Stable copper boron-imidazolate cage as Cu-riched enzyme for highly efficient electrocatalytic CO_(2)reduction to ethylene  

作　　者：Jun-Qiang Chen Qiao-Hong Li Qin-Long Hong Ping Shao Hai-Xia Zhang Jian Zhang 

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

出　　处：《Science China Chemistry》2025年第3期943-950,共8页中国科学(化学英文版)

基　　金：the support from the National Key Research and Development Program of China (2021YFA1501500);the National Natural Science Foundation of China (22275192,92161105);the STS Project of Fujian-CAS (2023T3054)。

摘　　要：Single-atom catalyst has garnered widespread attention to mimic mature enzymes due to its well-defined atomic structure and coordination environments.However,since the carbon-carbon(C-C)coupling reactions require synergistic catalysis of multiple sites,single-atom catalysts suffer from insufficient active sites and unclear reaction mechanisms.Controlling the reaction intermediates in a precisely targeted pocket through careful metal-organic cage design is therefore crucial.Here,we prepare a tetrahedral[Cu_(6)L_(4)]-type boron-imidazolate cage integrating highly active Cu sites and optimized cavity,which exhibits enzyme like specific catalytic performance in electrochemical CO_(2)reduction reaction(CO_(2)RR)to enhance the selectivity of C_(2)H_(4).Electrochemical analyses and computational calculations suggest that the single Cu site together with neighboring boron-imidazolate ligands provides suitably synergistic effects that enable the energetically favorable formation of an^(*)COCHO intermediate,a key step determining selectivity.As a result,the[Cu_(6)L_(4)]-type cage of BIC-145 achieves a Faradaic efficiency of 28%for C_(2)H_(4)maintaining an average current density of-3.54 m A cm^(-2)over a 5-hour electrolysis period.This work represents the first example for studying single-metal site catalysts with ultra-low coordination numbers through the rational design of metal-organic cages.

关 键 词：metal-organic cages CO_(2)reduction single-metal-site catalyst boron-imidazolate cages 

分 类 号：TQ426.97[化学工程] TQ221.211[环境科学与工程—环境工程] X701