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Title: Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl

Abstract

Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO 2 2+) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO 2 +, with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO 2 + ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO 2 +(H 2O) 4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO 2 + complexes indicates that both monodentate and bidentate forms may coexist inmore » thermodynamic equilibrium in solution, with the equilibrium balance leaning more towards the formation of monodentate species. Investigations of VO 2 + coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ~ 4.0 kcal/mol of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. Lastly, the difference in the most stable VO 2 + and UO 2 2+ binding conformation has important implications for the design of more selective UO 2 2+ ligands.« less

Authors:
 [1];  [2];  [3];  [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. 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 Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1327581
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 17; Journal Issue: 47; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Mehio, Nada, Johnson, J. Casey, Dai, Sheng, and Bryantsev, Vyacheslav S. Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl. United States: N. p., 2015. Web. doi:10.1039/C5CP06165B.
Mehio, Nada, Johnson, J. Casey, Dai, Sheng, & Bryantsev, Vyacheslav S. Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl. United States. doi:10.1039/C5CP06165B.
Mehio, Nada, Johnson, J. Casey, Dai, Sheng, and Bryantsev, Vyacheslav S. Wed . "Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl". United States. doi:10.1039/C5CP06165B. https://www.osti.gov/servlets/purl/1327581.
@article{osti_1327581,
title = {Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl},
author = {Mehio, Nada and Johnson, J. Casey and Dai, Sheng and Bryantsev, Vyacheslav S.},
abstractNote = {Poly(acrylamidoxime)-based fibers bearing random mixtures of carboxylate and amidoxime groups are the most widely utilized materials for extracting uranium from seawater. However, the competition between uranyl (UO22+) and vanadium ions poses a significant challenge to the industrial mining of uranium from seawater using the current generation of adsorbents. To design more selective adsorbents, a detailed understanding of how major competing ions interact with carboxylate and amidoxime ligands is required. In this work, we employ density functional theory (DFT) and wave-function methods to investigate potential binding motifs of the dioxovanadium ion, VO2+, with water, formate, and formamidoximate ligands. Employing higher level of theory calculations (CCSD(T)) resolve the existing controversy between the experimental results and previous DFT calculations for the structure of the hydrated VO2+ ion. Consistent with the EXAFS data, CCSD(T) calculations predict higher stability of the distorted octahedral geometry of VO2+(H2O)4 compared to the five-coordinate complex with a single water molecule in the second hydration shell, while all seven tested DFT methods yield the reverse stability of the two conformations. Analysis of the relative stabilities of formate-VO2+ complexes indicates that both monodentate and bidentate forms may coexist in thermodynamic equilibrium in solution, with the equilibrium balance leaning more towards the formation of monodentate species. Investigations of VO2+ coordination with the formamidoximate anion has revealed the existence of seven possible binding motifs, four of which are within ~ 4.0 kcal/mol of each other. Calculations establish that the most stable binding motif entails the coordination of oxime oxygen and amide nitrogen atoms via a tautomeric rearrangement of amidoxime to imino hydroxylamine. Lastly, the difference in the most stable VO2+ and UO22+ binding conformation has important implications for the design of more selective UO22+ ligands.},
doi = {10.1039/C5CP06165B},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 47,
volume = 17,
place = {United States},
year = {2015},
month = {10}
}

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    Works referencing / citing this record:

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