Elimination of CO                         2                         /N                         2                          Langmuir Sorption and Promotion of "n                         2                         -Phobicity" within High- T                         g                          Glassy Membranes

Christopher R. Maroon; Jacob Townsend; Kevin R. Gmernicki; Daniel J. Harrigan; Benjamin J. Sundell; John A. Lawrence; Shannon M. Mahurin; Konstantinos D. Vogiatzis; Brian K. Long

doi:10.1021/acs.macromol.8b02497

Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes

Christopher R. Maroon, Jacob Townsend, Kevin R. Gmernicki, Daniel J. Harrigan, Benjamin J. Sundell, John A. Lawrence, Shannon M. Mahurin, Konstantinos D. Vogiatzis, Brian K. Long

Nanomaterials Chemistry Group

Research output: Contribution to journal › Article › peer-review

45 Scopus citations

Abstract

We demonstrate that the CO ₂ /N ₂ 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 CO ₂ /N ₂ selectivity are realized with minimal decrease in CO ₂ permeability. This trend ignores the traditional permeability/selectivity "trade-off" relationship and yields an optimal membrane whose performance reaches the 2008 upper bound for CO ₂ /N ₂ separations. Though the inclusion of 5-tris(2-methoxyethoxy)-silyl-2-norbornene units was initially hypothesized to maximize CO ₂ solubility, detailed gas sorption studies reveal that these highly glassy materials essentially lack any Langmuir sorption component and indicate that their improved CO ₂ /N ₂ selectivity is due to decreased N ₂ solubility within the matrix. Computational modeling suggests that the source of this apparent "N ₂ -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.

Original language	English
Pages (from-to)	1589-1600
Number of pages	12
Journal	Macromolecules
Volume	52
Issue number	4
DOIs	https://doi.org/10.1021/acs.macromol.8b02497
State	Published - Feb 26 2019

Funding

This work is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under Award DE-SC0018179. This work is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under Award DE-SC0018179. J.T. and K.D.V. acknowledge the University of Tennessee for financial support of this work (start-up funds) and the Advanced Computer Facility (ACF) of the University of Tennessee for computational resources. S.M. performed X-ray diffraction measurements and contributed to data analysis and was supported by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Chemical Sciences, Geosciences, and Biosciences Division. The authors thank Huntsman Chemical for their generous donation of Matrimid 5218 and Prof. Benny Freeman for generously providing polycarbonate samples, which were each used to validate the permeation and sorption instruments used herein. The authors also thank Prof. Benny Freeman and Melanie Merrick for their invaluable insight during the construction and validation of these instruments.

Funders	Funder number
Advanced Computer Facility
Office of Basic Energy Sciences
U.S. Department of Energy
Office of Science
Basic Energy Sciences
University of Tennessee
Chemical Sciences, Geosciences, and Biosciences Division	DE-SC0018179

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Maroon, C. R., Townsend, J., Gmernicki, K. R., Harrigan, D. J., Sundell, B. J., Lawrence, J. A., Mahurin, S. M., Vogiatzis, K. D., & Long, B. K. (2019). Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes Macromolecules, 52(4), 1589-1600. https://doi.org/10.1021/acs.macromol.8b02497

Maroon, Christopher R. ; Townsend, Jacob ; Gmernicki, Kevin R. et al. / Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes In: Macromolecules. 2019 ; Vol. 52, No. 4. pp. 1589-1600.

