Boosting CO2Electroreduction over a Cadmium Single‐Atom Catalyst by Tuning of the Axial Coordination Structure

Abstract Guided by first‐principles calculations, it was found that Cd single‐atom catalysts (SACs) have excellent performance in activating CO 2 , and the introduction of axial coordination structure to Cd SACs cannot only further decrease the free energy barrier of CO 2 reduction, but also suppress the hydrogen evolution reaction (HER). Based on the above discovery, we designed and synthesized a novel Cd SAC that comprises an optimized CdN 4 S 1 moiety incorporated in a carbon matrix. It was shown that the catalyst exhibited outstanding performance in CO 2 electroreduction to CO. The faradaic efficiency (FE) of CO could reach up to 99.7 % with a current density of 182.2 mA cm −2 in a H‐type electrolysis cell, and the turnover frequency (TOF) value could achieve 73000 h −1 , which was much higher than that reported to date. This work shows a successful example of how to design highly efficient catalysts guided by theoretical calculations.