Langmuir, Vol.26, No.1, 570-580, 2010
Electrodeposition of Multilayered Bimetallic Nanoclusters of Ruthenium and Platinum via Surface-Limited Redox-Replacement Reactions for Electrocatalytic Applications
An electrochemical synthesis of multilayered bimetallic Ru vertical bar Pt nanoclusters, supported on glassy carbon, is reported for the First time. The novel nanoclusters were synthesized via surface-limited redox-replacement reactions involving sacrificial Cu, deposited prior to the formation of each individual noble metal layer, in a sequential fashion. It has been shown that the Cu adlayers control the morphology and electrochemical properties of the resultant nanostructures. Sequentially deposited Ru vertical bar Pt nanoclusters exhibited superior electrocatalytic activity (when compared to equivalent monometallic Pt and ail alloy-type codeposited Pt-Ru nanostructures) with respect to methanol electrooxidation in an acidic medium. Moreover, it has been established that the electrochemical process taking place at the Ru vertical bar Pt nanoclusters followed the bifunctional mechanism. Electrokinetic studies of the oxygen reduction reaction (ORR) were also performed. Analysis of hydrodynamic linear sweep voltammetric experiments, performed at various now rates oil oxygen-saturated acidic medium, revealed that the Pt and Ru vertical bar Pt nanoclusters exhibited direct four- and two-electron ORR pathways, respectively. A specially designed electrochemical flow-cell was used for automated sequential electrodeposition of the multilayered nanoclusters of predefined composition and electrochemical and elcctrocatalytic investigations.