Data from a combined cyclic voltammetry and dynamic electrochemical impedance spectroscopy (dEIS) study of the methanol oxidation reaction (MOR) at high temperatures was revisited using a new method for mechanistic modeling. Through iterative optimization of kinetic parameters, a total of ve reaction mechanisms of the indirect pathway of the MOR were modeled. The calculated dEIS spectra from the kinetic parameters were used to verify the reaction mechanisms and best ts were found where i) water adsorption is reversible and hinders the MOR at lower potentials (< 0.50 V vs RHE), and ii) the surface reaction between adsorbed CO and OH is chemical.
Bulk CO oxidation on smooth polycrystalline platinum was studied with a rotating disk electrode and cyclic voltammetry in CO-saturated 0.5 M sulfuric acid. The reaction rate was modelled with differential equations. The modelling goal was to build a model that reproduces the experimental currentpotential characteristics, with special attention to the platinum oxide region. Two different models were tested: one containing conventional chemical and electrochemical reaction steps, and one built around an empirical equation describing the rate of platinum oxide formation and reduction. The latter model produced good fits to the experimental results. Both models showed that CO oxidation in the platinum oxide range proceeds via direct reaction between an adsorbed species such as PtOH and dissolved CO.
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