Pt₃Ni nanoparticles have been obtained by shape-controlled synthesis and employed as oxygen reduction electrocatalysts for proton exchange membrane fuel cells (PEMFC). The effects of varying the synthesis parameters such as the types of the capping agent and the reducing agent, and the reaction time have been systematically studied. The as-prepared Pt₃Ni nanoparticles were subjected to a butylamine-based surface treatment in order to prepare carbon-supported electrocatalysts. The Pt₃Ni electrocatalysts show an area-specific activity of 0.76 mA/cm²(Pt) at 0.9 V in an alkaline electrolyte, which is 4.5 times that of a commercial Pt/C catalyst (0.17 mA/cm² (Pt)). The mass activity reached 0.30 A/mg(Pt) at 0.9 V, which is about twice that of the commercial Pt/C catalyst. Our results also show that the area-specific activities of these carbon-supported Pt₃Ni electrocatalysts depend strongly on the (111) surface fraction, which is consistent with the results of a study based on Pt₃Ni extended single-crystal surfaces.

Bimetallic PtAu heteronanostructures have been synthesized from Pt-on-Au nanoparticles, which were made from platinum acetylacetonate and gold nanoparticles. Using the Pt-on-Au nanoparticles as precursors, Pt-surface rich PtAu bimetallic heteronanostructures can be produced through controlled thermal treatments, as confirmed by field emission high-resolution transmission electron microscopy (HR-TEM) and elemental mapping using a high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM). Oxidation of formic acid was used as a model reaction to demonstrate the effects of varying composition and surface structure on the catalytic performance of PtAu bimetallic nanostructures. Cyclic voltammetry (CV) showed that these carbon-supported PtAu heteronanostructures were much more active than platinum in catalyzing the oxidation of formic acid, judging by the mass current density. The results showed that post-synthesis modification can be a very useful approach to the control of composition distributions in alloy nanostructures.