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      Environmentally benign dry-gel conversions of Zr-based UiO metal–organic frameworks with high yield and the possibility of solvent re-use

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          Abstract

          UiO-MOFs were synthesized using only 1/6 or upon solvent re-use only 1/30 of the DMF solvent volume compared to the solution synthesis on the same scale.

          Abstract

          Herein we report an alternative synthesis method for Zr-based UiO metal–organic frameworks (MOFs), namely dry-gel conversion (DGC). It was possible to synthesize nano- to microsized UiO-66, UiO-66-NH 2 and UiO-67 with high crystallinity, high surface area and increased yield using only one-sixth or less of the solvent volume compared to the solution synthesis on the same scale. Additionally, it is shown that solvent re-use is possible over at least five synthesis runs making the DGC method an ecological and extremely solvent-economical route to obtain Zr-based UiO-MOFs with reproducible results.

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          Most cited references 35

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          Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks.

          Secondary building units (SBUs) are molecular complexes and cluster entities in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers (1,4-benzenedicarboxylate, 1,3,5,7-adamantanetetracarboxylate, etc.). Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.
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            Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites.

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              Reticular chemistry: occurrence and taxonomy of nets and grammar for the design of frameworks.

              The structures of all 1127 three-periodic extended metal-organic frameworks (MOFs) reported in the Cambridge Structure Database have been analyzed, and their underlying topology has been determined. It is remarkable that among the almost infinite number of net topologies that are available for MOFs to adopt, only a handful of nets are actually observed. The discovery of this inversion between expected and observed nets led us to deduce a system of classification "taxonomy" for interpreting and rationalizing known MOF structures, as well as those that will be made in future. The origin of this inversion is attributed to the different modes with which MOF synthesis has been approached. Specifically, three levels of complexity are defined that embody rules "grammar" for the design of MOFs and other extended structures. This system accounts for the present proliferation of MOF structures of high symmetry nets, but more importantly, it provides the basis for designing a building block that "codes" for a specific structure and, indeed, only that structure.
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                Author and article information

                Journal
                ICHBD9
                Dalton Transactions
                Dalton Trans.
                Royal Society of Chemistry (RSC)
                1477-9226
                1477-9234
                2017
                2017
                : 46
                : 30
                : 9895-9900
                Affiliations
                [1 ]Institut für Anorganische Chemie und Strukturchemie
                [2 ]Heinrich-Heine-Universität Düsseldorf
                [3 ]40204 Düsseldorf
                [4 ]Germany
                Article
                10.1039/C7DT01717K
                © 2017
                Product
                Self URI (article page): http://xlink.rsc.org/?DOI=C7DT01717K

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