Enhanced electrocatalytic activity of Cu-modified, high-index single Pt NPs for formic acid oxidation.

A key goal of nanoparticle-based catalysis research is to correlate the structure of nanoparticles (NPs) to their catalytic function. The most common approach for achieving this goal is to synthesize ensembles of NPs, characterize the ensemble, and then evaluate its catalytic properties. This approach is effective, but it excludes the certainty of structural heterogeneity in the NP ensemble. One means of addressing this shortcoming is to carry out analyses on individual NPs. This approach makes it possible to establish direct correlations between structures of single NPs and, in the case reported here, their electrocatalytic properties. Accordingly, we report on enhanced electrocatalytic formic acid oxidation (FAO) activity using individual Cu-modified, high-indexed Pt NPs. The results show that the Cu-modified Pt NPs exhibit significantly higher currents for FAO than the Pt-only analogs. The increased activity is enabled by the Cu submonolayer on the highly stepped Pt surface, which enhances the direct FAO pathway but not the indirect pathway which proceeds surface-absorbed CO*.