Synergy of spatially adjacent redox sites and spin polarization in ZnIn2S4 for boosted H2O2 photosynthesis

doi:10.1016/S1872-2067(26)65206-0

Abstract

Abstract:

Proton-coupled electron transfer (PCET) is essential for driving the two-electron oxygen reduction pathway toward H₂O₂ production. However, the coupled integration of the adjacent water oxidation reaction and oxygen reduction reaction sites to amplify PCET presents a considerable challenge in the photocatalytic H₂O₂production. Addressing this challenge requires overcoming the inevitable carrier recombination problem at spatially adjacent redox sites. In this work, we incorporated Co and sulfur vacancies into ZnIn₂S₄ as a photocatalyst, in which the incorporation of Co induced spin polarization, significantly inhibiting the recombination of charge carriers. While the sulfur vacancies created an unsaturated coordination environment at the metal sites to promote the adsorption of reactants, forming the spatially adjacent redox sites. Extended X-ray absorption fine structure results and density functional theory simulations revealed the formation of Co-Vs dual sites. In-situ Fourier transform infrared and Raman spectroscopy confirmed the promoted PCET. This resulted in a 3.6-fold increase (215.4 μmol g^-1 h^-1) in H₂O₂ yield compared to pure ZIS (59.6 μmol g^-1 h^-1). This work exhibited a strategy for constructing spatially synergistic sites and manipulating the electronic spin polarization, providing an effective approach to enhance photocatalytic H₂O₂ production.

Key words: Spin polarization, Proton-coupled electron transfer, Spatially adjacent redox sites, ZnIn₂S₄, Photocatalytic H₂O₂ production

Zhiqi Li, Chen Guan, Kaiqiang Xu, Wei Xia, Dilshod D. Nematov, Quanjun Xiang. Synergy of spatially adjacent redox sites and spin polarization in ZnIn₂S₄ for boosted H₂O₂ photosynthesis[J]. Chinese Journal of Catalysis, 2026, 91: 252-262.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65206-0

https://www.cjcatal.com/EN/Y2026/V91/I12/252

Figures/Tables 6

Fig. 1. (a) Schematic diagram of Co-ZIS-Vs synthesis. TEM (b), HRTEM (c), SAED (d), and elemental mappings (e) of Co-ZIS-Vs. (f) XRD spectra of samples. (g) SEM image of Co-ZIS-Vs.

Fig. 2. (a) XPS spectrum of Co 2p for Co-ZIS-Vs. XPS spectra of Zn 2p (b) and S 2p (c) for Co-ZIS-Vs and ZIS-Vs. (d) Co K-edge XANES spectra of Co-ZIS-Vs along with those of CoO, CoS, and Co-foil as reference standards. (e) Fourier transformed EXAFS spectra of Co-ZIS-Vs, CoO, CoS, and Co-foil. (f) EXAFS curve-fitting at Co K-edge of Co-ZIS-Vs in k space. (g) EXAFS curve-fitting at Co K-edge of Co-ZIS-Vs in R-space. (h) Wavelet transform contour plots of Co K-edge at R space

Fig. 3. (a) Photocatalytic H2O2 production rates of ZIS, ZIS-Vs, Co-ZIS, and Co-ZIS-Vs in O2-saturated pure water. (b) Photocatalytic H2O2 production rate of Cox-ZIS-Vs under visible light for 1 h, x indicates the molar amount of Co doping in the synthesis of Co-ZIS-Vs samples (0.01, 0.05, 0.1, 0.15, and 0.2 mmol). (c) Photocatalytic H2O2 production over Co-ZIS-Vs in air, N2 and N2+NaIO3. (d) Recycling test of Co-ZIS-Vs for photocatalytic H2O2 production. Reaction condition: 20 mg of catalyst, 30 mL of H2O, 2 h. (e) Photocatalytic AQY of Co-ZIS-Vs. (f) Band structures of Co-ZIS-Vs and ZIS.

Fig. 4. Calculated total DOS of Co-ZIS-Vs (a) and ZIS (b). (c) The spin-resolved PDOS of Co-ZIS-Vs. (d) The EPR spectroscopy of Co-ZIS-Vs, ZIS-Vs, and ZIS. TRPL decay spectra (e) and the steady-state PL (f) for Co-ZIS-Vs and ZIS. (g) Schematic illustration of the mechanism for spin polarization inhibiting photogenerated carrier recombination.

Fig. 5. In-situ Zn 2p (a), S 2p (b), and Co 2p (c) XPS spectra of Co-ZIS-Vs. In-situ FTIR spectra for photocatalytic H2O2 production of Co-ZIS-Vs (d) and ZIS (e). (f) Formation energy of the key *OOH intermediate on Co-ZIS-Vs and ZIS. (g) In-situ Raman spectra for photocatalytic H2O2 production of Co-ZIS-Vs.

