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

Electrocatalytic reduction of CO2 (CO2RR) to value‐added chemicals is of great significance for CO2 utilization, however the CO2RR 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 CO2RR performance, featuring a high current density up to 50 mA cm−2 with an outstanding CO Faradaic efficiency of ≈95 %. The center ZnI atom coordinated with three N atoms and one N atom that bridges over two adjacent graphitic edges (Zn‐N3+1) is identified as the catalytically active site. Experimental results reveal that the twisted Zn‐N3+1 structure accelerates CO2 activation and protonation in the rate‐determining step of *CO2 to *COOH, while theoretical calculations elucidate that atomically dispersed Zn‐N3+1 moieties decrease the potential barriers for intermediate COOH* formation, promoting the proton‐coupled CO2RR kinetics and boosting the overall catalytic performance. An atomically dispersed twisted ZnI‐N3+1 structure was developed to accelerate a proton‐feeding process that reduces the energy barrier of, and thereby promotes, the kinetics of the CO2 reduction reaction.