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      Covalent organic framework nanosheets: preparation, properties and applications

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          Abstract

          Covalent organic frameworks are crystalline porous materials with 2- or 3-dimensional structures designed modularly from their molecular precursors. Using bottom-up or top-down strategies, single- or few-layer materials can be obtained from them.

          Abstract

          Covalent organic frameworks (COFs) are crystalline and porous materials with bi- or three-dimensional structures built up by connecting their molecular precursors by dynamic covalent bonds. Using bottom-up or top-down strategies, bi-dimensional COFs can be obtained as single- or few-layer materials, thus enlarging the family of 2D-materials based on graphene. The main advantage of 2D-materials based on COFs is the fact that they can be chemically designed, thus allowing the formation of á la carte materials with well-designed functionalities including their size and features of their pores. The aim of this perspective review is to illustrate in a rational way the current state-of-the-art in the field of COF nanosheet formation using the two general approaches of material nano-structuring. This article reviews a selected collection of samples that illustrates the essential concepts, strategies of preparation following the two general approaches, bottom-up and top-down, and a selection of COF nanolayers showing seminal properties and potential material applications. Finally, we provide some perspectives of this novel research field.

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          Most cited references55

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          Porous, crystalline, covalent organic frameworks.

          Covalent organic frameworks (COFs) have been designed and successfully synthesized by condensation reactions of phenyl diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly crystalline products (C3H2BO)6.(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P6(3)/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temperatures up to 500 degrees to 600 degrees C), permanent porosity, and high surface areas (711 and 1590 square meters per gram, respectively).
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            Progress, challenges, and opportunities in two-dimensional materials beyond graphene.

            Graphene's success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in field-effect transistors, spin- and valley-tronics, thermoelectrics, and topological insulators, among many other applications.
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              Two-dimensional atomic crystals

              We report free-standing atomic crystals that are strictly 2D and can be viewed as individual atomic planes pulled out of bulk crystals or as unrolled single-wall nanotubes. By using micromechanical cleavage, we have prepared and studied a variety of 2D crystals including single layers of boron nitride, graphite, several dichalcogenides, and complex oxides. These atomically thin sheets (essentially gigantic 2D molecules unprotected from the immediate environment) are stable under ambient conditions, exhibit high crystal quality, and are continuous on a macroscopic scale.
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                Author and article information

                Contributors
                (View ORCID Profile)
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                Journal
                CSRVBR
                Chemical Society Reviews
                Chem. Soc. Rev.
                Royal Society of Chemistry (RSC)
                0306-0012
                1460-4744
                April 27 2020
                2020
                : 49
                : 8
                : 2291-2302
                Affiliations
                [1 ]Department of Chemistry and Applied Biosciences
                [2 ]Institute for Chemical and Bioengineering
                [3 ]ETH Zurich
                [4 ]8093 Zurich
                [5 ]Switzerland
                [6 ]Departamento de Química Inorgánica
                [7 ]Universidad Autónoma de Madrid
                [8 ]28049 Madrid
                [9 ]Spain
                [10 ]Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid
                Article
                10.1039/C9CS00890J
                32182308
                55c85689-b675-436e-8b89-7a8595447a64
                © 2020

                http://rsc.li/journals-terms-of-use

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