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.