Electrocatalysis on Shape-Controlled Palladium Nanocrystals: Oxygen Reduction Reaction and Formic Acid Oxidation

Abstract

A systematic study was conducted on small Pd nanocrystals (5–6 nm) to understand the effects of catalyst structure and electrolyte on the oxygen reduction reaction (ORR) and formic acid oxidation (FAO). The ORR activities of Pd catalysts strongly depended on their structure and the electrolyte used. It was found that Pd cubes were 10 times more active than Pd octahedra for ORR in an aqueous HClO4 solution due to higher onset potential of OHad formation on the cubic surface. In the case of a H2SO4 solution, the ORR activity of Pd cubes was 17 times higher than that of Pd octahedra due to the stronger adsorption of (bi)sulfate on the surface of octahedral nanocrystals in addition to OHad. In alkaline solutions, however, no structure dependence was observed for ORR due to the outer-sphere electron-transfer mechanism in the potential region for Pd oxide formation. For FAO, no advantage was observed on shape-controlled Pd nanocrystals in comparison to conventional Pd catalysts. The FAO current densities, both ...