Dynamic Adaptation of Active Site Driven by Dual‐side Adsorption in Single‐Atomic Catalysts During CO2 Electroreduction

Abstract Single‐atom iron embedded in N‐doped carbon (Fe−N−C) is among the most representative single‐atomic catalysts (SACs) for electrochemical CO2 reduction reaction (CO2RR). Despite the simplicity of the active site, the CO2‐to‐CO mechanism on Fe−N−C remains controversial. Firstly, there is a long debate regarding the rate‐determining step (RDS) of the reactions. Secondly, recent computational and experimental studies are puzzled by the fact that the CO‐poisoned Fe centers still remain highly active at high potentials. Thirdly, there are ongoing challenges in elucidating the high selectivity of hydrogen evolution reaction (HER) over CO2RR at high potentials. In this work, we introduce a novel CO2RR mechanism on Fe−N−C, which was inspired by the dynamic of active sites in biological systems. By employing grand‐canonical density functional theory and kinetic Monte‐Carlo, we found that the RDS is not fixed but changes with the applied potential. We demonstrated that our proposed dual‐side mechanisms could clarify the reason behind the high catalytic activity of CO‐poisoned metal centers, as well as the high selectivity of HER over CO2RR at high potential. This study provides a fundamental explanation for long‐standing puzzles of an important catalyst and calls for the importance of considering the dynamic of active sites in reaction mechanisms.