Enhancement of oxidation of dimethyl ether through application of zirconia matrix for immobilization of noble metal catalytic nanoparticles

Electrocatalytic activity of Pt and bimetallic PtRu nanoparticles (both Vulcan supported and unsupported) toward electrooxidation of dimethyl ether (DME), a potential small organic molecule fuel, in an acid medium (0.5 mol dm−3 H2SO4) has been significantly enhanced by dispersing them over a thin film of zirconia (ZrO2). The enhancement effects concern increases of the DME electrocatalytic current densities recorded under both cyclic voltammetric and chronoamperometric conditions. Similar effects have been observed for the oxidation of methanol. Regarding the dissimilar DME electrooxidation mechanisms at Pt and PtRu catalytic centers, the activating capabilities of zirconia seem to originate from the high population of reactive –OH groups favoring mobility of protons and the capability of inducing the oxidative removal of poisoning (CO-type) intermediates both at platinum and ruthenium catalytic sites. In the presence of the zirconia matrix, the onset potential for the oxidation of DME (particularly at PtRu) is shifted more than 50 mV toward less positive potentials. Mutual metal-support interactions are also postulated.