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

Liu, Xiaoyang; O’Harra, Kathryn E.; Bara, Jason E.; Turner, C. Heath

doi:10.1039/d0cp03424j

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

Journal Article · Tue Sep 01 00:00:00 EDT 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d0cp03424j· OSTI ID:1803276

^[1]; O’Harra, Kathryn E. ^[1];

^[1];

^[1]

Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemical and Biological Engineering

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.

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Research Organization:: Univ. of Alabama, Tuscaloosa, AL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018181

OSTI ID:: 1803276

Alternate ID(s):: OSTI ID: 1658428

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 22, Issue 36; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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