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Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents

Journal Article · · Industrial and Engineering Chemistry Research
 [1];  [2];  [3];  [4];  [2]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  3. Georgia Inst. of Technology, Atlanta, GA (United States). Dept. of Environmental Engineering
  4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
+ Show Author Affiliations
Poly(acrylamidoxime) fibers are the current state of the art adsorbent for mining uranium from seawater. However, the competition between uranyl (UO22+) and vanadium ions poses a challenge to mining on the industrial scale. In this work, we employ density functional theory (DFT) and coupled-cluster methods (CCSD(T)) in the restricted formalism to investigate potential binding motifs of the oxovanadium(IV) ion (VO2+) with the formamidoximate ligand. Consistent with experimental EXAFS data, the hydrated six-coordinate complex is predicted to be preferred over the hydrated five-coordinate complex. Here, our investigation of formamidoximate-VO2+ complexes universally identified the most stable binding motif formed by chelating a tautomerically rearranged imino hydroxylamine via the imino nitrogen and hydroxylamine oxygen. The alternative binding motifs for amidoxime chelation via a non-rearranged tautomer and 2 coordination are found to be ~11 kcal/mol less stable. Ultimately, the difference in the most stable VO2+ and UO22+ binding conformation has important implications for the design of more selective UO22+ ligands.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
AC02-05CH11231; AC05-00OR22725
OSTI ID:
1327585
Journal Information:
Industrial and Engineering Chemistry Research, Journal Name: Industrial and Engineering Chemistry Research Journal Issue: 15 Vol. 55; ISSN 0888-5885
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (4)

Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater journal November 2017
Efficient removal of uranium( vi ) from simulated seawater using amidoximated polyacrylonitrile/FeOOH composites journal January 2017
Structural and computational characterization of a bridging zwitterionic-amidoxime uranyl complex journal January 2019
Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature journal November 2017

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Oxovanadium (IV) ion
VO2+
amidoxime functional group
coordination motifs
coupled-cluster calculations (CCSD(T))
density functional theory (DFT)