Fig. 6. (a) Differential charge density and Bader charge transfer between different structures and O2 (yellow and cyan iso-surfaces represent regions of electron accumulation and depletion, respectively). (b) The bond length of O2 molecule on ZIS and Co-ZIS-Vs. (c) PDOS for Co-3d and O-2p on Co-ZIS-Vs. (d) The Gibbs free energy (ΔG) diagram for H2O2 production on ZIS and Co-ZIS-Vs. (e) The COHP of ZIS and Co-ZIS-Vs. (f) Photocatalytic H2O2 production mechanism diagram of Co-ZIS-Vs.

References

[1]	X. Zhang, Y. Wan, Y. Wen, Y. Zhu, H. Liu, J. Qiu, Z. Zhu, Z. Sun, X. Gao, S. Bai, Y. Zhang, L. Zhang, X. Yan, J. Zhang, Y. Liu, S. Li, L.-D. Zhao, Nat. Catal., 2025, 8, 465-475.
[2]	W. Zhong, A. Meng, Y. Su, H. Yu, P. Han, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202425038.
[3]	X. Ruan, M. Xu, C. Ding, J. Leng, G. Fang, D. Meng, W. Zhang, Z. Jiang, S. K. Ravi, X. Cui, J. Yu, Adv. Energy Mater., 2025, 15, 2405478.
[4]	Y. Zhang, C. Pan, G. Bian, J. Xu, Y. Dong, Y. Zhang, Y. Lou, W. Liu, Y. Zhu, Nat. Energy, 2023, 8, 361-371.
[5]	L. Zhang, J. Zhang, J. Yu, Chem, 2026, 12, 102719.
[6]	Y. Bian, Z. Wang, M. Du, K. Dai, J. Yu, L. Zhang, Adv. Funct. Mater., 2026, 36, e19493.
[7]	X. Ruan, C. Ding, J. Leng, D. Jiao, X. Zhang, M. Xu, D. Meng, X. Cui, Z. Zheng, Y. Zhu, S. K. Ravi, Adv. Mater., 2025, 37, e11422.
[8]	Y. Ma, S. Wang, Y. Zhang, B. Cheng, L. Zhang, J. Materiomics, 2025, 11, 100978.
[9]	M. Sayed, H. Li, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100117.
[10]	W. Zhang, G. Liu, Chin. J. Catal., 2024, 66, 76-109.
[11]	H. Peng, H. Yang, J. Han, X. Liu, D. Su, T. Yang, S. Liu, C.-W. Pao, Z. Hu, Q. Zhang, Y. Xu, H. Geng, X. Huang, J. Am. Chem. Soc., 2023, 145, 27757-27766.
[12]	X. Li, Z. Wang, Acta Phys.-Chim. Sin., 2025, 41, 100080.
[13]	Z. Li, Z. Yu, C. Guan, K. Xu, Q. Xiang, J. Materiomics, 2025, 11, 100982.
[14]	C. Wu, F. Chu, Y. Hao, X. Li, X. Jia, Y. Sun, J. Gu, P. Jia, A. Wang, J. Jiang, Chin. J. Catal., 2025, 74, 329-340.
[15]	B. Liu, J. Zhang, H. Li, B. Cheng, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100121.
[16]	Y. Zhang, J. Qiu, B. Zhu, G. Sun, B. Cheng, L. Wang, Chin. J. Catal., 2024, 57, 143-153.
[17]	Y. Teng, X.-M. Zhang, R.-L. Zhu, S. Chen, M.-Y. Xie, K. Wu, Q.-P. Tian, X.-Y. Wang, Z. Wu, J.-L. Ma, L. Sun, D.-B. Kuang, Angew. Chem. Int. Ed., 2025, 64, e202516296.
[18]	Z. Jiang, J. Zhang, B. Cheng, Y. Zhang, J. Yu, L. Zhang, Small, 2025, 21, 2409079.
[19]	J. Zhou, Y. Mu, M. Qiao, M. Zhang, S. Yuan, M. Zhang, T. Lu, Angew. Chem. Int. Ed., 2025, 64, e202506963.
[20]	Y. Yang, X. Zhou, M. Gu, B. Cheng, Z. Wu, J. Zhang, Acta Phys.-Chim. Sin., 2025, 41, 100064.
[21]	X. Zhang, D. Gao, B. Zhu, B. Cheng, J. Yu, H. Yu, Nat. Commun., 2024, 15, 3212.
