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.
Bibliographical noteKAUST Repository Item: Exported on 2023-09-01
Acknowledgements: The authors gratefully acknowledge the financial support provided by the National Natural Science Foundation of China (No. 22178091 (H.W.), 72088101 (X.C.), 51708195 (H.W.), 51739004 (X.Y.) and 52202367 (X.W.), the Provincial Natural Science Foundation of Hunan (No. 2023JJ10012 (H.W.)), the Science and Technology Innovation Program of Hunan Province (No. 2022RC1120 (H.W.)), the National Key Research and Development Program of China (No. 2021YFC1910400 (L.T.)), the Nature Science Foundation of Jiangsu Province (No. BK20200711 (X.W.)), the Key Laboratory of Advanced Functional Composites Technology (No. 6142906210508 (X.W.)), the Fundamental Research Funds for the Central Universities (No. 531118010675 (H.W.)), and the Ministry of Education Singapore under its Academic Research Funds (No. RG3/21, RG85/22, and MOET2EP10120-0003 (Y.Z.)).
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Physics and Astronomy(all)