [Fe(CN)6] aqueous solution. (d) H2 and O2 yields of Z-type photocatalytic water splitting with different HEPs. (e) Time process of H2 and O2 yields of 6CoP-5NZCS-400 in the Z-scheme system. (f) The content of K and Fe elements on the surface of the catalyst after 10 h reaction. (g) Apparent quantum yields of Z-scheme system using 6CoP-5NZCS-400-Pt-CrOx and BiVO4-IrOx. OWS performance with different Pt (h) and CrOx (i) contents under the Z scheme system.

Fig. 5. (a) The mechanism of Z-type water decomposition reaction. Stability of H2 and O2 production over HEP (6CNZCS) and OER (BiVO4-0.8 wt%IrOx) (b) and HEP (6CNZCS-400) and OER (BiVO4-0.8 wt%IrOx) (c). XRD patterns (d), Raman spectra (e), and IR spectra (f) of different HEPs and OER used in the Z-scheme reaction. The structure of [Fe(CN)6]3− adsorption by the optimized ZCS (g) and 5NZCS-400 (h). Charge difference density of ZCS (i) and 5NZCS-400 (j) after adsorbing ferric cyanide.

参考文献

[1]	H. Zhang, H. Liu, Z. Yuan, F. Jin, Z. Jin, Appl. Catal. B, 2025, 381, 125826
[2]	C. Du, Q. Zhang, Z. Lin, B. Yan, C. Xia, G. Yang, Appl. Catal. B, 2019, 248, 193-201.
[3]	S. Chen, C. Li, K. Domen, F. Zhang, Joule, 2023, 7, 2445-2467.
[4]	H. Wang, F. Wang, X. Li, Q. Xiao, W. Luo, J. Xu, Chin. J. Catal., 2023, 46, 72-83.
[5]	B. Lian, J. Chen, L. Li, S. Deng, K. Wang, W. Yan, J. Zhang, Front. Energy, 2025, 19, 793-803.
[6]	H. Zhao, X. Zhao, L. Shen, H. Liu, X. Li, Chem. Eng. J., 2023, 470, 143925.
[7]	L. Sun, W. Wang, P. Lu, Q. Liu, L. Wang, H. Tang, Chin. J. Catal., 2023, 51, 90-100.
[8]	T. Xu, J. Shi, K.-S. Peng, Y.-H. Hsu, Y.-C. Liu, S. Wang, H. Zhang, Y. Wang, G. Zhang, S.-F. Hung, K. Liu, X. Wang, Angew. Chem. Int. Ed., 2025, 64, e202513029.
[9]	B. Zhong, C. Hu, K. Sun, W. Yan, J. Zhang, Z. Xie, Front. Energy, 2025, 19, 545-551.
[10]	Y. Zhang, X. Wu, Z.-H. Wang, Y. Peng, Y. Liu, S. Yang, C. Sun, X. Xu, X. Zhang, J. Kang, S.-H. Wei, P.-F. Liu, S. Dai, H.-G. Yang, J. Am. Chem. Soc., 2024, 146, 6618-6627.
[11]	D. Zhang, M. Zhu, R. Qin, P. Chen, M. Yin, D. Zhang, J. Liu, H. Li, X. Pu, P. Cai, J. Energy Chem., 2024, 92, 240-249.
[12]	X. Tan, M. Zhang, Y. Bai, X. Liu, J. Jing, Y. Su, Chin. J. Catal., 2025, 77, 199-209.
[13]	C. Zhang, S. You, A. Du, Z. Zhuang, W. Yan, J. Zhang, Front. Energy, 2025, 19, 471-499.
