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The chemical speciation of uranium oxides is sensitive to the provenance of the samples and their storage conditions. Here, we use diffraction methods to characterize the phases found in three aged (>10 years) uranium ore concentrates of different origins as well as in situ analysis of the thermally induced structural transitions of these materials. The structures of the crystalline phases found in the three samples have been refined, using high-resolution synchrotron X-ray diffraction data. Rietveld analysis of the samples from the Olympic Dam and Ranger uranium mines has revealed the presence of crystalline α-UO2(OH)2, together with metaschoepite (UO2)4O(OH)6·5H2O, in the aged U3O8 samples, and it is speculated that this forms as a consequence of the corrosion of U3O8 in the presence of metaschoepite. The third sample, from the Beverley uranium mine, contains the peroxide [UO2(η2-O2)(H2O)2] (metastudtite) together with α-UO2(OH)2 and metaschoepite. A core-shell model is proposed to account for the broadening of the diffraction peaks of the U3O8 evident in the samples.

In situ synchrotron powder X-ray diffraction measurements have demonstrated that the isostructural AUO4- x ( A = alkaline earth metal cation) oxides CaUO4- x and α-Sr0.4Ca0.6UO4- x undergo a reversible phase transformation under reducing conditions at high temperatures associated with the ordering of in-plane oxygen vacancies resulting in the lowering of symmetry. When rhombohedral (space group R3 m) CaUO4- x and α-Sr0.4Ca0.6UO4- x are heated to 450 and 400 °C, respectively, in a hydrogen atmosphere, they undergo a first-order phase transformation to a single phase structure which can be refined against a triclinic model in space group P1, δ-CaUO4- x and δ-Sr0.4Ca0.6UO4- x, where the oxygen vacancies are disordered initially. Continued heating results in the appearance of superlattice reflections, indicating the ordering of in-plane oxygen vacancies. Cooling ordered δ-CaUO4- x and δ-Sr0.4Ca0.6UO4- x to near room temperature results in the reformation of the disordered rhombohedral phases. Essential to the transformation is the generation of a critical amount of oxygen vacancies. Once these are formed, the transformation can be accessed continuously through thermal cycling, showing that the transformations are purely thermodynamic in origin. Stoichiometric structures of both oxides can be recovered by heating oxygen deficient CaUO4- x and α-Sr0.4Ca0.6UO4- x under pure oxygen to high temperatures. When heated in air, the amount of oxygen vacancy defects that form in CaUO4- x and α-Sr0.4Ca0.6UO4- x are found to correlate with the A site composition. The inclusion of the larger Sr2+ cation on the A site reduces defect-defect interactions, which increases the amount of defects that can form and lowers their formation temperature. The relative difference in the amount of defects that form can be understood on the basis of oxygen vacancy and U5+ disordering as shown by both ab initio calculations and estimated oxygen vacancy formation energies based on thermodynamic considerations. This difference in defect-defect interactions consequently introduces variations in the long-range ordered anionic lattice of the δ phases despite the isostructural relationship of the α structures of CaUO4- x and Sr0.4Ca0.6UO4- x. These results are discussed with respect to the influence the A site cation has upon anion defect formation and ordering and are also compared to δ-SrUO4- x, the only other material known to be able to undergo a reversible symmetry lowering and disorder-to-order transformation with increasing temperature.

The first comprehensive structural study of the Ni–U–O system is reported. Single crystals of α-NiUO4, β-NiUO4, and NiU3O10 were synthesized, and their structures were refined—using synchrotron single-crystal X-ray diffraction data supported by X-ray absorption spectroscopic measurements. α-NiUO4 adopts an orthorhombic structure in space group Pbcn and is isostructural to CrUO4 containing corrugated two-dimensional (2D) layers of corner-sharing UO6 polyhedra and edge-sharing one-dimensional (1D) zigzag α-PbO2 rutile-like chains of NiO6 polyhedra in the [001] direction. β-NiUO4 is isostructural to MgUO4 and has an orthorhombic structure in space group Ibmm, which contains alternating 1D chains of edge-sharing UO6 and NiO6 polyhedra in the [001] direction as in regular TiO2 rutile. NiU3O10 forms a triclinic structure in space group P1 and is isostructural with CuU3O10, where it forms a three-dimensional (3D) framework structure built through a mixture of UO6 and UO7 polyhedra in which the NiO6 polyhedra si...

