Monte Carlo simulation of surface segregation phenomena in extended and nanoparticle surfaces of Pt–Pd alloys

Abstract

The surface segregation phenomena in the extended and nanoparticle surfaces of Pt–Pd alloys have been studied using the Monte Carlo (MC) simulation method and the modified embedded-atom method (MEAM) potentials developed for Pt–Pd alloys. The MEAM potentials were fitted to reproduce the experimental values of the lattice parameters, cohesive energies and surface energies of pure Pt and Pd metals, as well as the density functional theory calculation results of the lattice parameters and heat of formation of L12 Pt3Pd, L10 PtPd and L12 PtPd3 crystal. Using the MC method and the developed MEAM potentials, we calculated the Pt concentrations in the outermost three layers of the equilibrium (111), (100) and (110) extended surfaces as well as the outermost surfaces of the equilibrium cubo-octahedral nanoparticles of Pt–Pd alloys. Our simulation results showed that the Pd atoms would segregate into the outermost layers of the extended surfaces and the Pt concentration would increase monotonically from the extended surfaces into the bulk. The equilibrium Pt–Pd nanoparticles were found to have Pd-enriched shells and Pt-enriched cores. In the shell of the Pt–Pd nanoparticles, the Pd atoms were predicted to preferably segregate to the (100) facets rather than the (111) facets.