[14]	H. Huang, Z. Wei, J. Yan, J. Chi, Q. Su, L. Ma, M. Chen, Z. Jiang, Y. Sun, W. Shangguan, Rare Met., 2025, 44, 10204-10214.
[15]	C. Yang, X. Li, M. Li, G. Liang, Z. Jin, Chin. J. Catal., 2024, 56, 88-103.
[16]	B. Hu, Y. Cao, Front. Energy, 2025, 19, 757-766.
[17]	R. Yuan, Z. Zhang, F. Bu, Z. Wei, J. Liu, W. Shangguan, Front. Energy, 2025, 19, 568-585.
[18]	J. Wu, P. Qiao, P. An, M. Zhang, H. Xiu, Z. Song, K. Li, Y. Cui, Y. Wang, W. Yao, Appl. Catal. B, 2025, 377, 125481
[19]	H. Huang, Z. Wei, J. Yan, J. Chi, Q. Su, M. Chen, Z. Jiang, Y. Sun, W. Shangguan, Acta Phys.-Chim. Sin., 2026, 42, 100141
[20]	Q. Luan, X. Xue, R. Li, L. Gu, W. Dong, D. Zhou, X. Wang, B. Li, G. Wang, C. Hou, Appl. Catal. B, 2022, 305, 121007.
[21]	Z. Zhang, J. Zhang, H. Wang, M. Liu, Y. Xu, K. Liu, B. Zhang, K. Shi, J. Zhang, G. Ma, Chin. J. Catal., 2025, 74, 341-351.
[22]	C. Li, J. He, T. Cai, X. Chen, H. Tao, Y. Zhou, M. Zhu, Chin. J. Catal., 2025, 74, 130-143.
[23]	N. Li, X. Gao, J. Su, Y. Gao, L. Ge, Chin. J. Catal., 2023, 47, 161-170.
[24]	F. Liu, B. Sun, Z. Liu, Y. Wei, T. Gao, G. Zhou, Chin. J. Catal., 2024, 64, 152-165.
[25]	M. Wang, S. Xu, Z. Zhou, C.-L. Dong, X. Guo, J.-L. Chen, Y.-C. Huang, S. Shen, Y. Chen, L. Guo, C. Burda, Angew. Chem. Int. Ed., 2022, 61, e202204711.
[26]	J. Chi, Z. Wei, W. Guo, W. Fang, J. Yan, H. Huang, Y. Zhang, H. Luo, J. Wang, J. Liu, Z. Jiang, W. Shangguan, ACS Catal., 2025, 15, 11293-11306.
[27]	J. Qu, Y. Dong, T. Zhang, C. Zhao, L. Wei, X. Guan, Front. Energy, 2024, 18, 850-862.
[28]	K. Liu, B. Zhang, J. Zhang, Y. Xu, J. Zhang, Z. Zhang, K. Shi, N. Wang, S. Chen, G. Ma, ACS Catal., 2024, 14, 10138-10147.
[29]	Y. Kang, H. Qi, G. Wan, C. Zhen, X. Xu, L.-C. Yin, L. Wang, G. Liu, H.-M. Cheng, Joule, 2022, 6, 1876-1886.
[30]	G. Zhao, S. Hao, J. Guo, Y. Xing, L. Zhang, X. Xu, Chin. J. Catal., 2021, 42, 501-509.
[31]	Z. Wei, W. Wang, W. Li, X. Bai, J. Zhao, E. C. M. Tse, D. L. Phillips, Y. Zhu, Angew. Chem. Int. Ed., 2021, 60, 8236-8242.
[32]	Y. Ding, Y. Zhang, F. Zhang, P. Tian, Y. Wang, S. Shen, J. Wei, J. Chen, Front. Energy, 2025, 19, 534-544.
[33]	J. Zhang, K. Liu, B. Zhang, J. Zhang, M. Liu, Y. Xu, K. Shi, H. Wang, Z. Zhang, P. Zhou, G. Ma, J. Am. Chem. Soc., 2024, 146, 4068-4077.
