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Pressurized Gas-Driven Elemental Redistribution Enables Ultrastable PtNi Catalysts for Heavy-Duty Vehicles
Xueru Zhao1, Kate Chen2, Zixian Jiao3
1Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973, United States.
Abstract:
Gas-driven element redistribution, characterized by the preferential enrichment of one element at the surface relative to the bulk, is frequently observed in multicomponent alloys. Using L10-ordered PtNi as a model system, we reveal that gas pressure plays a critical role in governing adsorption-driven surface composition during annealing in reducing gases: low pressure favors Pt surface segregation, while high pressure facilitates Ni surface enrichment. In this study, we developed a high-pressure nitriding (HPN) strategy that modulates the surface structure and composition of PtNi catalysts. The resulting HPN-PtNi exhibits enhanced performance and durability in membrane electrode assemblies for heavy-duty fuel cell applications, maintaining a high current density of 1.19 A cm-2 at 0.7 V after 90,000 voltage cycles. Through a combination of experimental and theoretical analyses, we reveal that the HPN process forms additional stabilizing Ni-N bonds and induces elemental redistribution with Ni surface enrichment and a Ni-deficient Pt subsurface. These modifications alter the atomic coordination environment of the ordered PtNi phase. This work presents a generalizable strategy to design robust and high-performing Pt-based catalysts by controlling gas-pressure-driven elemental redistribution and dopant incorporation.
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