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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