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A physicochemical model is developed for electrocatalytic reactions involving multiple electron transfer steps occurring in the electric double layer (EDL). The local reaction conditions are calculated using a mean-field EDL model, which is derived from a comprehensive grand potential that considers the steric effects, solvent polarization, and chemisorption-induced surface dipoles. Macroscopic mass transport in the so-called diffusion layer is controlled by the same set of controlling equations of the EDL model, without imposing the electroneutrality assumption as usual. The Gerischer's formulation of electron transfer theory, corrected with local reaction conditions, is used to describe the kinetics of elementary steps. Multistep kinetics of the electrocatalytic reaction is treated using microkinetics modelling, without resorting to the usual rate-determining step approximation. In formal analysis of the model, we retrieve canonical models with additional assumptions. Self-consistent numerical implementation of the model is demonstrated for oxygen reduction reaction (ORR) at Pt(111) in acidic solution, and the aptness of the model is verified by comparison with experimental data. A comparative study of the full model and its simplified versions allows us to examine how the ORR is influenced by asymmetric steric effects, finite concentration of ions, solvent polarization, surface charge effects, and metal electronic structure effects. We find that the difference in terms of the overpotential between the full model and the simplest model can be up to ∼0.1 V at a current density of -6 mAcm-2.
Zhang et al. (Wed,) studied this question.