The field of uranyl peroxo clusters chemistry has grown drastically in the last two decades due to their applications in the nuclear fuel cycle (e.g., waste management and uranium mining). Various sizes of clusters have been discovered, varying in topology (tetramer, pentamer, hexamer) templated and charged balanced with alkali (Li+, Na+, and K+) cations. Aside from templating, the role of the counterion in the formation and reaction mechanism of the uranyl triperoxide monomer (U1) to fully formed capsule has not been studied extensively. To date, the Li+, Na+, and K+ -U1 have been isolated and studied both in solution and solid state. However, the Cs+ and Rb+ analogs have not been isolated yet due to their reactivity and instability. For the first time, Cs-U1 has been isolated and structurally characterized as well as studied in solution. The primary goal of this study is to understand the role of the alkali in the stabilization and destabilization of U1. We have found that in solution the rate of U1 to a fully formed capsule drastically increases from 3 weeks to 2 days when we change the countercation from Li+ to Cs+. These reactions are characterized by the use of Small Angle X-Ray Scattering, Raman and Single Crystal X-Ray Diffraction. This chemistry is critical to understanding the role peroxide, and metals play in the dissolution and precipitation of uranium for separation and purification of mined material in the front end of the nuclear fuel cycle.

Reactivity of uranyl triperoxide monomers

2019 Fall National Meeting

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