Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

Chencheng Qin; Xiaodong Wu; Lin Tang; Xiaohong Chen; Miao Li; Yi Mou; Bo Su; Sibo Wang; Chengyang Feng; Jiawei Liu; Xingzhong Yuan; Yanli Zhao; Hou Wang

doi:10.1038/s41467-023-40991-7

Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

Nat Commun. 2023 Aug 28;14(1):5238. doi: 10.1038/s41467-023-40991-7.

Authors

Chencheng Qin^#¹, Xiaodong Wu^#², Lin Tang^#¹, Xiaohong Chen³, Miao Li¹, Yi Mou¹, Bo Su⁴, Sibo Wang⁴, Chengyang Feng⁵, Jiawei Liu⁶, Xingzhong Yuan⁷, Yanli Zhao⁸, Hou Wang^{9

10}

Affiliations

¹ College of Environmental Science and Engineering and Key Laboratory of Environmental Biology and Pollution Control (Ministry of Education), Hunan University, Changsha, 410082, China.
² College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, China.
³ School of Frontier Crossover Studies, Hunan University of Technology and Business, Changsha, 410205, China.
⁴ State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fujian, 350002, China.
⁵ Catalysis Centre, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Saudi Arabia.
⁶ School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore, Singapore.
⁷ College of Environmental Science and Engineering and Key Laboratory of Environmental Biology and Pollution Control (Ministry of Education), Hunan University, Changsha, 410082, China. yxz@hnu.edu.cn.
⁸ School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore, Singapore. zhaoyanli@ntu.edu.cn.
⁹ College of Environmental Science and Engineering and Key Laboratory of Environmental Biology and Pollution Control (Ministry of Education), Hunan University, Changsha, 410082, China. wangh@hnu.edu.cn.
¹⁰ School of Chemistry, Chemical Engineering and Biotechnology, Nanyang Technological University, 21 Nanyang Link, 637371, Singapore, Singapore. wangh@hnu.edu.cn.

^# Contributed equally.

Abstract

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 H₂O₂ 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 O₂* and OOH* intermediates during the formation of H₂O₂.