Metalloporphyrin-based covalent organic frameworks composed of the electron donor-acceptor dyads for visible-light-driven selective CO2 reduction  

作　　者：Haowei Lv Rongjian Sa Pengyue Li Daqiang Yuan Xinchen Wang Ruihu Wang 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [2]Institute of Oceanography,Ocean College,Minjiang University,Fuzhou 350108,China [3]State Key Laboratory of Photocatalysis on Energy and Environment,Fuzhou University,Fuzhou 350108,China

出　　处：《Science China Chemistry》2020年第9期1289-1294,共6页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China(21673241,21975259);STS Program of Chinese Academy of Science(KF-STS-QYZX-068);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)。

摘　　要：The visible-light-driven photocatalytic CO2 reduction with high efficiency is highly desirable but challenging.Herein,we present porphyrin-tetraphenylethene-based covalent organic frameworks(MP-TPE-COF,where M=H2,Co and Ni;TPE=4,4′,4″,4?-(ethane-1,1,2,2-tetrayl)tetrabenzaldehyde;COF=covalent organic framework)as ideal platforms for understanding photocatalytic CO2 reduction at molecular level.Experimental and theoretical investigations have demonstrated crucial roles of metalloporphyrin units in selective adsorption,activation and conversion of CO2 as well as in the separation of charge carriers and electron transfer,thus allowing for flexible modulation of photocatalytic activity and selectivity.Co P-TPE-COF exhibits high CO evolution rate of 2,414μmol g-^1 h^-1 with the selectivity of 61%over H2 generation under visible-light irradiation,while Ni P-TPE-COF provides CO evolution rate of 525μmol g^-1 h^-1 and 93%selectivity with superior durability.Moreover,the photocatalytic system is feasible for the simulated flue gas,which provides CO evolution rate of 386μmol g-1 h-1 and selectivity of 77%.This work provides in-depth insight into the structure-activity relationships toward the activation and photoreduction of CO2.

关 键 词：covalent organic frameworks PHOTOCATALYSIS porous materials CO2reduction METALLOPORPHYRIN 

分 类 号：X701[环境科学与工程—环境工程] O643.36[理学—物理化学] O644.1[理学—化学]