Improving CO2‐to‐C2 Conversion of Atomic CuFONC Electrocatalysts through F, O‐Codrived Optimization of Local Coordination Environment

Abstract Electrocatalytic CO 2 to multi‐carbon products is an attractive strategy to achieve a carbon‐neutral energy cycle. Single‐atom catalysts (SACs) that achieve the C 2 selectivity always have low metal loading and inevitably undergo in situ reversible/irreversible metallic agglomerations under working conditions. Herein, a high‐density Cu SA anchored F, O, N co‐doped carbon composites (CuFONC) with a stable CuN 2 O 1 configuration is provided, which can reach a remarkable C 2 selectivity of ≈80.5% in Faradaic efficiency at −1.3 V versus RHE. In situ/ex situ experimental characterization and density functional theory (DFT) calculations verified that the excellent stability of CuN 2 O 1 during the CO 2 RR process can be attributed to F/O co‐derived regulation for CuFONC. Remarkably, as confirmed by DFT, it is atomic Cu sites and the adjacent bonded N motifs in CuFONC that act as the adsorption sites for CO * during the C─C coupling process. This work brings a prospective on designing novel but stable atomic Cu coordination for electrolytic CO 2 ‐to‐C 2 pathway.