Rationalization of the sub-surface segregation in nanoalloys of weakly miscible metals

The origin of the stability of sub-surface precipitates in core-shell bimetallic nanoparticles is investigated from the perspective of atomic-size effects for systems where the core atoms have a size equal to, or lower than, the shell atoms. With the aim of providing more general assessments, a systematic study is proposed by considering three model systems combining weakly miscible metals: IrPd (negligible lattice mismatch, Δr/r_Pd = -1%), AuRh (moderate lattice mismatch, Δr/r_Au = -7%) and AuCo (large lattice mismatch, Δr/r_Au = -13%). The main driving forces for sub-surface segregation and the characteristic core morphologies are quantified from the combination of Monte Carlo and quenched molecular dynamics simulations. The preferential occupation of the sub-surface shell by an impurity of Ir or (Co or Rh) in a Pd or Au nanoparticle, respectively, in particular at the sub-vertex sites, is found to be a common feature in these dilute nanosystems. With the help of a model of the decomposition of the segregation enthalpies, it is shown that the dominant driving forces leading to the preferential sub-surface segregation at the vertex sites can be very different from one system to another: atomic size (AuCo, large lattice mismatch), coupled alloy-size-cohesion (AuRh, moderate lattice mismatch) or coupled alloy-cohesion (IrPd, negligible lattice mismatch) effects. As a consequence, in the core-shell nanoalloys, in the first stage of enrichment of an Au nanoparticle with Co or Rh core atoms, or a Pd nanoparticle with Ir core atoms, all the equilibrium structures consist of similar off-center solute clusters anchored at sub-vertex sites, and this is regardless of the lattice mismatch.