Elimination of CO2/N 2 Langmuir Sorption and Promotion of “N2-Phobicity” within High-Tg Glassy Membranes
Abstract
In this work, we demonstrate that the CO2/N2 gas separation performance of alkoxysilyl-substituted vinyl-added polynorbornenes (VAPNBs) may be significantly enhanced via incorporation of the monomer 5-tris(2-methoxyethoxy)-silyl-2-norbornene. As the molar ratio of this monomer is increased, substantial increases in CO2/N2 selectivity are realized with minimal decrease in CO2 permeability. This trend ignores the traditional permeability/selectivity “tradeoff” relationship and yields an optimal membrane whose performance reaches the 2008 upper bound for CO2/N2 separations. Though the inclusion of 5-tris(2-methoxyethoxy)-silyl-2-norbornene units was initially hypothesized to maximize CO2 solubility, detailed gas sorption studies reveal that these highly glassy materials essentially lack any Langmuir sorption component and indicate that their improved CO2/N2 selectivity is due to decreased N2 solubility within the matrix. Computational modeling suggests that the source of this apparent “N2-phobicity” is likely explained through comparative analyses of polymer–polymer and polymer–gas interactions. Lastly, mixed-gas permeation tests are performed to provide a more realistic look at real-world gas separation performance.
- Authors:
-
[2];
[2];
[4];
[1];
[1]
- Univ. of Tennessee, Knoxville, TN (United States)
- Aramco Services Company: Aramco Research Center, Boston, MA (United States)
- Aramco Services Company: Aramco Research Center, Boston, Massachusetts 02139, United States
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Institute for Computational Sciences (JIBS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1595310
- Grant/Contract Number:
- SC0018179
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 52; Journal Issue: 4; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Monomers; Solubility; Selectivity; Permeability; Polymers
Citation Formats
Maroon, Christopher R., Townsend, Jacob, Gmernicki, Kevin R., Harrigan, Daniel J., Sundell, Benjamin J., Lawrence, John A., Mahurin, Shannon M., Vogiatzis, Konstantinos D., and Long, Brian K. Elimination of CO2/N 2 Langmuir Sorption and Promotion of “N2-Phobicity” within High-Tg Glassy Membranes. United States: N. p., 2019.
Web. doi:10.1021/acs.macromol.8b02497.
Maroon, Christopher R., Townsend, Jacob, Gmernicki, Kevin R., Harrigan, Daniel J., Sundell, Benjamin J., Lawrence, John A., Mahurin, Shannon M., Vogiatzis, Konstantinos D., & Long, Brian K. Elimination of CO2/N 2 Langmuir Sorption and Promotion of “N2-Phobicity” within High-Tg Glassy Membranes. United States. https://doi.org/10.1021/acs.macromol.8b02497
Maroon, Christopher R., Townsend, Jacob, Gmernicki, Kevin R., Harrigan, Daniel J., Sundell, Benjamin J., Lawrence, John A., Mahurin, Shannon M., Vogiatzis, Konstantinos D., and Long, Brian K. Wed .
"Elimination of CO2/N 2 Langmuir Sorption and Promotion of “N2-Phobicity” within High-Tg Glassy Membranes". United States. https://doi.org/10.1021/acs.macromol.8b02497. https://www.osti.gov/servlets/purl/1595310.
@article{osti_1595310,
title = {Elimination of CO2/N 2 Langmuir Sorption and Promotion of “N2-Phobicity” within High-Tg Glassy Membranes},
author = {Maroon, Christopher R. and Townsend, Jacob and Gmernicki, Kevin R. and Harrigan, Daniel J. and Sundell, Benjamin J. and Lawrence, John A. and Mahurin, Shannon M. and Vogiatzis, Konstantinos D. and Long, Brian K.},
abstractNote = {In this work, we demonstrate that the CO2/N2 gas separation performance of alkoxysilyl-substituted vinyl-added polynorbornenes (VAPNBs) may be significantly enhanced via incorporation of the monomer 5-tris(2-methoxyethoxy)-silyl-2-norbornene. As the molar ratio of this monomer is increased, substantial increases in CO2/N2 selectivity are realized with minimal decrease in CO2 permeability. This trend ignores the traditional permeability/selectivity “tradeoff” relationship and yields an optimal membrane whose performance reaches the 2008 upper bound for CO2/N2 separations. Though the inclusion of 5-tris(2-methoxyethoxy)-silyl-2-norbornene units was initially hypothesized to maximize CO2 solubility, detailed gas sorption studies reveal that these highly glassy materials essentially lack any Langmuir sorption component and indicate that their improved CO2/N2 selectivity is due to decreased N2 solubility within the matrix. Computational modeling suggests that the source of this apparent “N2-phobicity” is likely explained through comparative analyses of polymer–polymer and polymer–gas interactions. Lastly, mixed-gas permeation tests are performed to provide a more realistic look at real-world gas separation performance.},
doi = {10.1021/acs.macromol.8b02497},
journal = {Macromolecules},
number = 4,
volume = 52,
place = {United States},
year = {Wed Feb 06 00:00:00 EST 2019},
month = {Wed Feb 06 00:00:00 EST 2019}
}
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