Weakening the Oxophilicity of PtGd Alloy via Nitrogen‐Induced 5d/4f‐2p Orbital Interaction for Efficient Fuel Cell Cathode Performance

Abstract Platinum‐rare earth (PtRE) alloys exhibit exceptional oxygen reduction reaction (ORR) activity via 5d‐4f orbital coupling, yet their overly strong binding to oxygen intermediates limits catalytic efficiency. Herein, this limitation is addressed by nitrogen doping into the PtGd alloy to reconstruct orbital interactions and systematically evaluate its impact on ORR performance. In situ hydrogen treatment reveals a linear correlation between N content and activity enhancement. Theoretical calculations demonstrate that N 2p‐Pt 5d/Gd 4f coupling downshifts the Pt d‐band center, effectively modulating the hybridization behavior between the Pt 5d z 2 orbital and the * OH 2p z orbital. By increasing the antibonding orbital occupancy, this interaction promotes the dissociation of * OH, which is the rate‐determining step for PtGd alloy. The optimized PtGdN/C catalyst achieves a mass activity (MA) of 0.85 A mg Pt −1 in acidic electrolytes, over twice that of the PtGd/C. In H 2 ‐O 2 fuel cells, it achieves a peak power density of 1.68 W cm −2 and a MA of 0.49 A mg Pt −1 , with only a 16.3% decay in MA after 30k cycles, far outperforming PtGd/C and the U.S. DOE 2025 targets. This work highlights heteroatom‐induced orbital reconstruction as an effective strategy to attenuate oxophilicity and enhance both activity and durability of PtRE catalysts.