U(v) in metal uranates: A combined experimental and theoretical study of MgUO4, CrUO4, and FeUO4

Guo, Xiaofeng; Tiferet, Eitan; Qi, Liang; Solomon, Jonathan M.; Lanzirotti, Antonio; Newville, Matthew; Engelhard, Mark H.; Kukkadapu, Ravi K.; Wu, Di; Ilton, Eugene S.; Asta, Mark; Sutton, Stephen R.; Xu, Hongwu; Navrotsky, Alexandra

doi:10.1039/C6DT00066E

U(v) in metal uranates: A combined experimental and theoretical study of MgUO₄, CrUO₄, and FeUO₄

Journal Article · Tue Feb 02 00:00:00 EST 2016 · Dalton Transactions

DOI:https://doi.org/10.1039/C6DT00066E· OSTI ID:1256103

Guo, Xiaofeng ^[1]; Tiferet, Eitan ^[2]; Qi, Liang ^[3]; Solomon, Jonathan M. ^[4]; Lanzirotti, Antonio ^[5]; Newville, Matthew ^[5]; Engelhard, Mark H. ^[6]; Kukkadapu, Ravi K. ^[6]; Wu, Di ^[7]; Ilton, Eugene S. ^[6]; Asta, Mark ^[4]; Sutton, Stephen R. ^[5]; Xu, Hongwu ^[8]; Navrotsky, Alexandra ^[7]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of California, Davis, CA (United States)
Univ. of California, Davis, CA (United States); Negev Be'er-Sheva (Israel)
Univ. of California, Berkeley, CA (United States); Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of Chicago, Chicago, IL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of California, Davis, CA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Although pentavalent uranium can exist in aqueous solution, its presence in the solid state is uncommon. Metal monouranates, MgUO₄, CrUO₄ and FeUO₄ were synthesized for detailed structural and energetic investigations. Structural characteristics of these uranates used powder X-ray diffraction, synchrotron X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57Fe-Mossbauer spectroscopy. Enthalpies of formation were measured by high temperature oxide melt solution calorimetry. Density functional theory (DFT) calculations provided both structural and energetic information. The measured structural and thermodynamic properties show good consistency with those predicted from DFT. The presence of U⁵⁺ has been solidly confirmed in CrUO₄ and FeUO₄, which are thermodynamically stable compounds, and the origin and stability of U⁵⁺ in the system was elaborated by DFT. Lastly, the structural and thermodynamic behaviour of U⁵⁺ elucidated in this work is relevant to fundamental actinide redox chemistry and to applications in the nuclear industry and radioactive waste disposal.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC52-06NA25396; SC0001089

OSTI ID:: 1256103

Alternate ID(s):: OSTI ID: 1243119
OSTI ID: 1243177

Report Number(s):: LA-UR--15-28081

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 11 Vol. 45; ISSN 1477-9226; ISSN ICHBD9

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
Inorganic and Physical Chemistry
Material Science
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calorimetry
structure
uranate
uranium