skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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 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.

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)
OSTI Identifier:
1419451
Alternate Identifier(s):
OSTI ID: 1423083
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357; AC02-76SF00515; AC05-00OR22725
Resource 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
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. https://doi.org/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. https://doi.org/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. https://doi.org/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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Novel poly(imide dioxime) sorbents: Development and testing for enhanced extraction of uranium from natural seawater
journal, August 2016


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Elution of Uranium and Transition Metals from Amidoxime-Based Polymer Adsorbents for Sequestering Uranium from Seawater
journal, December 2015

  • Pan, Horng-Bin; Kuo, Li-Jung; Wai, Chien M.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03307

Vanadium speciation and cycling in coastal waters
journal, December 2009


Radiation-grafted copolymers for separation and purification purposes: Status, challenges and future directions
journal, December 2012


Highly selective extraction of the uranyl ion with hydrophobic amidoxime-functionalized ionic liquids via η2 coordination
journal, January 2012

  • Barber, Patrick S.; Kelley, Steven P.; Rogers, Robin D.
  • RSC Advances, Vol. 2, Issue 22
  • DOI: 10.1039/c2ra21344c

Seven chemical separations to change the world
journal, April 2016

  • Sholl, David S.; Lively, Ryan P.
  • Nature, Vol. 532, Issue 7600
  • DOI: 10.1038/532435a

Sequestering uranium from seawater: binding strength and modes of uranyl complexes with glutarimidedioxime
journal, January 2012

  • Tian, Guoxin; Teat, Simon J.; Zhang, Zhiyong
  • Dalton Transactions, Vol. 41, Issue 38
  • DOI: 10.1039/c2dt30978e

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

Structural and spectroscopic studies of a rare non-oxido V( v ) complex crystallized from aqueous solution
journal, January 2016

  • Leggett, C. J.; Parker, B. F.; Teat, S. J.
  • Chemical Science, Vol. 7, Issue 4
  • DOI: 10.1039/C5SC03958D

Solvation of the vanadate ion in seawater conditions from molecular dynamics simulations
journal, March 2017


A protein engineered to bind uranyl selectively and with femtomolar affinity
journal, January 2014

  • Zhou, Lu; Bosscher, Mike; Zhang, Changsheng
  • Nature Chemistry, Vol. 6, Issue 3
  • DOI: 10.1038/nchem.1856

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds
journal, February 2004

  • Crans, Debbie C.; Smee, Jason J.; Gaidamauskas, Ernestas
  • Chemical Reviews, Vol. 104, Issue 2
  • DOI: 10.1021/cr020607t

Molecular biological approaches to the accumulation and reduction of vanadium by ascidians
journal, February 2003


The extraction of uranium from seawater by poly(amidoxime)/poly(hydroxamic acid) resins and fibre
journal, October 1983


Hyperquad simulation and speciation (HySS): a utility program for the investigation of equilibria involving soluble and partially soluble species
journal, April 1999


Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010

  • Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 21
  • DOI: 10.1039/b926434e

Extracting Uranium from Seawater: Promising AF Series Adsorbents
journal, November 2015

  • Das, S.; Oyola, Y.; Mayes, Richard T.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03136

Assessing ligand selectivity for uranium over vanadium ions to aid in the discovery of superior adsorbents for extraction of UO 2 2+ from seawater
journal, January 2016

  • Ivanov, Alexander S.; Bryantsev, Vyacheslav S.
  • Dalton Transactions, Vol. 45, Issue 26
  • DOI: 10.1039/C6DT01752E

Extracting Minerals from Seawater: An Energy Analysis
journal, April 2010


Extracting Uranium from Seawater: Promising AI Series Adsorbents
journal, November 2015

  • Das, S.; Oyola, Y.; Mayes, R. T.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03135

Theoretical Study of Oxovanadium(IV) Complexation with Formamidoximate: Implications for the Design of Uranyl-Selective Adsorbents
journal, December 2015

  • Mehio, Nada; Ivanov, Alexander S.; Ladshaw, Austin P.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03398

Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater
journal, October 2015

  • Das, S.; Liao, W. -P.; Flicker Byers, M.
  • Industrial & Engineering Chemistry Research, Vol. 55, Issue 15
  • DOI: 10.1021/acs.iecr.5b03210

XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies
journal, January 2016

  • Abney, C. W.; Mayes, R. T.; Piechowicz, M.
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE02913A

Extraction of Uranium from Sea Water
journal, September 1964

  • Davies, R. V.; Kennedy, J.; McILROY, R. W.
  • Nature, Vol. 203, Issue 4950
  • DOI: 10.1038/2031110a0

Vanadium (IV) and vanadium (V) complexes of deferoxamine B in aqueous solution
journal, October 1995


Theoretical study of the coordination behavior of formate and formamidoximate with dioxovanadium( v ) cation: implications for selectivity towards uranyl
journal, January 2015

  • Mehio, Nada; Johnson, J. Casey; Dai, Sheng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 47
  • DOI: 10.1039/C5CP06165B

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

Complexation of glutarimidedioxime with Fe(iii), Cu(ii), Pb(ii), and Ni(ii), the competing ions for the sequestration of U(vi) from seawater
journal, January 2013

  • Sun, Xiaoqi; Xu, Chao; Tian, Guoxin
  • Dalton Transactions, Vol. 42, Issue 40
  • DOI: 10.1039/c3dt51767e

Solution Structure of Vanabin2, a Vanadium(IV)-Binding Protein from the Vanadium-Rich Ascidian Ascidia s ydneiensis samea
journal, March 2005

  • Hamada, Toshiyuki; Asanuma, Miwako; Ueki, Tatsuya
  • Journal of the American Chemical Society, Vol. 127, Issue 12
  • DOI: 10.1021/ja042687j

Amidoximes as ligand functionalities for braided polymeric materials for the recovery of uranium from seawater
journal, April 2016


A report on emergent uranyl binding phenomena by an amidoxime phosphonic acid co-polymer
journal, January 2016

  • Abney, C. W.; Das, S.; Mayes, R. T.
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 34
  • DOI: 10.1039/C6CP04772F

Uranium recovery from seawater: development of fiber adsorbents prepared via atom-transfer radical polymerization
journal, January 2014

  • Saito, Tomonori; Brown, Suree; Chatterjee, Sabornie
  • J. Mater. Chem. A, Vol. 2, Issue 35
  • DOI: 10.1039/C4TA03276D

Thermodynamic studies of U(vi) complexation with glutardiamidoxime for sequestration of uranium from seawater
journal, January 2013

  • Tian, Guoxin; Teat, Simon J.; Rao, Linfeng
  • Dalton Transactions, Vol. 42, Issue 16
  • DOI: 10.1039/c3dt32940b

The Chemistry and Biochemistry of Vanadium and the Biological Activities Exerted by Vanadium Compounds
journal, May 2004

  • Crans, Debbie C.; Smee, Jason J.; Gaidamauskas, Ernestas
  • ChemInform, Vol. 35, Issue 20
  • DOI: 10.1002/chin.200420288

    Works referencing / citing this record:

    Rational Design of Porous Nanofiber Adsorbent by Blow-Spinning with Ultrahigh Uranium Recovery Capacity from Seawater
    journal, November 2018

    • Yuan, Yihui; Zhao, Shilei; Wen, Jun
    • Advanced Functional Materials, Vol. 29, Issue 2
    • DOI: 10.1002/adfm.201805380

    A Marine‐Inspired Hybrid Sponge for Highly Efficient Uranium Extraction from Seawater
    journal, May 2019

    • Wang, Dong; Song, Jianan; Lin, Sen
    • Advanced Functional Materials, Vol. 29, Issue 32
    • DOI: 10.1002/adfm.201901009

    An Ion‐Crosslinked Supramolecular Hydrogel for Ultrahigh and Fast Uranium Recovery from Seawater
    journal, January 2020


    Significantly Enhanced Uranium Extraction from Seawater with Mass Produced Fully Amidoximated Nanofiber Adsorbent
    journal, October 2018


