Boosting Electrocatalytic Carbon Dioxide Reduction via Self‐Relaxation of Asymmetric Coordination in Fe‐Based Single Atom Catalyst

Abstract Addressing the limitations arising from the consistent catalytic behavior observed for various intermediates during the electrochemical carbon dioxide reduction reaction (CO 2 RR) poses a significant challenge in the optimization of catalytic activity. In this study, we aimed to address this challenge by constructing an asymmetric coordination Fe single atom catalyst (SCA) with a dynamically evolved structure. Our catalyst, consisting of a Fe atom coordinated with one S atom and three N atoms (Fe−S 1 N 3 ), exhibited exceptional selectivity (CO Faradaic efficiency of 99.02 %) and demonstrated a high intrinsic activity (TOF of 7804.34 h −1 ), and remarkable stability. Using operando XAFS spectra and Density Functional Theory (DFT) calculations, we elucidated the self‐relaxation of geometric distortion and dynamic evolution of bond lengths within the catalyst. These structure changes enabled independent regulation of the *COOH and *CO intermediate adsorption energies, effectively breaking the linear scale relationship and enhancing the intrinsic activity of CO 2 RR. This study provides valuable insights into the dynamic evolution of SACs and paves the way for targeted catalyst designs aimed to disrupt the linear scaling relationships.