Interfacial Cu‒S bond and localized surface plasmon resonance modulated Cu3P@Cu/Mn0.3Cd0.7S S-scheme heterojunction for efficient photocatalytic hydrogen evolution

doi:10.1016/S1872-2067(26)65049-8

Abstract

Abstract:

Photocatalytic hydrogen evolution is an economically viable and environmentally friendly synthesis method. However, its photocatalytic efficiency is hindered by the sluggish reaction kinetics and rapid recombination of photogenerated charge carriers. Herein, an interfacial Cu‒S bond and localized surface plasmon resonance (LSPR)-synchronously mediated Cu₃P@Cu/Mn_0.3Cd_0.7S (Cu₃P@Cu/MCS) S-scheme heterojunction was designed and synthesized for accelerated photogenerated electron transfer. Under light illumination, the optimized 5%-Cu₃P@Cu/MCS composite exhibited a photocatalytic hydrogen production rate of 93.25 mmol g^-1 h^-1, representing a 7.3-fold increase compared to that of pristine MCS (12.69 mmol g^-1 h^-1). Experimental results revealed that the interfacial Cu‒S bonds between MCS and Cu₃P@Cu accelerated charge separation, thereby enhancing the reaction kinetics. Simultaneously, Cu-induced LSPR converted long-wavelength photons into localized heat, thereby increasing the interfacial temperature and accelerating the transfer of charge carriers. The synergistic effect of this chemical bond established in the S-scheme heterojunction with the LSPR effect provides new insights into photocatalytic H₂ evolution.

Key words: S-scheme heterojunction, Interface Cu-S bond, Localized surface plasmon resonance, Photocatalytic hydrogen evolution

Ruiqi Zhang, Xintong Yao, Junchang Liu, Zhi Chen, Dafeng Zhang, Xipeng Pu. Interfacial Cu‒S bond and localized surface plasmon resonance modulated Cu₃P@Cu/Mn_0.3Cd_0.7S S-scheme heterojunction for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 89: 258-268.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65049-8

https://www.cjcatal.com/EN/Y2026/V89/I10/258

Figures/Tables 6

Fig. 1. (a) Schematic illustration for the synthesis of Cu3P@Cu/MCS. (b) XRD patterns of MCS, Cu3P@Cu, and X-Cu3P@Cu/MCS. High-resolution XPS spectra of Mn (c), Cd (d), S (e), Cu (f), and P (g) elements in MCS, Cu3P@Cu, and Cu3P@Cu/MCS.

Fig. 2. SEM images of MCS (a), Cu3P@Cu (b), and Cu3P@Cu/MCS (c). TEM (d,e) and high-resolution TEM (f) images of Cu3P@Cu/MCS. (g-l) Elemental mapping images of Cu3P@Cu/MCS.

Fig. 3. Photocatalytic H2 evolution activity of the samples: time-yield curves (a) and H2 production rate (b). (c) UV-vis absorption spectrum of the optimized 5%-Cu3P@Cu/MCS together with its wavelength-dependent AQE. (d) H2 evolution stability test results of 5%-Cu3P@Cu/MCS. (e) Comparison of H2 production activity of the MnxCd1?xS-based composites in Table S2.

Fig. 4. UV-Vis DRS (a) and infrared images (b) of as-prepared materials under irradiation. (c) Mott-Schottky plots of MCS. (d) Schematic energy-level diagram. PL spectra (e), TRPL spectra (f), and I-t (g) curves of different samples. (h) EPR spectra of DMPO-?O2- under irradiation.

Fig. 5. PDOS of MCS (a) and Cu3P@Cu (b). (c) EDD maps of Cu3P@Cu/MCS. Wf of MCS (d) and Cu3P@Cu (e).

Fig. 6. Structure of CZS/ZWO S-scheme heterojunction before (a) and after (b) optimization. (c) ΔGH* of 5%-Cu3P@Cu/MCS systems. (d,e) Local enlarged views of CZS/ZWO S-scheme heterojunction. (f) High-resolution in-situ XPS spectra of Mn 2p under illumination and dark conditions. (g) Detailed charge transfer pathways in S-Scheme heterojunction.