A systematic investigation examining the origins of structural distortions in rutile-related ternary uranium AUO4 oxides using a combination of high-resolution structural and spectroscopic measurements supported by ab initio calculations is presented. The structures of β-CdUO4, MnUO4, CoUO4, and MgUO4 are determined at high precision by using a combination of neutron powder diffraction (NPD) and synchrotron X-ray powder diffraction (S-XRD) or single crystal X-ray diffraction. The structure of β-CdUO4 is best described by space group Cmmm whereas MnUO4, CoUO4, and MgUO4 are described by the lower symmetry Ibmm space group and are isostructural with the previously reported β-NiUO4 [Murphy et al. Inorg. Chem.2018, 57, 13847]. X-ray absorption spectroscopy (XAS) analysis shows all five oxides contain hexavalent uranium. The difference in space group can be understood on the basis of size mismatch between the A2+ and U6+ cations whereby unsatisfactory matching results in structural distortions manifested through tilting of the AO6 polyhedra, leading to a change in symmetry from Cmmm to Ibmm. Such tilts are absent in the Cmmm structure. Heating the Ibmm AUO4 oxides results in reduction of the tilt angle. This is demonstrated for MnUO4 where in situ S-XRD measurements reveal a second-order phase transition to Cmmm near T = 200 °C. Based on the extrapolation of variable temperature in situ S-XRD data, CoUO4 is predicted to undergo a continuous phase transition to Cmmm at ∼1475 °C. Comparison of the measured and computed data highlights inadequacies in the DFT+U approach, and the conducted analysis should guide future improvements in computational methods. The results of this investigation are discussed in the context of the wider AUO4 family of oxides.

A systematic investigation is presented which examines the structural chemistry of anhydrous and hydrous ternary hexavalent uranium and neptunium dinitrato, trinitrato, and tetranitrato complexes. Using slow evaporation methods under acidic conditions the uranium and neptunium nitrate complexes γ-K[UO

In situ synchrotron powder X-ray diffraction measurements have demonstrated that SrUO4 undergoes a reversible phase transformation under reducing conditions at high temperatures, associated with the ordering of oxygen defects resulting in a lowering of crystallographic symmetry. When substoichiometric rhombohedral α-SrUO4–x, in space group R3m with disordered in-plane oxygen defects, is heated above 200 °C in a hydrogen atmosphere it undergoes a first order phase transformation to a (disordered) triclinic polymorph, δ-SrUO4–x, in space group P1. Continued heating to above 450 °C results in the appearance of superlattice reflections, due to oxygen-vacancy ordering forming an ordered structure δ-SrUO4–x. Cooling δ-SrUO4–x toward room temperature results in the reformation of the rhombohedral phase α-SrUO4–x with disordered defects, confirming the reversibility of the transformation. This suggests that the transformation, resulting from oxygen vacancy ordering, is not a consequence of sample reduction or d...

Two novel alkali-metal uranyl borophosphates have been prepared and characterized for the first time, namely, K5(UO2)2[B2P3O12(OH)]2(OH)(H2O)2 and K2(UO2)12[B(H2PO4)4](PO4)8(OH)(H2O)6 denoted as KUPB1 and KUPB2, respectively. KUPB1 was obtained hydrothermally at 220 °C and crystallizes in a monoclinic structure in the chiral space group P21. The unit cell parameters of KUPB1 are a = 6.7623(2) A, b = 19.5584(7) A, c = 11.0110(4) A, α = γ = 90°, β = 95.579(3)°, and V = 1449.42(8) A3. It features a unique three-dimensional (3D) open-framework structure, composed of two corner-sharing linked one-dimensional (1D) anionic borophosphates (BP), [B2P3O13]5–, along the a axis and uranyl phosphate (UP), [(UO2)(PO4)3]7–, chains along the c axis, further bridged by PO4 tetrahedra. Multi-intersectional channels can be observed within the structure, in which the largest 11-ring (11-R) tunnel size is ∼7.0 A × 8.8 A. Its simplified framework can be described as a new 4-nodal net topological type with a point symbol of {4....

In situ neutron and synchrotron X-ray diffraction studies demonstrate that SrUO4 acts as an oxygen transfer agent, forming oxygen vacancies under both oxidizing and reducing conditions. Two polymorphs of SrUO4 are stable at room temperature, and the transformation between these is observed to be associated with thermally regulated diffusion of oxygen ions, with partial reduction of the U(6+) playing a role in both the formation of oxygen deficient α-SrUO4-δ and its subsequent transformation to stoichiometric β-SrUO4. This is supported by ab initio calculations using density functional theory calculations. The oxygen vacancies play a critical role in the first order transition that SrUO4 undergoes near 830 °C. The changes in the oxidation states and U geometry associated with the structural phase transition have been characterized using X-ray absorption spectroscopy, synchrotron X-ray diffraction, and neutron diffraction.

In situ synchrotron powder X-ray diffraction measurements have demonstrated that SrUO

Herein we describe the synthesis of a new heterodinuclear Fe(III)Cu(II) model complex for the active site of purple acid phosphatases and its binding to a polyamine chain, a model for the amino acid residues around the active site. The properties of these systems and their catalytic activity in the hydrolysis of bis(2,4-dinitrophenyl)phosphate are compared, and conclusions regarding the effects of the second coordination sphere are drawn. The positive effect of the polymeric chain on DNA hydrolysis is also described and discussed.