Application of metal oxides as active matrices in electrocatalysis is particular importance. The hydrous behavior, which favors proton mobility and affects overall reactivity, reflects not only the oxide’s chemical properties but its texture and morphology as well. What is of importance to electrochemical science and technology, certain nonstoichiometric mixed-valence oxides could exhibit pseudo-metallic conductivity and possess appreciable catalytic activity.

Recently, mixed oxide systems stabilized through Zr-O-W bonds have been demonstrated to be very attractive acid catalysts exhibiting high catalytic activities and good stabilities in many demanding industrial reactions. For electrocatalytic applications, mixed-valent tungsten(VI,V) oxide and zirconium(IV) oxide have been sequentially deposited and integrated through voltammetric potential cycling to form sub-microstructured films on glassy carbon electrode. The mixed WO₃/ZrO₂ systems are characterized by fast charge (electron, proton) propagation during the system’s redox transitions. By dispersing metallic Pt or Cu electrocatalytic nanoparticles over such active WO₃/ZrO₂ supports, the electrocatalytic activities of the respective systems toward the reduction of oxygen or carbon dioxide have been enhanced even at decreased loadings in acid media. The enhancement effects should be attributed to features of the mixed metal oxide support such as porosity and high population of hydroxyl groups (due to presence of ZrO₂), high Broensted acidity of sites formed on mixed WO₃/ZrO₂, fast electron transfers coupled to unimpeded proton displacements (e.g. in H_xWO₃), as well as strong metal-support interactions between nanosized metals (Pt or Cu) and the metal (W, Zr) oxo species. The fact that WO₃/ZrO₂ nanostructures are in immediate contact with the metallic catalytic sites leads to the specific interactions (via the surface hydroxyl groups) with the reaction intermediates (H₂O₂ or CO adsorbates). Further mechanistic studies involving rotating ring disk voltammetry and gas-diffusion electrode measurements are planned in addition to spectroscopic and XPS measurements. The mixed-metal systems will also be considered together with nanostructured carbon carriers such as reduced graphene oxide, carbon nanotubes or carbon black.