Tailoring ORR Activity in Fe‐N‐C Catalysts through Phosphorus Incorporation

Abstract Atomically dispersed iron and nitrogen co‐doped carbon materials (Fe−N−C) represent promising non‐precious metal catalysts for the oxygen reduction reaction (ORR), offering potential alternatives to noble metal‐based benchmarks. In our study, we investigated the influence of phosphorus doping on the catalytic activity of Fe−N−C. The experimental research demonstrate that the doping of phosphorus significantly enhances the ORR activity. Specifically, the resulting Fe‐NPC exhibits high metal loading and excellent ORR activity in 0.1 M KOH with an onset potential of 1.00 V and a half‐wave potential of 0.864 V. Density functional theory (DFT) simulations reveal that phosphorus improves the electrocatalytic activity by activating O2 molecules and reducing the energy barrier (the hydrogenation reaction *OH→H2O) of the rate‐determining step. Furthermore, Fe‐NPC exhibits promising application prospects as an air cathode in Zn‐air batteries, delivering a high maximum discharge power density of 180.3 mW cm −2 and outstanding discharge specific capacity (758.8 mAh g −1 Zn ) at a discharge current density of 10 mA cm −2 .