Carbon-supported Pd-Co as cathode catalyst for APEMFCs and validation by DFT

Carbon supported PdCo catalysts in varying atomic ratios of Pd to Co, namely 1 : 1, 2 : 1 and 3 : 1, were prepared. The oxygen reduction reaction (ORR) was studied on commercial carbon-supported Pd and carbon-supported PdCo nanocatalysts in aqueous 0.1 M KOH solution with and without methanol. The structure, dispersion, electrochemical characterization and surface area of PdCo/C were determined by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and Cyclic Voltammetry (CV), respectively. The electrochemical activity for ORR was evaluated from Linear Sweep Voltammograms (LSV) obtained using a rotating ring disk electrode. The catalysts were evaluated for their electrocatalytic activity towards oxygen reduction reaction (ORR) in Alkaline Polymer Electrolyte Membrane Fuel Cells (APEMFCs). PdCo(3 : 1)/C gives higher performance (85 mW cm(-2)) than PdCo(1 : 1)/C, PdCo(2 : 1)/C and Pd/C. The maximum electrocatalytic activity for ORR in the presence of methanol was observed for PdCo(3 : 1)/C. First principles calculations within the framework of density functional theory were performed to understand the origin of its catalytic activity based on the energy of adsorption of an O(2) molecule on the cluster, structural variation and charge transfer mechanism.