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Title: Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction

Abstract

Chemical separations, particularly liquid extractions, are pervasive in academic and industrial laboratories, yet a mechanistic understanding of the events governing their function are obscured by interfacial phenomena that are notoriously difficult to measure. In this work, we investigate the fundamental steps of ligand self-assembly as driven by changes in the interfacial H-bonding network using vibrational sum frequency generation. Our results show how the bulk pH modulates the interfacial structure of extractants at the buried oil/aqueous interface via the formation of unique H-bonding networks that order and bridge ligands to produce self-assembled aggregates. These extended H-bonded structures are key to the subsequent extraction of Co2+ from the aqueous phase in promoting micelle formation and subsequent ejection of the said micelle into the oil phase. The combination of static and time-resolved measurements reveals the events underlying complexities of liquid extractions at high [Co2+]:[ligand] ratios by showing an evolution of interfacially assembled structures that are readily tuned on a chemical basis by altering the compositions of the aqueous phase. The results of this work point to new principles to design-applied separations through the manipulation of surface charge, electrostatic screening, and the associated H-bonding networks that arise at the interface to facilitate organization andmore » subsequent extraction.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. 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 Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1649322
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 12; Journal Issue: 28; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; liquid extraction; micelle; aggregation; nonlinear spectroscopy; kinetics; interfaces; nonlinear optics; ligands; interfacial structure; extraction

Citation Formats

Chowdhury, Azhad U., Lin, Lu, and Doughty, Benjamin. Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction. United States: N. p., 2020. Web. doi:10.1021/acsami.0c06176.
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Chowdhury, Azhad U., Lin, Lu, & Doughty, Benjamin. Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction. United States. https://doi.org/10.1021/acsami.0c06176
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Chowdhury, Azhad U., Lin, Lu, and Doughty, Benjamin. Wed . "Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction". United States. https://doi.org/10.1021/acsami.0c06176. https://www.osti.gov/servlets/purl/1649322.
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@article{osti_1649322,
title = {Hydrogen-Bond-Driven Chemical Separations: Elucidating the Interfacial Steps of Self-Assembly in Solvent Extraction},
author = {Chowdhury, Azhad U. and Lin, Lu and Doughty, Benjamin},
abstractNote = {Chemical separations, particularly liquid extractions, are pervasive in academic and industrial laboratories, yet a mechanistic understanding of the events governing their function are obscured by interfacial phenomena that are notoriously difficult to measure. In this work, we investigate the fundamental steps of ligand self-assembly as driven by changes in the interfacial H-bonding network using vibrational sum frequency generation. Our results show how the bulk pH modulates the interfacial structure of extractants at the buried oil/aqueous interface via the formation of unique H-bonding networks that order and bridge ligands to produce self-assembled aggregates. These extended H-bonded structures are key to the subsequent extraction of Co2+ from the aqueous phase in promoting micelle formation and subsequent ejection of the said micelle into the oil phase. The combination of static and time-resolved measurements reveals the events underlying complexities of liquid extractions at high [Co2+]:[ligand] ratios by showing an evolution of interfacially assembled structures that are readily tuned on a chemical basis by altering the compositions of the aqueous phase. The results of this work point to new principles to design-applied separations through the manipulation of surface charge, electrostatic screening, and the associated H-bonding networks that arise at the interface to facilitate organization and subsequent extraction.},
doi = {10.1021/acsami.0c06176},
journal = {ACS Applied Materials and Interfaces},
number = 28,
volume = 12,
place = {United States},
year = {Wed Jun 17 00:00:00 EDT 2020},
month = {Wed Jun 17 00:00:00 EDT 2020}
}
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https://doi.org/10.1021/acsami.0c06176
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