Simulation of the Oxygen Reduction Reaction at an RDE in 0.5 M H[sub 2]SO[sub 4] Including an Adsorption Mechanism

Oxygen reduction on the surface of a rotating disk electrode (RDE) in 0.5 M H2 S O4 is simulated by including mass transfer, adsorption, and charge transfer. A generalized model for the adsorption and reaction of several species is introduced. The oxygen reduction reaction is simulated as a limiting case where oxygen is the only species adsorbed, and oxygen reduction is the only reaction that takes place on the surface of the electrode. The model is based on the Nernst-Planck equations for mass transfer and the Butler-Volmer equation for electrochemical kinetics. The simulated polarization curves capture the change in the Tafel slopes, which are observed experimentally but cannot be explained by the normal four-electron-transfer mechanism. The adsorption model is compared with the four-electron-transfer model by fitting experimental data to both models using a nonlinear parameter estimation technique. The effects of changes in some important kinetic parameters are demonstrated. © 2007 The Electrochemical Society.