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Title: Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity

Abstract

The deployment of transformational non-aqueous CO2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, this work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
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  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1254559
Report Number(s):
PNNL-SA-114453
Journal ID: ISSN 1948-7185; AA6510000
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 7; Journal Issue: 9; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 capture solvent systems; ab Initio molecular dynamics; classical molecular dynamics; switchable ionic liquids; viscosity

Citation Formats

Cantu, David C., Lee, Juntaek, Lee, Mal -Soon, Heldebrant, David J., Koech, Phillip K., Freeman, Charles J., Rousseau, Roger, and Glezakou, Vassiliki -Alexandra. Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity. United States: N. p., 2016. Web. doi:10.1021/acs.jpclett.6b00395.
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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. United States. https://doi.org/10.1021/acs.jpclett.6b00395
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Cantu, David C., Lee, Juntaek, Lee, Mal -Soon, Heldebrant, David J., Koech, Phillip K., Freeman, Charles J., Rousseau, Roger, and Glezakou, Vassiliki -Alexandra. Mon . "Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity". United States. https://doi.org/10.1021/acs.jpclett.6b00395. https://www.osti.gov/servlets/purl/1254559.
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@article{osti_1254559,
title = {Dynamic acid/base equilibrium in single component switchable ionic liquids and consequences on viscosity},
author = {Cantu, David C. and Lee, Juntaek and Lee, Mal -Soon and Heldebrant, David J. and Koech, Phillip K. and Freeman, Charles J. and Rousseau, Roger and Glezakou, Vassiliki -Alexandra},
abstractNote = {The deployment of transformational non-aqueous CO2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, this work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.},
doi = {10.1021/acs.jpclett.6b00395},
journal = {Journal of Physical Chemistry Letters},
number = 9,
volume = 7,
place = {United States},
year = {Mon Mar 28 00:00:00 EDT 2016},
month = {Mon Mar 28 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.jpclett.6b00395
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    Development of High‐Capacity and Water‐Lean CO 2 Absorbents by a Concise Molecular Design Strategy through Viscosity Control
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