Synergistic N,P Dual-Doping in ZIF-67-Derived Carbon Frameworks Enables Crystallinity-Optimized PtCo3 for Enhanced Oxygen Reduction Catalysis

Pt-based alloy catalysts are critical for enhancing the oxygen reduction reaction (ORR) in fuel cells due to their tunable electronic structures and high activity. However, achieving precise control over alloy crystallization and optimizing the chemical environment of catalyst supports remain significant challenges. Herein, a PtCo 3 /N,P-CoNC electrocatalyst was synthesized through pyrolysis of ZIF-67 precursors followed by Pt deposition. Synergistic N and P dual-doping adjusts the electronic configuration of the carbon matrix, promotes strong metal-support interactions (MSI), and increases accessible active sites. The catalyst delivers exceptional ORR activity with a half-wave potential (E 1/2 ) of 0.934   V and a high electrochemical surface area (ECSA) of 121.55 m 2 g Pt -1 . Accelerated durability test (ADT) reveals that PtCo 3 /N,P-CoNC exhibits only 16   mV decay in E 1/2 and 81.40% ECSA retention after 30k cycles. This enhanced stability stems from the strong nanoparticle anchoring effect induced by N, P co-doping, which effectively suppresses nanoparticle aggregation. Density functional theory (DFT) calculations reveal that N, P co-doping synergistically enhances catalytic activity and durability by inducing pronounced electron localization through non-planar P configurations to create an electron-deficient Co environment that strengthens MSI, while simultaneously optimizing the ORR pathway on PtCo 3 (111) surfaces to reduce the Gibbs free energy barrier for the rate-determining step. This work demonstrates a morphology and doping-engineered strategy to design durable, high-performance ORR catalysts, advancing cost-effective fuel cell systems.