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.

构建包含氧化和还原反应中心的光催化活性和稳定的共价有机框架仍然是一个挑战。在这项研究中，合理设计了具有空间分离的氧化还原中心的基于苯并三噻吩的共价有机框架，用于在没有牺牲剂的情况下从水和氧气光催化生产过氧化氢。含三嗪的骨架对H ₂ O ₂光生具有高选择性，产率为2111 μM h ^-1（21.11 μmol h ^-1和1407 μmol g ^-1 h ^-1）和太阳能-化学转化效率0.296%。在周期性框架的双供体-受体结构中验证了键和连接体之间的同向电荷转移和巨大的能量差异。活性位点主要集中在亚胺键附近的电子受体片段上，其调节相邻碳原子的电子分布，以最佳地降低H ₂ O ₂形成过程中O ₂ * 和OOH * 中间体的吉布斯自由能。