Boosting Electrochemical Nitrogen Reduction via Axial Coordination Engineering on Single‐Iron‐Atom Catalysts

Abstract Electrocatalytic nitrogen (N 2 ) reduction reaction (NRR) presents a sustainable alternative to the Haber–Bosch process for ammonia (NH 3 ) synthesis. Iron phthalocyanine (FePc) is demonstrated as a promising catalyst for the electrocatalytic NRR. However, FePc with planar symmetric Fe‐N 4 sites exhibits poor N 2 adsorption and activation capabilities, resulting in an unsatisfactory NRR performance. Herein, an axial oxygen coordination strategy is developed to optimize the local electron distribution on FePc for improving N 2 adsorption and activation. The as‐obtained FePc‐O‐CP shows a superior NH 3 yield rate (59.72 µg h −1 mg −1 cat. ) and a considerable Faradaic efficiency (13.76%) in 0.1 m HCl. Density functional theory (DFT) calculations verify that the axial oxygen ligand on FePc inhibits the adsorption of H + and enhances the N 2 adsorption and activation, thereby greatly promoting NH 3 generation. This work reveals the significance of regulating the local coordination environment of single‐atom catalysts for improving electrocatalytic NRR performance and provides a feasible strategy for the rational design of atomic‐scale active sites.