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      High Volumetric Hydrogen Adsorption in a Porous Anthracene-Decorated Metal–Organic Framework

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          Abstract

          We report an unprecedented ligand-based binding domain for D 2 within a porous metal–organic framework (MOF) material as confirmed by neutron powder diffraction studies of D 2-loaded MFM-132a. A tight pocket of 6 Å diameter is formed by the close packing of three anthracene panels, and it is here rather than the open metal sites where D 2 binds preferentially. As a result, MFM-132a shows exceptional volumetric hydrogen adsorption (52 g L –1 at 60 bar and 77 K) and the highest density of adsorbed H 2 within its pores among all the porous materials reported to date under the same conditions. This work points to a new direction for H 2 storage in porous materials using polyaromatic ligand-based sites.

          Abstract

          The anthracene-functionalized metal−organic framework MFM-132a shows exceptional volumetric hydrogen adsorption (52 g L −1 at 60 bar and 77 K) and the highest density of adsorbed H2 within its pores among all porous materials reported to date under the same conditions. Neutron powder diffraction studies reveal that a tight pocket of 6 Å diameter created by three close anthracene panels binds D2 preferentially over the open metal sites.

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          Most cited references 30

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          Hydrogen storage in metal-organic frameworks.

          New materials capable of storing hydrogen at high gravimetric and volumetric densities are required if hydrogen is to be widely employed as a clean alternative to hydrocarbon fuels in cars and other mobile applications. With exceptionally high surface areas and chemically-tunable structures, microporous metal-organic frameworks have recently emerged as some of the most promising candidate materials. In this critical review we provide an overview of the current status of hydrogen storage within such compounds. Particular emphasis is given to the relationships between structural features and the enthalpy of hydrogen adsorption, spectroscopic methods for probing framework-H(2) interactions, and strategies for improving storage capacity (188 references).
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            Ultrahigh porosity in metal-organic frameworks.

            Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn4O(CO2)6 unit was joined with either one or two kinds of organic link, 4,4',4''-[benzene-1,3,5-triyl-tris(ethyne-2,1-diyl)]tribenzoate (BTE), 4,4',44''-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)]tribenzoate (BBC), 4,4',44''-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.
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              Impact of preparation and handling on the hydrogen storage properties of Zn4O(1,4-benzenedicarboxylate)3 (MOF-5).

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                Author and article information

                Journal
                Inorg Chem
                Inorg Chem
                ic
                inocaj
                Inorganic Chemistry
                American Chemical Society
                0020-1669
                1520-510X
                19 September 2018
                01 October 2018
                : 57
                : 19
                : 12050-12055
                Affiliations
                []School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom
                []ISIS facility, Science and Technology Facilities Council (STFC), Rutherford Appleton Laboratory , Didcot OX11 0QX, United Kingdom
                [§ ]School of Chemistry, University of Nottingham , University Park, Nottingham NG7 2RD, United Kingdom
                []Chemical and Environmental Sciences Laboratory, General Motors Corporation , Warren, Michigan 48090, United States
                Author notes
                Article
                10.1021/acs.inorgchem.8b01607
                6168839
                30230330
                ba708500-4561-4b01-8909-045792aaf2f3
                Copyright © 2018 American Chemical Society

                This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

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                ic8b01607
                ic-2018-01607p

                Inorganic & Bioinorganic chemistry

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