A microkinetic description of electrocatalytic reactions: the role of self-organized phenomena

Abstract

Herein, we summarized the main stages in the construction of a microkinetic model of a surface chemical reaction. Unlike the more traditional bottom-up approach, in which the kinetic parameters are intended to be calculated using first principles, herein we show a phenomenological alternative to determine them. In this case, the model parameters are fitted by comparison between the empirical and simulated kinetic responses. From this perspective, it can be clearly observed that a kinetic model simulating only the stationary response of a system, as is usual in many studies reported in the literature, is not very representative of the chemical process under study. In this way, a mechanistic proposal of a chemical reaction gains greater credibility when it is supported by a robust microkinetic model that also simulates the dynamic response, i.e. the evolution of variables over time. In this sense, we highlight the advantages of the self-organized phenomena, observed in many chemical reactions, to validate a microkinetic model. Our discussion is focused on the electrocatalytic oxidation reactions of low-molar-mass organic compounds as case studies, but this approach can be extrapolated to other complex catalyzed reactions.