Phase diagrams and dynamical evolution of the triple-pathway electro-oxidation of formic acid on platinum

Abstract

Recently, an electro-kinetic model based on a specified reaction scheme for the electro-oxidation of formic acid on platinum was reported. The model evaluated three reaction pathways towards the production of CO₂: the dehydrogenation and the dehydration of formic acid, and the third and most active pathway includes fast oxidation of the formate ion. Numerical integrations showed that the model is well-suited to describe the experimental results in voltammetric and oscillatory regimes. In the present paper, we provide detailed stability phase diagrams characterizing the dynamical evolution of this system under galvanostatic and potentiostatic regimes. We find the triple-pathway electro-oxidation of formic acid on platinum to have rather intertwined stability phases and, surprisingly, a total absence of chaotic oscillations. To the best of our knowledge, this is the first study in this direction using a realistic electrochemical model.