Exploring the effect of intra-chain rigidity on mixed-gas separation performance of a Triptycene-Tröger's base ladder polymer (PIM-Trip-TB) by atomistic simulations

Marcel Balcik; Yingge Wang; Ingo Pinnau

doi:10.1016/j.memsci.2023.121614

Exploring the effect of intra-chain rigidity on mixed-gas separation performance of a Triptycene-Tröger's base ladder polymer (PIM-Trip-TB) by atomistic simulations

Marcel Balcik, Yingge Wang, Ingo Pinnau

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

12 Scopus citations

Abstract

Atomistic simulations were performed to investigate pure- and mixed-gas CO2/CH4 separation properties of a ladder polymer of intrinsic microporosity, PIM-Trip-TB. Despite expected intra-chain rigidity of the polymer, previous experimental reports observed significant loss in CO2/CH4 perm-selectivity under high-pressure mixed-gas conditions. In this work, all-atomistic simulations were applied to accurately predict density, gas uptakes and gas diffusion properties of PIM-Trip-TB. Competitive sorption favoring CO2 over CH4 was apparent in mixed-gas sorption simulations, as previously demonstrated by experimental studies from our group. This effect resulted in enhanced mixed-gas CO2/CH4 solubility selectivity. However, this increase did not translate to increased mixed-gas perm-selectivity because a significant increase in CH4 permeability was observed by co-permeation of CO2 relative to the pure-gas value. Back-calculated diffusion coefficients indicated very low CO2/CH4 diffusion selectivity under mixed-gas conditions, eliminating any gain from competitive sorption. Structural analysis confirmed intact intra-chain rigidity of the polymer; on the other hand, a significant increase in fractional free volume (FFV) and shift to larger pores in the pore size distribution was revealed by our simulations which may be attributed to polymer dilation due a reduction in inter-chain packing.

Original language	English (US)
Pages (from-to)	121614
Journal	Journal of Membrane Science
DOIs	https://doi.org/10.1016/j.memsci.2023.121614
State	Published - Mar 31 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-04-03
Acknowledged KAUST grant number(s): BAS/1/1323-01-01
Acknowledgements: The research reported in this paper was funded (BAS/1/1323-01-01) by King Abdullah University of Science and Technology (KAUST), Saudi Arabia. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.

ASJC Scopus subject areas

Biochemistry
Filtration and Separation
General Materials Science
Physical and Theoretical Chemistry

Access to Document

10.1016/j.memsci.2023.121614

https://repository.kaust.edu.sa/bitstream/10754/690790/1/1-s2.0-S0376738823002703-main_removed.pdf

Cite this

@article{ec003097486d41358ba2674cac4abd2e,

title = "Exploring the effect of intra-chain rigidity on mixed-gas separation performance of a Triptycene-Tr{\"o}ger's base ladder polymer (PIM-Trip-TB) by atomistic simulations",

abstract = "Atomistic simulations were performed to investigate pure- and mixed-gas CO2/CH4 separation properties of a ladder polymer of intrinsic microporosity, PIM-Trip-TB. Despite expected intra-chain rigidity of the polymer, previous experimental reports observed significant loss in CO2/CH4 perm-selectivity under high-pressure mixed-gas conditions. In this work, all-atomistic simulations were applied to accurately predict density, gas uptakes and gas diffusion properties of PIM-Trip-TB. Competitive sorption favoring CO2 over CH4 was apparent in mixed-gas sorption simulations, as previously demonstrated by experimental studies from our group. This effect resulted in enhanced mixed-gas CO2/CH4 solubility selectivity. However, this increase did not translate to increased mixed-gas perm-selectivity because a significant increase in CH4 permeability was observed by co-permeation of CO2 relative to the pure-gas value. Back-calculated diffusion coefficients indicated very low CO2/CH4 diffusion selectivity under mixed-gas conditions, eliminating any gain from competitive sorption. Structural analysis confirmed intact intra-chain rigidity of the polymer; on the other hand, a significant increase in fractional free volume (FFV) and shift to larger pores in the pore size distribution was revealed by our simulations which may be attributed to polymer dilation due a reduction in inter-chain packing.",

author = "Marcel Balcik and Yingge Wang and Ingo Pinnau",

note = "KAUST Repository Item: Exported on 2023-04-03 Acknowledged KAUST grant number(s): BAS/1/1323-01-01 Acknowledgements: The research reported in this paper was funded (BAS/1/1323-01-01) by King Abdullah University of Science and Technology (KAUST), Saudi Arabia. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.",

year = "2023",

month = mar,

day = "31",

doi = "10.1016/j.memsci.2023.121614",

language = "English (US)",

pages = "121614",

journal = "Journal of Membrane Science",

issn = "0376-7388",

publisher = "Elsevier",

}

TY - JOUR

T1 - Exploring the effect of intra-chain rigidity on mixed-gas separation performance of a Triptycene-Tröger's base ladder polymer (PIM-Trip-TB) by atomistic simulations

