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      A solution-processable and ultra-permeable conjugated microporous thermoset for selective hydrogen separation

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          Abstract

          The synthesis of a polymer that combines the processability of plastics with the extreme rigidity of cross-linked organic networks is highly attractive for molecular sieving applications. However, cross-linked networks are typically insoluble or infusible, preventing them from being processed as plastics. Here, we report a solution-processable conjugated microporous thermoset with permanent pores of ~0.4 nm, prepared by a simple heating process. When employed as a two-dimensional molecular sieving membrane for hydrogen separation, the membrane exhibits ultrahigh permeability with good selectivity for H 2 over CO 2, O 2, N 2, CH 4, C 3H 6 and C 3H 8. The combined processability, structural rigidity and easy feasibility make this polymeric membrane promising for large-scale hydrogen separations of commercial and environmental relevance.

          Abstract

          Rigidity, as seen in crosslinked polymers, and plastic processability are mutually exclusive properties. Here, the authors prepare a solution-processable conjugated microporous thermoset with permanent pores and demonstrate its application as a two-dimensional molecular sieving membrane for hydrogen separation.

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          Most cited references31

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          Maximizing the right stuff: The trade-off between membrane permeability and selectivity

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            Membranes. Metal-organic framework nanosheets as building blocks for molecular sieving membranes.

            Layered metal-organic frameworks would be a diverse source of crystalline sheets with nanometer thickness for molecular sieving if they could be exfoliated, but there is a challenge in retaining the morphological and structural integrity. We report the preparation of 1-nanometer-thick sheets with large lateral area and high crystallinity from layered MOFs. They are used as building blocks for ultrathin molecular sieve membranes, which achieve hydrogen gas (H2) permeance of up to several thousand gas permeation units (GPUs) with H2/CO2 selectivity greater than 200. We found an unusual proportional relationship between H2 permeance and H2 selectivity for the membranes, and achieved a simultaneous increase in both permeance and selectivity by suppressing lamellar stacking of the nanosheets.
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              Conjugated microporous polymers: design, synthesis and application.

              Conjugated microporous polymers (CMPs) are a class of organic porous polymers that combine π-conjugated skeletons with permanent nanopores, in sharp contrast to other porous materials that are not π-conjugated and with conventional conjugated polymers that are nonporous. As an emerging material platform, CMPs offer a high flexibility for the molecular design of conjugated skeletons and nanopores. Various chemical reactions, building blocks and synthetic methods have been developed and a broad variety of CMPs with different structures and specific properties have been synthesized, driving the rapid growth of the field. CMPs are unique in that they allow the complementary utilization of π-conjugated skeletons and nanopores for functional exploration; they have shown great potential for challenging energy and environmental issues, as exemplified by their excellent performance in gas adsorption, heterogeneous catalysis, light emitting, light harvesting and electrical energy storage. This review describes the molecular design principles of CMPs, advancements in synthetic and structural studies and the frontiers of functional exploration and potential applications.
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                Author and article information

                Contributors
                guiver@tju.edu.cn
                chezhangsui@nus.edu.sg
                chmlohkp@nus.edu.sg
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                2 April 2020
                2 April 2020
                2020
                : 11
                : 1633
                Affiliations
                [1 ]ISNI 0000 0001 2180 6431, GRID grid.4280.e, Department of Chemistry, , National University of Singapore, ; 3 Science Drive 3, 117543 Singapore, Singapore
                [2 ]ISNI 0000 0001 2180 6431, GRID grid.4280.e, Department of Chemical and Biomolecular Engineering, , National University of Singapore, ; 4 Engineering Drive 4, 117585 Singapore, Singapore
                [3 ]ISNI 0000 0004 1798 1132, GRID grid.497420.c, School of Materials Science and Engineering, , China University of Petroleum, ; 266580 Qingdao, Shandong China
                [4 ]ISNI 0000 0004 1761 2484, GRID grid.33763.32, State Key Laboratory of Engines, , Tianjin University, ; 300072 Tianjin, China
                [5 ]ISNI 0000 0004 1761 2484, GRID grid.33763.32, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), ; 300072 Tianjin, China
                Author information
                http://orcid.org/0000-0002-6812-6107
                http://orcid.org/0000-0002-7777-6849
                http://orcid.org/0000-0002-5627-4153
                http://orcid.org/0000-0003-3408-5033
                http://orcid.org/0000-0002-5265-2735
                http://orcid.org/0000-0003-1371-6641
                http://orcid.org/0000-0001-9868-4946
                http://orcid.org/0000-0003-2619-6809
                http://orcid.org/0000-0002-2767-8634
                http://orcid.org/0000-0002-1491-743X
                Article
                15503
                10.1038/s41467-020-15503-6
                7118162
                32242012
                e8e7fb86-718e-4560-ba15-8e10984aa6cf
                © The Author(s) 2020

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 26 November 2019
                : 11 March 2020
                Categories
                Article
                Custom metadata
                © The Author(s) 2020

                Uncategorized
                conjugated polymers,hydrogen energy,porous materials
                Uncategorized
                conjugated polymers, hydrogen energy, porous materials

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