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
College of Environmental Science and Engineering and Key Laboratory of Environmental Biology and Pollution Control (Ministry of Education), Hunan University, Changsha, 410082, China.
College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, China.
Nat Commun. 2023 Aug 28;14(1):5238. 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 HO photogeneration, with a yield rate of 2111 μM h (21.11 μmol h and 1407 μmol g h) 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* and OOH* intermediates during the formation of HO.
构建同时包含氧化和还原反应中心的光催化活性且稳定的共价有机框架仍然是一项挑战。在本研究中，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，用于在无牺牲剂的情况下由水和氧气光催化生产过氧化氢。含三嗪的框架对光生羟基表现出高选择性，产率为2111 μM·h⁻¹（21.11 μmol·h⁻¹ g⁻¹和1407 μmol·g⁻¹·h⁻¹），太阳能到化学能的转换效率为0.296%。在周期性框架的双供体-受体结构中验证了同向电荷转移以及连接体和连接基之间的大能量差异。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，以在羟基形成过程中最优地降低O和OOH中间体的吉布斯自由能。
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