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      Metal-organic framework glasses with permanent accessible porosity

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          Abstract

          To date, only several microporous, and even fewer nanoporous, glasses have been produced, always via post synthesis acid treatment of phase separated dense materials, e.g. Vycor glass. In contrast, high internal surface areas are readily achieved in crystalline materials, such as metal-organic frameworks (MOFs). It has recently been discovered that a new family of melt quenched glasses can be produced from MOFs, though they have thus far lacked the accessible and intrinsic porosity of their crystalline precursors. Here, we report the first glasses that are permanently and reversibly porous toward incoming gases, without post-synthetic treatment. We characterize the structure of these glasses using a range of experimental techniques, and demonstrate pores in the range of 4 – 8 Å. The discovery of MOF glasses with permanent accessible porosity reveals a new category of porous glass materials that are elevated beyond conventional inorganic and organic porous glasses by their diversity and tunability.

          Abstract

          Metal–organic framework glasses have emerged as a new family of melt-quenched glass, but have yet to display the accessible porosity of their crystalline counterparts. Here, Bennett and colleagues report that glasses derived from ZIF-76 parent materials possess 4 – 8 Å pores and exhibit reversible gas adsorption.

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          Most cited references 40

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          Flexible metal-organic frameworks.

          Advances in flexible and functional metal-organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009-2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host-guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal-organic frameworks for separation, catalysis, sensing, and biomedicine.
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            RASPA: molecular simulation software for adsorption and diffusion in flexible nanoporous materials

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              Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials

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                Author and article information

                Contributors
                S.Telfer@massey.ac.nz
                tdb35@cam.ac.uk
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                28 November 2018
                28 November 2018
                2018
                : 9
                Affiliations
                [1 ]ISNI 0000000121885934, GRID grid.5335.0, Department of Materials Science and Metallurgy, , University of Cambridge, ; Charles Babbage Road, Cambridge, CB3 0FS UK
                [2 ]ISNI 0000 0001 0742 471X, GRID grid.5117.2, Department of Chemistry and Bioscience, , Aalborg University, ; DK-9220 Aalborg, Denmark
                [3 ]ISNI 0000 0001 0661 0844, GRID grid.454324.0, Department of Inorganic Chemistry and Technology, , National Institute of Chemistry, ; SI-1001 Ljubljana, Slovenia
                [4 ]ISNI 0000000121901201, GRID grid.83440.3b, Department of Chemistry, , University College London, ; Gordon Street, London, WC1H 0AJ UK
                [5 ]Diamond Light Source Ltd, Diamond House, Harwell Science and Innovation Campus, Didcot, OX11 0DE UK
                [6 ]ISNI 0000 0000 9291 3229, GRID grid.162110.5, State Key Laboratory of Silicate Materials for Architectures, , Wuhan University of Technology, ; Wuhan, 430070 China
                [7 ]ISNI 0000 0004 0391 6022, GRID grid.28009.33, Department of Natural and Mathematical Sciences, Faculty of Engineering, , Ozyegin University, ; Istanbul, Turkey
                [8 ]GRID grid.1016.6, Future Industries, , Commonwealth Scientific and Industrial Research Organisation, ; Clayton South, VIC 3168 Australia
                [9 ]ISNI 0000 0001 0696 9806, GRID grid.148374.d, MacDiarmid Institute for Advanced Materials and Nanotechnology, Institute of Fundamental Sciences, , Massey University, ; Palmerston North, 4442 New Zealand
                [10 ]GRID grid.443420.5, School of Materials Science and Engineering, , Qilu University of Technology, ; Jinan, 250353 China
                [11 ]ISNI 0000 0001 2296 6998, GRID grid.76978.37, ISIS Facility, , Rutherford Appleton Laboratory Harwell Campus, ; Didcot, Oxon OX11 0QX UK
                Article
                7532
                10.1038/s41467-018-07532-z
                6262007
                30487589
                © The Author(s) 2018

                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/.

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