Phosphorus‐Doping Drives the Formation of a Pt‐Skin@PtFe Alloy Catalyst With Modulated d‐Band Center for Oxygen Reduction

ABSTRACT Platinum (Pt)‐based catalysts are crucial for the commercialization of hydrogen/metal air batteries, but they suffer from Pt scarcity, high cost, and nanoparticle dissolution/agglomeration, mainly leading to performance degradation. We address this by synthesizing a PtFe alloy catalyst (PtFe–PA–NC) via a phytic acid (PA) assisted pyrolysis strategy, featuring Pt‐skin‐coated PtFe alloy nanoparticles on hierarchically porous N‐doped carbon (NC). PA treatment simultaneously enhances the support's surface area and pore structure for better mass transport, and incorporates P into the carbon framework via P–C bonds. It can induce charge delocalization, regulating the electronic structure of PtFe alloys and strengthening Pt–Fe coupling. The Pt‐skin suppresses Fe dissolution, whereas the PtFe core optimizes oxygen reduction reaction (ORR) intermediate adsorption (e.g., *OH). Theoretical calculations confirm that the Fe atom adjusts the d‐band center of the Pt atom, intensifying oxygen binding and shifting the rate‐determining step. Electrochemically, PtFe–PA–NC achieves a half‐wave potential of 0.85 V and retains 95.8% of specific energy density after more than 140 h in zinc‐air batteries. In alkaline fuel cells, it delivers a peak power density of 508 mW cm −2 at an ultralow Pt loading (0.017 mg cm −2 ), approximately twice that of 5 wt% Pt/C (0.025 mg cm −2 ). This work showcases synergistic electronic and interfacial regulation through heteroatom doping and alloying, promoting high‐performance hydrogen/metal air batteries.