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Title: Ion-specific clustering of metal–amphiphile complexes in rare earth separations

Abstract

The nanoscale structure of a complex fluid can play a major role in the selective adsorption of ions at the nanometric interfaces, which is crucial in industrial and technological applications. Here we study the effect of anions and lanthanide ions on the nanoscale structure of a complex fluid formed by metal-amphiphile complexes, using small angle X-ray scattering. The nano- and mesoscale structures we observed can be directly connected to the preferential transfer of light (La and Nd) or heavy (Er and Lu) lanthanides into the complex fluid from an aqueous solution. While toluene-based complex fluids containing trioctylmethylammonium-nitrate (TOMA-nitrate) always show the same mesoscale hierarchical structure regardless of lanthanide loading and prefer light lanthanides, those containing TOMA-thiocyanate show an evolution of the mesoscale structure as a function of the lanthanide loading and prefer heavy lanthanides. The hierarchical structure indicates the presence of attractive interactions between ion-amphiphile aggregates, causing them to form clusters. A clustering model that accounts for the hard sphere repulsions and short-range attractions between the aggregates has been adapted to model the X-ray scattering results. The new model successfully describes the nanoscale structure and helps in understanding the mechanisms responsible for amphiphile assisted ion transport between immiscible liquids. Accordingly,more » our results imply different mechanisms of lanthanide transport depending on the anion present in the complex fluid and correspond with anion-dependent trends in rare earth separations.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1664619
Alternate Identifier(s):
OSTI ID: 1783277
Grant/Contract Number:  
AC02- 06CH11357; AC02-06CH11357.; AC02-06CH11357
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Name: Nanoscale Journal Volume: 12 Journal Issue: 39; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Solvent extraction; small angle X-ray scattering; specific ion effects; complex fluids; amphiphile aggregation

Citation Formats

Nayak, Srikanth, Lovering, Kaitlin, and Uysal, Ahmet. Ion-specific clustering of metal–amphiphile complexes in rare earth separations. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0NR04231E.
Nayak, Srikanth, Lovering, Kaitlin, & Uysal, Ahmet. Ion-specific clustering of metal–amphiphile complexes in rare earth separations. United Kingdom. https://doi.org/10.1039/D0NR04231E
Nayak, Srikanth, Lovering, Kaitlin, and Uysal, Ahmet. Thu . "Ion-specific clustering of metal–amphiphile complexes in rare earth separations". United Kingdom. https://doi.org/10.1039/D0NR04231E.
@article{osti_1664619,
title = {Ion-specific clustering of metal–amphiphile complexes in rare earth separations},
author = {Nayak, Srikanth and Lovering, Kaitlin and Uysal, Ahmet},
abstractNote = {The nanoscale structure of a complex fluid can play a major role in the selective adsorption of ions at the nanometric interfaces, which is crucial in industrial and technological applications. Here we study the effect of anions and lanthanide ions on the nanoscale structure of a complex fluid formed by metal-amphiphile complexes, using small angle X-ray scattering. The nano- and mesoscale structures we observed can be directly connected to the preferential transfer of light (La and Nd) or heavy (Er and Lu) lanthanides into the complex fluid from an aqueous solution. While toluene-based complex fluids containing trioctylmethylammonium-nitrate (TOMA-nitrate) always show the same mesoscale hierarchical structure regardless of lanthanide loading and prefer light lanthanides, those containing TOMA-thiocyanate show an evolution of the mesoscale structure as a function of the lanthanide loading and prefer heavy lanthanides. The hierarchical structure indicates the presence of attractive interactions between ion-amphiphile aggregates, causing them to form clusters. A clustering model that accounts for the hard sphere repulsions and short-range attractions between the aggregates has been adapted to model the X-ray scattering results. The new model successfully describes the nanoscale structure and helps in understanding the mechanisms responsible for amphiphile assisted ion transport between immiscible liquids. Accordingly, our results imply different mechanisms of lanthanide transport depending on the anion present in the complex fluid and correspond with anion-dependent trends in rare earth separations.},
doi = {10.1039/D0NR04231E},
journal = {Nanoscale},
number = 39,
volume = 12,
place = {United Kingdom},
year = {2020},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D0NR04231E

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