Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

Yuan, Ke; Antonio, Mark R.; Ilton, Eugene S.; Li, Zhongrui; Becker, Udo

doi:10.1021/acsearthspacechem.1c00413

Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

Journal Article · Fri Mar 18 00:00:00 EDT 2022 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.1c00413· OSTI ID:1871895

^[1]; Antonio, Mark R. ^[2]; ^[3]; Li, Zhongrui ^[4]; ^[4]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Univ. of Michigan, Ann Arbor, MI (United States)

Redox reactions of uranium (U) in aqueous environments have important impacts on the mobility and isotopic fractionation of U in the geosphere. Pentavalent U as the cationic uranyl ion, UO₂+, is rarely observed in naturally occurring samples because of its limited lifetime, but it may be an important intermediate state controlling the redox kinetics between hexavalent and tetravalent U. Increasing evidence has indicated that U(V) can be stabilized under laboratory conditions. Here, we showed that U(V) is the dominant species on the magnetite (Fe₃O₄) surface under reducing conditions controlled by electrochemical methods. Cyclic voltammetry reveals coupled redox peaks corresponding to the U(VI)O₂²⁺/U(V)O²⁺ one-electron redox reaction. Magnetite electrodes polarized at a series of potentials to reduce U(VI)O₂²⁺ were characterized by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and Auger electron mapping. Overall, the results showed that up to twice the amount of U(V) to U(VI) was present on the magnetite surface. U(V) adopted a typical uranyl-type structure, and the U coverage on the magnetite surface increased with decreasing potentials. The formation of mixed-valence U(V)/U(VI) species on the surface of magnetite may hinder the U(V) disproportionation reaction, thereby eliminating the presence of tetravalent U. These results show that U(V) can exist over short time scales as the dominant U species on mineral surfaces under selected reducing conditions by the controlled polarization of a mineral electrode.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357; AC05-00OR22725; FG02-06ER15783

OSTI ID:: 1871895

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 5 Vol. 6; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Pentavalent Uranium Enriched Mineral Surface under Electrochemically Controlled Reducing Environments

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