Electrochemical Degradation of Nafion Ionomer to Functionalize Graphene as a Support for Core-Shell Palladium-Ruthenium Alloy @ Platinum Electrocatalysts

Abstract

A simple but effective electrochemical route to functionalize graphene is demonstrated. Cyclic voltammetric sweeps are performed in H2SO4 aqueous solution on electrodes containing carbon cloth, graphene, and Nafion ionomer. With supply of ambient oxygen, the formation of hydroxyl radicals from the oxygen reduction reaction during CV cycles initiates the decomposition of Nafion ionomer that engenders oxygenated functional groups on the graphene surface. Raman analysis suggests a minor change for the graphene structure. Exploring various amounts of Nafion ionomer, we determine the optimized conditions for graphene functionalization. Contact angle is used to evaluate the effect of Nafion ionomer decomposition. X-ray photoelectron spectroscopy is employed to study relevant functional groups. Afterwards, nanoparticles of Pd9Ru are synthesized and impregnated on those functionalized graphene (FGN) via a wet chemical reflux process. X-ray diffraction patterns of the as-synthesized samples suggest successful formation of alloy. Images from transmission electron microscope confirm the average size of 3-4 nm. As expected, the Pd9Ru alloy are much more dispersive in FGN rather than in the one without functionalization.