    Ultrafast and Highly Selective Uranium Extraction from Seawater by Hydrogel‐like Spidroin‐based Protein Fiber
    journal, July 2019


    Photoinduced Multiple Effects to Enhance Uranium Extraction from Natural Seawater by Black Phosphorus Nanosheets
    journal, November 2019


    A Bio‐inspired Nano‐pocket Spatial Structure for Targeting Uranyl Capture
    journal, March 2020


    Ultrafast and Highly Selective Uranium Extraction from Seawater by Hydrogel-like Spidroin-based Protein Fiber
    journal, July 2019

    • Yuan, Yihui; Yu, Qiuhan; Wen, Jun
    • Angewandte Chemie International Edition, Vol. 58, Issue 34
    • DOI: 10.1002/anie.201906191

    Photoinduced Multiple Effects to Enhance Uranium Extraction from Natural Seawater by Black Phosphorus Nanosheets
    journal, December 2019

    • Yuan, Yihui; Niu, Biye; Yu, Qiuhan
    • Angewandte Chemie International Edition, Vol. 59, Issue 3
    • DOI: 10.1002/anie.201913644

    A Bio‐inspired Nano‐pocket Spatial Structure for Targeting Uranyl Capture
    journal, January 2020

    • Yuan, Yihui; Feng, Shiwei; Feng, Lijuan
    • Angewandte Chemie International Edition, Vol. 59, Issue 11
    • DOI: 10.1002/anie.201916450

    Polypropylene nonwoven fabric modified with oxime and guanidine for antibiofouling and highly selective uranium recovery from seawater
    journal, May 2019

    • Yang, Sen; Ji, Guoxun; Cai, Suya
    • Journal of Radioanalytical and Nuclear Chemistry, Vol. 321, Issue 1
    • DOI: 10.1007/s10967-019-06578-7

    Siderophore-inspired chelator hijacks uranium from aqueous medium
    journal, February 2019

    • Ivanov, Alexander S.; Parker, Bernard F.; Zhang, Zhicheng
    • Nature Communications, Vol. 10, Issue 1
    • DOI: 10.1038/s41467-019-08758-1

    Interactions of vanadium( iv ) with amidoxime ligands: redox reactivity
    journal, January 2018

    • Parker, B. F.; Hohloch, S.; Pankhurst, J. R.
    • Dalton Transactions, Vol. 47, Issue 16
    • DOI: 10.1039/c7dt04069e

    The role of mid-gap states in all-inorganic CsPbBr 3 nanoparticle one photon up-conversion
    journal, January 2018

    • Roman, Benjamin J.; Sheldon, Matthew
    • Chemical Communications, Vol. 54, Issue 50
    • DOI: 10.1039/c8cc02430h

    Complexation-assisted reduction: complexes of glutaroimide-dioxime with tetravalent actinides (Np( iv ) and Th( iv ))
    journal, January 2018

    • Zhang, Zhicheng; Parker, Bernard F.; Lohrey, Trevor D.
    • Dalton Transactions, Vol. 47, Issue 24
    • DOI: 10.1039/c8dt01191e

    Highly fluorescent conjugated microporous polymers for concurrent adsorption and detection of uranium
    journal, January 2019

    • Xu, Meiyun; Wang, Tao; Gao, Peng
    • Journal of Materials Chemistry A, Vol. 7, Issue 18
    • DOI: 10.1039/c8ta11764k

    A highly efficient uranium grabber derived from acrylic fiber for extracting uranium from seawater
    journal, January 2020

    • Pan, Horng-Bin; Wai, Chien M.; Kuo, Li-Jung
    • Dalton Transactions, Vol. 49, Issue 9
    • DOI: 10.1039/c9dt04562g

    3D hierarchical porous amidoxime fibers speed up uranium extraction from seawater
    journal, January 2019

    • Xu, Xiao; Zhang, Hongjun; Ao, Junxuan
    • Energy & Environmental Science, Vol. 12, Issue 6
    • DOI: 10.1039/c9ee00626e