Controlling the intermediate structure of an ionic liquid for f-block element separations

Abney, Carter W.; Do, Changwoo; Luo, Huimin; Wright, Joshua; He, Lilin; Dai, Sheng

doi:10.1021/acs.jpclett.7b00755

Title: Controlling the intermediate structure of an ionic liquid for f-block element separations

Full Record
Other Related Research

Abstract

Recent research has revealed molecular structure beyond the inner coordination sphere is essential in defining the performance of separations processes, but nevertheless remains largely unexplored. Here we apply small angle neutron scattering (SANS) and x-ray absorption fine structure (XAFS) spectroscopy to investigate the structure of an ionic liquid system studied for f-block element separations. SANS data reveal dramatic changes in the ionic liquid microstructure (~150 Å) which we demonstrate can be controlled by judicious selection of counter ion. Mesoscale structural features (> 500 Å) are also observed as a function of metal concentration. XAFS analysis supports formation of extended aggregate structures, similar to those observed in traditional solvent extraction processes, and suggest additional parallels may be drawn from further study. As a result, achieving precise tunability over the intermediate features is an important development in controlling mesoscale structure and realizing advanced new forms of soft matter.

Authors:

^[1]; Do, Changwoo ^[1]; Luo, Huimin ^[1]; Wright, Joshua ^[2]; He, Lilin ^[1];

^[3]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Argonne National Lab. (ANL), Lemont, IL (United States); Illinois Inst. of Technology, Chicago, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Publication Date:: 2017-04-19

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1364322

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry Letters

Additional Journal Information:: Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 1948-7185

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Abney, Carter W., Do, Changwoo, Luo, Huimin, Wright, Joshua, He, Lilin, and Dai, Sheng. Controlling the intermediate structure of an ionic liquid for f-block element separations.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.jpclett.7b00755.

Copy to clipboard


                    Abney, Carter W., Do, Changwoo, Luo, Huimin, Wright, Joshua, He, Lilin, & Dai, Sheng. Controlling the intermediate structure of an ionic liquid for f-block element separations.  United States.  doi:https://doi.org/10.1021/acs.jpclett.7b00755

Copy to clipboard


                    Abney, Carter W., Do, Changwoo, Luo, Huimin, Wright, Joshua, He, Lilin, and Dai, Sheng. Wed .  
        "Controlling the intermediate structure of an ionic liquid for f-block element separations".  United States.  doi:https://doi.org/10.1021/acs.jpclett.7b00755.  https://www.osti.gov/servlets/purl/1364322.

Copy to clipboard


                    
@article{osti_1364322,

  title        = {Controlling the intermediate structure of an ionic liquid for f-block element separations},

  author       = {Abney, Carter W. and Do, Changwoo and Luo, Huimin and Wright, Joshua and He, Lilin and Dai, Sheng},

  abstractNote = {Recent research has revealed molecular structure beyond the inner coordination sphere is essential in defining the performance of separations processes, but nevertheless remains largely unexplored. Here we apply small angle neutron scattering (SANS) and x-ray absorption fine structure (XAFS) spectroscopy to investigate the structure of an ionic liquid system studied for f-block element separations. SANS data reveal dramatic changes in the ionic liquid microstructure (~150 Å) which we demonstrate can be controlled by judicious selection of counter ion. Mesoscale structural features (> 500 Å) are also observed as a function of metal concentration. XAFS analysis supports formation of extended aggregate structures, similar to those observed in traditional solvent extraction processes, and suggest additional parallels may be drawn from further study. As a result, achieving precise tunability over the intermediate features is an important development in controlling mesoscale structure and realizing advanced new forms of soft matter.},

  doi          = {10.1021/acs.jpclett.7b00755},

  journal      = {Journal of Physical Chemistry Letters},

  number       = 9,

  volume       = 8,

  place        = {United States},

  year         = {2017},

  month        = {4}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: https://doi.org/10.1021/acs.jpclett.7b00755

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers

Journal Article Sternhagen, Garrett L. ; Gupta, Sudipta ; Zhang, Yueheng ; ... - Journal of the American Chemical Society

