Influence of Nanocrystalline Palladium Morphology on Alkaline Oxygen Reduction Kinetics

Abstract

The structure sensitivity of the alkaline oxygen reduction reaction (ORR) on palladium is of great interest as cost considerations drive the need to find a replacement for platinum catalysts. The kinetics of alkaline ORR were investigated on nanocrystalline palladium (Pd) films with domain sizes between 14 and 30 nm that were synthesized by electrodeposition from aqueous electrolytes. Ten Pd films were prepared under varying electrodeposition parameters leading to each having a unique texture and morphology. The sensitivity of initial alkaline ORR kinetics to the Pd surface structure was evaluated by measuring the kinetic current density and number of electrons transferred for each film. We show through scanning electron microscopy (SEM), x-ray diffraction (XRD), atomic force microscopy (AFM), and voltammetry from rotating disc electrodes (RDEs) that the fastest alkaline ORR kinetics are found on Pd surfaces with high surface roughness, which themselves are composed of fine grains. Such a study is useful for developing membrane electrode assemblies (MEAs) based on directly electrodepositing catalyst onto a conductive diffusion layer.