Engineering Atomically Dispersed FeN4 Active Sites for CO2 Electroreduction

Abstract Atomically dispersed FeN 4 active sites have exhibited exceptional catalytic activity and selectivity for the electrochemical CO 2 reduction reaction (CO2RR) to CO. However, the understanding behind the intrinsic and morphological factors contributing to the catalytic properties of FeN 4 sites is still lacking. By using a Fe‐N‐C model catalyst derived from the ZIF‐8, we deconvoluted three key morphological and structural elements of FeN 4 sites, including particle sizes of catalysts, Fe content, and Fe−N bond structures. Their respective impacts on the CO2RR were comprehensively elucidated. Engineering the particle size and Fe doping is critical to control extrinsic morphological factors of FeN 4 sites for optimal porosity, electrochemically active surface areas, and the graphitization of the carbon support. In contrast, the intrinsic activity of FeN 4 sites was only tunable by varying thermal activation temperatures during the formation of FeN 4 sites, which impacted the length of the Fe−N bonds and the local strains. The structural evolution of Fe−N bonds was examined at the atomic level. First‐principles calculations further elucidated the origin of intrinsic activity improvement associated with the optimal local strain of the Fe−N bond.