Covalent-organic frameworks with keto-enol tautomerism for efficient photocatalytic oxidative coupling of amines to imines under visible light

作     者：Zhenyu Wu Xiubing Huang Xiangjun Li Guangtong Hai Baozhen Li Ge Wang Zhenyu Wu;Xiubing Huang;Xiangjun Li;Guangtong Hai;Baozhen Li;Ge Wang

作者机构：Beijing Advanced Innovation Center for Materials Genome EngineeringBeijing Key Laboratory of Function Materials for Molecule&Structure ConstructionSchool of Materials Science and EngineeringUniversity of Science and Technology BeijingBeijing100083China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2021年第64卷第12期

页      面：2169-2179页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 0702[理学-物理学] 

基　　金：supported by the National Natural Science Foundation of China (51802015, 51972024) the Fundamental Research Funds for the Central Universities (FRF-TP-20-005A3) the Interdisciplinary Research Project for Young Teachers of USTB (Fundamental Research Funds for the Central Universities) (FRF-IDRY-19-020) 

主　　题：covalent-organic frameworks photocatalysts aerobic/anaerobic benzylamine oxidation keto-enol tautomerism 

摘      要：Photocatalytic oxidation of organic molecules into highly value-added products is an innovative and challenging research which has gradually attracted remarkable attention of *** this work,it is demonstrated that the COF-TpPa with keto-enol tautomerism equilibrium structure shows excellent performance(yield99%after 8 h)in the selective photocatalytic oxidative coupling of amines to imines under visible light *** is revealed that three kinds of reactive oxygen species(superoxide radical,hydroxyl radical and singlet oxygen)participate in this photocatalytic oxidation *** addition,hydrogen protons cleaved from the benzyl are proven to be reduced to hydrogen in the conduction band of COF-TpPa in anaerobic atmosphere,accompanied with the formation of *** direct hydrogen evolution from amine provides an effective way to extract clean energy from organic molecule as well as the production of value-added *** a contrast,COF-LZU1 with similar structure and chemical composition to COF-TpPa but without keto-enol tautomerism exhibits worse optical properties and photocatalytic *** is also demonstrated that keto-enol tautomerism favors the adsorption of benzylamine based on the characterization results and theoretical calculations.