Structural Evolution of Sub-10 nm Octahedral Platinum-Nickel Bimetallic Nanocrystals

Octahedral Pt alloy nanocrystals (NCs) have shown excellent activities as electrocatalysts toward oxygen reduction reaction (ORR). As the activity and stability of NCs are highly dependent on their structure and the elemental distribution, it is of great importance to understand the formation mechanism of octahedral NCs and to rationally synthesize shape-controlled alloy catalysts with optimized ORR activity and stability. However, the factors controlling the structural and compositional evolution during the synthesis have not been well understood yet. Here, we systematically investigated the structure and composition evolution pathways of Pt-Ni octahedra synthesized with the assistance of W(CO)₆ and revealed a unique core-shell structure consisting of a Pt core and a Pt-Ni alloy shell. Below 140 °C, sphere-like pure Pt NCs with the diameter of 3-4 nm first nucleated, followed by the isotropic growth of Pt-Ni alloy on the seeds at temperatures between 170 and 230 °C forming Pt@Pt-Ni core-shell octahedra with {111} facets. Owing to its unique structure, the Pt@Pt-Ni octahedra show an unparalleled stability during potential cycling, that is, no activity drop after 10 000 cycles between 0.6 and 1.0 V. This work proposes the Pt@Pt-Ni octahedra as a high profile electrocatalyst for ORR and reveals the structural and composition evolution pathways of Pt-based bimetallic NCs.