Sub-stoichiometric Covalent Organic Frameworks with Boosted Photocatalytic Production of Hydrogen Peroxide via Promoting Proton-coupled Electron Transfer Kinetics

doi:10.1007/s40242-025-5009-9

Chemical Research in Chinese Universities ›› 2025, Vol. 41 ›› Issue (3): 495-503.doi: 10.1007/s40242-025-5009-9

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Sub-stoichiometric Covalent Organic Frameworks with Boosted Photocatalytic Production of Hydrogen Peroxide via Promoting Proton-coupled Electron Transfer Kinetics

YAN Shengrong^1,2,3, ZHANG Bingyan¹, LIU Wenhao¹, DUAN Fang¹, LI Yujie¹, REN Yanyan¹, LU Shuanglong¹, DU Mingliang¹, CHEN Mingqing¹

1. Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, P. R. China;
2. School of Environmental and Biological Engineering, Nantong College of Science and Technology, Nantong 226007, P. R. China;
3. Jiangsu Engineering Research Center of Environmental Functional Materials and Pollution Control, Nantong 226007, P. R. China

Received:2025-01-12 Revised:2025-02-18 Online:2025-06-01 Published:2025-05-27
Contact: DUAN Fang,E-mail:duanfang@jiangnan.edu.cn;CHEN Mingqing,E-mail:mqchen@jiangnan.edu.cn E-mail:duanfang@jiangnan.edu.cn;mqchen@jiangnan.edu.cn
Supported by:
This work was supported by the National Key Research and Development Program of China (No. 2023YFF1105200), the National Natural Science Foundation of China (No. 52173201), the Postgraduate Research & Practice Innovation Program of Jiangsu Province, China (No. KYCX18_1808), and the High-end Training Program for Teachers' Professional Leaders in Higher Vocational Colleges of Jiangsu Province (China) in 2023 (No. 2023GRFX045).

Abstract

Abstract: Promoting the photocatalytic proton-coupled electron transfer (PCET) kinetics in the two-electron oxygen reduction reaction (2e^- ORR) is crucial for the photocatalytic hydrogen peroxide (H₂O₂) production. Herein, four kinds of covalent organic frameworks (COFs) were successfully prepared via a sub-stoichiometric strategy through a one-step solvothermal method. Among them, B_1.5T₁-COF with polar aldehyde groups displays a high photocatalytic H₂O₂ generation rate of 1081.8 μmol·g^-1·h^-1, which is 3 times higher than that of B₁T_1.5-COF and 2 times higher than that of B₁T₁-COF. Through the corresponding experiments and density functional theory (DFT) calculation, the photocatalytic mechanism is revealed that B_1.5T₁-COF with free aldehyde groups can raise the PCET kinetics for 2e^- ORR with the aid of a stable transfer channel for e^- and a favorable hydrogen donation for H⁺. This work might provide some insights for design and preparation of COFs with functional groups through a sub-stoichiometric strategy to modulate their photocatalytic activities.

Key words: Photocatalytic H₂O₂ production, Sub-stoichiometric, Covalent organic framework

YAN Shengrong, ZHANG Bingyan, LIU Wenhao, DUAN Fang, LI Yujie, REN Yanyan, LU Shuanglong, DU Mingliang, CHEN Mingqing. Sub-stoichiometric Covalent Organic Frameworks with Boosted Photocatalytic Production of Hydrogen Peroxide via Promoting Proton-coupled Electron Transfer Kinetics[J]. Chemical Research in Chinese Universities, 2025, 41(3): 495-503.

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Sub-stoichiometric Covalent Organic Frameworks with Boosted Photocatalytic Production of Hydrogen Peroxide via Promoting Proton-coupled Electron Transfer Kinetics

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