Expanding the crystal chemistry of uranyl peroxides: four hybrid uranyl-peroxide structures containing EDTA.

The first four uranyl peroxide compounds containing ethylenediaminetetra-acetate (EDTA) were synthesized and characterized from aqueous uranyl peroxide nitrate solutions with a pH range of 5-7. Raman spectra demonstrated that reaction solutions that crystallized [NaK15[(UO2)8(O2)8(C10H12O10N2)2(C2O4)4]·(H2O)14] (1) and [Li4K6[(UO2)8(O2)6(C10H12O10N2)2(NO3)6]·(H2O)26] (2) contained excess peroxide, and their structures contained oxidized ethylenediaminetetraacetate, EDTAO2(4-). The solutions from which [K4[(UO2)4(O2)2(C10H13O8N2)2(IO3)2]·(H2O)16] (3) and LiK3[(UO2)4(O2)2(C10H12O8N2)2(H2O)2]·(H2O)18 (4) crystallized contained no free peroxide, and the structures incorporated intact EDTA(4-). In contrast to the large family of uranyl peroxide cage clusters, coordination of uranyl peroxide units in 1-4 by EDTA(4-) or EDTAO2(4-) results in isolated tetramers or dimers of uranyl ions that are bridged by bidentate peroxide groups. Two tetramers are bridged by EDTAO2(4-) to form octamers in 1 and 2, and dimers of uranyl polyhedra are linked through iodate groups in 3 and EDTA(4-) in 4, forming chains in both cases. In each structure the U-O2-U dihedral angle is strongly bent, at ∼140°, consistent with the configuration of this linkage in cage clusters and other recently reported uranyl peroxides.

Ultrafiltration of uranyl peroxide nanoclusters for the separation of uranium from aqueous solution.

Uranyl peroxide cluster species were produced in aqueous solution by the treatment of uranyl nitrate with hydrogen peroxide, lithium hydroxide, and potassium chloride. Ultrafiltration of these cluster species using commercial sheet membranes with molecular mass cutoffs of 3, 8, and 20 kDa (based on polyethylene glycol) resulted in U rejection values of 95, 85, and 67% by mass, respectively. Ultrafiltration of untreated uranyl nitrate solutions using these membranes resulted in virtually no rejection of U. These results demonstrate the ability to use the filtration of cluster species as a means for separating U from solutions on the basis of size. Small-angle X-ray scattering, Raman spectroscopy, and electrospray ionization mass spectrometry confirmed the presence of uranyl peroxide cluster species in solution and were used to characterize their size, shape, and dispersity.