References

[1]	X. Sun, M. Song, F. Liu, H. Peng, T. Zhao, S.-F. Yin, P. Chen, Appl. Catal. B, 2024, 342, 123436.
[2]	S. Wang, Q. Liu, W. Zhang, J. Liu, X. Ji, P. Cai, R. Chen, S. Liu, W. Ma, D. Zhang, X. Pu, Carbon Neutralization, 2025, 4, e70054.
[3]	X. Sun, T. Xian, C. Sun, J. Zhang, G. Liu, H. Yang, J. Mater. Sci. Technol., 2025, 228, 256-268.
[4]	X. Wang, K. Qi, K. Xu, Chin. J. Catal., 2025, 70, 1-4.
[5]	W. H. Lee, C. W. Lee, G. D. Cha, B.-H. Lee, J. H. Jeong, H. Park, J. Heo, M. S. Bootharaju, S.-H. Sunwoo, J. H. Kim, K. H. Ahn, D.-H. Kim, T. Hyeon, Nat. Nanotechnol., 2023, 18, 754-762.
[6]	Z. Kong, D. Zhang, J. Liu, X.-Y. Ji, P. Cai, X. Pu, H. Zhang, Nano Energy, 2025, 138, 110890.
[7]	X. Sun, J. Zhang, M. Luo, J. Ma, T. Xian, G. Liu, H. Yang, Chem. Eng. J., 2024, 499, 156455.
[8]	K. Qi, Z. Wei, H. Wang, H. Liang, D. Ma, J. Shi, Y. Li, X. Xiang, Y. Chen, B. Yu, C. Wang, Z. Xing, C. Imparato, A. Bifulco, D. A. Lukyanov, E. V. Alekseeva, O. V. Levin, M. I. Chebanenko, V. I. Popkov, T. Zhang, J. Li, G. Liu, W. Li, L. Song, R. Ren, Z. Wang, J. Ma, Chin. Chem. Lett., 2026, 37, 111661.
[9]	B. Deng, J. Shen, J. Lu, C. Huang, Z. Chen, F. Peng, Y. Liu, J. Energy Chem., 2025, 100, 317-326.
[10]	J. Zhang, X. Sun, W. Zhu, G. Liu, T. Xian, H. Yang, J. Environ. Chem. Eng., 2024, 12, 114405.
[11]	C. You, X. Zhang, Y. Zhao, R. Yan, Y. Shen, Q. Xue, W. Li, T. Liu, J. Jiang, X. Chen, S. Li, J. Mater. Sci. Technol., 2026, 242, 64-74.
[12]	J. Zhang, K. Qi, R. Pitcheri, C. Duan, J. Photochem. Photobiol. C, 2025, 65, 100722.
[13]	A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[14]	H. Wu, S. Qu, Y. H. Ng, J. Am. Chem. Soc., 2025, 147, 10829-10833.
[15]	X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson, K. Domen, M. Antonietti, Nat. Mater., 2009, 8, 76-80.
[16]	J. He, W. Zhang, Z. Liu, Z. Wang, K. Lu, K. Yang, J. Liaocheng Univ. (Nat. Sci. Ed.), 2025, 38, 421-429.
[17]	H. Jing, M. Luan, H. Ye, C. Zhang, S. Ding, B. Zhou, J. Liaocheng Univ. (Nat. Sci. Ed.), 2025, 38, 927-934.
[18]	W. Deng, X. Hao, J. Yang, Z. Jin, Appl. Catal. B, 2025, 360, 124551.
[19]	W. Wang, Z. Chen, C. Li, B. Cheng, K. Yang, S. Zhang, G. Luo, J. Yu, S. Cao, Adv. Funct. Mater., 2025, 35, 2422307.
[20]	J. Yu, X. Yao, P. Su, S. Wang, D. Zhang, B. Ge, X. Pu, J. Liaocheng Univ. (Nat. Sci. Ed.), 2024, 37, 52-61.
[21]	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.
[22]	C. Cheng, J. Wang, X. Guo, F. Xing, C. Huang, M. Song, Appl. Surf. Sci., 2021, 557, 149812.
