Stabilization of Au at edges of bimetallic PdAu nanocrystallites

Density functional calculations were performed to study the distribution of Au atoms in bimetallic PdAu nanoparticles. A series of Pd(79-n)Au(n) clusters of truncated octahedral shape with different content of Au ranging from n = 1 to 60 was used to model such bimetallic nanosystems. Segregation of Au to the particle surface is found to be thermodynamically favorable. The most stable sites for Au substitution are located at the edges of the PdAu nanoclusters. The stabilization at the edges is rationalized by their higher flexibility for surface relaxation which minimizes the strain induced by larger atomic radius of Au as compared to Pd. This stabilization of Au at the edges indicates the possibility to synthesize PdAu particles with Pd atoms located mainly on the facets, and edges "decorated" by Au atoms. Such nanocrystallites are expected to exhibit peculiar catalytic properties and, being thermodynamically stable, should be prone to retaining their initial shape under catalytic conditions.