4.2 Article

Quantitative modeling of the oscillatory electrooxidation of hydrogen on Pt in the presence of poisons

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WALTER DE GRUYTER GMBH
DOI: 10.1524/zpch.217.4.365.20387

Keywords

hydrogen oxidation; electrochemical oscillations; nonlinear dynamics; Cu underpotential deposition

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A quantitative model of oscillations observed during hydrogen oxidation on platinum in the presence of electrosorbing metal ions and specifically adsorbing anions is presented and the model predictions are compared with experiments. Mass and charge balances of all reactants lead in a first step to a seven variable model which is governed by reaction steps that have been widely studied. We demonstrate that attractive interactions between metal and halide ions on the electrode surface, which were recently reported [1], are crucial for the observed dynamics. The model parameters were almost exclusively taken out of the literature. The model is then reduced to its minimal form without losing dynamic features arriving at a four variable system. Experimental time series of three of the four variables of the model and measured bifurcation diagrams are presented. It is shown that the integrated time evolution and the calculated bifurcation diagrams of the model agree almost quantitatively with the experiment.

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