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Title: Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater

Amidoxime-functionalized polymeric adsorbents are the current state-of-the-art materials for collecting uranium (U) from seawater. However, marine tests show that vanadium (V) is preferentially extracted over U and many other cations. Here in this paper, we report a complementary and comprehensive investigation integrating ab initio simulations with thermochemical titrations and XAFS spectroscopy to understand the unusually strong and selective binding of V by polyamidoximes. While the open-chain amidoxime functionalities do not bind V, the cyclic imide-dioxime group of the adsorbent forms a peculiar non-oxido V 5+ complex, exhibiting the highest stability constant value ever observed for the V 5+ species. XAFS analysis of adsorbents following deployment in environmental seawater confirms V binding solely by the imide-dioximes. Our fundamental findings offer not only guidance for future optimization of selectivity in amidoxime-based sorbent materials, but may also afford insight to understanding the extensive accumulation of V in some marine organisms.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [3] ;  [4] ;  [3] ; ORCiD logo [1] ;  [1] ; ORCiD logo [1] ;  [4]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); US Nuclear Regulatory Commission, Rockville, MD (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231; AC02-06CH11357; AC02-76SF00515; AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thermodynamics; Soft materials; Polymer chemistry
OSTI Identifier:
1419451
Alternate Identifier(s):
OSTI ID: 1423083

Ivanov, Alexander S., Leggett, Christina J., Parker, Bernard F., Zhang, Zhicheng, Arnold, John, Dai, Sheng, Abney, Carter W., Bryantsev, Vyacheslav S., and Rao, Linfeng. Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater. United States: N. p., Web. doi:10.1038/s41467-017-01443-1.
Ivanov, Alexander S., Leggett, Christina J., Parker, Bernard F., Zhang, Zhicheng, Arnold, John, Dai, Sheng, Abney, Carter W., Bryantsev, Vyacheslav S., & Rao, Linfeng. Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater. United States. doi:10.1038/s41467-017-01443-1.
Ivanov, Alexander S., Leggett, Christina J., Parker, Bernard F., Zhang, Zhicheng, Arnold, John, Dai, Sheng, Abney, Carter W., Bryantsev, Vyacheslav S., and Rao, Linfeng. 2017. "Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater". United States. doi:10.1038/s41467-017-01443-1. https://www.osti.gov/servlets/purl/1419451.
@article{osti_1419451,
title = {Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater},
author = {Ivanov, Alexander S. and Leggett, Christina J. and Parker, Bernard F. and Zhang, Zhicheng and Arnold, John and Dai, Sheng and Abney, Carter W. and Bryantsev, Vyacheslav S. and Rao, Linfeng},
abstractNote = {Amidoxime-functionalized polymeric adsorbents are the current state-of-the-art materials for collecting uranium (U) from seawater. However, marine tests show that vanadium (V) is preferentially extracted over U and many other cations. Here in this paper, we report a complementary and comprehensive investigation integrating ab initio simulations with thermochemical titrations and XAFS spectroscopy to understand the unusually strong and selective binding of V by polyamidoximes. While the open-chain amidoxime functionalities do not bind V, the cyclic imide-dioxime group of the adsorbent forms a peculiar non-oxido V5+ complex, exhibiting the highest stability constant value ever observed for the V5+ species. XAFS analysis of adsorbents following deployment in environmental seawater confirms V binding solely by the imide-dioximes. Our fundamental findings offer not only guidance for future optimization of selectivity in amidoxime-based sorbent materials, but may also afford insight to understanding the extensive accumulation of V in some marine organisms.},
doi = {10.1038/s41467-017-01443-1},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {11}
}

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