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Title: Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides

Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions between metal ions and donor groups of ligands, while the effects on the selectivity resulting from molecular interactions in the outer-sphere region have been largely overlooked. Herein, we explore the fundamental origins of the selectivity of the solvating extractant N,N,N',N'-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides in a liquid–liquid extraction system, which is of relevance to nuclear fuel reprocessing and rare-earth refining technologies. Complementary investigations integrating distribution studies, quantum mechanical calculations, and classical molecular dynamics simulations establish a relationship between coextracted water and lanthanide extraction by TODGA across the series, pointing to the importance of the hydrogen-bonding interactions between outer-sphere nitrate ions and water clusters in a nonpolar environment. Lastly, our findings have significant implications for the design of novel efficient separation systems and processes, emphasizing the importance of tuning both inner- and outer-sphere interactions to obtain total control over selectivity in the biphasic extraction of lanthanides.
Authors:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [1]
  1. Colorado School of Mines, Golden, CO (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725; 2012-DN-130-NF0001; AC02-05CH11231; SC0014664
Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 6; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1454293
Alternate Identifier(s):
OSTI ID: 1458359

Baldwin, Anna G., Ivanov, Alexander S., Williams, Neil J., Ellis, Ross J., Moyer, Bruce A., Bryantsev, Vyacheslav S., and Shafer, Jenifer C.. Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides. United States: N. p., Web. doi:10.1021/acscentsci.8b00223.
Baldwin, Anna G., Ivanov, Alexander S., Williams, Neil J., Ellis, Ross J., Moyer, Bruce A., Bryantsev, Vyacheslav S., & Shafer, Jenifer C.. Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides. United States. doi:10.1021/acscentsci.8b00223.
Baldwin, Anna G., Ivanov, Alexander S., Williams, Neil J., Ellis, Ross J., Moyer, Bruce A., Bryantsev, Vyacheslav S., and Shafer, Jenifer C.. 2018. "Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides". United States. doi:10.1021/acscentsci.8b00223.
@article{osti_1454293,
title = {Outer-Sphere Water Clusters Tune the Lanthanide Selectivity of Diglycolamides},
author = {Baldwin, Anna G. and Ivanov, Alexander S. and Williams, Neil J. and Ellis, Ross J. and Moyer, Bruce A. and Bryantsev, Vyacheslav S. and Shafer, Jenifer C.},
abstractNote = {Fundamental understanding of the selective recognition and separation of f-block metal ions by chelating agents is of crucial importance for advancing sustainable energy systems. Current investigations in this area are mostly focused on the study of inner-sphere interactions between metal ions and donor groups of ligands, while the effects on the selectivity resulting from molecular interactions in the outer-sphere region have been largely overlooked. Herein, we explore the fundamental origins of the selectivity of the solvating extractant N,N,N',N'-tetraoctyl diglycolamide (TODGA) for adjacent lanthanides in a liquid–liquid extraction system, which is of relevance to nuclear fuel reprocessing and rare-earth refining technologies. Complementary investigations integrating distribution studies, quantum mechanical calculations, and classical molecular dynamics simulations establish a relationship between coextracted water and lanthanide extraction by TODGA across the series, pointing to the importance of the hydrogen-bonding interactions between outer-sphere nitrate ions and water clusters in a nonpolar environment. Lastly, our findings have significant implications for the design of novel efficient separation systems and processes, emphasizing the importance of tuning both inner- and outer-sphere interactions to obtain total control over selectivity in the biphasic extraction of lanthanides.},
doi = {10.1021/acscentsci.8b00223},
journal = {ACS Central Science},
number = 6,
volume = 4,
place = {United States},
year = {2018},
month = {6}
}