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

• Published in: Chemical research in Chinese universities Vol. 41; no. 3; pp. 495 - 503
• Main Authors: Yan, Shengrong, Zhang, Bingyan, Liu, Wenhao, Duan, Fang, Li, Yujie, Ren, Yanyan, Lu, Shuanglong, Du, Mingliang, Chen, Mingqing
• Format: Journal Article
• Language: English
• Published: Changchun Jilin University and The Editorial Department of Chemical Research in Chinese Universities 01.06.2025; Springer Nature B.V
• Subjects: Aldehydes; Analytical Chemistry; Chemical reduction; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Density functional theory; Electron transfer; Functional groups; Hydrogen peroxide; Hydrogen production; Inorganic Chemistry; Kinetics; Organic Chemistry; Oxygen reduction reactions; Physical Chemistry; Protons; Stoichiometry; Covalent organic framework; production; Photocatalytic H; Sub-stoichiometric; O
• ISSN: 1005-9040; 2210-3171
• DOI: 10.1007/s40242-025-5009-9

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 (H 2 O 2 ) 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 1.5 T 1 -COF with polar aldehyde groups displays a high photocatalytic H 2 O 2 generation rate of 1081.8 µmol·g −1 ·h −1 , which is 3 times higher than that of B 1 T 1.5 -COF and 2 times higher than that of B 1 T 1 -COF. Through the corresponding experiments and density functional theory (DFT) calculation, the photocatalytic mechanism is revealed that B 1.5 T 1 -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.