[34]	M. Shi, X. Wu, Y. Zhao, R. Li, C. Li, J. Am. Chem. Soc., 2025, 147, 3641-3649
[35]	H. Li, K. Wahab Ahmed, M. A. Abdelsalam, M. Fowler, X.-Y. Wu, Front. Energy, 2024, 18, 291-307.
[36]	P. Wang, S. Zhan, H. Wang, Y. Xia, Q. Hou, Q. Zhou, Y. Li, R. R. Kumar, Appl. Catal. B, 2018, 230, 210-219.
[37]	Z. Kong, J. Dong, J. Yu, D. Zhang, J. Liu, X.-Y. Ji, P. Cai, X. Pu, Chem. Eng. J., 2024, 496, 153960.
[38]	Y. Cao, L. Ye, Y. Yuan, R. Yang, H. Hong, J. Chen, J. Lu, E. Cui, J. Jiang, Chin. J. Catal., 2025, 78, 229-241.
[39]	Q. Yu, S. Sun, A. R. Puente-Santiago, C. Wu, X. Xiong, Y. Jin, B. Weng, Appl. Catal. B, 2025, 367, 125098.
[40]	S. Cao, Y. Chen, H. Wang, J. Chen, X. Shi, H. Li, P. Cheng, X. Liu, M. Liu, L. Piao, Joule, 2018, 2, 549-557.
[41]	J.-Y. Li, M.-Y. Qi, Y.-J. Xu, Chin. J. Catal., 2022, 43, 1084-1091
[42]	Y. Ma, G. Hai, J. Liu, J. Bao, Y. Li, G. Wang, Chem. Eng. J., 2022, 441, 136002.
[43]	D. Zhou, X. Xue, X. Wang, Q. Luan, A. Li, L. Zhang, B. Li, W. Dong, G. Wang, C. Hou, Appl. Catal. B, 2022, 310, 121337.
[44]	X. Zheng, Y. Song, Q. Gao, J. Lin, J. Zhai, Z. Shao, J. Li, D. Wu, X. Shi, W. Liu, X. Tian, Y. Liu, Adv. Funct. Mater., 2025, 35, 2506159.
[45]	J. Wang, X. Niu, R. Wang, K. Zhang, X. Shi, H.-Y. Yang, J. Ye, Y. Wu, Appl. Catal. B, 2025, 362, 124763.
[46]	J. Liu, G. Ren, G. Hu, C. Wang, T. Guo, Q. Guo, P. S. Goh, J. Phys. Chem. Lett., 2025, 16, 7337-7345.
[47]	Y. Li, Z. Jin, N. Tsubaki, ACS Appl. Nano Mater., 2022, 5, 14677-14688.
[48]	X. Wang, B. Liu, S. Ma, Y. Zhang, L. Wang, G. Zhu, W. Huang, S. Wang, Nat. Commun., 2024, 15, 2600.
[49]	R. Li, P. Feng, B. Li, J. Zhu, Y. Zhang, Z. Zhang, J. Zhang, Y. Ding, Chin. J. Catal., 2025, 73, 242-251.
[50]	H. Yu, J. Zhang, K. Zhou, H. Wang, Front. Energy, 2025, 19, 694-702.
[51]	Y. Lei, Y. Zhang, Z. Li, S. Xu, J. Huang, K. Hoong Ng, Y. Lai, Chem. Eng. J., 2021, 425, 131478.
[52]	X. Guo, L. Fan, J. Liu, B. Wen, Y. Li, Z. Jin, Appl. Catal. B, 2025, 378, 125586.
[53]	L. Zhang, G. Wang, X. Hao, Z. Jin, Y. Wang, Chem. Eng. J., 2020, 395, 125113.
[54]	J. Zhang, J. Ma, R. Cui, W. Ling, M. Hong, R. Sun, Chem. Eng. J., 2025, 503, 158427.
[55]	X. Xue, W. Dong, Q. Luan, H. Gao, G. Wang, Appl. Catal. B, 2023, 334, 122860.
[56]	J. Tao, M. Wang, X. Zhang, L. Lu, H. Tang, Q. Liu, S. Lei, G. Qiao, G. Liu, Appl. Catal. B, 2023, 320, 122004.
