Network electrocatalytic films of conducting polymer-linked polyoxometallate-stabilized platinum nanoparticles

To fabricate electrocatalytic network films containing Pt nanoparticles, the ability of a Keggin-type polyoxometallate, phosphododecatungstate (PW12O403−), to form stable anionic monolayers on solid surfaces is explored. Three-dimensional assemblies on electrode (glassy carbon or platinum) surfaces are grown using the layer-by-layer method involving repeated alternate treatments in the solution of PW12O403− (or in the colloidal suspension of polyoxometallate-protected Pt-nanoparticles) and in the solution of monomer (e.g., anilinium) cations. In the resulting structured (organic–inorganic) films, the layers of negatively charged polyoxometallate, or polyoxometallate-protected (stabilized) Pt-nanoparticles, interact electrostatically with the ultra-thin layers of such a positively charged conducting polymer as polyaniline. Consequently, physicochemical properties of organic conducting polymers, and reactivities of inorganic polyoxometallate and/or noble metal particles can be combined. The modification of Pt nanoparticles by adsorbing monolayers of phosphododecatungstate tends to activate them towards efficient electrocatalytic reduction of oxygen in acid medium.