Search

Two uranium oxide hydrate frameworks (UOHFs) with either Dy3+ or Lu3+ ions, Dy1.36(H2O)6[(UO2)10UO13(OH)4] (UOHF‐Dy) or Lu2(H2O)8[(UO2)10UO14(OH)3] (UOHF‐Lu), were synthesized hydrothermally and characterized with a range of structural and spectroscopic techniques. Although SEM‐EDS analysis confirmed the same atomic ratio of ~5.5 for U : Dy and U : Lu, they displayed different crystal morphologies, needles for UOHF‐Dy in the orthorhombic C2221 space group and plates for UOHF‐Lu in the triclinic P‐1 space group. Both frameworks are composed of β‐U3O8 type layers linked by pentagonal bipyramidal uranium polyhedra, with the Dy3+/Lu3+ ions inside the channels. However, the arrangements of Dy3+/Lu3+ ions are different, with disordered Dy3+ ions well aligned at the centers of the channels and single Lu3+ ions well‐separated in a zigzag pattern in the channels. While the characteristic vibrational modes were revealed by Raman spectroscopy, the presence of a pentavalent uranium center in UOHF‐Lu was confirmed with diffuse reflectance spectroscopy. The formation of two types of UOHFs with lanthanide ions, high or low symmetry, and the structure trend were discussed regards to synthesis conditions and lanthanide ionic radius. This work highlights the complex chemistry driving the formation of UOHFs with lanthanide ions and has implications to the spent nuclear fuel under geological disposal. [ABSTRACT FROM AUTHOR]

Alkaline earth metal ions play an important role in the formation of secondary uranium minerals due to their abundance in the Earth's crust. Although uranium oxide hydrate (UOH) minerals and synthetic phases with calcium, strontium and barium ions have been investigated, their counterparts with magnesium ions are much less studied. In this work, synthetic UOH materials with magnesium ions have been investigated with three new compounds being synthesised and characterised. Compound Mg2(H3O)2(H2O)6[(UO2)3O4(OH)]2 (U-Mg1 with a U : Mg ratio of 3 : 1) crystallises in the monoclinic P21/c space group having a layered crystal structure, constructed by β-U3O8 layers with 6-fold coordinated Mg2+ ions as interlayer cations. Compound Na2Mg(H2O)4[(UO2)3O3(OH)2]2 (U-Mg2p with U : Mg : Na ratios of 6 : 1 : 2) crystallises in the triclinic P1¯ space group having a layered structure, constructed by a unique type of uranium oxide hydroxide layer containing both α-U3O8 and β-U3O8 features, with alternating layers of 6-fold coordinated Mg2+ and 6-/8-fold coordinated Na+ interlayer cations. Compound Na2Mg(H2O)4[(UO2)4O3(OH)4]2 (U-Mg2n with U : Mg : Na ratios of 8 : 1 : 2) crystallises in the triclinic P1¯ space group having a corrugated layer structure, constructed by a unique type of uranium oxide hydroxide layer with mixed 6-fold coordinated Mg2+ and 7-fold coordinated Na+ interlayer cations. The structural diversity in the UOH-Mg system was achieved by adjusting the solution pH using NaOH, highlighting the importance of solution pH control and the additional Na+ ions in the formation of UOH phases. The extra structural flexibility offered by the Na+ ions emphasizes the opportunity for synthesising UOHs with dual-cations to further improve our understanding of the alteration products of spent nuclear fuel under geological disposal. [ABSTRACT FROM AUTHOR]

Although barium(II) ions play an important role in the natural weathering of the mineral uraninite (UO2+x) and are expected to therefore do the same for spent nuclear fuel in geological disposal, the detailed structural understanding of this role is rather limited. In this work, we report the synthesis and characterisation of two new uranium oxide hydrate (UOH) phases with barium(II) ions, a layer-structured UOH-Ba1 constructed with undulating uranyl oxide hydroxide layers incorporating hydrated interlayer barium(II) ions; and UOH-Ba2 forming a complex three-dimensional structure by linking six different types of uranium polyhedrons with barium(II) ions located in the narrow channels. Both crystal structures were revealed using synchrotron single crystal X-ray diffraction and confirmed with powder X-ray or electron diffractions. While vibrational modes were elucidated by Raman, electronic structures and the presence of pentavalent uranium were investigated using diffuse reflectance spectroscopy. This work has provided insights into the complexity of uranium crystal chemistry in the presence of barium(II) ions and has implications to both uranium geochemistry in terms of the natural weathering of uraninite and the disposal of spent nuclear fuel in the underground repository. [ABSTRACT FROM AUTHOR]