[57]	K. Ge, Z. Li, A. Wang, Z. Bai, X. Zhang, X. Zheng, Z. Liu, F. Gao, ACS Nano, 2023, 17, 2222-2234.
[58]	B. Fang, Z. Xing, W. Kong, Z. Li, W. Zhou, Nano Energy, 2022, 101, 107616.
[59]	X. Yan, M. Xia, H. Liu, B. Zhang, C. Chang, L. Wang, G. Yang, Nat. Commun., 2023, 14, 1741.
[60]	X. Huang, X. Xu, X. Luan, D. Cheng, Nano Energy, 2020, 68, 104332.
[61]	X. Zhang, L. Song, L. Tong, M. Zeng, Y. Wang, Chem. Eng. J., 2022, 440, 135884.
[62]	Z. Lin, W. Xie, M. Zhu, C. Wang, J. Guo, Chin. J. Catal., 2024, 64, 87-97.
[63]	J. Yan, H. Wu, H. Chen, Y. Zhang, F. Zhang, S. F. Liu, Appl. Catal. B, 2016, 191, 130-137.
[64]	L. Wang, Y. Kong, Y. Fang, P. Cai, W. Lin, X. Wang, Adv. Funct. Mater., 2022, 32, 2208101.
[65]	X. Tao, H. Zhou, C. Zhang, N. Ta, R. Li, C. Li, Adv. Mater., 2023, 35, 2211182
[66]	Z. Wei, J. Yan, W. Guo, W. Shangguan, Chin. J. Catal., 2023, 48, 279-289.
[67]	L. Lu, Z. Wang, J. Cai, Z. Bao, Y. Lan, Y. Zuo, Y. Jiang, W. Yan, J. Zhang, Front. Energy, 2025, 19, 382-394.
[68]	Z. Zhao, R. V. Goncalves, S. K. Barman, E. J. Willard, E. Byle, R. Perry, Z. Wu, M. N. Huda, A. J. Moulé, F. E. Osterloh, Energy Environ. Sci., 2019, 12, 1385-1395.
[69]	D. H. K. Murthy, V. Nandal, A. Furube, K. Seki, R. Katoh, H. Lyu, T. Hisatomi, K. Domen, H. Matsuzaki, Adv. Energy Mater., 2023, 13, 2302064.
[70]	J. Guo, X. Liao, M.-H. Lee, G. Hyett, C.-C. Huang, D. W. Hewak, S. Mailis, W. Zhou, Z. Jiang, Appl. Catal. B, 2019, 243, 502-512.
[71]	Q. Chen, G. Gao, H. Guo, S.-A. Wang, Q. Wang, Y. Fang, X. Hu, R. Duan, Chem. Eng. J., 2023, 470, 144199.
[72]	W. Zhan, N. Yang, T. Zhou, J. Zhang, T. He, Q. Liu, Chin. J. Catal., 2025, 79, 162-173.

Zn_0.5Cd_0.5S中金属‒硫键的极化率调控及其可见光驱动光催化完全分解水研究

Regulation of Metal‒Sulfur bond polarizability in Zn_0.5Cd_0.5S for visible-light-driven photocatalytic overall water splitting

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Zn0.5Cd0.5S中金属‒硫键的极化率调控及其可见光驱动光催化完全分解水研究

Regulation of Metal‒Sulfur bond polarizability in Zn0.5Cd0.5S for visible-light-driven photocatalytic overall water splitting

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Zn_0.5Cd_0.5S中金属‒硫键的极化率调控及其可见光驱动光催化完全分解水研究

Regulation of Metal‒Sulfur bond polarizability in Zn_0.5Cd_0.5S for visible-light-driven photocatalytic overall water splitting