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

Author

Listed:
  • Alexander S. Ivanov

    (Oak Ridge National Laboratory)

  • Christina J. Leggett

    (Lawrence Berkeley National Laboratory
    U. S. Nuclear Regulatory Commission)

  • Bernard F. Parker

    (Lawrence Berkeley National Laboratory
    University of California-Berkeley)

  • Zhicheng Zhang

    (Lawrence Berkeley National Laboratory)

  • John Arnold

    (Lawrence Berkeley National Laboratory
    University of California-Berkeley)

  • Sheng Dai

    (Oak Ridge National Laboratory)

  • Carter W. Abney

    (Oak Ridge National Laboratory)

  • Vyacheslav S. Bryantsev

    (Oak Ridge National Laboratory)

  • Linfeng Rao

    (Lawrence Berkeley National Laboratory)

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. Herein, 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.

Suggested Citation

  • Alexander S. Ivanov & Christina J. Leggett & Bernard F. Parker & Zhicheng Zhang & John Arnold & Sheng Dai & Carter W. Abney & Vyacheslav S. Bryantsev & Linfeng Rao, 2017. "Origin of the unusually strong and selective binding of vanadium by polyamidoximes in seawater," Nature Communications, Nature, vol. 8(1), pages 1-10, December.
    • Handle: RePEc:nat:natcom:v:8:y:2017:i:1:d:10.1038_s41467-017-01443-1
    DOI: 10.1038/s41467-017-01443-1
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    Cited by:

    1. Oluwatomiwa A. Osin & Shuo Lin & Benjamin S. Gelfand & Stephanie Ling Jie Lee & Sijie Lin & George K. H. Shimizu, 2024. "A molecular extraction process for vanadium based on tandem selective complexation and precipitation," Nature Communications, Nature, vol. 15(1), pages 1-10, December.

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