Current separation and purification technologies utilized in the nuclear fuel cycle rely primarily on liquid-liquid extraction and ion-exchange processes. Here, we report a laboratory-scale aqueous process that demonstrates nanoscale control for the recovery of uranium from simulated used nuclear fuel (SIMFUEL). The selective, hydrogen peroxide induced oxidative dissolution of SIMFUEL material results in the rapid assembly of persistent uranyl peroxide nanocluster species that can be separated and recovered at moderate to high yield from other process-soluble constituents using sequestration-assisted ultrafiltration. Implementation of size-selective physical processes like filtration could results in an overall simplification of nuclear fuel cycle technology, improving the environmental consequences of nuclear energy and reducing costs of processing.

Hybrid uranyl-vanadium oxide clusters intermediate between transition metal polyoxometalates and uranyl peroxide cage clusters were obtained by dissolving uranyl nitrate in the ionic liquid 3-ethyl-1-methylimidazolium ethyl sulfate mixed with an aqueous solution containing vanadium. Where sulfate was present, wheel-shaped {U20V20} crystallized and contains ten sulfate tetrahedra, and in the absence of added sulfate, {U2V16}, a derivative of {V18}, was obtained.

Hybrid Uranyl-Vanadium Nano-Wheels. -The crystal structures of (IVa, b) and (V) are determined by single crystal XRD. (IVa) crystallizes in the orthorhombic space group Cmcm with Z = 4. The compound contains a novel wheel-shaped cluster which is built from 20 uranyl pentagonal bipyramids, 20 vanadate square pyramids, and 10 sulfate tetrahedra. (IVb) crystallizes in the orthorhombic space group Pccn with Z = 4 and contains the same uranyl vanadate cluster but in a different packing arrangement. Compound (V) crystallizes in the monoclinic space group C2/c with Z = 4. Its major structural components are distorted vanadate square pyramids. -(SENCHYK, G. A.; WYLIE, E. M.; PRIZIO, S.; SZYMANOWSKI, J. E. S.; SIGMON, G. E.; BURNS*, P. C.; Chem. Commun. (Cambridge) 51 (2015) 50, 10134-10137, http://dx.