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Title: Multiscale investigations of europium(III) complexation with tetra-n-octyl diglycolamide confined in porous solid supports

Abstract

The microscopic, short-range coordination environments and mesoscopic, long-range structures of Eu3+ contacted with tetra-n-octyl diglycolamide (TODGA) confined on ordered mesoporous carbon (OMC) nanoparticles and Amberchrom CG 71 resin were probed using Eu L3-edge extended X ray absorption fine structure (EXAFS) as well as small-angle and wide-angle X ray scattering, SAXS and WAXS, respectively. A homoleptic Eu(TODGA)33+ coordination complex typical of liquid-liquid extraction (LLE) chemistry is present under low Eu3+ loading conditions on both solid supports. Deviations from this traditional structure motif appear at hyperstoichiometric Eu3+ loadings, above the 1:3 Eu3+ to TODGA mole ratio. Microcrystalline-like domains with multinuclear Eu speciation are templated by use of these high Eu3+ loading conditions with the functionalized OMC materials, highlighting a major departure of liquid-solid extraction chromatography (EXC) from the coordination chemistry of LLE. No such long-range spatial coherence was observed for analogous polyacrylic resin materials. Furthermore, these results demonstrate both the similarities and differences between multiscale structures in LLE and EXC, underscoring the opportunities for improved separation techniques based on solid supports with long-range spatial coherence (e.g., OMC systems) and without it (e.g., resin materials). Since crystallization was the first approach to adjacent lanthanide separations, the prospect of templating microcrystalline TODGA-lanthanide complexes thatmore » are otherwise not prone to crystallization by use of OMC nanoparticles represents a new entry to addressing long-standing issues in purification by liquid-solid phase separation.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Colorado School of Mines, Golden, CO (United States)
  2. Argonne National Laboratory (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Colorado School of Mines, Golden, CO (United States); Argonne National Laboratory, Argonne, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC) Graduate Student Research (SCGSR) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Defense Threat Reduction Agency (DTRA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1657542
Alternate Identifier(s):
OSTI ID: 1670488; OSTI ID: 1777140
Grant/Contract Number:  
SC0020189; AC02-06CH11357; HDTRA1-16-0015
Resource Type:
Accepted Manuscript
Journal Name:
CrystEngComm
Additional Journal Information:
Journal Volume: 22; Journal Issue: 41; Journal ID: ISSN 1466-8033
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats

Bertelsen, Erin R., Kovach, Nolan C., Reinhart, Benjamin J., Trewyn, Brian G., Antonio, Mark R., and Shafer, Jenifer C.. Multiscale investigations of europium(III) complexation with tetra-n-octyl diglycolamide confined in porous solid supports. United States: N. p., 2020. Web. https://doi.org/10.1039/D0CE00956C.
Bertelsen, Erin R., Kovach, Nolan C., Reinhart, Benjamin J., Trewyn, Brian G., Antonio, Mark R., & Shafer, Jenifer C.. Multiscale investigations of europium(III) complexation with tetra-n-octyl diglycolamide confined in porous solid supports. United States. https://doi.org/10.1039/D0CE00956C
Bertelsen, Erin R., Kovach, Nolan C., Reinhart, Benjamin J., Trewyn, Brian G., Antonio, Mark R., and Shafer, Jenifer C.. Sat . "Multiscale investigations of europium(III) complexation with tetra-n-octyl diglycolamide confined in porous solid supports". United States. https://doi.org/10.1039/D0CE00956C. https://www.osti.gov/servlets/purl/1657542.
@article{osti_1657542,
title = {Multiscale investigations of europium(III) complexation with tetra-n-octyl diglycolamide confined in porous solid supports},
author = {Bertelsen, Erin R. and Kovach, Nolan C. and Reinhart, Benjamin J. and Trewyn, Brian G. and Antonio, Mark R. and Shafer, Jenifer C.},
abstractNote = {The microscopic, short-range coordination environments and mesoscopic, long-range structures of Eu3+ contacted with tetra-n-octyl diglycolamide (TODGA) confined on ordered mesoporous carbon (OMC) nanoparticles and Amberchrom CG 71 resin were probed using Eu L3-edge extended X ray absorption fine structure (EXAFS) as well as small-angle and wide-angle X ray scattering, SAXS and WAXS, respectively. A homoleptic Eu(TODGA)33+ coordination complex typical of liquid-liquid extraction (LLE) chemistry is present under low Eu3+ loading conditions on both solid supports. Deviations from this traditional structure motif appear at hyperstoichiometric Eu3+ loadings, above the 1:3 Eu3+ to TODGA mole ratio. Microcrystalline-like domains with multinuclear Eu speciation are templated by use of these high Eu3+ loading conditions with the functionalized OMC materials, highlighting a major departure of liquid-solid extraction chromatography (EXC) from the coordination chemistry of LLE. No such long-range spatial coherence was observed for analogous polyacrylic resin materials. Furthermore, these results demonstrate both the similarities and differences between multiscale structures in LLE and EXC, underscoring the opportunities for improved separation techniques based on solid supports with long-range spatial coherence (e.g., OMC systems) and without it (e.g., resin materials). Since crystallization was the first approach to adjacent lanthanide separations, the prospect of templating microcrystalline TODGA-lanthanide complexes that are otherwise not prone to crystallization by use of OMC nanoparticles represents a new entry to addressing long-standing issues in purification by liquid-solid phase separation.},
doi = {10.1039/D0CE00956C},
journal = {CrystEngComm},
number = 41,
volume = 22,
place = {United States},
year = {2020},
month = {11}
}

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