Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO4 and Th–ReO4 Frameworks and Solutions

Shohel, Mohammad; Bustos, Jenna; Stroscio, Gautam D.; Sarkar, Arup; Nyman, May

doi:10.1021/acs.inorgchem.3c01430

Title: Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO₄ and Th–ReO₄ Frameworks and Solutions

Journal Article · Wed Jun 21 00:00:00 EDT 2023 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.3c01430· OSTI ID:1986489

Shohel, Mohammad ^[1]; Bustos, Jenna ^[1];

^[2];

^[1]

Oregon State University, Corvallis, OR (United States)
University of Chicago, IL (United States)

Technetium-99, a β-emitter produced from ²³⁵U fission, poses a challenge for the nuclear industry due to co-extraction of pertechnetate (TcO₄^–) with the actinides (An) during nuclear fuel reprocessing. Previous studies suggested that direct coordination of pertechnetate with An plays an important role in the coextraction process. However, few studies have provided direct evidence for An–TcO₄^– bonding in the solid state, and even fewer in solution. The present study describes synthesis and structural elucidation of a family of thorium(IV)-pertechnetate/perrhenate (ReO₄^–, nonradioactive surrogate) compounds, which is obtained by dissolution of thorium oxyhydroxide in perrhenic/pertechnic acid followed by crystallization, with or without heating. For reaction ratios of 3:1, 4:1, and 6:1 MO₄^–/Th(IV) (M = Tc, Re), the crystallized compounds reflect the same ratio, suggesting facile and flexible coordination. Furthermore, nine structures reveal 1-dimensional and 2-dimensional frameworks with varying topologies. While a multitude of compounds isolated from 4:1 (and 6:1) reaction solutions feature Th monomers linked by MO₄^–, the 3:1 reaction solution yielded the well-known dihydroxide-bridged thorium dimer, linked, and capped by MO₄^–. Density functional theory calculations on ReO₄^–/TcO₄^– isomorphs suggest similar bonding characteristics in the solid state, but experimental solution characterization noted differences. Specifically, small-angle X-ray scattering studies suggest the bonding of Th–TcO₄^– persists in solution, while Th–ReO₄^– bonding is less apparent.

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

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

Grant/Contract Number:: NA0003763; SR-2017297

OSTI ID:: 1986489

Journal Information:: Inorganic Chemistry, Vol. 62, Issue 26; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO4 and Th–ReO4 Frameworks and Solutions

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Title: Elucidating Actinide–Pertechnetate and Actinide–Perrhenate Bonding via a Family of Th–TcO₄ and Th–ReO₄ Frameworks and Solutions