Spontaneous Metal‐Chelation Strategy for Highly Dense Ni Single‐Atom Catalysts with Asymmetric Coordination in CO₂ Electroreduction

Developing metal-nitrogen-doped carbon single-atom catalysts (M-NC SACs) with high loadings for the electrochemical CO₂ reduction reaction (eCO₂RR) remains challenging owing to the risk of metal aggregation. Herein, the study presents a facile strategy for synthesizing M-NC SACs using metal-chelating ligands, eliminating the need for additional processing steps. Specifically, using ethylenediaminetetraacetic acid as a strong metal-chelating ligand, the formation of Ni nanoparticles is effectively prevented and a high loading of ≈2.7 wt.% is achieved, leading to the development of high-loading Ni SACs. The resulting catalysts exhibit a high CO faradaic efficiency (FE_CO) of 96.6% and CO partial current density of -120.2 mA cm^-2 and retain a FE_CO over 90% in a broad potential range of -0.4 to -0.9 V versus the reversible hydrogen electrode. Furthermore, theoretical calculations indicate that the asymmetric Ni-N₃C₁ local coordination structure within the catalyst reveals an optimal balance between *COOH formation and *CO desorption, which enhances the activity for eCO₂RR to CO. This study offers an efficient strategy to suppress metal nanoparticle formation while simultaneously improving the metal loading in M-NC SACs.