Salt Effect Engineering Single Fe‐N₂P₂‐Cl Sites on Interlinked Porous Carbon Nanosheets for Superior Oxygen Reduction Reaction and Zn‐Air Batteries

Abstract Developing efficient metal‐nitrogen‐carbon (M‐N‐C) single‐atom catalysts for oxygen reduction reaction (ORR) is significant for the widespread implementation of Zn‐air batteries, while the synergic design of the matrix microstructure and coordination environment of metal centers remains challenges. Herein, a novel salt effect‐induced strategy is proposed to engineer N and P coordinated atomically dispersed Fe atoms with extra‐axial Cl on interlinked porous carbon nanosheets, achieving a superior single‐atom Fe catalyst (denoted as Fe‐NP‐Cl‐C) for ORR and Zn‐air batteries. The hierarchical porous nanosheet architecture can provide rapid mass/electron transfer channels and facilitate the exposure of active sites. Experiments and density functional theory (DFT) calculations reveal the distinctive Fe‐N₂P₂‐Cl active sites afford significantly reduced energy barriers and promoted reaction kinetics for ORR. Consequently, the Fe‐NP‐Cl‐C catalyst exhibits distinguished ORR performance with a half‐wave potential (E_1/2) of 0.92 V and excellent stability. Remarkably, the assembled Zn‐air battery based on Fe‐NP‐Cl‐C delivers an extremely high peak power density of 260 mW cm⁻² and a large specific capacity of 812 mA h g⁻¹, outperforming the commercial Pt/C and most reported congeneric catalysts. This study offers a new perspective on structural optimization and coordination engineering of single‐atom catalysts for efficient oxygen electrocatalysis and energy conversion devices.