Harnessing Controlled Dealloying–Support Coupling for Ultrastable PtNi Catalysts in PEMFC Applications

Platinum-transition metal (PtM) alloys are among the most promising oxygen reduction reaction (ORR) catalysts, yet their practical deployment in proton-exchange membrane fuel cells (PEMFCs) is hindered by transition-metal dissolution, particle coarsening, and insufficient durability. Moreover, conventional alloying or intermetallic ordering strategies often aggravate these issues by inducing severe nanoparticle aggregation and instability. Here we report a controllable alloying-dealloying strategy to construct PtNi nanoparticles confined in an N-doped carbon framework (Pt₁Ni_1-x@Ni_x_NC). Ammonia-assisted dealloying produces a Pt-rich shell with an alloyed core, while the N-doped carbon anchors the released Ni atoms form Ni-N/C moieties, thereby suppressing agglomeration and strengthening metal-support interactions. This coordination-support coupling optimizes Pt 5d orbital occupation, weakens oxygen adsorption, and accelerates ORR kinetics. Consequently, Pt₁Ni_1-x@Ni_x_NC exhibits a half-wave potential of 0.932 V and an ultrahigh mass activity of 2.028 A mgPt^-1, which is 8.75-fold higher than commercial Pt/C and among the best values reported to date for PtNi-based catalysts. Remarkably, it shows only a 6 mV half-wave potential loss after 30,000 cycles, demonstrating exceptional durability. In PEMFCs, the fuel cell delivers 975 mW cm^-2 peak power density and retains 91.9% of initial performance, underscoring a generalizable approach for designing durable, high-performance low-PGM catalysts for next generation PEMFCs.