Uranium oxide hydrate frameworks with Er() or Y() ions: revealing structural insights leading to the low symmetry

• Published in: Dalton transactions : an international journal of inorganic chemistry 2022-10, Vol.51 (41), p.15965-15973
• Main Authors: Ablott, Timothy A, Lu, Kimbal T, Aughterson, Robert D, Zhang, Yingjie
• Format: Article
• Language: English
• Subjects: Chemical synthesis; Crystal structure; Erbium; Single crystals; Spent nuclear fuels; Uranium; Uranium oxides; Yttrium
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/d2dt02763a

Two new mixed-valence uranium oxide hydrate frameworks (UOFs), incorporating either Er 3+ or Y 3+ ions, were successfully synthesised under hydrothermal conditions and characterised with single-crystal X-ray diffraction and a variety of other structural and spectroscopic techniques. Both frameworks are isostructural and crystallise in the triclinic P 1&cmb.macr; space group, consisting of β-U 3 O 8 type layers pillared by additional uranyl centres, with the Er 3+ /Y 3+ ions lying in the channels of the framework. SEM-EDS analysis found that both materials existed in plate-like morphologies, with a U:Er/Y ratio of 5.5. Bond valence sum analysis revealed the possible existence of pentavalent uranium centres, which was confirmed with diffuse reflectance spectroscopy. Being the first reported UOFs in this space group, this work highlights the complex and flexible nature of these materials, and the broader uranium oxide hydrate systems which exist in the surrounds of spent nuclear fuel disposal in the underground repository. Two uranium oxide hydrate frameworks with trivalent Er or Y ions crystallised in the triclinic P 1&cmb.macr; space group have been synthesised and characterised.