Golden single-atomic-site platinum electrocatalysts

Bimetallic nanoparticles with tailored structures constitute a desirable model system for catalysts, as crucial factors such as geometric and electronic effects can be readily controlled by tailoring the structure and alloy bonding of the catalytic site. Here we report a facile colloidal method to prepare a series of platinum–gold (PtAu) nanoparticles with tailored surface structures and particle diameters on the order of 7 nm. Samples with low Pt content, particularly Pt 4 Au 96 , exhibited unprecedented electrocatalytic activity for the oxidation of formic acid. A high forward current density of 3.77 A mg Pt −1 was observed for Pt 4 Au 96 , a value two orders of magnitude greater than those observed for core–shell structured Pt 78 Au 22 and a commercial Pt nanocatalyst. Extensive structural characterization and theoretical density functional theory simulations of the best-performing catalysts revealed densely packed single-atom Pt surface sites surrounded by Au atoms, which suggests that their superior catalytic activity and selectivity could be attributed to the unique structural and alloy-bonding properties of these single-atomic-site catalysts

A theory of surface enrichment in ordered alloys

A simple theory was developed to explain exptl. data on surface enrichment in Pt3Sn. The computed surface enrichment is in accord with exptl. findings. The theory predicts that in the Pt3Sn system enrichment occurs by interchange of atoms of the element with the lower heat of sublimation from the layer just below the surface with atoms of the other element in the surface. Arguments are presented why an expt. performed on Au-Cu alloys should be capable of verifying an assumption basic to the theory