Colloidally prepared core@shell nanoparticles (NPs) were converted to monodisperse high entropy alloy (HEA) NPs by annealing, including quinary, senary, and septenary phases comprised of PdCuPtNi with Co, Ir, Rh, Fe, and/or Ru. Intraparticle heterogeneity, i.e., subdomains within individual NPs with different metal distributions, was observed for NPs containing Ir and Ru, with the phase stabilities of the HEAs studied by atomistic simulations. The quinary HEA NPs were found to be durable catalysts for the oxygen reduction reaction, with all but the PdCuPtNiIr NPs presenting better activities than commercial Pt. Density functional theory (DFT) calculations for PdCuPtNiCo and PdCuPtNiIr surfaces (the two extremes in performance) found agreement with experiment by weighting the adsorption energy contributions by the probabilities of each active site based on their DFT energies. This finding highlights how intraparticle heterogeneity, which we show is likely overlooked in many systems due to analytical limitations, can be leveraged toward efficient catalysis.

Galvanic replacement (GR) of bimetallic nanoparticles (NPs) provides a versatile route to interesting trimetallic nanostructures, with the reaction stoichiometry governing the overall architecture of the product NPs.

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