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Plutonium and Cerium Perrhenate/Pertechnetate Coordination Polymers and Frameworks

Journal Article · · Inorganic Chemistry
 [1];  [2];  [2];  [3]
  1. Oregon State University, Corvallis, OR (United States); University of Notre Dame
  2. University of Notre Dame, IN (United States)
  3. Oregon State University, Corvallis, OR (United States)
+ Show Author Affiliations
Spent nuclear fuel (SNF) contains transuranic and lanthanide species, which are sometimes recovered and repurposed. One particularly problematic fission product, 99TcO4–, hampers this recovery via coextraction with high valence metals, perhaps by complexation during aqueous reprocessing of SNF. There is limited molecular-level knowledge concerning the coordination chemistry between TcO4– or its well-known surrogate ReO4– and transuranic/lanthanide species. In the current study, we investigated the coordination of ReO4–/TcO4– with plutonium and cerium cations by structural and chemical characterization of a series of isolated extended solids. In this study, Ce represents both trivalent lanthanides and is considered a surrogate for Pu, respectively, in its common trivalent and tetravalent oxidation states. The structural elucidation of the seven isolated crystalline solids revealed that ReO4–/TcO4– directly connects to PuIV, PuVIO2 2+, CeIII, and CeIV in the terminal and bridging coordination modes, leading to 1-, 2-, and 3-dimensional frameworks. For example, ReO4– coordination to Pu(IV) formed a 1D chain or 2D framework, isostructural with previously isolated Th(IV) compounds. However, PuVIO2 2+ alternating with ReO4– led to a unique 1D chain, different from the prior-reported U(VI)/Np(VI)-ReO4–/TcO4– structures. Coordination of ReO4–/TcO4– with Ce(III) promotes the assembly of 3D frameworks. Finally, attempted synthesis of a Ce(IV)-ReO4– compound resulted in a 2D framework with a mixed-valence CeIII/IV. The highly acidic reaction conditions supported the reduction of both CeIV and TcVII, challenging isolation of compounds featuring these species. Only one TcO4-containing structure was obtained in this study (CeIII–TcO4 3D framework), vs the six total Ce/Pu-ReO4 compounds. Furthermore, our three Pu-ReO4 crystal structures are the first reported and translated to atomic-level information about Pu-TcO4 coordination in nuclear fuel reprocessing scenarios, in addition to broadening our knowledge of bonding trends in the early, high-valence actinides.
Research Organization:
University of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0003763
OSTI ID:
2299507
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 4 Vol. 63; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
Chemical structure
Crystals
Materials
Organic polymers
Vinyl