Atomic Design of Copper Active Sites in Pristine Metal–Organic Coordination Compounds for Electrocatalytic Carbon Dioxide Reduction

Abstract Electrocatalytic carbon dioxide reduction reaction (CO 2 RR) has emerged as a promising and sustainable approach to cut carbon emissions by converting greenhouse gas CO 2 to value‐added chemicals and fuels. Metal–organic coordination compounds, especially the copper (Cu)‐based coordination compounds, which feature well‐defined crystalline structures and designable metal active sites, have attracted much research attention in electrocatalytic CO 2 RR. Herein, the recent advances of electrochemical CO 2 RR on pristine Cu‐based coordination compounds with different types of Cu active sites are reviewed. First, the general reaction pathways of electrocatalytic CO 2 RR on Cu‐based coordination compounds are briefly introduced. Then the highly efficient conversion of CO 2 on various kinds of Cu active sites (e.g., single‐Cu site, dimeric‐Cu site, multi‐Cu site, and heterometallic site) is systematically discussed, along with the corresponding catalytic reaction mechanisms. Finally, some existing challenges and potential opportunities for this research direction are provided to guide the rational design of metal–organic coordination compounds for their practical application in electrochemical CO 2 RR.