Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Colliard, Ian; Falaise, Clement; Nyman, May

doi:10.1021/acs.inorgchem.0c02267

Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Journal Article · Thu Nov 19 00:00:00 EST 2020 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.0c02267· OSTI ID:1725817

Colliard, Ian ^[1]; ^[2]; ^[2]

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

Isolating isomorphic compounds of tetravalent actinides (i.e., Th^IV, U^IV, Np^IV, and Pu^IV) improve our understanding of the bonding behavior across the series, in addition to their relationship with tetravalent transition metals (Zr and Hf) and lanthanides (Ce). Similarities between these tetravalent metals are particularly illuminated in their hydrolysis and condensation behavior in aqueous systems, leading to polynuclear clusters typified by the hexamer [M^IV ₆O₄(OH)₄]¹²⁺ building block. Prior studies have shown the predominance and coexistence of smaller species for Th^IV (monomers, dimers, and hexamers) and larger species for U^IV, Np^IV, and Pu^IV (including 38-mers and 70-mers). We show here that aqueous uranium(IV) sulfate also displays behavior similar to that of Th^IV (and Zr^IV) in its isolated solidphase and solution speciation. Two single-crystal X-ray structures are described: a dihydroxide-bridged dimer (U₂) formulated as U₂(OH)₂(SO₄)₃(H₂O)₄ and a monomer-linked hexamer framework (U-U₆) as (U(H₂O)_3.5)₂U₆O₄(OH)₄(SO₄)₁₀(H₂O)₉. These structures are similar to those previously described for ThIV. Moreover, cocrystallization of monomer and dimer and of dimer and monomer–hexamer phases for both Th^IV (prior) and U^IV (current) indicates the coexistence of these species in solution. Because it was not possible to effectively study the sulfate-rich solutions via X-ray scattering from which U₂ and U-U₆ crystallized, we provide a parallel solution speciation study in low sulfate conditions, as a function of the pH. Raman spectroscopy, UV–vis spectroscopy, and small-angle X-ray scattering of these show decreasing sulfate binding, increased hydrolysis, increased species size, and increased complexity, with increasing pH. Furthermore, this study describes a bridge across the first half the actinide series, highlighting U^IV similarities to Th^IV, in addition to the previously known similarities to the transuranic elements.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003763

OSTI ID:: 1725817

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 59; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

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