Crystallization of a Neptunyl Oxalate Hydrate from Solutions Containing NpV and the Uranyl Peroxide Nanocluster U60Ox30

Uranyl peroxide nanoclusters are an evolving family of materials with potential applications throughout the nuclear fuel cycle. While several studies have investigated their interactions with alkali and alkaline earth metals, no studies have probed their interactions with the actinide elements. This work describes a system containing U(60)Ox(30), [((UO2)(O-2))(60)(C2O4)(30)](60-), and neptunium(V) as a function of neptunium concentration. Ultra-small and small angle X-ray scattering were used to observe these interactions in the aqueous phase, and X-ray diffraction was used to observe solid products. The results show that neptunium induces aggregation of U(60)Ox(30) when the neptunium concentration is <= 10 mM, whereas (NpO2)(2)C2O4 center dot 6H(2)O(cr) and studtite ultimately form at 15-25 mM neptunium. The latter result suggests that neptunium coordinates with the bridging oxalate ligands in U(60)Ox(30), leaving metastable uranyl peroxide species in solution. This is an important finding given the potential application of uranyl peroxide nanoclusters in the recycling of used nuclear fuel.

Automated summary

This study investigates the interactions between U(60)Ox(30), [((UO2)(O-2))(60)(C2O4)(30)](60-), and Np(V) at different neptunium concentrations. The results show that neptunium induces aggregation of U(60)Ox(30) at neptunium concentrations of <= 10 mM, whereas (NpO2)(2)C2O4 center dot 6H(2)O(cr) and studtite form at 15-25 mM neptunium. These findings are important for understanding and applying uranyl peroxide nanoclusters in the recycling of used nuclear fuel.