Particle swarm optimization of the stable structure of tetrahexahedral Pt-based bimetallic nanoparticles

• We explore the structural stability of Pt-based alloy NPs by a discrete PSO.
• Our study discovers the different structural characteristics for Pt-based NPs.
• Alloy composition and size have important effects on the surface segregation.
• Our work shows strong phase separation for Pt–Ag NPs while weak for Pt–Pd NPs.

Bimetallic nanoparticles, enclosed by high-index facets, have great catalytic activity and selectivity owing to the synergy effects of high-index facets and the electronic structures of alloy. In this paper, a discrete particle swarm optimization algorithm was employed to systematically investigate the structural stability and features of tetrahexahedral Pt-based bimetallic nanoparticles with high-index facets. Different Pt/Ag, Pt/Cu, Pt/Pd atom ratios and particle sizes were considered in this work. The simulation results reveal that these alloy nanoparticles exhibit considerably different structural characteristics. Pt–Ag nanoparticles tend to form Pt–Ag core–shell structure. Pt–Cu nanoparticles are preferred to take multi-shell structure with Cu on the outer surface while Pt–Pd nanoparticles present a mixing structure in the interior and Pd-dominated surface. Atomic distribution and bonding characteristics were applied to further characterize the structural features of Pt-based nanoparticles. This study provides an important insight into the structural stability and features of Pt-based nanoparticles with different alloys.