Monte Carlo simulations of segregation in Pt-Ni catalyst nanoparticles

We have investigated the segregation of Pt atoms in the surfaces of Pt-Ni nanoparticles, using modified embedded atom method potentials and the Monte Carlo method. The nanoparticles are constructed with disordered fcc configurations at two fixed overall concentrations (50 at. % Pt and 75 at. % Pt). We use octahedral and cubo-octahedral nanoparticles terminated by {111} and {100} facets to examine the extent of the Pt segregation to the nanoparticle surfaces at T=600 K. The model particles contain between 586 and 4033 atoms (particle size ranging from 2.5 to 5 nm). Our results imply that a complete {100}-facet reconstruction could make the cubo-octahendral Pt-Ni nanoparticles most energetically favorable. We predict that at 600 K due to segregation the equilibrium cubo-octahedral Pt50Ni50 nanoparticles with fewer than 1289 atoms and Pt75Ni25 nanoparticles with fewer than 4033 atoms would achieve a surface-sandwich structure, in which the Pt atoms are enriched in the outermost and third atomic shells while the Ni atoms are enriched in the second atomic shell. We also find that, due to an order-disorder transition, the Pt50Ni50 cubo-octahedral nanoparticles containing more than 2406 atoms would form a core-shell structure with a Pt-enriched surface and a Pt-deficient homogenous core.