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

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 UVspecies. The results are discussed in terms of a mixed potential model for the prediction of nuclear fuel dissolution rates under permanent disposal conditions.

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Acknowledgments

This work was funded under the Industrial Research Chair Agreement between NSERC and Ontario Power Generation, Toronto, Canada.

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Correspondence to Jon S. Goldik.

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Goldik, J.S., Noël, J.J. & Shoesmith, D.W. Corrosion/Electrochemistry of Uranium Dioxide in Slightly Alkaline Hydrogen Peroxide Solutions. MRS Online Proceedings Library 824, 526–531 (2004). https://doi.org/10.1557/PROC-824-CC9.10

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