Reductive hydrothermal conversion of uranyl oxalates into UO monitored by XANES analyses.

Hydrothermal conversion of actinide oxalates has recently gained attention as an innovative fabrication route for nuclear fuels but has remained mainly limited to tetra- or tri-valent cations. We report herein the reductive conversion of mixtures of uranyl and oxalate ions into UO oxides under mild hydrothermal conditions ( = 250 °C). A multi-parametric study first led to specifying the optimal conditions in terms of pH, oxalate/U ratio and duration to provide a quantitative precipitation of uranium in the hyper-stoichiometric dioxide form with pH = 0.8; = / = 3, and = 72 hours. Particularly, pH was evidenced as a key parameter, with 3 different compounds obtained over a range of only 0.4 units. The mechanism leading to the formation of UO was then investigated thanks to an XANES study. Analysis of the supernatant showed that U(VI) was quickly reduced into U(IV) thanks to the presence of oxalates and/or their decomposition products in solution, following first-order kinetics. Tetravalent uranium was then hydrolysed, leading to the precipitation of UO as the only crystalline phase. This study thus demonstrates that the hydrothermal conversion of actinide oxalates into oxides is an extremely versatile tool that can be implemented in a large variety of chemical systems, particularly in terms of the oxidation state of the cations initially present in solution.