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 CO2-to-CO reduction reaction (CO2RR), a method that uses density functional theory calculation is presented to evaluate their selectivity, activity, and structural stability. Twenty-three M—N4—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 CO2-to-CO conversion. Different key descriptors, including the maximum reaction energy, differences of the *H and *CO binding energy (ΔG*H−ΔG*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 CO2RR electrocatalysts.