Creation of Well-Defined “Mid-Sized” Micropores in Carbon Molecular Sieve Membranes

Ma, Yao; Jue, Melinda L.; Zhang, Fengyi; Mathias, Ronita; Jang, Hye Youn; Lively, Ryan P.

doi:10.1002/anie.201903105

Title: Creation of Well-Defined “Mid-Sized” Micropores in Carbon Molecular Sieve Membranes

Journal Article · Sat Jun 22 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201903105· OSTI ID:1566018

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Georgia Inst. of Technology, Atlanta, GA (United States)

Carbon molecular sieve (CMS) membranes are choices for the separation of organic molecules due to their stability, ability to be scaled at practical form factors, and the avoidance of expensive supports or complex multi-step fabrication processes. A critical challenge is the creation of “mid-range” (e.g., 5–9 Å) microstructures that allow for facile permeation of organic solvents and selection between similarly-sized guest molecules. In this work, we create these microstructures via the pyrolysis of a microporous polymer (PIM-1) under low concentrations of hydrogen gas. The introduction of H₂ inhibits aromatization of the decomposing polymer and ultimately results in the creation of a well-defined bimodal pore network that exhibits an ultramicropore size of 5.1 Å. The H₂ assisted CMS dense membranes show a dramatic increase in p-xylene ideal permeability (≈15 times), with little loss in p-xylene/o-xylene selectivity (18.8 vs. 25.0) when compared to PIM-1 membranes pyrolyzed under a pure argon atmosphere. This method is successfully extended to hollow fiber membranes operating in organic solvent reverse osmosis mode, highlighting the potential of this approach to be translated from the laboratory to the field.

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Research Organization:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); ExxonMobil Research and Engineering

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1566018

Report Number(s):: LLNL-JRNL-769201; 960479

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 38; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 48 works

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References (35)

