Catalytic properties of nanoparticles can be significantly enhanced by controlling nanoscale alloying and its structure. In this work, by using a facet-controlled Pt@Ni coreshell octahedron nanoparticle, we show that the nanoscale phase segregation can have directionality and be geometrically controlled to produce a Ni octahedron that is penetrated by Pt atoms along three orthogonal Cartesian axes and is coated by Pt atoms along its edges. This peculiar anisotropic diffusion of Pt core atoms along the Æ100æ vertex, and then toward theÆ110æedges, is explained viathe minimum strain energy for NiNi pair interactions. The selective removal of the Ni-rich phase by etching then results in structurally fortified Pt-rich skeletal PtNi alloy framework nanostructures. Electrochemical evaluation of this hollow nanoframe suggests that the oxygen reduction reaction (ORR) activity is greatly improved compared to conventional Pt catalysts.
http://pubs.acs.org/doi/abs/10.1021/nn5068539
