Promoting CO2 Electroreduction Kinetics on Atomically Dispersed Monovalent ZnI Sites by Rationally Engineering Proton‐Feeding Centers

Abstract Electrocatalytic reduction of CO 2 (CO 2 RR) to value‐added chemicals is of great significance for CO 2 utilization, however the CO 2 RR process involving multi‐electron and proton transfer is greatly limited by poor selectivity and low yield. Herein, We have developed an atomically dispersed monovalent zinc catalyst anchored on nitrogenated carbon nanosheets (Zn/NC NSs). Benefiting from the unique coordination environment and atomic dispersion, the Zn/NC NSs exhibit a superior CO 2 RR performance, featuring a high current density up to 50 mA cm −2 with an outstanding CO Faradaic efficiency of ≈95 %. The center Zn I atom coordinated with three N atoms and one N atom that bridges over two adjacent graphitic edges (Zn‐N 3+1 ) is identified as the catalytically active site. Experimental results reveal that the twisted Zn‐N 3+1 structure accelerates CO 2 activation and protonation in the rate‐determining step of *CO 2 to *COOH, while theoretical calculations elucidate that atomically dispersed Zn‐N 3+1 moieties decrease the potential barriers for intermediate COOH* formation, promoting the proton‐coupled CO 2 RR kinetics and boosting the overall catalytic performance.