Boosting photocatalytic CO_(2)-to-CO conversion using a biomimetic dinuclear Co(Ⅱ)complex through an HCO_(3)^(-)-mediated pathway  

作　　者：Yuchen Wang Wenjie Shi Weixue Tao Jihong Zhang Di-Chang Zhong Tongbu Lu 

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,China

出　　处：《Science China Chemistry》2025年第3期974-979,共6页中国科学(化学英文版)

基　　金：supported by the National Key R&D Program of China (2022YFA1502902);the National Natural Science Foundation of China (22271218,22071182,22201209,and 21931007)。

摘　　要：Dinuclear metal synergistic catalysis(DMSC)has been evidenced to be effective in enhancing the catalytic activity for CO_(2)reduction.However,the reaction kinetics of CO_(2)reduction is still limited by the local CO_(2)concentration around the dinuclear catalytic centers.Inspired by the structure of carbonic anhydrase,we have designed and synthesized a dinuclear cobalt(Ⅱ)complex with an-OH group.This complex not only exhibits DMSC for CO_(2)reduction but also possesses excellent capture capacity for CO_(2)molecules.Consequently,the complex demonstrates high efficiency for the photocatalytic reduction of CO_(2)to CO,with turnover number reaching as high as 43,400 and a selectivity of 97%.Even in 10%CO_(2),the complex still shows stateof-the-art catalytic activity.The results of experiments and theoretical calculations reveal that besides the DMSC contributing to the enhanced catalytic activity,the-OH group in the dinuclear cobalt(Ⅱ)complex facilitates the capture of CO_(2)by the formation of HCO_(3)^(-)intermediates,thereby enhancing the affinity towards CO_(2)and boosting the catalytic activity for CO_(2)-to-CO conversion.

关 键 词：homogeneous catalyst dinuclear metal synergistic catalysis CO_(2)reduction photocatalysis enzyme mimics 

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