Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents
Abstract
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.
- Authors:
-
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Georgia Inst. of Technology, Atlanta, GA (United States). Dept. of Environmental Engineering
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1327585
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Industrial and Engineering Chemistry Research
- Additional Journal Information:
- Journal Volume: 55; Journal Issue: 15; Journal ID: ISSN 0888-5885
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Oxovanadium (IV) ion; VO2+; amidoxime functional group; coordination motifs; density functional theory (DFT); coupled-cluster calculations (CCSD(T))
Citation Formats
Mehio, Nada, Ivanov, Alexander S., Ladshaw, Austin P., Dai, Sheng, and Bryantsev, Vyacheslav S. Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents. United States: N. p., 2015.
Web. doi:10.1021/acs.iecr.5b03398.
Mehio, Nada, Ivanov, Alexander S., Ladshaw, Austin P., Dai, Sheng, & Bryantsev, Vyacheslav S. Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents. United States. https://doi.org/10.1021/acs.iecr.5b03398
Mehio, Nada, Ivanov, Alexander S., Ladshaw, Austin P., Dai, Sheng, and Bryantsev, Vyacheslav S. Sun .
"Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents". United States. https://doi.org/10.1021/acs.iecr.5b03398. https://www.osti.gov/servlets/purl/1327585.
@article{osti_1327585,
title = {Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents},
author = {Mehio, Nada and Ivanov, Alexander S. and Ladshaw, Austin P. and Dai, Sheng and Bryantsev, Vyacheslav S.},
abstractNote = {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.},
doi = {10.1021/acs.iecr.5b03398},
journal = {Industrial and Engineering Chemistry Research},
number = 15,
volume = 55,
place = {United States},
year = {Sun Nov 22 00:00:00 EST 2015},
month = {Sun Nov 22 00:00:00 EST 2015}
}
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Works referencing / citing this record:
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