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    High-Pressure CO2 Sorption in Polymers of Intrinsic Microporosity under Ultrathin Film Confinement

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    Type
    Article
    Authors
    Ogieglo, Wojciech
    Ghanem, Bader cc
    Ma, Xiaohua
    Wessling, Matthias
    Pinnau, Ingo cc
    KAUST Department
    Advanced Membranes and Porous Materials Research Center
    Chemical Engineering Program
    Physical Science and Engineering (PSE) Division
    KAUST Grant Number
    OSR-2015-SEED-2445-01
    Date
    2018-03-12
    Online Publication Date
    2018-03-12
    Print Publication Date
    2018-04-04
    Permanent link to this record
    http://hdl.handle.net/10754/627479
    
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    Abstract
    Ultrathin microporous polymer films are pertinent to the development and further spread of nanotechnology with very promising potential applications in molecular separations, sensors, catalysis, or batteries. Here, we report high-pressure CO2 sorption in ultrathin films of several chemically different polymers of intrinsic microporosity (PIMs), including the prototypical PIM-1. Films with thicknesses down to 7 nm were studied using interference-enhanced in situ spectroscopic ellipsometry. It was found that all PIMs swell much more than non-microporous polystyrene and other high-performance glassy polymers reported previously. Furthermore, chemical modifications of the parent PIM-1 strongly affected the swelling magnitude. By investigating the behavior of relative refractive index, nrel, it was possible to study the interplay between micropores filling and matrix expansion. Remarkably, all studied PIMs showed a maximum in nrel at swelling of 2-2.5% indicating a threshold point above which the dissolution in the dense matrix started to dominate over sorption in the micropores. At pressures above 25 bar, all PIMs significantly plasticized in compressed CO2 and for the ones with the highest affinity to the penetrant, a liquidlike mixing typical for rubbery polymers was observed. Reduction of film thickness below 100 nm revealed pronounced nanoconfinement effects and resulted in a large swelling enhancement and a quick loss of the ultrarigid character. On the basis of the partial molar volumes of the dissolved CO2, the effective reduction of the Tg was estimated to be ∼200 °C going from 128 to 7 nm films.
    Citation
    Ogieglo W, Ghanem B, Ma X, Wessling M, Pinnau I (2018) High-Pressure CO2 Sorption in Polymers of Intrinsic Microporosity under Ultrathin Film Confinement. ACS Applied Materials & Interfaces 10: 11369–11376. Available: http://dx.doi.org/10.1021/acsami.8b01402.
    Sponsors
    This publication is based on work supported by the King Abdullah University of Science and Technology (KAUST) Office of Sponsored Research (OSR) under Award No. SEED Fund OSR-2015-SEED-2445-01.
    Publisher
    American Chemical Society (ACS)
    Journal
    ACS Applied Materials & Interfaces
    DOI
    10.1021/acsami.8b01402
    PubMed ID
    29528618
    Additional Links
    https://pubs.acs.org/doi/10.1021/acsami.8b01402
    ae974a485f413a2113503eed53cd6c53
    10.1021/acsami.8b01402
    Scopus Count
    Collections
    Articles; Advanced Membranes and Porous Materials Research Center; Physical Science and Engineering (PSE) Division; Chemical Engineering Program

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