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Title: Molecular insight into the anion effect and free volume effect of CO2 solubility in multivalent ionic liquids

Abstract

For many years, experimental and theoretical studies have investigated the solubility of CO2 in a variety of ionic liquids (ILs), but the overarching absorption mechanism is still unclear. Currently, two different factors are believed to dominate the absorption performance: (a) the fractional free volume (FFV) accessible for absorption; and (b) the nature of the CO2 interactions with the anion species. The FFV is often more influential than the specific choice of the anion, but neither mechanism provides a complete picture. Herein, we have attempted to decouple these mechanisms in order to provide a more definitive molecular-level perspective of CO2 absorption in IL solvents. We simulate a series of nine different multivalent ILs comprised of imidazolium cations and sulfonate/sulfonimide anions tethered to benzene rings, along with a comprehensive analysis of the CO2 absorption and underlying molecular-level features. We find that the CO2 solubility has a very strong, linear correlation with respect to FFV, but only when comparisons are constrained to a common anion species. The choice of anion results in a fundamental remapping of the correlation between CO2 solubility and FFV. Overall, the free volume effect dominates in the ILs with smaller FFV values, while the choice of anion becomes moremore » important in the systems with larger FFVs. Our proposed mechanistic map is intended to provide a more consistent framework for guiding further IL design for gas absorption applications.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Alabama, Tuscaloosa, AL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1803276
Alternate Identifier(s):
OSTI ID: 1658428
Grant/Contract Number:  
SC0018181
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 22; Journal Issue: 36; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Xiaoyang, O’Harra, Kathryn E., Bara, Jason E., and Turner, C. Heath. Molecular insight into the anion effect and free volume effect of CO2 solubility in multivalent ionic liquids. United States: N. p., 2020. Web. doi:10.1039/d0cp03424j.
Liu, Xiaoyang, O’Harra, Kathryn E., Bara, Jason E., & Turner, C. Heath. Molecular insight into the anion effect and free volume effect of CO2 solubility in multivalent ionic liquids. United States. https://doi.org/10.1039/d0cp03424j
Liu, Xiaoyang, O’Harra, Kathryn E., Bara, Jason E., and Turner, C. Heath. Tue . "Molecular insight into the anion effect and free volume effect of CO2 solubility in multivalent ionic liquids". United States. https://doi.org/10.1039/d0cp03424j. https://www.osti.gov/servlets/purl/1803276.
@article{osti_1803276,
title = {Molecular insight into the anion effect and free volume effect of CO2 solubility in multivalent ionic liquids},
author = {Liu, Xiaoyang and O’Harra, Kathryn E. and Bara, Jason E. and Turner, C. Heath},
abstractNote = {For many years, experimental and theoretical studies have investigated the solubility of CO2 in a variety of ionic liquids (ILs), but the overarching absorption mechanism is still unclear. Currently, two different factors are believed to dominate the absorption performance: (a) the fractional free volume (FFV) accessible for absorption; and (b) the nature of the CO2 interactions with the anion species. The FFV is often more influential than the specific choice of the anion, but neither mechanism provides a complete picture. Herein, we have attempted to decouple these mechanisms in order to provide a more definitive molecular-level perspective of CO2 absorption in IL solvents. We simulate a series of nine different multivalent ILs comprised of imidazolium cations and sulfonate/sulfonimide anions tethered to benzene rings, along with a comprehensive analysis of the CO2 absorption and underlying molecular-level features. We find that the CO2 solubility has a very strong, linear correlation with respect to FFV, but only when comparisons are constrained to a common anion species. The choice of anion results in a fundamental remapping of the correlation between CO2 solubility and FFV. Overall, the free volume effect dominates in the ILs with smaller FFV values, while the choice of anion becomes more important in the systems with larger FFVs. Our proposed mechanistic map is intended to provide a more consistent framework for guiding further IL design for gas absorption applications.},
doi = {10.1039/d0cp03424j},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 36,
volume = 22,
place = {United States},
year = {Tue Sep 01 00:00:00 EDT 2020},
month = {Tue Sep 01 00:00:00 EDT 2020}
}

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