Oxidation of methanol at the network film of polyoxometallate-linked ruthenium-stabilized platinum nanoparticles

We explore here the ability of ruthenium hydroxo species to undergo spontaneous deposition on Pt nanoparticles and to form colloidal solutions of oxoruthenium-protected (-stabilized) nanoparticles of Pt. These particles can be spontaneously attracted to carbon substrates, and they form ultrathin self-assembled films. Fabrication of the multilayer network films on electrodes has been achieved by linking the positively charged oxoruthenium-covered Pt clusters with heteropolyanions of tungsten. By repeated alternate treatments in a solution of phosphododecatungstate (PW12O403-) and in a colloidal suspension of oxoruthenium-protected (-stabilized) Pt nanoparticles, the film thickness can be increased systematically (layer by layer) to form stable three-dimensional assemblies on carbon electrodes. It is apparent from cyclic voltammetric and chronoamperometric measurements (that were performed at 20 and 60 degreesC) that the resulting hybrid films show attractive properties towards the oxidation of methanol at fairly low potentials (0.25-0.4 V versus the saturated calomel electrode). With approximately the same loading of oxoruthenium-covered Pt nanoparticles and under analogous conditions, linking or derivatizing the nanoparticles with phosphotungstate leads to the system's higher electrocatalytic activity. It is possible that, in addition to ruthenium hydroxo species, PW12O403- exhibits an activating effect on dispersed Pt particles. An alternative explanation may involve the possibility of different morphologies of the catalytic films in the presence and absence of phosphotungstate anions.