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      Construction of hierarchically porous metal–organic frameworks through linker labilization

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          Abstract

          A major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.

          Abstract

          Expanding pore sizes and volumes in metal-organic frameworks is challenging, but crucial for the encapsulation of larger guest molecules. Here, Zhou and colleagues report a linker labilization strategy to construct MOFs containing hierarchical pore architectures with dimensions ranging from 1.5 to 18 nm.

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          Most cited references49

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          Synthesis of metal-organic frameworks (MOFs): routes to various MOF topologies, morphologies, and composites.

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            Tuning the structure and function of metal-organic frameworks via linker design.

            Metal-organic frameworks (MOFs) are constructed from metal ions/clusters coordinated by organic linkers (or bridging-ligands). The hallmark of MOFs is their permanent porosity, which is frequently found in MOFs constructed from metal-clusters. These clusters are often formed in situ, whereas the linkers are generally pre-formed. The geometry and connectivity of a linker dictate the structure of the resulting MOF. Adjustments of linker geometry, length, ratio, and functional-group can tune the size, shape, and internal surface property of a MOF for a targeted application. In this critical review, we highlight advances in MOF synthesis focusing on linker design. Examples of building MOFs to reach unique properties, such as unprecedented surface area, pore aperture, molecular recognition, stability, and catalysis, through linker design are described. Further search for application-oriented MOFs through judicious selection of metal clusters and organic linkers is desirable. In this review, linkers are categorized as ditopic (Section 1), tritopic (Section 2), tetratopic (Section 3), hexatopic (Section 4), octatopic (Section 5), mixed (Section 6), desymmetrized (Section 7), metallo (Section 8), and N-heterocyclic linkers (Section 9).
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              Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals.

              We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH(2) (UiO-66-NH(2)), Zr-bpdc (UiO-67), and Zr-tpdc-NH(2) (UiO-68-NH(2)) (H(2) bdc: terephthalic acid, H(2) bpdc: biphenyl-4,4'-dicarboxylic acid, H(2) tpdc: terphenyl-4,4''-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH(2) . Zr-tpdc-NH(2), a material with a structure analogous to that of Zr-bdc and Zr-bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1''-terphenyl-4,4''-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                25 May 2017
                2017
                : 8
                : 15356
                Affiliations
                [1 ]Department of Chemistry, Texas A&M University , 3255 TAMU, College Station, Texas 77843-3255, USA
                [2 ]Chemistry Department, College of Science, King Saud University , Riyadh 11451, Saudi Arabia
                [3 ]Department of Materials Science and Engineering, Texas A&M University , College Station, Texas 77843-3003, USA
                [4 ]Artie McFerrin Department of Chemical Engineering, Texas A&M University , College Station, Texas 77843-3022, USA
                Author notes
                Author information
                http://orcid.org/0000-0001-9164-6947
                http://orcid.org/0000-0002-9029-3788
                Article
                ncomms15356
                10.1038/ncomms15356
                5458506
                28541301
                ec222cc2-0427-45cb-83d4-16b483518473
                Copyright © 2017, The Author(s)

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 25 November 2016
                : 23 March 2017
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