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      Metal-organic framework crystal-glass composites

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          Abstract

          The majority of research into metal-organic frameworks (MOFs) focuses on their crystalline nature. Recent research has revealed solid-liquid transitions within the family, which we use here to create a class of functional, stable and porous composite materials. Described herein is the design, synthesis, and characterisation of MOF crystal-glass composites, formed by dispersing crystalline MOFs within a MOF-glass matrix. The coordinative bonding and chemical structure of a MIL-53 crystalline phase are preserved within the ZIF-62 glass matrix. Whilst separated phases, the interfacial interactions between the closely contacted microdomains improve the mechanical properties of the composite glass. More significantly, the high temperature open pore phase of MIL-53, which spontaneously transforms to a narrow pore upon cooling in the presence of water, is stabilised at room temperature in the crystal-glass composite. This leads to a significant improvement of CO 2 adsorption capacity.

          Abstract

          The formation of composite materials has been widely exploited to alter the chemical and physical properties of their components. Here the authors form metal–organic framework (MOF) crystal–glass composites in which a MOF glass matrix stabilises the open pore structure of MIL-53, leading to enhanced CO 2 adsorption.

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          Functional Porous Coordination Polymers

          The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
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            A First-Order Primal-Dual Algorithm for Convex Problems with Applications to Imaging

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              A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration.

              Aluminum 1,4-benzenedicarboxylate Al(OH)[O(2)C-C(6)H(4)-CO(2)]. [HO(2)C-C(6)H(4)-CO(2)H](0.70) or MIL-53 as (Al) has been hydrothermally synthesized by heating a mixture of aluminum nitrate, 1,4-benzenedicarboxylic acid, and water, for three days at 220 degrees C. Its 3 D framework is built up of infinite trans chains of corner-sharing AlO(4)(OH)(2) octahedra. The chains are interconnected by the 1,4-benzenedicarboxylate groups, creating 1 D rhombic-shaped tunnels. Disordered 1,4-benzenedicarboxylic acid molecules are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420 degrees C, leads to a nanoporous open-framework (MIL-53 ht (Al) or Al(OH)[O(2)C-C(6)H(4)-CO(2)]) with empty pores of diameter 8.5 A. This solid exhibits a Langmuir surface area of 1590(1) m(2)g(-1) together with a remarkable thermal stability, since it starts to decompose only at 500 degrees C. At room temperature, the solid reversibly absorbs water in its tunnels, causing a very large breathing effect and shrinkage of the pores. Analysis of the hydration process by solid-state NMR ((1)H, (13)C, (27)Al) has clearly indicated that the trapped water molecules interact with the carboxylate groups through hydrogen bonds, but do not affect the hydroxyl species bridging the aluminum atoms. The hydrogen bonds between water and the oxygen atoms of the framework are responsible for the contraction of the rhombic channels. The structures of the three forms have been determined by means of powder X-ray diffraction analysis. Crystal data for MIL-53 as (Al) are as follows: orthorhombic system, Pnma (no. 62), a = 17.129(2), b = 6.628(1), c = 12.182(1) A; for MIL-53 ht (Al), orthorhombic system, Imma (no. 74), a = 6.608(1), b = 16.675(3), c = 12.813(2) A; for MIL-53 lt (Al), monoclinic system, Cc (no. 9), a = 19.513(2), b = 7.612(1), c = 6.576(1) A, beta = 104.24(1) degrees.
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                Author and article information

                Contributors
                tdb35@cam.ac.uk
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                12 June 2019
                12 June 2019
                2019
                : 10
                : 2580
                Affiliations
                [1 ]ISNI 0000000121885934, GRID grid.5335.0, Department of Materials Science and Metallurgy, , University of Cambridge, ; Cambridge, CB3 0FS UK
                [2 ]ISNI 0000 0001 0661 0844, GRID grid.454324.0, Department of Inorganic Chemistry and Technology, , National Institute of Chemistry, ; 1001 Ljubljana, Slovenia
                [3 ]Diamond Light Source Ltd., Diamond House, Harwell Science & Innovation Campus, Didcot, Oxfordshire OX11 0DE UK
                [4 ]ISNI 0000 0004 0369 4132, GRID grid.249079.1, Institute of Chemical Materials, , China Academy of Engineering Physics, ; Mianyang, 621900 China
                [5 ]Aix-Marseille Univ, CNRS, MADIREL (UMR 7246), Centre de St. Jérôme, 13397 Marseille cedex 20, France
                [6 ]ISNI 0000 0001 2112 9282, GRID grid.4444.0, Chimie ParisTech, , PSL University, CNRS, Institut de Recherche de Chimie Paris, ; 75005 Paris, France
                [7 ]ISNI 0000 0001 2296 6998, GRID grid.76978.37, ISIS Facility, Rutherford Appleton Laboratory, Harwell Campus, ; Didcot, Oxon OX11 0QX UK
                [8 ]ISNI 0000 0004 4902 0432, GRID grid.1005.4, School of Chemical Engineering, , University of New South Wales, ; Sydney, NSW 2052 Australia
                [9 ]ISNI 0000 0000 9320 7537, GRID grid.1003.2, School of Chemical Engineering, , University of Queensland, ; St. Lucia, QLD 4072 Australia
                Author information
                http://orcid.org/0000-0002-9528-6595
                http://orcid.org/0000-0002-5151-6360
                http://orcid.org/0000-0003-0218-3114
                http://orcid.org/0000-0002-9178-9603
                http://orcid.org/0000-0003-3663-3793
                http://orcid.org/0000-0002-5513-9400
                http://orcid.org/0000-0001-5318-3910
                http://orcid.org/0000-0003-0376-2767
                http://orcid.org/0000-0002-9012-2495
                http://orcid.org/0000-0003-3717-3119
                Article
                10470
                10.1038/s41467-019-10470-z
                6561910
                31189892
                b54fd07a-ee9f-4409-ac95-ecbe5c46b23c
                © The Author(s) 2019

                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
                : 5 April 2019
                : 13 May 2019
                Funding
                Funded by: FundRef https://doi.org/10.13039/501100000266, RCUK | Engineering and Physical Sciences Research Council (EPSRC);
                Award ID: EP/R015481/1
                Award Recipient :
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                © The Author(s) 2019

                Uncategorized
                metal-organic frameworks,porous materials,organic-inorganic nanostructures,glasses

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