Dual donor-acceptor covalent organic frameworks for hydrogen peroxide photosynthesis

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.

In this study, benzotrithiophene-based covalent organic frameworks with spatially separated oxidative and reductive reaction centers are rationally designed for photocatalytic production of H₂O₂ from water and oxygen without sacrificial agents.