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      Metal–organic and covalent organic frameworks as single-site catalysts

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          Abstract

          The potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly.

          Abstract

          Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions.

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          Most cited references653

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          Van der Waals Density Functional for General Geometries

          A scheme within density functional theory is proposed that provides a practical way to generalize to unrestricted geometries the method applied with some success to layered geometries [H. Rydberg, et al., Phys. Rev. Lett. 91, 126402 (2003)]. It includes van der Waals forces in a seamless fashion. By expansion to second order in a carefully chosen quantity contained in the long range part of the correlation functional, the nonlocal correlations are expressed in terms of a density-density interaction formula. It contains a relatively simple parametrized kernel, with parameters determined by the local density and its gradient. The proposed functional is applied to rare gas and benzene dimers, where it is shown to give a realistic description.
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            A chromium terephthalate-based solid with unusually large pore volumes and surface area.

            We combined targeted chemistry and computational design to create a crystal structure for porous chromium terephthalate, MIL-101, with very large pore sizes and surface area. Its zeotype cubic structure has a giant cell volume (approximately 702,000 cubic angstroms), a hierarchy of extra-large pore sizes (approximately 30 to 34 angstroms), and a Langmuir surface area for N2 of approximately 5900 +/- 300 square meters per gram. Beside the usual properties of porous compounds, this solid has potential as a nanomold for monodisperse nanomaterials, as illustrated here by the incorporation of Keggin polyanions within the cages.
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              Metal-organic frameworks: opportunities for catalysis.

              The role of metal-organic frameworks (MOFs) in the field of catalysis is discussed, and special focus is placed on their assets and limits in light of current challenges in catalysis and green chemistry. Their structural and dynamic features are presented in terms of catalytic functions along with how MOFs can be designed to bridge the gap between zeolites and enzymes. The contributions of MOFs to the field of catalysis are comprehensively reviewed and a list of catalytic candidates is given. The subject is presented from a multidisciplinary point of view covering solid-state chemistry, materials science, and catalysis.
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                Author and article information

                Journal
                Chem Soc Rev
                Chem Soc Rev
                Chemical Society Reviews
                Royal Society of Chemistry
                0306-0012
                1460-4744
                7 June 2017
                24 March 2017
                : 46
                : 11
                : 3134-3184
                Affiliations
                [a ] Center for Molecular Modeling , Ghent University , Technologiepark 903 , 9052 Zwijnaarde , Belgium . Email: veronique.vanspeybroeck@ 123456ugent.be
                [b ] Delft University of Technology , Chemical Engineering Department , Catalysis Engineering , Van der Maasweg 9 , 2629 HZ Delft , The Netherlands . Email: j.gascon@ 123456tudelft.nl
                [c ] Instituto de Tecnología Química UPV-CSIC , Universitat Politècnica de Valencia , Consejo Superior de Investigaciones Científicas , Avda. de los Naranjos, s/n , 46022 , Valencia , Spain . Email: fllabres@ 123456itq.upv.es
                [d ] Inorganic Chemistry Department , University Institute of Materials , University of Alicante , Ctra. San Vicente-Alicante s/n , Alicante , Spain . Email: enrique.ramos@ 123456ua.es
                [e ] Normandie Université , ENSICAEN , UNICAEN , CNRS , Laboratoire Catalyse et Spectrochimie , 14000 Caen , France . Email: Marco.Daturi@ 123456ensicaen.fr
                Author information
                http://orcid.org/0000-0003-4493-5708
                http://orcid.org/0000-0002-9664-493X
                http://orcid.org/0000-0003-0575-7953
                http://orcid.org/0000-0002-4238-5784
                http://orcid.org/0000-0001-7558-7123
                Article
                c7cs00033b
                10.1039/c7cs00033b
                5708534
                28338128
                19323fae-9781-45b4-9b20-31833ea2cf06
                This journal is © The Royal Society of Chemistry 2017

                This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)

                History
                : 17 January 2017
                Categories
                Chemistry

                Chemistry
                Chemistry

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