Abstract
Our study presents the electrochemical characterization of PtxCo1-x and PtxCu1-x nanoparticle electrocatalysts after the voltammetric treatment in basic and acidic electrolytes at room temperature. The chemical composition and mean particle size of the Pt alloy nanoparticles were determined before and after the voltage cycling using TEM and EDS. The electrochemical experiments were conducted with the RDE technique. We show that the electrochemical conditioning is a critical step for the formation of highly active Pt alloy nanoparticle electrocatalysts for ORR. The voltage cycling in acid leads to the leaching of less noble metal to generate a reactive Pt enriched particle surface, while in basic stable metal hydroxide/oxide are primarily formed on the surface of the Pt alloy particles. In particular, in basic voltammetric pretreated PtM3 shows the lowest Pt mass based activity for ORR. In contrast, in acid dealloyed PtCu3 and PtCo3 exhibit 3 - 4 fold increase in jmass compared with Pt/HSAC.