Polymers of intrinsic microporosity (PIMs): organic materials for membrane separations, heterogeneous catalysis and hydrogen storage McKeown, Neil B.; Budd, Peter M. Chemical Society Reviews, Vol. 35, Issue 8, p. 675-683 https://doi.org/10.1039/b600349d	journal	January 2006
Carbon molecular sieve membranes derived from Matrimid® polyimide for nitrogen/methane separation Ning, Xue; Koros, William J. Carbon, Vol. 66, p. 511-522 https://doi.org/10.1016/j.carbon.2013.09.028	journal	January 2014
A Carbonaceous Membrane based on a Polymer of Intrinsic Microporosity (PIM-1) for Water Treatment Kim, Hee Joong; Kim, Dong-Gyun; Lee, Kyuchul Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep36078	journal	October 2016
Carbon molecular sieve structure development and membrane performance relationships Rungta, Meha; Wenz, Graham B.; Zhang, Chen Carbon, Vol. 115 https://doi.org/10.1016/j.carbon.2017.01.015	journal	May 2017
para -Xylene Ultra-selective Zeolite MFI Membranes Fabricated from Nanosheet Monolayers at the Air-Water Interface Kim, Donghun; Jeon, Mi Young; Stottrup, Benjamin L. Angewandte Chemie International Edition, Vol. 57, Issue 2 https://doi.org/10.1002/anie.201708835	journal	December 2017
Seven chemical separations to change the world Sholl, David S.; Lively, Ryan P. Nature, Vol. 532, Issue 7600 https://doi.org/10.1038/532435a	journal	April 2016
Defect-free PIM-1 hollow fiber membranes Jue, Melinda L.; Breedveld, Victor; Lively, Ryan P. Journal of Membrane Science, Vol. 530 https://doi.org/10.1016/j.memsci.2017.02.012	journal	May 2017
Materials for next-generation molecularly selective synthetic membranes Koros, William J.; Zhang, Chen Nature Materials, Vol. 16, Issue 3 https://doi.org/10.1038/nmat4805	journal	January 2017
Xylene Vapor Mixture Separation in Nanocomposite MFI-Alumina Tubular Membranes: Influence of Operating Variables Daramola, M. O.; Burger, A. J.; Pera-Titus, M. Separation Science and Technology, Vol. 45, Issue 1 https://doi.org/10.1080/01496390903402141	journal	December 2009
Effect of dead volumes on the performance of an industrial-scale simulated moving-bed Parex unit for p -xylene purification Silva, Marta S. P.; Rodrigues, Alírio E.; Mota, José P. B. AIChE Journal, Vol. 62, Issue 1 https://doi.org/10.1002/aic.15022	journal	September 2015
Sub-10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation Karan, S.; Jiang, Z.; Livingston, A. G. Science, Vol. 348, Issue 6241 https://doi.org/10.1126/science.aaa5058	journal	June 2015
Ordered Mesoporous Carbons Ryoo, R.; Joo, S. H.; Kruk, M. Advanced Materials, Vol. 13, Issue 9, p. 677-681 https://doi.org/10.1002/1521-4095(200105)13:9<677::AID-ADMA677>3.0.CO;2-C	journal	May 2001
Creating New Types of Carbon-Based Membranes Paul, D. R. Science, Vol. 335, Issue 6067, p. 413-414 https://doi.org/10.1126/science.1216923	journal	January 2012
High-Flux Carbon Molecular Sieve Membranes for Gas Separation Richter, Hannes; Voss, Hartwig; Kaltenborn, Nadine Angewandte Chemie, Vol. 129, Issue 27 https://doi.org/10.1002/ange.201701851	journal	June 2017
Ultra-selective high-flux membranes from directly synthesized zeolite nanosheets Jeon, Mi Young; Kim, Donghun; Kumar, Prashant Nature, Vol. 543, Issue 7647 https://doi.org/10.1038/nature21421	journal	March 2017
Synthesis of new nanoporous carbon materials using nanostructured silica materials as templates Lee, Jinwoo; Han, Sangjin; Hyeon, Taeghwan Journal of Materials Chemistry, Vol. 14, Issue 4 https://doi.org/10.1039/b311541k	journal	January 2004
First Clear-Cut Experimental Evidence of a Glass Transition in a Polymer with Intrinsic Microporosity: PIM-1 Yin, Huajie; Chua, Yeong Zen; Yang, Bin The Journal of Physical Chemistry Letters, Vol. 9, Issue 8 https://doi.org/10.1021/acs.jpclett.8b00422	journal	April 2018
Solution-Processed, Organophilic Membrane Derived from a Polymer of Intrinsic Microporosity Budd, P. M.; Elabas, E. S.; Ghanem, B. S. Advanced Materials, Vol. 16, Issue 5, p. 456-459 https://doi.org/10.1002/adma.200306053	journal	March 2004
