Axial and Planar Electronic Modulation of Ni Single‐Atoms to Enhance the Ni─C Bonding Strength for Neutral CO ₂ Electroreduction

CO 2 electroreduction catalyzed by single‐atoms (SAs) offers sustainable solutions for carbon dioxide emission and carbon neutrality, but the precise structural modulation of the SA for enhanced catalytic performance remains a challenge. Herein, atomically dispersed Ni‐N 4 site on nitrogen‐doped carbon support is spontaneously modulated via axial Cl coordination and planar second‐shell P coordination (Ni‐N 4 Cl‐P 2 @NC). Experiments and theoretical calculations reveal that the axial and planar coordination enrich the charge density of Ni SAs and significantly strengthens the Ni─C bond when *COOH is formed on Ni SAs, thus promoting the further reduction of *COOH to CO. Ni‐N 4 Cl‐P 2 @NC exhibits a FE for CO (FE CO ) >99% across all reaction potentials with the highest partial current densities for CO of ‐504 mA cm −2 at −1.4 V versus reversible hydrogen electrode in neutral electrolyte. Meanwhile, Ni‐N 4 Cl‐P 2 @NC exhibits a FE CO >98% across all reaction potentials in acidic electrolyte.