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 »
- Authors:
-
- 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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