Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO4 Co–Mobility in the Nuclear Fuel Cycle

Shohel, Mohammad; Bustos, Jenna; Roseborough, Alexander; Nyman, May

doi:10.1002/chem.202303218

Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO₄ Co–Mobility in the Nuclear Fuel Cycle

Journal Article · Sun Dec 17 23:00:00 EST 2023 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.202303218· OSTI ID:2279027

^[1]; ^[2]; Roseborough, Alexander ^[2]; ^[2]

Oregon State University, Corvallis, OR (United States); University of Notre Dame
Oregon State University, Corvallis, OR (United States)

Spent nuclear fuel contains heavy element fission products that must be separated for effective reprocessing for a safe and sustainable nuclear fuel cycle. ⁹³Zr and ⁹⁹Tc are high-yield fission products that co-transport in liquid-liquid extraction processes. Here we seek atomic-level information of this co-extraction process, as well as fundamental knowledge about Zr^IV (and Hf^IV) aqueous speciation in the presence of topology-directing ligands such as pertechnetate (TcO₄^–) and non-radioactive surrogate perrhenate (ReO₄^–). In this context, we show that the flat tetrameric oxyhydroxyl-cluster [M^IV₄(OH)₈(H₂O)₁₆]⁸⁺ (and related polymers) is dissociated by perrhenate/pertechnetate to yield isostructural dimers, M₂(OH)₂(XO₄^–)₆(H₂O)₆ • 3H₂O (M=Zr/Hf^IV; X=Re/Tc^VII), elucidated by single-crystal X-ray diffraction. We used these model compounds to understand the pervasive ⁹³Zr-⁹⁹Tc coextraction with further speciation studies in water, nitric acid, and tetrabutylphosphate (TBP) -kerosene; where the latter two media are relevant to nuclear fuel reprocessing. SAXS (small angle X-ray scattering), compositional evaluation, and where experimentally feasible, ESI-MS (electrospray ionization mass spectrometry) showed that perrhenate/pertechnetate influence Zr/Hf^IV-speciation in water. Here, in Zr-XO₄ solvent extraction studies to simulate fuel reprocessing, we provide evidence that TcO₄^– enhances extraction of Zr^IV, and compositional analysis of the extracted metal-complexes (Zr-ReO₄ study) is consistent with the crystallized Zr^IV₂(OH)₂(Re^VIIO₄^–)₆(H₂O)₆•dimer.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); Murdock Charitable Trust

Grant/Contract Number:: NA0003763

OSTI ID:: 2279027

Alternate ID(s):: OSTI ID: 2274837

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 10 Vol. 30; ISSN 0947-6539

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Pertechnetate/perrhenate–capped Zr/Hf–Dihydroxide Dimers: Elucidating Zr–TcO4 Co–Mobility in the Nuclear Fuel Cycle

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