Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity

David C. Cantu, Juntaek Lee, Mal Soon Lee, David J. Heldebrant, Phillip K. Koech, Charles J. Freeman, Roger Rousseau, Vassiliki Alexandra Glezakou

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

The deployment of transformational nonaqueous CO2-capture solvent systems is encumbered by high viscosities even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we present key molecular features that control bulk viscosity. Fast CO2-uptake kinetics arise from close proximity of the alcohol and amine sites involved in CO2 binding in a concerted fashion, resulting in a Zwitterion containing both an alkyl-carbonate and a protonated amine. The population of internal hydrogen bonds between the two functional groups determines the solution viscosity. Unlike the ion pair interactions in ionic liquids, these observations are novel and specific to a hydrogen-bonding network that can be controlled by chemically tuning single molecule CO2 capture solvents. We present a molecular design strategy to reduce viscosity by shifting the proton transfer equilibrium toward a neutral acid/amine species, as opposed to the ubiquitously accepted zwitterionic state. The molecular design concepts proposed here are readily extensible to other CO2 capture technologies.

Original languageEnglish
Pages (from-to)1646-1652
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume7
Issue number9
DOIs
Publication statusPublished - May 5 2016

Fingerprint

acid base equilibrium
Ionic Liquids
Ionic liquids
Viscosity
viscosity
Amines
amines
liquids
Hydrogen bonds
Molecules
zwitterions
Proton transfer
organic liquids
Carbonates
Functional groups
proximity
molecules
carbonates
alcohols
Alcohols

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Cantu, D. C., Lee, J., Lee, M. S., Heldebrant, D. J., Koech, P. K., Freeman, C. J., ... Glezakou, V. A. (2016). Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity. Journal of Physical Chemistry Letters, 7(9), 1646-1652. https://doi.org/10.1021/acs.jpclett.6b00395

Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity. / Cantu, David C.; Lee, Juntaek; Lee, Mal Soon; Heldebrant, David J.; Koech, Phillip K.; Freeman, Charles J.; Rousseau, Roger; Glezakou, Vassiliki Alexandra.

In: Journal of Physical Chemistry Letters, Vol. 7, No. 9, 05.05.2016, p. 1646-1652.

Research output: Contribution to journalArticle

Cantu, David C. ; Lee, Juntaek ; Lee, Mal Soon ; Heldebrant, David J. ; Koech, Phillip K. ; Freeman, Charles J. ; Rousseau, Roger ; Glezakou, Vassiliki Alexandra. / Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity. In: Journal of Physical Chemistry Letters. 2016 ; Vol. 7, No. 9. pp. 1646-1652.
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