Alloying Pt with transition metals can significantly improve the catalytic properties for the oxygen reduction reaction (ORR). However, the application of Pt-transition metal alloys in fuel cells is largely limited by poor long-term durability because transition metals can easily leach. In this study, we developed a nonmetallic doping approach and prepared a P-doped Pt catalyst with excellent durability for the ORR. Carbon-supported core-shell nanoparticles with a P-doped Pt core and Pt shell (denoted as PtP_x@Pt/C) were synthesized via heat-treatment phosphorization of commercial Pt/C, followed by acid etching. Compositional analysis using electron energy loss spectroscopy and X-ray photoelectron spectroscopy clearly demonstrated that Pt was enriched in the near-surface region (approximately 1 nm) of the carbon-supported core-shell nanoparticles. Owning to P doping, the ORR specific activity and mass activity of the PtP_1.4@Pt/C catalyst were as high as 0.62 mA cm⁻² and 0.31 mA μg_Pt⁻¹, respectively, at 0.90 V, and they were enhanced by 2.8 and 2.1 times, respectively, in comparison with the Pt/C catalyst. More importantly, PtP_1.4@Pt/C exhibited superior stability with negligible mass activity loss (6% after 30000 potential cycles and 25% after 90000 potential cycles), while Pt/C lost 46% mass activity after 30000 potential cycles. The high ORR activity and durability were mainly attributed to the core-shell nanostructure, the electronic structure effect, and the resistance of Pt nanoparticles against aggregation, which originated from the enhanced ability of the PtP_1.4@Pt to anchor to the carbon support. This study provides a new approach for constructing nonmetal-doped Pt-based catalysts with excellent activity and durability for the ORR.

将 Pt 与过渡金属合金化可以显着提高氧还原反应 (ORR) 的催化性能。然而，Pt-过渡金属合金在燃料电池中的应用在很大程度上受到长期耐久性差的限制，因为过渡金属很容易浸出。在这项研究中，我们开发了一种非金属掺杂方法，并制备了一种对 ORR 具有优异耐久性的 P 掺杂 Pt 催化剂。具有 P 掺杂 Pt 核和 Pt 壳的碳负载核壳纳米粒子（表示为 PtP _x@Pt/C) 是通过对商用 Pt/C 进行热处理磷化，然后进行酸蚀刻合成的。使用电子能量损失谱和 X 射线光电子能谱的成分分析清楚地表明，Pt 在碳负载的核壳纳米粒子的近表面区域（约 1 nm）中富集。由于P掺杂，PtP _1.4 @Pt/C催化剂的ORR比活性和质量活性在0.90 V时分别高达0.62 mA cm ^-2和0.31 mA μg _Pt ^-1，并提高了2.8与 Pt/C 催化剂相比，分别为 2.1 倍和 2.1 倍。更重要的是，PtP _1.4@Pt/C 表现出优异的稳定性，质量活性损失可忽略不计（30000 次潜在循环后为 6%，90000 次潜在循环后为 25%），而 Pt/C 在 30000 次潜在循环后失去了 46% 的质量活性。高 ORR 活性和耐久性主要归因于核壳纳米结构、电子结构效应和 Pt 纳米粒子对聚集的抵抗力，这源于 PtP _1.4 @Pt 锚定碳载体的能力增强。该研究为构建具有优异 ORR 活性和耐久性的非金属掺杂 Pt 基催化剂提供了一种新方法。