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Title: Assessing ligand selectivity for uranium over vanadium ions to aid in the discovery of superior adsorbents for extraction of UO22+ from seawater

Journal Article · · Dalton Transactions
DOI:https://doi.org/10.1039/C6DT01752E· OSTI ID:1331080
 [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

Uranium is used as the basic fuel for nuclear power plants, which generate significant amounts of electricity and have life cycle carbon emissions that are as low as renewable energy sources. However, the extraction of this valuable energy commodity from the ground remains controversial, mainly because of environmental and health impacts. Alternatively, seawater offers an enormous uranium resource that may be tapped at minimal environmental cost. Nowadays, amidoxime polymers are the most widely utilized sorbent materials for large-scale extraction of uranium from seawater, but they are not perfectly selective for uranyl, UO22+. In particular, the competition between UO22+ and VO2+/VO2+ cations poses a significant challenge to the effi-cient mining of UO22+. Thus, screening and rational design of more selective ligands must be accomplished. One of the key components in achieving this goal is the establishment of computational techniques capable of assessing ligand selec-tivity trends. Here, we report an approach based on quantum chemical calculations that achieves high accuracy in repro-ducing experimental aqueous stability constants for VO2+/VO2+ complexes with ten different oxygen donor lig-ands. The predictive power of the developed computational protocol was demonstrated for amidoxime-type ligands, providing greater insights into new design strategies for the development of the next generation of adsorbents with high selectivity toward UO22+over VO2+/VO2+ ions. Furthermore, the results of calculations suggest that alkylation of amidox-ime moieties present in poly(acrylamidoxime) sorbents can be a potential route to better discrimination between the uranyl and competing vanadium ions within seawater.

Research Organization:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Nuclear Energy (NE)
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1331080
Journal Information:
Dalton Transactions, Vol. 45, Issue 26; ISSN 1477-9226
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

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Cited By (4)

Extraction and adsorption of U(VI) from aqueous solution using affinity ligand-based technologies: an overview journal July 2019
Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater journal November 2017
Polyamidoxime chain length drives emergent metal-binding phenomena journal January 2019
Amidoxime Polymers for Uranium Adsorption: Influence of Comonomers and Temperature journal November 2017

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