@article{2f037fc64374431eacfd43a489e28811,

title = " Elimination of CO 2 /N 2 Langmuir Sorption and Promotion of {"}n 2 -Phobicity{"} within High- T g Glassy Membranes ",

abstract = " We demonstrate that the CO 2 /N 2 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 CO 2 /N 2 selectivity are realized with minimal decrease in CO 2 permeability. This trend ignores the traditional permeability/selectivity {"}trade-off{"} relationship and yields an optimal membrane whose performance reaches the 2008 upper bound for CO 2 /N 2 separations. Though the inclusion of 5-tris(2-methoxyethoxy)-silyl-2-norbornene units was initially hypothesized to maximize CO 2 solubility, detailed gas sorption studies reveal that these highly glassy materials essentially lack any Langmuir sorption component and indicate that their improved CO 2 /N 2 selectivity is due to decreased N 2 solubility within the matrix. Computational modeling suggests that the source of this apparent {"}N 2 -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.",

author = "Maroon, {Christopher R.} and Jacob Townsend 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.}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = feb,

day = "26",

doi = "10.1021/acs.macromol.8b02497",

language = "English",

volume = "52",

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Maroon, CR, Townsend, J, Gmernicki, KR, Harrigan, DJ, Sundell, BJ, Lawrence, JA, Mahurin, SM, Vogiatzis, KD & Long, BK 2019, ' Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes ', Macromolecules, vol. 52, no. 4, pp. 1589-1600. https://doi.org/10.1021/acs.macromol.8b02497

Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes . / Maroon, Christopher R.; Townsend, Jacob; Gmernicki, Kevin R. et al.
In: Macromolecules, Vol. 52, No. 4, 26.02.2019, p. 1589-1600.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Elimination of CO 2 /N 2 Langmuir Sorption and Promotion of "n 2 -Phobicity" within High- T g Glassy Membranes

AU - Maroon, Christopher R.

AU - Townsend, Jacob

AU - Gmernicki, Kevin R.

AU - Harrigan, Daniel J.

AU - Sundell, Benjamin J.

AU - Lawrence, John A.

AU - Mahurin, Shannon M.

AU - Vogiatzis, Konstantinos D.

AU - Long, Brian K.

PY - 2019/2/26

Y1 - 2019/2/26

N2 - We demonstrate that the CO 2 /N 2 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 CO 2 /N 2 selectivity are realized with minimal decrease in CO 2 permeability. This trend ignores the traditional permeability/selectivity "trade-off" relationship and yields an optimal membrane whose performance reaches the 2008 upper bound for CO 2 /N 2 separations. Though the inclusion of 5-tris(2-methoxyethoxy)-silyl-2-norbornene units was initially hypothesized to maximize CO 2 solubility, detailed gas sorption studies reveal that these highly glassy materials essentially lack any Langmuir sorption component and indicate that their improved CO 2 /N 2 selectivity is due to decreased N 2 solubility within the matrix. Computational modeling suggests that the source of this apparent "N 2 -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.

AB - We demonstrate that the CO 2 /N 2 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 CO 2 /N 2 selectivity are realized with minimal decrease in CO 2 permeability. This trend ignores the traditional permeability/selectivity "trade-off" relationship and yields an optimal membrane whose performance reaches the 2008 upper bound for CO 2 /N 2 separations. Though the inclusion of 5-tris(2-methoxyethoxy)-silyl-2-norbornene units was initially hypothesized to maximize CO 2 solubility, detailed gas sorption studies reveal that these highly glassy materials essentially lack any Langmuir sorption component and indicate that their improved CO 2 /N 2 selectivity is due to decreased N 2 solubility within the matrix. Computational modeling suggests that the source of this apparent "N 2 -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.

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U2 - 10.1021/acs.macromol.8b02497

DO - 10.1021/acs.macromol.8b02497

M3 - Article

AN - SCOPUS:85061546704

SN - 0024-9297

VL - 52

SP - 1589

EP - 1600

JO - Macromolecules

JF - Macromolecules

IS - 4

ER -

Maroon CR, Townsend J, Gmernicki KR, Harrigan DJ, Sundell BJ, Lawrence JA et al. Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes Macromolecules. 2019 Feb 26;52(4):1589-1600. doi: 10.1021/acs.macromol.8b02497

Elimination of CO ₂ /N ₂ Langmuir Sorption and Promotion of "n ₂ -Phobicity" within High- T _g Glassy Membranes

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