[22]	C. Jiang, C. Yuan, K. Xu, X. Zhou, C. Bie, J. Mater. Sci. Technol., 2025, 231, 36-44.
[23]	M. Li, X. Li, J. B. Ghasemi, Chin. J. Catal., 2025, 73, 12-15.
[24]	Z. Yu, D. Zhang, C. Ai, J. Zhang, Q. Xiang, Chin. J. Catal., 2024, 67, 71-81.
[25]	L. Li, Q. Bu, T. Lang, R. Zhang, Y. Pang, Y. Zhang, Y. Lin, D. Wang, T. Xie, D. Wang, Angew. Chem. Int. Ed., 2025, 64, e202501357.
[26]	D. Chu, C. Xing, D. Sun, S. Li, L. Ling, Adv. Funct. Mater., 2026, 36, e16500.
[27]	R. Zhang, H. Xu, Z. Huang, J. Zhang, L. Liu, Z. Ma, Z. Zhang, K. Wang, P. Liu, H. Liu, X. Zheng, Adv. Funct. Mater., 2025, 35, 2420504.
[28]	M. Li, S. Wu, D. Liu, Z. Ye, L. Wang, M. Kan, Z. Ye, M. Khan, J. Zhang, J. Am. Chem. Soc., 2024, 146, 15538-15548.
[29]	F. Xu, L. Zheng, J. Zhang, Y. He, H. Cao, X. Zheng, H. García, J. Yu, Nat. Catal., 2026, 9, 73-86.
[30]	H. Du, Y. Fu, R. Shi, Z. Cao, S. Zhang, K. Liu, J. Wang, B. Jiang, H. Li, Angew. Chem. Int. Ed., 2026, 65, e20354.
[31]	C. Cheng, J. Yu, D. Xu, L. Wang, G. Liang, L. Zhang, M. Jaroniec, Nat. Commun., 2024, 15, 1313.
[32]	M. Li, S. Wu, D. Liu, Z. Ye, C. He, J. Wang, X. Gu, Z. Zhang, H. Li, J. Zhang, ACS Catal., 2024, 14, 14098-14109.
[33]	Y. Li, X. Ma, J. Bai, F. Si, W. Zhang, T. Hou, Y. Li, Angew. Chem. Int. Ed., 2025, 64, e202512876.
[34]	K. Sun, Y. Huang, Q. Wang, W. Zhao, X. Zheng, J. Jiang, H.-L. Jiang, J. Am. Chem. Soc., 2024, 146, 3241-3249.
[35]	K. Meng, J. Zhang, B. Zhu, C. Jiang, H. García, J. Yu, Adv. Mater., 2025, 37, 2505088.
[36]	Z. Jiang, K. Tong, Z. Li, H. Tao, M. Zhu, Angew. Chem. Int. Ed., 2025, 64, e202500791.
[37]	H. Chi, Y. Leng, C. Ding, T. Li, Y. Zhang, J. Yuan, W. Tu, W. Gao, Y. Yao, X. Zhu, Y. Zhou, Z. Zou, Angew. Chem. Int. Ed., 2025, 64, e202425630.
[38]	Z. Liu, W. Gao, L. Liu, Y. Gao, C. Zhang, L. Chen, F. Lv, J. Xi, T. Du, L. Luo, J. Zhuo, W. Zhang, Y. Ji, Y. Shen, W. Liu, J. Wang, M. Luo, S. Guo, Nat. Commun., 2025, 16, 197.
[39]	C.-C. Lin, T.-R. Liu, S.-R. Lin, K. M. Boopathi, C.-H. Chiang, W.-Y. Tzeng, W. C. Chien, H.-S. Hsu, C.-W. Luo, H.-Y. Tsai, H.-A. Chen, P.-C. Kuo, J. Shiue, J.-W. Chiou, W.-F. Pong, C.-C. Chen, C.-W. Chen, J. Am. Chem. Soc., 2022, 144, 15718-15726.
[40]	Y. Su, Z. Wei, Y. Lian, Q. Mu, W. Pan, D. Song, Y. Qin, W. Hua, J. Cheng, Z. Deng, Y. Peng, Appl. Catal. B, 2023, 334, 122827.
[41]	J. Zhang, X. Tian, M. Liu, H. Guo, J. Zhou, Q. Fang, Z. Liu, Q. Wu, J. Lou, J. Am. Chem. Soc., 2019, 141, 19269-19275.
[42]	X. Tan, S. Si, D. Xiao, X. Bao, K. Song, Z. Wang, Y. Liu, Z. Zheng, P. Wang, Y. Dai, B. Huang, H. Cheng, ACS Catal., 2023, 13, 14395-14403.
[43]	B. Shao, T. Liu, D. Li, L. Meng, J. Wang, W. Zhai, L. Li, Adv. Mater., 2025, 37, 2504135.
[44]	Z. Qi, J. Chen, Q. Li, N. Wang, S. A. C. Carabineiro, K. Lv, Small, 2023, 19, 2303318.
