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

Abstract

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:
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)
OSTI Identifier:
1419451
Alternate Identifier(s):
OSTI ID: 1423083
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; AC02-76SF00515; AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Thermodynamics; Soft materials; Polymer chemistry

Citation Formats

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., 2017. 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. Thu . "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 = {Thu Nov 16 00:00:00 EST 2017},
month = {Thu Nov 16 00:00:00 EST 2017}
}

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Works referenced in this record:

Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009

  • Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
  • DOI: 10.1021/jp810292n

Preparation of hydrophilic amidoxime fibers by cografting acrylonitrile and methacrylic acid from an optimized monomer composition
journal, October 2000

  • Kawai, Tomomi; Saito, Kyoichi; Sugita, Kazuyuki
  • Radiation Physics and Chemistry, Vol. 59, Issue 4, p. 405-411
  • DOI: 10.1016/S0969-806X(00)00298-X