Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

• Published in: Nature communications Vol. 14; no. 1; pp. 5238 - 12
• Main Authors: Qin, Chencheng, Wu, Xiaodong, Tang, Lin, Chen, Xiaohong, Li, Miao, Mou, Yi, Su, Bo, Wang, Sibo, Feng, Chengyang, Liu, Jiawei, Yuan, Xingzhong, Zhao, Yanli, Wang, Hou
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 28.08.2023; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/131; 140/146; 147/135; 147/143; 639/301/299/1013; 639/638/541/966; 639/638/77/890; Charge transfer; Covalence; Electron distribution; Free energy; Gibbs free energy; Humanities and Social Sciences; Hydrogen peroxide; Hydrogen production; Intermediates; multidisciplinary; Oxygen; Photocatalysis; Photosynthesis; Reaction centers; Science; Science (multidisciplinary); Triazine
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-023-40991-7

Constructing photocatalytically active and stable covalent organic frameworks containing both oxidative and reductive reaction centers remain a challenge. In this study, benzotrithiophene-based covalent organic frameworks with spatially separated redox centers are rationally designed for the photocatalytic production of hydrogen peroxide from water and oxygen without sacrificial agents. The triazine-containing framework demonstrates high selectivity for H 2 O 2 photogeneration, with a yield rate of 2111 μM h −1 (21.11 μmol h −1 and 1407 μmol g −1 h −1 ) and a solar-to-chemical conversion efficiency of 0.296%. Codirectional charge transfer and large energetic differences between linkages and linkers are verified in the double donor-acceptor structures of periodic frameworks. The active sites are mainly concentrated on the electron-acceptor fragments near the imine bond, which regulate the electron distribution of adjacent carbon atoms to optimally reduce the Gibbs free energy of O 2 * and OOH* intermediates during the formation of H 2 O 2 . In this study, benzotrithiophene-based covalent organic frameworks with spatially separated oxidative and reductive reaction centers are rationally designed for photocatalytic production of H 2 O 2 from water and oxygen without sacrificial agents.