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      PolyCOFs: A New Class of Freestanding Responsive Covalent Organic Framework Membranes with High Mechanical Performance

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          Abstract

          Traditional covalent organic frameworks (COFs) are prepared via polymerization based on small molecular monomers. However, the employment of polymers as building blocks to construct COFs has not been reported yet. Herein, we create a new concept of polymer covalent organic frameworks (polyCOFs) formed by linear polymers as structural building blocks, which inherit the merits from both COFs and linear polymers. PolyCOFs represent a new category of porous COF materials that demonstrate good crystallinity and high stability. More importantly, benefiting from the flexibility and processability of a linear polymer, polyCOFs can spontaneously form defect-free, flexible, and freestanding membranes that exhibit excellent mechanical properties and undergo reversible mechanical transformation upon exposure to various organic vapors. For the first time, we demonstrated that polyCOF membranes can be used as artificial muscles to perform various complicated motions (e.g., lifting objects, doing “sit-ups”) triggered by vapors. This study bridges the gap between one-dimensional amorphous linear polymers and crystalline polymer frameworks and paves a new avenue to prepare stimuli-responsive actuators using porous COF materials.

          Abstract

          Linear polymers are employed as building blocks to fabricate polyCOF membranes, which exhibit excellent mechanical properties and interesting vapor-triggered artificial muscle performance.

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          Most cited references31

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          Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications.

          Covalent organic-frameworks (COFs) are an emerging class of porous and ordered materials formed by condensation reactions of organic molecules. Recently, the Schiff-base chemistry or dynamic imine-chemistry has been widely explored for the synthesis of COFs. The main reason for this new tendency is based on their high chemical stability, porosity and crystallinity in comparison to previously reported COFs. This critical review article summarizes the current state-of-the-art on the design principles and synthetic strategies toward COFs based on Schiff-base chemistry, collects and rationalizes their physicochemical properties, as well as aims to provide perspectives of potential applications which are at the forefront of research in materials science.
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            Two-dimensional sp2 carbon-conjugated covalent organic frameworks.

            We synthesized a two-dimensional (2D) crystalline covalent organic framework (sp2c-COF) that was designed to be fully π-conjugated and constructed from all sp2 carbons by C=C condensation reactions of tetrakis(4-formylphenyl)pyrene and 1,4-phenylenediacetonitrile. The C=C linkages topologically connect pyrene knots at regular intervals into a 2D lattice with π conjugations extended along both x and y directions and develop an eclipsed layer framework rather than the more conventionally obtained disordered structures. The sp2c-COF is a semiconductor with a discrete band gap of 1.9 electron volts and can be chemically oxidized to enhance conductivity by 12 orders of magnitude. The generated radicals are confined on the pyrene knots, enabling the formation of a paramagnetic carbon structure with high spin density. The sp2 carbon framework induces ferromagnetic phase transition to develop spin-spin coherence and align spins unidirectionally across the material.
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              Molecular Separation with Organic Solvent Nanofiltration: A Critical Review

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                Author and article information

                Journal
                ACS Cent Sci
                ACS Cent Sci
                oc
                acscii
                ACS Central Science
                American Chemical Society
                2374-7943
                2374-7951
                25 June 2019
                28 August 2019
                : 5
                : 8
                : 1352-1359
                Affiliations
                []College of Chemistry, Nankai University , Tianjin 300071, People’s Republic of China
                []Department of Chemistry, University of South Florida , 4202 East Fowler Avenue, Tampa, Florida 33620, United States
                [§ ]State Key Laboratory of Medicinal Chemical Biology, Nankai University , Tianjin 300071, People’s Republic of China
                []College of Pharmacy, Nankai University , Tianjin 300071, People’s Republic of China
                []College of Precision Instrument and Optoelectronics Engineering, Tianjin University , Tianjin 300072, People’s Republic of China
                [# ]School of Materials Science and Engineering, Nankai University , Tianjin 300071, People’s Republic of China
                []School of Chemical Engineering and Technology, Tianjin University , Tianjin 300072, People’s Republic of China
                Author notes
                Article
                10.1021/acscentsci.9b00212
                6716131
                31482117
                169f390e-22b3-4979-bc03-328d58ada888
                Copyright © 2019 American Chemical Society

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                : 03 March 2019
                Categories
                Research Article
                Custom metadata
                oc9b00212
                oc-2019-00212z

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