Modulating the Binding of Metal Centers with Reaction Intermediates to Boost Photocatalytic CO_(2)Reduction  

作　　者：Ji-Hong Zhang Hong-Juan Wang Wen-Jie Shi Wei Yang Jian-Hua Mei Yu-Chen Wang Tong-Bu Lu Di-Chang Zhong 

机构地区：[1]Institute for New Energy Materials and Low Carbon Technologies,School of Materials Science and Engineering,Tianjin University of Technology,Tianjin 300384

出　　处：《CCS Chemistry》2024年第12期2961-2970,共10页中国化学会会刊(英文)

基　　金：the National Key R&D Program of China(grant no.2022YFA1502902);the National Natural Science Foundation of China(NSFC;grant nos.22271218 and 22071182);the Natural Science Foundation of Tianjin City,China(grant no.23JCQNJC00570);the Tianjin University of Technology Innovation Project for Postgraduate Students,China(grant no.YJ2233);the Tianjin Research Innovation Project for Postgraduate Students,China(grant no.2022BKY155).

摘　　要：It is a consensus that the process involving photocatalytic CO_(2)reduction to CO undergoes a*COOH/*CO pathway,in which the binding of the catalytic centers with the*COOH/*CO reaction intermediates greatly influences the catalytic activity.The modulation of the binding of catalytic centers to*COOH and*CO,is thus,significant in developing efficient catalysts.Herein,we found that regulation of the coordination numbers could modulate the binding of catalytic centers to the reaction intermediates to obtain metal complexes with high efficiency in the photocatalytic CO_(2)reduction to CO.Specifically,three mononuclear Co(II)complexes CoNx(x=3-5)with different N coordination numbers were designed and synthesized for photocatalytic CO_(2)reduction.We found that CoN4 exhibited the best photocatalytic activity,with a turnover number(TON)value as high as 20,832 and a selectivity of 97.4%to CO,much higher than CoN3 and CoN5.Moreover,CoN4 was active in the photocatalytic reduction of CO_(2)in low CO_(2)concentrations such as human-exhaled gas.Further experimental and density functional theory calculations revealed that the remarkable performance of CoN4 for photocatalytic CO_(2)reduction could be attributed to a moderate binding of Co(Ⅱ)with*COOH and*CO intermediates in the process of CO_(2)-to-CO conversion.

关 键 词：homogeneous catalysis CO_(2)reduction PHOTOCATALYSIS moderate binding coordination environment 

分 类 号：O64[理学—物理化学]