[45]	X. Wang, X. Wang, J. Huang, S. Li, A. Meng, Z. Li, Nat. Commun., 2021, 12, 4112.
[46]	Q. Xu, J. Han, F. Tian, X. Zhao, J. Rong, J. Zhang, P. She, J.-S. Qin, H. Rao, J. Am. Chem. Soc., 2025, 147, 10587-10597.
[47]	G. Tang, J. Zhang, C. Bie, X. Zheng, C. Jiang, J. Yu, Adv. Mater., 2025, 37, e14576.
[48]	Y. Liu, Y. Liu, Z. Yao, Z. Yu, H. Zhu, C. Xing, Y. Wang, X. Tan, Y. Huang, Y. Hou, S. Wang, Appl. Catal. B, 2025, 371, 125275.
[49]	C. Li, Z. Sun, J. Song, B. Tang, P. Ma, R. Zhang, L. Lu, K. Zheng, Angew. Chem. Int. Ed., 2025, 64, e202514661.
[50]	X. Zhou, S. Yang, X. Wang, Z. Wu, Y. Huo, J. Zhang, J. Mater. Sci. Technol., 2025, 234, 60-70.
[51]	W. Yu, Chin. J. Catal., 2025, 73, 8-11.
[52]	X. Zhou, C. Ai, X. Wang, Z. Wu, J. Zhang, J. Materiomics, 2025, 11, 100974.
[53]	C. Zhu, L. Lu, Q. Fang, S. Song, B. Chen, Y. Shen, Adv. Funct. Mater., 2023, 33, 2210905.
[54]	M. Guo, A. Talebian-Kiakalaieh, E. M. Hashem, B. Xia, J. Ran, S.-Z. Qiao, Adv. Funct. Mater., 2024, 34, 2406356.
[55]	C. Guan, X. Yue, Y. Liao, Q. Xiang, Angew. Chem. Int. Ed., 2025, 64, e202415538.
[56]	J. Li, Q. Pei, R. Wang, Y. Zhou, Z. Zhang, Q. Cao, D. Wang, W. Mi, Y. Du, ACS Nano, 2018, 12, 3351-3359.
[57]	M. Ai, L. Pan, C. Shi, Z.-F. Huang, X. Zhang, W. Mi, J.-J. Zou, Nat. Commun., 2023, 14, 4562.
[58]	L. Wang, B. Cheng, L. Zhang, J. Yu, Small, 2021, 17, 2103447.
[59]	Y. Wang, H. Zhao, P. Li, J. Zhang, X. Sun, R. Zhang, Y. Guo, Y. Dong, Y. Zhu, Chem. Eng. J., 2024, 491, 151825.
[60]	M. Xu, X. Ruan, J. Guo, C. Ding, D. Jiao, D. Meng, G. Fang, J. Leng, K. Ba, T. Xie, W. Zhang, S. K. Ravi, X. Cui, Nano Lett., 2025, 25, 13315-13325.
[61]	B. Liu, X. Zhou, H. Ma, X. Hu, R. Fang, W. Xu, F. Dong, ACS Catal., 2025, 15, 17715-17725.
[62]	Y. Wu, Q. Yuan, Y. Zhao, K. Sun, H. Sun, K. Wang, S. Hu, G. I. N. Waterhouse, J. Wu, Z. Wang, J. Jiang, M. Fan, J. Am. Chem. Soc., 2025, 147, 25295-25305.
[63]	J. Qiu, C. Cheng, H. García, G. Liang, B. Zhu, L. Zhang, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202515898.
[64]	F. Chen, G. Cao, Q. Liu, Y. Duan, W. Li, Z. Shen, Angew. Chem. Int. Ed., 2025, 64, e202518232.
[65]	X. Wang, K. Qi, K. Xu, Chin. J. Catal., 2025, 70, 1-4.
[66]	K. Zhang, L. Tian, J. Yang, F. Wu, L. Wang, H. Tang, Z. Liu, Angew. Chem. Int. Ed., 2024, 63, e202317816.
[67]	D. Jiao, C. Ding, M. Xu, X. Ruan, S. K. Ravi, X. Cui, Adv. Funct. Mater., 2025, 35, 2416753.
[68]	Y. Luo, B. Zhang, C. Liu, D. Xia, X. Ou, Y. Cai, Y. Zhou, J. Jiang, B. Han, Angew. Chem. Int. Ed., 2023, 62, e202305355.
[69]	L. Wang, J. Zhao, J. Mater. Sci. Technol., 2026, 241, 18-20.

Synergy of spatially adjacent redox sites and spin polarization in ZnIn₂S₄ for boosted H₂O₂ photosynthesis

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