Structural‐Electronic Synergistic Engineering Enhances Ni Single‐Atom Electrocatalysts for CO 2 Reduction at Industrial Current Densities

There are still significant challenges in designing highly efficient CO 2 reduction electrocatalysts under industrially relevant conditions. Herein, we propose a structural‐electronic synergistic engineering by anchoring unsaturately coordinated Ni‐N 3 active sites on hollow double‐shelled carbon nanoparticles (Ni SACs‐DS NP) through the solvent‐assisted ligand exchange and pyrolysis process. The Ni SACs‐DS NP catalyst exhibited an ultra‐high CO selectivity of over 91% across the current density range from −50 to −400 mA cm −2 in a gas‐diffusion flow cell, achieved a turnover frequency (TOF) of 35 247 h −1 at −400 mA cm −2 , and maintained stable operation for over 6 h at −150 mA cm −2 . Advanced electrochemical tests and theoretical calculations revealed the critical role of the structural‐electronic synergistic engineering. Specifically, the electron‐deficient Ni‐N 3 active sites synergized with the double‐shelled hollow support to promote CO 2 adsorption and activation, reduce the formation energy barrier of the key * COOH intermediate, and facilitate CO desorption. Concurrently, this synergy enhanced ion conduction, charge transfer, and mass transfer efficiency. This work offers an insightful perspective on developing high‐performance single‐atom catalysts by synergizing coordination environment with nanostructure, enabling efficient and stable CO 2 RR at industrially relevant current densities.