The Dissociation and Reduction of Molecular Oxygen on Platinum, Palladium, Iridium, Rhodium, and Gold

Herein, a method is presented to determine the kinetics of the oxygen dissociation on different metals, allowing for the determination of the oxygen reduction reaction mechanism. This analysis reveals that molecular oxygen rapidly dissociates to underpotentially deposited oxygen species on platinum and rhodium surfaces. The surface charge of these species leads to a simple kinetic model of the oxygen reduction reaction, which agrees well with experiment and predicts the Volcano relationship of the oxygen reduction reaction.