Reduction of uranyl and uranyl-organic complexes mediated by magnetite and ilmenite: A combined electrochemical AFM and DFT study

Kim, YoungJae; Marcano, Maria C.; Kim, Sooyeon; Becker, Udo

doi:10.1016/j.gca.2020.10.016

Reduction of uranyl and uranyl-organic complexes mediated by magnetite and ilmenite: A combined electrochemical AFM and DFT study

Journal Article · Wed Oct 21 00:00:00 EDT 2020 · Geochimica et Cosmochimica Acta

DOI:https://doi.org/10.1016/j.gca.2020.10.016· OSTI ID:1849673

Kim, YoungJae ^[1]; Marcano, Maria C. ^[2]; Kim, Sooyeon ^[2]; Becker, Udo ^[2]

Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Earth and Environmental Sciences; Univ. of Michigan, Ann Arbor, MI (United States)
Univ. of Michigan, Ann Arbor, MI (United States). Dept. of Earth and Environmental Sciences

Reduction of mobile aqueous uranyl complexes can be hindered by the strength of the uranyl-ligand complex and the resistivity of the complexes to electron transfer. Semiconducting solids, such as magnetite (Fe₃O₄) and ilmenite (FeTiO₃), can facilitate otherwise-slow electron transfer between the reductant and oxidant, especially if these species are adsorbed on their surfaces as inner-sphere complexes. Electrons can then be shuttled through the surface or the structure. This process can be facilitated by either finding a new electron transfer path or by weakening or destroying the ligand-uranyl complex. Using in situ electrochemical atomic force microscopy (EC-AFM), we imaged reduction products of uranyl as mediated by magnetite and ilmenite in the absence or presence of the organic ligands, ethylenediaminetetraacetate (EDTA) and oxalate. In situ images of uranyl reduction show gradual nucleation and growth of reduced uranium on the mineral surfaces with decreasing reduction potentials. X-ray photoelectron spectroscopy (XPS) measurements indicate pentavalent uranium as the dominant uranium species resulting from uranyl reduction mediated by magnetite and ilmenite. The reduction potentials of uranyl-organic species relevant to our reaction system, (U^VIO₂∙oxalate)⁰ and (U^VIO₂∙HEDTA)^-, are derived using quantum–mechanical modeling and compared with the midpoint potentials obtained from cyclic voltammetry measurements. The spectroscopic, electrochemical, and computational data suggest that the catalysis of Fe-bearing minerals facilitates the reduction of uranyl-organic complexes. U(VI)-oxalate complexes are redox-active and participate directly in the reduction mediated by magnetite. In the presence of EDTA, reduction of uranyl may proceed in concert with ligand exchange between metals (i.e., U and Fe) on the mineral surface. Finally, the proposed mechanism is the breaking of uranyl-organic bonds upon interaction with the mineral surface followed by the formation of Fe-organic bonds, thereby allowing the reduction of hexavalent uranyl to pentavalent one.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Michigan, Ann Arbor, MI (United States)

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

Grant/Contract Number:: FG02-06ER15783

OSTI ID:: 1849673

Alternate ID(s):: OSTI ID: 1775807

Journal Information:: Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Journal Issue: C Vol. 293; ISSN 0016-7037

Publisher:: Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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58 GEOSCIENCES
Atomic Force Microscopy (AFM)
Density Functional Theory (DFT)
Ethylenediaminetetraacetate (EDTA)
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Magnetite
Oxalate
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Reduction of uranyl and uranyl-organic complexes mediated by magnetite and ilmenite: A combined electrochemical AFM and DFT study

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