A series of amphiphilic ionic peptoid block copolymers where the total number (1 or 3) and position of ionic monomers along the polymer chain are precisely controlled have been synthesized by the submonomer method. Upon dissolution in water at pH = 9, the amphiphilic peptoids self-assemble into small spherical micelles having hydrodynamic radius in ~5–10 nm range and critical micellar concentration (CMC) in the 0.034–0.094 mg/mL range. Small-angle neutron scattering (SANS) analysis of the micellar solutions revealed unprecedented dependence of the micellar structure on the number and position of ionic monomers along the chain. It was found that the micellarmore »« less
Cited by 11
DOI: https://doi.org/10.1021/jacs.8b00461

Full Text Available
Electrolyte Solvation and Ionic Association. VI. Acetonitrile-Lithium Salt Mixtures. Highly Associated Salts Revisited

Journal Article Borodin, Oleg ; Han, Sang D. ; Daubert, James S. ; ... - Journal of the Electrochemical Society

Molecular dynamics (MD) simulations of acetonitrile (AN) mixtures with LiBF₄, LiCF₃SO₃ and LiCF₃CO₂ provide extensive details about the molecular- and mesoscale-level solution interactions and thus explanations as to why these electrolytes have very different thermal phase behavior and electrochemical/physicochemical properties. The simulation results are in full accord with a previous experimental study of these (AN)n-LiX electrolytes. This computational study reveals how the structure of the anions strongly influences the ionic association tendency of the ions, the manner in which the aggregate solvates assemble in solution and the length of time in which the anions remain coordinated to the Li⁺ cationsmore »« less
DOI: https://doi.org/10.1149/2.0891503jes
SANS study on the solvated structure and molecular interactions of a thermo-responsive polymer in a room temperature ionic liquid

Journal Article Hirosawa, Kazu ; Fujii, Kenta ; Ueki, Takeshi ; ... - Physical Chemistry Chemical Physics. PCCP (Print)

Here, we utilized small-angle neutron scattering (SANS) to quantitatively characterize the LCST-type phase behavior of the poly(benzyl methacrylate) (PBnMA) derivative poly(2-phenylethyl methacrylate) (PPhEtMA) in the deuterated ionic liquid (IL) d₈-1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (d₈-[C₂mIm⁺][TFSA^-]). The SANS curves showed a discontinuous change from those characteristics of dispersed polymer chains to those of large aggregates of PPhEtMA chains suspended in the IL solution, indicating that phase separation occurs discontinuously at T_c. We also evaluated the enthalpic and entropic contributions to the effective interaction parameter χ_eff of PPhEtMA in [C₂mIm⁺][TFSA^-] and compared them with those of PBnMA. The absolute value of the enthalpic contribution observedmore »« less
Cited by 6
DOI: https://doi.org/10.1039/C6CP02254E

Full Text Available
Colloidal three-dimensional covalent organic frameworks and their application as porous liquids

Journal Article Mow, Rachel E. ; Lipton, Andrew S. ; Shulda, Sarah ; ... - Journal of Materials Chemistry. A

Developing solid porous materials into free-flowing liquids with permanent porosity is a promising strategy for overcoming certain limitations of conventional sorbent materials employed in gas storage and separation applications. The ability to control the pore size and chemical functionalities of organic frameworks gives these particular nanoporous materials distinct advantages over other small cage-like molecules or hollow particles that have been developed into porous liquids. In this paper, we describe the synthesis of a 3D imine-linked colloidal covalent organic framework (COF)-based porous liquid, designed for efficient size-exclusion of solvent, as well as for long-term stability. By tethering ionic liquids to themore »« less
DOI: https://doi.org/10.1039/d0ta06768g
Colloidal Three-Dimensional Covalent Organic Frameworks and Their Application as Porous Liquids

Journal Article Mow, Rachel E. ; Lipton, Andrew S. ; Shulda, Sarah ; ... - Journal of Materials Chemistry A

Developing solid porous materials into free-flowing liquids with permanent porosity is a promising strategy for overcoming certain limitations of conventional sorbent materials employed in gas storage and separation applications. The ability to control the pore size and chemical functionalities of organic frameworks gives these particular nanoporous materials distinct advantages over other small cage-like molecules or hollow particles that have been developed into porous liquids. Here, we describe the synthesis of a 3D imine-linked colloidal covalent organic framework (COF)-based porous liquid, designed for efficient size-exclusion of solvent, as well as for long-term stability. By tethering ionic liquids to the colloid surface,more »« less
DOI: https://doi.org/10.1039/D0TA06768G

Similar Records