Enhancement of oxygen reduction at Co-porphyrin catalyst by supporting onto hybrid multi-layered film of polypyrrole and polyoxometalate-modified gold nanoparticles

Abstract

Three-dimensional multi-layered films (on glassy carbon) composed of networks of polyoxometallate (PMo12O403−)-modified gold nanoparticles linked together through the alternately deposited ultra-thin layers of polypyrrole have served as active supports for Co-porphyrin catalytic centers. The hybrid organic-inorganic films (supports) have been prepared by using the layer-by-layer approach. The fact that polyanionic (phosphomolybdate) adsorbates on gold nanoparticles are attracted by positively charged sites of conducting polymer (polypyrrole) structures leads to the stabilizing effect and facilitates distribution of Au nanostructures. The systems have been characterized using scanning electron microscopy, as well as with chronoamperometric and voltammetric techniques. By supporting Co-porphyrin centers onto the hybrid film of the polymer-linked phosphomolybdate-stabilized gold nanoparticles, significant electrocatalytic enhancement effects (namely voltammetric current increases) have been observed during the electroreduction of oxygen in acid medium relative to a standard response of the simple porphyrin deposit on glassy carbon measured under analogous conditions. Among important issues is the high activity of the hybrid film (support) itself toward the reductive decomposition of hydrogen peroxide to water. When it comes to performance of the Co-porphyrin-containing system, it is reasonable to expect that the O2 reduction process is initiated at Co-porphyrin catalytic sites (two-electron reduction to H2O2) and continued (two-electron reduction to H2O) at the hybrid film containing gold nanoparticles dispersed within the highly porous cauliflower-like structures of polypyrrole multi-layers. While the gold networks facilitate charge distribution within the hybrid electrocatalytic film, non-covalent π-π interactions of porphyrin rings with polypyrrole interlayers and charge transfers between negatively charged (PMo12O403− modified) gold nanoparticles and positively charged nitrogen sites of polypyrrole could also cause synergism.