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      Metal–Organic Framework Materials with Ultrahigh Surface Areas: Is the Sky the Limit?

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          Abstract

          We have synthesized, characterized, and computationally simulated/validated the behavior of two new metal-organic framework (MOF) materials displaying the highest experimental Brunauer-Emmett-Teller (BET) surface areas of any porous materials reported to date (~7000 m(2)/g). Key to evacuating the initially solvent-filled materials without pore collapse, and thereby accessing the ultrahigh areas, is the use of a supercritical CO(2) activation technique. Additionally, we demonstrate computationally that by shifting from phenyl groups to "space efficient" acetylene moieties as linker expansion units, the hypothetical maximum surface area for a MOF material is substantially greater than previously envisioned (~14600 m(2)/g (or greater) versus ~10500 m(2)/g).

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          Most cited references53

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          Design and synthesis of an exceptionally stable and highly porous metal-organic framework

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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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                Author and article information

                Journal
                Journal of the American Chemical Society
                J. Am. Chem. Soc.
                American Chemical Society (ACS)
                0002-7863
                1520-5126
                September 12 2012
                August 31 2012
                September 12 2012
                : 134
                : 36
                : 15016-15021
                Affiliations
                [1 ]Department of Chemistry and International Institute for Nanotechnology, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States
                [2 ]Department of Emerging Materials Science, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu 711-873, Korea
                [3 ]Department of Chemical & Biological Engineering, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
                [4 ]Department of Chemical Engineering, University of Surrey, Guildford, GU2 7XH, United Kingdom
                Article
                10.1021/ja3055639
                8088cc34-9fd5-4186-bdf7-97552408efde
                © 2012
                History

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