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

Abstract Electrocatalytic nitrogen (N₂) reduction reaction (NRR) presents a sustainable alternative to the Haber–Bosch process for ammonia (NH₃) synthesis. Iron phthalocyanine (FePc) is demonstrated as a promising catalyst for the electrocatalytic NRR. However, FePc with planar symmetric Fe‐N₄ sites exhibits poor N₂ 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 N₂ adsorption and activation. The as‐obtained FePc‐O‐CP shows a superior NH₃ 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 N₂ adsorption and activation, thereby greatly promoting NH₃ 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.