Carbon-Supported Gold and Silver Nanoparticles As Catalysts for Electroreduction of Oxygen in Alkaline Media
Authors: Kulesza Pawel J , Zoladek Sylwia , Dembinska Beata , Miecznikowski Krzysztof , Rutkowska Iwona Agnieszka 
Published: February 2020

The present study refers to a novel and unique approach of fabrication and deposition of gold nanoparticles on the surfaces of reduced graphene oxide and multi-walled carbon nanotubes. Among important issues is application of inorganic (rather than organic) capping ligand, heteropolymolybdate, to modify and stabilize (as well as probably also to link with the oxygen or hydroxyl groups on graphene surfaces) gold nanoparticles. During operation in alkaline medium or neutral media, polyoxometallates disappear but catalytically highly active gold remains and it exhibits excellent stability. The resulting material has occurred to show highly potent electrocatalytic properties toward electroreductions of carbon dioxide in neutral medium and oxygen in alkaline solution. What is even more important is that both carbon nanotubes and graphene have occurred to act effectively as carriers for gold nanostructures. Mutual activating interactions are feasible. The conclusions are reached on the basis of diagnostic electrochemical (e.g. rotating ring disk voltammetry), spectroscopic (FTIR) and microscopic (SEM, TEM) experiments. A series of comparative experiments with different carbon carriers and model catalytic materials (e.g. Vulcan-supported platinum) have also been performed. With respect to oxygen reduction, our diagnostic experiments at different concentrations of H2O2, support a view that the effect of the fast following chemical (H2O2-reductive-decomposition) reaction could be the dominating factor in explaining the observed positive potential shift observed during the oxygen reduction. The fact, that the optimum graphene-based catalytic system produced the oxygen reduction peak current comparable to that observed at the model platinum containing catalyst, would imply the efficient four-electron-type reduction mechanism.
Graphene and other distinct carbon nanostructures are explored as supports (carriers) for dispersed metallic silver nanocenters which exhibit electrocatalytic activity toward reduction of oxygen in alkaline media. To facilitate fabrication, immobilization and distribution of Ag(0) nanoparticles, various types of graphene (e.g. reduced graphene oxide, RGO, and CFx graphene with carbon black) have been modified with the silver analogue of polynuclear Prussian Blue, namely with ultra-thin silver(I) hexacyanoferrate(II,III) layers. Following the heat-treatment step at temperatures as high as 400-600oC, some thermal decomposition of the cyanometallate network occurs and, consequently, metallic silver sites are generated. Their formation and distribution are facilitated by the voltammetric potential cycling in KOH electrolyte. The most promising electrocatalytic results with respect to the reduction of oxygen (the highest currents and the most positive electroreduction potentials) have been obtained when graphene nanostructures are combined or intermixed with Vulcan XC-72R nanoparticles. What is even more important that, due to the presence of the polynuclear cyanoferrate modifier or linker, the amounts of the undesirable hydrogen peroxide intermediate are significantly decreased.