Fluorinated Covalent Organic Frameworks Coupled with Molecular Cobalt Cocatalysts for Efficient Photocatalytic CO_(2)Reduction  

作　　者：Zhiwei Fu Chang Shu Xiaoyan Wang Linjiang Chen Xue Wang Lunjie Liu Kewei Wang Rob Clowes Samantha Y.Chong Xiaofeng Wu Andrew I.Cooper 

机构地区：[1]Department of Chemistry and Materials Innovation Factory,University of Liverpool,Liverpool L73NY [2]Key Laboratory of Material Chemistry for Energy Conversion and Storage,Ministry of Education,Hubei Key Laboratory of Material Chemistry and Service Failure,School of Chemistry and Chemical Engineering,Huazhong University of Science and Technology,Wuhan,Hubei 430074 [3]School of Chemistry and School of Computer Science,University of Birmingham,Birmingham B152TT [4]Leverhulme Research Centre for Functional Materials Design,University of Liverpool,Liverpool L73NY [5]Department of Chemistry and Chemical Engineering,Shanxi Datong University,Datong 037009

出　　处：《CCS Chemistry》2023年第10期2290-2300,共11页中国化学会会刊（英文）

摘　　要：The combination of covalent organic framework(COF)photosensitizers with molecular cocatalysts is a promising avenue for photocatalytic carbon dioxide(CO_(2))reduction.Here,a series of isostructural COFs was synthesized using linkers of different lengths,with or without partial fluorination.These COFs were investigated for photocatalytic CO_(2)reduction under visible-light irradiation when combined with cobalt(II)bipyridine complexes as a cocatalyst.Fluorination was found to enhance both CO_(2)affinity and catalytic activity,and a partially fluorinated COF,FBP-COF,achieved the highest CO_(2)-to-CO conversion efficiency,showing a carbon monoxide(CO)generation rate of 2.08 mmol h−1 g−1 and a 90%CO selectivity.FBP-COF also showed good stability under sacrificial conditions,generating CO for 50 h with a turnover number of 91.5.This activity is much higher than a homogeneous system using ruthenium bipyridine complexes as the photosensitizer combined with the same cobalt bipyridine complexes.

关 键 词：carbon dioxide conversion PHOTOCATALYSIS covalent organic frameworks FLUORINATED solar energy conversion 

分 类 号：O621.251[理学—有机化学]