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Title: XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies

Abstract

In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η2 motifs proposed by small molecule and computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.

Authors:
 [1];  [2];  [2];  [1];  [1];  [2];  [3];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Chicago, Chicago, IL (United States)
  3. Univ. of Chicago, Chicago, IL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1244198
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; XAFS; uranium; nuclear fuel cycle; amidoxime; seawater; unconventional resources

Citation Formats

Mayes, Richard T., Piechowicz, Marek, Lin, Zekai, Veith, Gabriel M., Dai, Sheng, Lin, Wenbin, Abney, C. W., and Bryantsev, V. S.. XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies. United States: N. p., 2015. Web. https://doi.org/10.1039/C5EE02913A.
Mayes, Richard T., Piechowicz, Marek, Lin, Zekai, Veith, Gabriel M., Dai, Sheng, Lin, Wenbin, Abney, C. W., & Bryantsev, V. S.. XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies. United States. https://doi.org/10.1039/C5EE02913A
Mayes, Richard T., Piechowicz, Marek, Lin, Zekai, Veith, Gabriel M., Dai, Sheng, Lin, Wenbin, Abney, C. W., and Bryantsev, V. S.. Thu . "XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies". United States. https://doi.org/10.1039/C5EE02913A. https://www.osti.gov/servlets/purl/1244198.
@article{osti_1244198,
title = {XAFS investigation of polyamidoxime-bound uranyl contests the paradigm from small molecule studies},
author = {Mayes, Richard T. and Piechowicz, Marek and Lin, Zekai and Veith, Gabriel M. and Dai, Sheng and Lin, Wenbin and Abney, C. W. and Bryantsev, V. S.},
abstractNote = {In this study, limited resource availability and population growth have motivated interest in harvesting valuable metals from unconventional reserves, but developing selective adsorbents for this task requires structural knowledge of metal binding environments. Amidoxime polymers have been identified as the most promising platform for large-scale extraction of uranium from seawater. However, despite more than 30 years of research, the uranyl coordination environment on these adsorbents has not been positively identified. We report the first XAFS investigation of polyamidoxime-bound uranyl, with EXAFS fits suggesting a cooperative chelating model, rather than the tridentate or η2 motifs proposed by small molecule and computational studies. Samples exposed to environmental seawater also display a feature consistent with a μ2-oxo-bridged transition metal in the uranyl coordination sphere, suggesting in situ formation of a specific binding site or mineralization of uranium on the polymer surface. These unexpected findings challenge several long-held assumptions and have significant implications for development of polymer adsorbents with high selectivity.},
doi = {10.1039/C5EE02913A},
journal = {Energy & Environmental Science},
number = 2,
volume = 9,
place = {United States},
year = {2015},
month = {11}
}

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