On the behavior of CO oxidation on shape-controlled Pt nanoparticles in alkaline medium

• CO oxidation in alkaline medium at Pt nanoparticles is studied.
• Two peaks appear in the voltammogram depending on the nanoparticle’s shape.
• The peak at low potentials corresponds to (1 1 1) ordered domains.
• The remaining orientations contribute to the second peak.

In this work, the behavior of the CO electro-oxidation reaction on shape-controlled Pt nanoparticles in alkaline medium was examined in order to understand the effect of the surface structure on this reaction. A series of experiments using Pt nanoparticles of different surface structures/shapes was used and the results obtained were compared with the previous knowledge gained from stepped platinum single crystal electrodes. Independently of the preferential orientation of the nanoparticles, the CO oxidation voltammetry exhibits two main peaks: one at ca. 0.56–0.59 V and the second one at 0.66–0.67 V, being the intensity of the peaks dependent on the shape of the nanoparticle. These two peaks have been assigned to the oxidation of CO on the (1 1 1) terraces and on the rest of the sites, respectively. The appearance of two differentiated peaks reveals that these (1 1 1) terraces and the rest of the sites on the nanoparticle surface behave independently of the presence of the other type of sites, that is, they are not connected. The results are discussed considering the effects of the surface mobility of CO and of the OH adsorption properties on the different sites in the oxidation peaks.