Over the past decade, advances in the colloidal syntheses of octahedral-shaped Pt-Ni alloy nanocatalysts for use in fuel cell cathodes have raised our atomic-scale control of particle morphology and surface composition, which, in turn, helped raise their catalytic activity far above that of benchmark Pt catalysts. Future fuel cell deployment in heavy-duty vehicles caused the scientific priorities to shift from alloy particle activity to stability. Larger particles generally offer enhanced thermodynamic stability, yet synthetic approaches toward larger octahedral Pt-Ni alloy nanoparticles have remained elusive. In this study, we show how a simple manipulation of solvothermal synthesis reaction kinetics involving depressurization of the gas phase at different stages of the reaction allows tuning the size of the resulting octahedral nanocatalysts to previously unachieved scales. We then link the underlying mechanism of our approach to the classical "LaMer" model of nucleation and growth. We focus on large, annealed Mo-doped Pt-Ni octahedra and investigate their synthesis, post-synthesis treatments, and elemental distribution using advanced electron microscopy. We evaluate the electrocatalytic ORR performance and stability and succeed to obtain a deeper understanding of the enhanced stability of a new class of relatively large, active, and long-lived Mo-doped Pt-Ni octahedral catalysts for the cathode of PEMFCs.
Keywords: LaMer model; Mo dopant; durability; oxygen reduction; platinum−nickel alloy; synthesis.