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Corrosion/Electrochemistry of Uranium Dioxide in Slightly Alkaline Hydrogen Peroxide Solutions

Published online by Cambridge University Press:  17 March 2011

Jon S. Goldik
Affiliation:
Department of Chemistry, The University of Western Ontario, London, ON, Canada. N6A 5B7, jgoldik@uwo.ca
James J. Noël
Affiliation:
Department of Chemistry, The University of Western Ontario, London, ON, Canada. N6A 5B7, jjnoel@uwo.ca
David W. Shoesmith
Affiliation:
Department of Chemistry, The University of Western Ontario, London, ON, Canada. N6A 5B7, dwshoesm@uwo.ca
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Abstract

The kinetics of H2O2 reduction have been studied in slightly alkaline (pH 9.7 NaCl) solution on 1.5 at.% SIMFUEL. Using cyclic voltammetric techniques, we have shown that the cathodic reduction of H2O2 is kinetically facile on UIVUVO2+x surfaces. Carbonate ions are found to have a significant effect on the kinetics of H2O2 reduction. Suppression of the reaction rate is observed at very cathodic potentials, and has been attributed to a competition between carbonate and hydrogen peroxide for catalytic sites on the electrode surface. A small enhancement of the reduction current occurs between –200 and +100 mV vs. SCE, which appears to be due to a surface adsorbed carbonate complex. The large values of the Tafel slopes for H2O2 reduction have been interpreted in terms of a chemical-electrochemical mechanism involving surface UV species. The results are discussed in terms of a mixed potential model for the prediction of nuclear fuel dissolution rates under permanent disposal conditions.

Type
Research Article
Copyright
Copyright © Materials Research Society 2004

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