Multilayered nanoclusters of platinum and gold: insights on electrodeposition pathways, electrocatalysis, surface and bulk compositional properties

Abstract

Electrochemical, surface and bulk compositional properties of multilayered nanoclusters of Pt and Au, electrochemically deposited on glassy carbon under conditions involving sequential surface–limited redox–replacement reactions (performed at open–circuit) and voltammetric dealloying of templating adlayers of electrodeposited Cu, have been studied in the direction of electrocatalytic applications. Variations in open–circuit potentials during redox–replacement steps indicated thermodynamically–favored formation of Pt(s) and Au(s). Unique bimetallic interfacial active sites, Pt|Au or Au|Pt, were effectively generated as evidenced by their distinct surface electrochemistry and multicomponent X–ray photoelectron spectral features. The bulk and surface–to–near surface distribution of Pt and Au appeared to be influenced by the stoichiometry of the surface redox–replacement reactions and sequential dealloying processes through which the nanoclusters were synthesized. Interactions between metal centers, carbon and oxygen containing surface functional groups on the glassy carbon appeared to have played a significant role in the overall stabilization and catalytic activity of the nanoclusters. Profound effects were also found on interfacial charge–transfer and adsorptive properties involving carbon monoxide and its subsequent electrooxidation to CO2, as well as on the electrocatalytic activity involving formic acid oxidation reaction, where the Pt–rich (Pt|Au) exhibited the highest activity.