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

Electrocatalytic CO2 to multi‐carbon products is an attractive strategy to achieve a carbon‐neutral energy cycle. Single‐atom catalysts (SACs) that achieve the C2 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 CuN2O1 configuration is provided, which can reach a remarkable C2 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 CuN2O1 during the CO2RR 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 CO2‐to‐C2 pathway. Benefitting from the F, O‐codrived optimization of the local coordination environment, CuN2O1‐FC configuration not only maintains site stability during CO2RR but also exhibits excellent C─C coupling catalytic performance compared to CuN3‐C configuration.