Evidence for entropic diffusion selection of xylene isomers in carbon molecular sieve membranes Ma, Yao; Zhang, Fengyi; Yang, Shaowei Journal of Membrane Science, Vol. 564 https://doi.org/10.1016/j.memsci.2018.07.040	journal	October 2018
Reverse osmosis molecular differentiation of organic liquids using carbon molecular sieve membranes Koh, D. -Y.; McCool, B. A.; Deckman, H. W. Science, Vol. 353, Issue 6301 https://doi.org/10.1126/science.aaf1343	journal	August 2016
High-flux MFI membranes Hedlund, Jonas; Sterte, Johan; Anthonis, Marc Microporous and Mesoporous Materials, Vol. 52, Issue 3 https://doi.org/10.1016/S1387-1811(02)00316-5	journal	May 2002
Amorphous, turbostratic and crystalline carbon membranes with hydrogen selectivity Wollbrink, A.; Volgmann, K.; Koch, J. Carbon, Vol. 106 https://doi.org/10.1016/j.carbon.2016.04.062	journal	September 2016
Molecular Sieving MFI-Type Zeolite Membranes for Pervaporation Separation of Xylene Isomers Yuan, Wenhui; Lin, Y. S.; Yang, Weishen Journal of the American Chemical Society, Vol. 126, Issue 15 https://doi.org/10.1021/ja031653t	journal	April 2004
New insights into structural evolution in carbon molecular sieve membranes during pyrolysis Adams, Jason S.; Itta, Arun K.; Zhang, Chen Carbon, Vol. 141 https://doi.org/10.1016/j.carbon.2018.09.039	journal	January 2019
High-Flux Carbon Molecular Sieve Membranes for Gas Separation Richter, Hannes; Voss, Hartwig; Kaltenborn, Nadine Angewandte Chemie International Edition, Vol. 56, Issue 27 https://doi.org/10.1002/anie.201701851	journal	June 2017
para -Xylene Ultra-selective Zeolite MFI Membranes Fabricated from Nanosheet Monolayers at the Air-Water Interface Kim, Donghun; Jeon, Mi Young; Stottrup, Benjamin L. Angewandte Chemie, Vol. 130, Issue 2 https://doi.org/10.1002/ange.201708835	journal	December 2017
Xylene separation on a diverse library of exchanged faujasite zeolites Khabzina, Yoldes; Laroche, Catherine; Perez-Pellitero, Javier Microporous and Mesoporous Materials, Vol. 247 https://doi.org/10.1016/j.micromeso.2017.03.026	journal	July 2017
Transport properties of alumina-supported MFI membranes made by secondary (seeded) growth Xomeritakis, George; Nair, Sankar; Tsapatsis, Michael Microporous and Mesoporous Materials, Vol. 38, Issue 1 https://doi.org/10.1016/S1387-1811(99)00300-5	journal	July 2000
Direct evaluation of the sp3 content in diamond-like-carbon films by XPS Mérel, P.; Tabbal, M.; Chaker, M. Applied Surface Science, Vol. 136, Issue 1-2 https://doi.org/10.1016/S0169-4332(98)00319-5	journal	October 1998
Ethylene/ethane permeation, diffusion and gas sorption properties of carbon molecular sieve membranes derived from the prototype ladder polymer of intrinsic microporosity (PIM-1) Salinas, Octavio; Ma, Xiaohua; Litwiller, Eric Journal of Membrane Science, Vol. 504 https://doi.org/10.1016/j.memsci.2015.12.052	journal	April 2016
Selective Fabrication of Carbon Nanocapsules and Mesocellular Foams by Surface-Modified Colloidal Silica Templating Jang, J.; Lim, B. Advanced Materials, Vol. 14, Issue 19 https://doi.org/10.1002/1521-4095(20021002)14:19<1390::AID-ADMA1390>3.0.CO;2-T	journal	October 2002
Carbon molecular sieve membrane structure–property relationships for four novel 6FDA based polyimide precursors Fu, Shilu; Sanders, Edgar S.; Kulkarni, Sudhir S. Journal of Membrane Science, Vol. 487 https://doi.org/10.1016/j.memsci.2015.03.079	journal	August 2015
Streamlined Fabrication of Asymmetric Carbon Molecular Sieve Hollow Fiber Membranes Jue, Melinda L.; Ma, Yao; Lively, Ryan P. ACS Applied Polymer Materials, Vol. 1, Issue 8 https://doi.org/10.1021/acsapm.9b00567	journal	July 2019
Ordered Mesoporous Carbons Ryoo, R.; Joo, S. H.; Kruk, M. Advanced Materials, Vol. 13, Issue 9 https://doi.org/10.1002/1521-4095(200105)13:9<677::aid-adma677>3.3.co;2-3	journal	May 2001
Polymers of Intrinsic Microporosity (PIMs): Organic Materials for Membrane Separations, Heterogeneous Catalysis and Hydrogen Storage McKeown, Neil B.; Budd, Peter M. ChemInform, Vol. 37, Issue 45 https://doi.org/10.1002/chin.200645246	journal	November 2006

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