Dixon Wilkins, M. orcid.org/0000-0003-1520-7672, Mottram, L., Maddrell, E. et al. (4 more authors) (2021) Synthesis, characterization, and crystal structure of dominant uranium(V) brannerites in the UTi2–xAlxO6 system. Inorganic Chemistry, 60 (23). pp. 18112-18121. ISSN 0020-1669
Abstract
The synthesis, characterization, and crystal structure of a novel (dominant) uranium(V) brannerite of composition U1.09(6)Ti1.29(3)Al0.71(3)O6 is reported, as determined from Rietveld analysis of the high-resolution neutron powder diffraction data. Examination of the UTi2–xAlxO6 system demonstrated the formation of brannerite-structured compounds with varying Al3+ and U5+ contents, from U0.93(6)Ti1.64(3)Al0.36(3)O6 to U0.89(6)Ti1.00(3)Al1.00(3)O6. Substitution of Al3+ for Ti4+, with U5+ charge compensation, resulted in near-linear changes in the b and c unit cell parameters and the overall unit cell volume, as expected from ionic radii considerations. The presence of U5+ as the dominant oxidation state in near-single-phase brannerite compositions was evidenced by complementary laboratory U L3-edge and high-energy-resolution fluorescence-detected U M4-edge X-ray absorption near-edge spectroscopy. No brannerite phase was found for compositions with Al3+/Ti4+ > 1, which would require a U6+ contribution for charge compensation. These data expand the crystal chemistry of uranium brannerites to the stabilization of dominant uranium(V) brannerites by the substitution of trivalent cations, such as Al3+, on the Ti4+ site.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2021 American Chemical Society. This is an author-produced version of a paper subsequently published in Inorganic Chemistry. Uploaded in accordance with the publisher's self-archiving policy. |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Engineering (Sheffield) > Department of Materials Science and Engineering (Sheffield) |
Funding Information: | Funder Grant number Engineering and Physical Sciences Research Council 1963750 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 09 Nov 2021 11:22 |
Last Modified: | 17 Nov 2022 01:13 |
Status: | Published |
Publisher: | American Chemical Society |
Refereed: | Yes |
Identification Number: | 10.1021/acs.inorgchem.1c02733 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:179865 |