[23]	R. Zhang, X. Yao, X. Meng, X. Li, D. Zhang, J. Liu, P. Cai, X. Pu, Sep. Purif. Technol., 2025, 354, 129479.
[24]	Q. Ma, J. Ren, X. Sun, X. Chen, G. Liu, S. Wang, H. Yang, Appl. Surf. Sci., 2025, 679, 161275.
[25]	X. Wu, M. Sayed, G. Wang, W. Yu, B. Zhu, Adv. Mater., 2026, 38, e11322.
[26]	H. Zhang, H. Liu, Z. Yuan, F. Jin, Z. Jin, Appl. Catal. B, 2026, 381, 125826.
[27]	P. Su, J. Yu, P. Deng, D. Qu, T. Liang, H. Zhao, N. Yang, D. Zhang, B. Ge, X. Pu, J. Liaocheng Univ. (Nat. Sci. Ed.), 2024, 37(5), 123-131.
[28]	H. Li, C. Jin, D. Zhang, J. Liaocheng Univ. (Nat. Sci. Ed.), 2025, 38, 259-267.
[29]	J. Deng, D. Xu, J. Zhang, Q. Xu, Y. Yang, Z. Wei, Z. Su, J. Mater. Sci. Technol., 2024, 180, 150-159.
[30]	Z. Meng, J. Zhang, H. Long, H. Garcia, L. Zhang, B. Zhu, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202505456.
[31]	H. Li, Q. Shen, Z. Sun, W. Wang, J. Xue, J. Yu, ACS Catal., 2025, 15, 9717-9727.
[32]	S. Li, X. Li, Y. Liu, P. Zhang, J. Zhang, B. Zhang, Chin. J. Catal., 2025, 72, 130-142.
[33]	H. Ran, X. Liu, L. Ye, J. Fan, B. Zhu, Q. Xu, Y. Wei, J. Mater. Sci. Technol., 2025, 234, 24-30.
[34]	Y. Yang, X. Zhou, M. Gu, B. Cheng, Z. Wu, J. Zhang, Acta Phys.-Chim. Sin., 2025, 41, 100064.
[35]	L. Zhang, J. Zhang, J. Yu, H. García, Nat. Rev. Chem., 2025, 9, 328-342.
[36]	X. Li, T. Han, Y. Zhou, M. Wang, Z. Tian, F. Deng, Y. Luo, Y. Xie, J. Huang, L. Han, Z. Chen, Z. Feng, W. Chen, Appl. Catal. B, 2024, 350, 123913.
[37]	D. Zhang, C. Zhang, H. Song, Z. Guo, J. Hu, Z. Lv, J. Clean. Prod., 2023, 427, 139273.
[38]	M. Sayed, K. Qi, X. Wu, L. Zhang, H. García, J. Yu, Chem. Soc. Rev., 2025, 54, 4874-4921.
[39]	Z. Fu, X. Ma, B. Xia, X. Hu, J. Fan, E. Liu, Int. J. Hydrogen Energy, 2021, 46, 19373-19384.
[40]	X. Wang, S. Xue, T. Shi, Z. Zhao, A. Song, G. Li, L. Wang, J. Huang, A. Meng, Z. Li, Adv. Funct. Mater., 2025, 35, 2424853.
[41]	Y. Tang, Y. Sun, Y. Li, Y. Guo, B. Liu, X. Tan, Z. Hu, D. Zhong, J. Ye, T. Yu, Adv. Funct. Mater., 2024, 34, 2405527.
[42]	S. Xu, J. Zhang, X. Sun, H. Yang, J. Ma, Colloids Surf. A, 2024, 689, 133757.
[43]	S. Li, X. Wang, B. Xue, D. Feng, Y. Liu, W. Jiang, J. Mater. Sci. Technol., 2026, 246, 237-246.
[44]	Y. Deng, Y. Chen, L. Zhang, H. Jin, Y. Yang, Q. Xu, S. Wang, Acta Phys.-Chim. Sin., 2025, DOI: 10.1016/j.actphy.2025.100193.
[45]	R. Zhang, R. Liu, Z. Ding, J. Ma, T. Wang, D. Zhang, J. Liu, P. Cai, X. Pu, J. Colloid Interface Sci., 2025, 682, 568-577.
