Oxidation of carbon monoxide and formic acid on bulk and nanosized Pt-Co alloys

Bulk Pt3Co and nanosized Pt3Co and PtCo alloys supported on high area carbon were investigated as the electrocatalysts for the COads and HCOOH oxidation. Pt3Co alloy with Co electrochemically leached from the surface (Pt skeleton) was employed to separate electronic from ensemble and bifunctional effects of Co. Cyclic voltammetry in 0.1 M HClO4 showed reduced amount of adsorbed hydrogen on Pt sites on Pt3Co alloy compared to pure Pt. However, no significant difference in hydrogen adsorption/desorption and Pt-oxide reduction features between Pt3Co with Pt skeleton structure and bulk Pt was observed. The oxidation of COads on Pt3Co alloy commenced earlier than on Pt, but this effect on Pt3Co with Pt skeleton structure was minor indicating that bifunctional mechanism is stronger than the electronic modification of Pt by Co. The HCOOH oxidation rate on Pt3Co alloy was about seven times higher than on bulk Pt when the reaction rates were compared at 0.4 V, i.e., in the middle of the potential range for the HCOOH oxidation. Like in the case of COads oxidation, Pt skeleton showed similar activity as bulk Pt indicating that the ensemble effect is responsible for the enhanced activity of Pt3Co alloy toward HCOOH oxidation. The comparison of COads and HCOOH oxidation on Pt3Co/C and PtCo/C with the same reaction on Pt/C were qualitatively the same as on bulk materials.