Effective Screening Route for Highly Active and Selective Metal−Nitrogen‐Doped Carbon Catalysts in CO2 Electrochemical Reduction

Abstract To identify high‐efficiency metal—nitrogen‐doped ( M —N—C) electrocatalysts for the electrochemical CO 2 ‐to‐CO reduction reaction (CO 2 RR), a method that uses density functional theory calculation is presented to evaluate their selectivity, activity, and structural stability. Twenty‐three M —N 4 —C catalysts are evaluated, and three of them ( M = Fe, Co, or Ni) are identified as promising candidates. They are synthesized and tested as proof‐of‐concept catalysts for CO 2 ‐to‐CO conversion. Different key descriptors, including the maximum reaction energy, differences of the *H and *CO binding energy (Δ G *H −Δ G *CO ), and *CO desorption energy ( ΔG *CO→CO( g ) ), are used to clarify the reaction mechanism. These computational descriptors effectively predict the experimental observations in the entire range of electrochemical potential. The findings provide a guideline for rational design of heterogeneous CO 2 RR electrocatalysts.