AU - Balcik, Marcel

AU - Wang, Yingge

AU - Pinnau, Ingo

N1 - KAUST Repository Item: Exported on 2023-04-03 Acknowledged KAUST grant number(s): BAS/1/1323-01-01 Acknowledgements: The research reported in this paper was funded (BAS/1/1323-01-01) by King Abdullah University of Science and Technology (KAUST), Saudi Arabia. For computer time, this research used the resources of the Supercomputing Laboratory at King Abdullah University of Science & Technology (KAUST) in Thuwal, Saudi Arabia.

PY - 2023/3/31

Y1 - 2023/3/31

N2 - Atomistic simulations were performed to investigate pure- and mixed-gas CO2/CH4 separation properties of a ladder polymer of intrinsic microporosity, PIM-Trip-TB. Despite expected intra-chain rigidity of the polymer, previous experimental reports observed significant loss in CO2/CH4 perm-selectivity under high-pressure mixed-gas conditions. In this work, all-atomistic simulations were applied to accurately predict density, gas uptakes and gas diffusion properties of PIM-Trip-TB. Competitive sorption favoring CO2 over CH4 was apparent in mixed-gas sorption simulations, as previously demonstrated by experimental studies from our group. This effect resulted in enhanced mixed-gas CO2/CH4 solubility selectivity. However, this increase did not translate to increased mixed-gas perm-selectivity because a significant increase in CH4 permeability was observed by co-permeation of CO2 relative to the pure-gas value. Back-calculated diffusion coefficients indicated very low CO2/CH4 diffusion selectivity under mixed-gas conditions, eliminating any gain from competitive sorption. Structural analysis confirmed intact intra-chain rigidity of the polymer; on the other hand, a significant increase in fractional free volume (FFV) and shift to larger pores in the pore size distribution was revealed by our simulations which may be attributed to polymer dilation due a reduction in inter-chain packing.

AB - Atomistic simulations were performed to investigate pure- and mixed-gas CO2/CH4 separation properties of a ladder polymer of intrinsic microporosity, PIM-Trip-TB. Despite expected intra-chain rigidity of the polymer, previous experimental reports observed significant loss in CO2/CH4 perm-selectivity under high-pressure mixed-gas conditions. In this work, all-atomistic simulations were applied to accurately predict density, gas uptakes and gas diffusion properties of PIM-Trip-TB. Competitive sorption favoring CO2 over CH4 was apparent in mixed-gas sorption simulations, as previously demonstrated by experimental studies from our group. This effect resulted in enhanced mixed-gas CO2/CH4 solubility selectivity. However, this increase did not translate to increased mixed-gas perm-selectivity because a significant increase in CH4 permeability was observed by co-permeation of CO2 relative to the pure-gas value. Back-calculated diffusion coefficients indicated very low CO2/CH4 diffusion selectivity under mixed-gas conditions, eliminating any gain from competitive sorption. Structural analysis confirmed intact intra-chain rigidity of the polymer; on the other hand, a significant increase in fractional free volume (FFV) and shift to larger pores in the pore size distribution was revealed by our simulations which may be attributed to polymer dilation due a reduction in inter-chain packing.

UR - http://hdl.handle.net/10754/690790

UR - https://linkinghub.elsevier.com/retrieve/pii/S0376738823002703

U2 - 10.1016/j.memsci.2023.121614

DO - 10.1016/j.memsci.2023.121614

M3 - Article

SN - 0376-7388

SP - 121614

JO - Journal of Membrane Science

JF - Journal of Membrane Science

ER -

Exploring the effect of intra-chain rigidity on mixed-gas separation performance of a Triptycene-Tröger's base ladder polymer (PIM-Trip-TB) by atomistic simulations

Abstract

Bibliographical note

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this