The surface structures of cubo-octahedral Pt-Mo nanoparticles have been investigated using the Monte Carlo method and modified embedded atom method potentials that we developed for Pt-Mo alloys. The cubo-octahedral Pt-Mo nanoparticles are constructed with disordered fcc configurations, with sizes from 2.5 to 5.0 nm, and with Pt concentrations from 60 to 90 at. percent. The equilibrium Pt-Mo nanoparticle configurations were generated through Monte Carlo simulations allowing both atomic displacements and element exchanges at 600 K. We predict that the Pt atoms weakly segregate to the surfaces of such nanoparticles. The Pt concentrations in the surface are calculated to be 5 to 14 at. percent higher than the Pt concentrations of the nanoparticles. Moreover, the Pt atoms preferentially segregate to the facet sites of the surface, while the Pt and Mo atoms tend to alternate along the edges and vertices of these nanoparticles. We found that decreasing the size or increasing the Pt concentration leads to higher Pt concentrations but fewer Pt-Mo pairs in the Pt-Mo nanoparticle surfaces.

We have investigated the segregation of Pt atoms in the surfaces of Pt-Ni nanoparticles, using Modified Embedded Atom Model potentials and the Monte Carlo method. The nanoparticles are assumed to have disordered fcc configurations at two fixed overall concentrations (50 at. percent Pt and 75 at. percent Pt). We use four kinds of nanoparticle shapes [cube, tetrahedron, octahedron, and cubo-octahedron] terminated by {111} and {100} facets to examine the extent of the Pt segregation to the nanoparticle surfaces and determine the equilibrium structures of Pt-Ni nanoparticles at T=600 K. The model particles contain between 560 and 4631 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, consistent with experimental observations. We predict that at 600 K due to segregation the equilibrium Pt50Ni50 nanoparticles with fewer than 2000 atoms and Pt75Ni25 nanoparticles with fewer than 4000 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 2000 atoms would form a core-shell structure with a Pt-enriched surface and a Pt-deficient homogenous core.

We have developed interatomic potentials for Pt-Ni and Pt-Re alloys within the modified embedded atom method (MEAM). Furthermore, we applied these potentials to study the equilibrium structures of Pt75Ni25 and Pt75Re25 nanoparticles at T=600 K using the Monte Carlo method. In this work, the nanoparticles are assumed to have disordered fcc cubo-octahedral shapes (terminated by {111} and {100} facets) and contain from 586 to 4033 atoms (corresponding to a diameter from 2.5 to 5 nm). It was found that, due to surface segregation, (1) the Pt75Ni25 nanoparticles form a surface-sandwich structure: the Pt atoms are enriched in the outermost and third atomic shells, while the Ni atoms are enriched in the second atomic shell; (2) the equilibrium Pt75Re25 nanoparticles adopt a core-shell structure: a Pt-enriched shell surrounding a Pt-deficient core.

We have investigated the segregation of Pt atoms to the surfaces of Pt-Re nanoparticles using the Monte Carlo method and Modified Embedded Atom Method potentials that we have developed for Pt-Re alloys. The Pt75Re25 nanoparticles (containing from 586 to 4033 atoms) are assumed to have disordered fcc configurations and cubo-octahedral shapes (terminated by 111 and 100 facets), while the Pt50Re50 and Pt25Re75 nanoparticles (containing from 587 to 4061 atoms) are assumed to have disordered hcp configurations and truncated hexagonal bipyramidal shapes (terminated by 0001 and 101 bar 1 facets). We predict that due to the segregation process the equilibrium Pt-Re nanoparticles would achieve a core-shell structure, with a Pt-enriched shell surrounding a Pt-deficient core. For fcc cubo-octahedral Pt75Re25 nanoparticles, the shells consist of almost 100 at. percent of Pt atoms. Even in the shells of hcp truncated hexagonal bipyramidal Pt50Re50 nanoparticles, the concentrations of Pt atoms exceed 85 at. percent (35 at. percent higher than the overall concentration of Pt atoms in these nanoparticles). Most prominently, all Pt atoms will segregate to the surfaces in the hcp truncated hexagonal bipyramidal Pt25Re75 nanoparticles containing less than 1000 atoms. We also find that the Pt atoms segregate preferentially to the vertex sites, less to edge sites, and least to facet sites on the shell of Pt-Re nanoparticles.

This review addresses the issue of surface segregation in bimetallic alloy nanoparticles, which are relevant to heterogeneous catalysis, in particular for electro-catalysts of fuel cells. We describe and discuss a theoretical approach to predicting surface segregation in such nanoparticles by using the Modified Embedded Atom Method and Monte Carlo simulations. In this manner it is possible to systematically explore the behavior of such nanoparticles as a function of component metals, composition, and particle size, among other variables. We chose to compare Pt75Ni25, Pt75Re25, and Pt80Mo20 alloys as example systems for this discussion, due to the importance of Pt in catalytic processes and its high-cost. It is assumed that the equilibrium nanoparticles of these alloys have a cubo-octahedral shape, the face-centered cubic lattice, and sizes ranging from 2.5 nm to 5.0 nm. By investigating the segregation of Pt atoms to the surfaces of the nanoparticles, we draw the following conclusions from our simulations at T= 600 K. (1) Pt75Ni25 nanoparticles form a surface-sandwich structure in which the Pt atoms are strongly enriched in the outermost and third layers while the Ni atoms are enriched in the second layer. In particular, a nearly pure Pt outermost surface layer can be achieved in those nanoparticles. (2) Equilibrium Pt75Re25 nanoparticles adopt a core-shell structure: a nearly pure Pt shell surrounding a more uniform Pt-Re core. (3) In Pt80Mo20 nanoparticles, the facets are fully occupied by Pt atoms, the Mo atoms only appear at the edges and vertices, and the Pt and Mo atoms arrange themselves in an alternating sequence along the edges and vertices. Our simulations quantitatively agree with previous experimental and theoretical results for the extended surfaces of Pt-Ni, Pt-Re, and Pt-Mo alloys. We further discuss the reasons for the different types of surface segregation found in the different alloys, and some of their implications.