[46]	F. Liu, X. Li, B. Sun, Y. He, T. Gao, G. Zhou, J. Mater. Sci. Technol., 2026, 250, 233-242.
[47]	R. Zhang, Q. Liu, T. Wang, P. Xiao, X.-Y. Ji, J. Liu, P. Cai, D. Zhang, X. Pu, H. Zhang, X. Liu, J. Colloid Interface Sci., 2026, 703, 139176.
[48]	T. Wu, J. Chen, L. Liu, X. Qu, S. Zheng, D. Zhu, Appl. Catal. B, 2024, 358, 124408.
[49]	K. Saini, R. Shree Pandey, Adv. Mater. Lett., 2017, 8, 1080-1088.
[50]	R. Han, K. Wang, Q. Jiang, G. Zhang, Q. Lu, E. Guo, J. Colloid Interface Sci., 2024, 671, 680-691.
[51]	Z. Chen, Y. Yan, P. Shan, A. Bian, W. Kong, A. Proskurin, L. Guo, J. Hou, Z. Liu, G. Wang, W. Shi, C. Lu, J. Alloys Compd., 2024, 1009, 176891.
[52]	F. Zhao, X. Yao, Y. Zhao, J. Yu, J. Dong, X. Liu, J. Cao, D. Zhang, X. Pu, J. Colloid Interface Sci., 2024, 675, 471-480.
[53]	Y. Shao, X. Hao, W. Deng, Z. Jin, J. Colloid Interface Sci., 2025, 678, 885-901.
[54]	J. Huang, B. Chai, J. Xiao, X. Zhang, G. Fan, G. Song, Chem. Eng. J., 2024, 481, 148501.
[55]	J. Zhou, F. Pan, Q. Yao, Y. Zhu, H. Ma, J. Niu, J. Xie, Appl. Catal. B, 2022, 317, 121811.
[56]	G. Wu, X. Gao, P. Sun, Z. Mo, Q. Wang, H. Chen, H. Liao, P. Yan, X. She, H. Xu, Appl. Catal. B, 2025, 371, 125265.
[57]	B. Yang, F. Jin, Z. Jin, N. Tsubaki, Appl. Catal. B, 2025, 378, 125624.
[58]	X. Zhang, D. Kim, X. Guo, Y. Zhu, L. Y. S. Lee, Appl. Catal. B, 2021, 298, 120515.
[59]	Z. Shao, T. Zeng, Y. He, D. Zhang, X. Pu, Chem. Eng. J., 2019, 359, 485-495.
[60]	X. Yao, X. Jiang, D. Zhang, S. Lu, M. Wang, S. Pan, X. Pu, J. Liu, P. Cai, J. Colloid Interface Sci., 2023, 644, 95-106.
[61]	P. Su, S. Wang, D. Zhang, T. Liang, H. Zhao, N. Yang, D. Zhang, P. Cai, X. Pu, J. Colloid Interface Sci., 2025, 680, 529-540.
[62]	L. Cao, C. Wang, H. Wang, X. Xu, X. Tao, H. Tan, G. Zhu, Angew. Chem. Int. Ed., 2024, 63, e202402095.
[63]	Y. Shi, L. Li, Z. Xu, F. Guo, W. Shi, Chem. Eng. J., 2023, 459, 141549.
[64]	S. Zhang, G. Zhang, S. Wu, Z. Guan, Q. Li, J. Yang, J. Colloid Interface Sci., 2023, 650, 1974-1982.
[65]	S. Wang, D. Zhang, X. Pu, L. Zhang, D. Zhang, J. Jiang, Small, 2024, 20, 2311504.
[66]	P. Sun, X. Zheng, A. Chen, G. Zheng, Y. Wu, M. Long, Q. Zhang, Y. Chen, Adv. Sci., 2024, 11, 2309927.

Interfacial Cu‒S bond and localized surface plasmon resonance modulated Cu₃P@Cu/Mn_0.3Cd_0.7S S-scheme heterojunction for efficient photocatalytic hydrogen evolution

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