Complexation of Lanthanides and Heavy Actinides with Aqueous Sulfur-Donating Ligands

Bessen, Nathan P.; Popov, Ivan A.; Heathman, Colt R.; Grimes, Travis S.; Zalupski, Peter R.; Moreau, Liane M.; Smith, Kurt F.; Booth, Corwin H.; Abergel, Rebecca J.; Batista, Enrique R.; Yang, Ping; Shafer, Jenifer C.

doi:10.1021/acs.inorgchem.1c00257

Title: Complexation of Lanthanides and Heavy Actinides with Aqueous Sulfur-Donating Ligands

Journal Article · Sun Apr 18 00:00:00 EDT 2021 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.1c00257· OSTI ID:1780968

Bessen, Nathan P. ^[1]; Popov, Ivan A. ^[2];

^[3];

^[3]; Moreau, Liane M. ^[4]; Smith, Kurt F. ^[4]; Booth, Corwin H. ^[4];

^[4];

^[2];

^[1]

Colorado School of Mines, Golden, CO (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Idaho National Lab. (INL), Idaho Falls, ID (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The separation of trivalent lanthanides and actinides is challenging because of their similar sizes and charge densities. S-donating extractants have shown significant selectivity for trivalent actinides over lanthanides, with single-stage americium/ lanthanide separation efficiencies for some thiol-based extractants reported at >99.999%. While such separations could transform the nuclear waste management landscape, these systems are often limited by the hydrolytic and radiolytic stability of the extractant. Progress away from thiol-based systems is limited by the poorly understood and complex interactions of these extractants in organic phases, where molecular aggregation and micelle formation obfuscates assessment of the metal–extractant coordination environment. Because S-donating thioethers are generally more resistant to hydrolysis and oxidation and the aqueous phase coordination chemistry is anticipated to lack complications brought on by micelle formation, we have considered three thioethers, 2,2'-thiodiacetic acid (TDA), (2R,5S)- tetrahydrothiophene-2,5-dicarboxylic acid, and 2,5-thiophenedicarboxylic acid (TPA), as possible trivalent actinide selective reagents. Formation constants, extended X-ray absorption fine structure spectroscopy, and computational studies were completed for thioether complexes with a variety of trivalent lanthanides and actinides including Nd, Eu, Tb, Am, Cm, Bk, and Cf. TPA was found to have moderately higher selectivity for the actinides because of its ability to bind actinides in a different manner than lanthanides, but the utility of TPA is limited by poor water solubility and high rigidity. While significant competition with water for the metal center limits the efficacy of aqueous-based thioethers for separations, the characterization of these solution-phase, S-containing lanthanide and actinide complexes is the most comprehensively available in the literature to date. Here, this is due to the breadth of lanthanides and actinides considered as well as the techniques deployed and serves as a platform for the further development of Scontaining reagents for actinide separations. Additionally, this paper reports on the first bond lengths for Cf and Bk with a neutral S donor.

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Research Organization:: Colorado School of Mines, Golden, CO (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: SC0020189; AC02-76SF00515; AC02-05CH11231; AC07-05ID14517; 89233218CNA000001

OSTI ID:: 1780968

Alternate ID(s):: OSTI ID: 1833250

Report Number(s):: LA-UR-20-27724

Journal Information:: Inorganic Chemistry, Vol. 60, Issue 9; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Complexation of Lanthanides and Heavy Actinides with Aqueous Sulfur-Donating Ligands

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