We report a flux crystal growth of Ba2[(UO2)2Ti2O8] and subsequent structural and spectroscopic studies using multiple techniques. The layered crystal structure, built up with sheets of edge‐sharing dimeric uranyl pentagonal bipyramids and dimeric TiO5 square pyramids with interlayer Ba(II) ions, was revealed by synchrotron single crystal x‐ray diffraction and confirmed with electron diffraction using a transmission electron microscope. The presence of only hexavalent uranium was confirmed by both diffuse reflectance and x‐ray absorption near‐edge structure spectroscopies, consistent with the bond valence sum calculations. Its vibrational modes were revealed by Raman spectroscopy. In addition, its implications as a potential hexavalent uranium waste form for the immobilization of uranium‐rich radioactive wastes were discussed. [ABSTRACT FROM AUTHOR]

We report a comprehensive study on lanthanide monouranate–based glass–ceramic (GC) composites as potential waste forms for the immobilization of the lanthanide actinide fraction waste arising from the reprocessing of spent nuclear fuel (SNF). Although the crystalline LnUO4 precursor prepared via a nitrate route can be well stabilized in a sodium aluminoborosilicate glass, the in situ crystallization of EuUO4 in glass from oxide precursors (Eu2O3 and U3O8) is rather robust with regards to various processing conditions such as waste loadings, ceramic‐to‐glass ratios, and cooling rates. Scanning electron microscopy and transmission electron microscopy investigations revealed the detailed microstructures, where ∼1–5‐μm spheres for NdUO4 and EuUO4, and ∼1–5‐μm rectangular crystals for DyUO4 and HoUO4 were observed in residual glasses. As designed, the pentavalent uranium has been confirmed by diffuse reflectance spectroscopy. Overall, LnUO4‐based GC composite waste forms are chemically durable, offering flexible processing options with wide operating windows for SNF and process waste stream management. [ABSTRACT FROM AUTHOR]

The synthesis of two zinc-bearing uranium oxide hydrate (UOH) materials has been achieved, and their crystal structures, obtained via single-crystal X-ray diffraction using synchrotron radiation, and additional structural and spectroscopic properties are reported herein. Although both structures incorporate Zn 2+ cations, the two differ significantly. The compound Zn 2 (OH) 2 (H 2 O) 5 [(UO 2 ) 10 UO 14 (H 2 O) 3 ] ( UOHF-Zn ), forming a framework-type structure in the P 1̅ space group, was composed of β-U 3 O 8 layers pillared by uranyl polyhedra, with the Zn 2+ cations incorporated within the framework channels. In contrast, the compound Cs 2 Zn(H 2 O) 4 [(UO 2 ) 4 O 3 (OH) 4 ] 2 ·3H 2 O ( UOH-Zn ) crystallized in the Cmc 2 1 space group with a schoepite-like uranyl oxide hydroxide layered topology and both Zn 2+ and Cs + cations making up the interlayer species. The apparent driving force for the differences in the structures was the change from KOH to CsOH during synthesis, with the smaller K + ions excluded in lieu of a higher proportion of Zn 2+ (U/Zn ratio of 5.5:1) in UOHF-Zn , whereas in UOH-Zn , the larger Cs + ions were preferentially incorporated at the expense of fewer Zn 2+ cations (U/Cs/Zn ratio of 8:2:1). Highlighted in this work is the effect of the chemical species and, in particular, their ionic radius on UOH formation, further improving the understanding of UO 2 alteration in the setting of deep geological repositories., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A uranium oxide hydrate framework, [U(H 2 O) 2 ]{[(UO 2 ) 10 O 10 (OH) 2 ][(UO 4 )(H 2 O) 2 ]} ( UOF1 ), was synthesized hydrothermally using schoepite as a uranium precursor. The crystal strucutre of UOF1 was revealed with synchrotron single-crystal X-ray diffraction and confirmed with transmission electron miscroscopy. The typical uranyl oxide hydroxide layers similar to those in β-U 3 O 8 are further connected via double-pentagonal-bipyramidal uranium polyhedra to form a three-dimensional (3D) framework structure with tetravalent uranium species inside the channels. The presence of mixed-valence uranium was investigated with a combination of X-ray absorption near-edge structure and diffuse reflectance spectroscopy. Apart from the major hexavalent uranium, evidence for tetravalent uranium was also found, consistent with the bond valence sum calculations. The successful preparation of UOF1 as the first pure uranium oxide hydrate framework sheds light on the structural understanding of the alteration of UO 2+ x as either a mineral or spent nuclear fuel.