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      Heterogeneous catalysis based on supramolecular association

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          Abstract

          Non-covalent assembly of individual components can develop a material with activity to promote the transformation of substrates into products.

          Abstract

          Heterogeneous catalysis is based mostly on materials built with strong covalent bonds. However, supramolecular aggregation in which individual components self-assemble due to non-covalent interactions to create a larger entity offers also considerable potential for the preparation of materials with application in catalysis. The present article provides a perspective on the use of supramolecular aggregation for the development of heterogeneous catalysts. One of the main advantages of this approach is that the preparation procedure based on spontaneous self-assembly is frequently simpler than those that require the formation of covalent bonds. The emphasis in this article has been placed on the use in the preparation of heterogeneous catalysts of not only carbon materials, particularly graphene and carbon nanotubes, but also dendrimers and organic capsules. Examples of hybrid organic–inorganic materials such as mesoporous organosilicas, metal–organic frameworks and heteropolyacids are also briefly described. The purpose is to illustrate the breadth of the field and the diverse array of possibilities already developed to apply the concepts of supramolecular association in heterogeneous catalysis.

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          Most cited references80

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          Fabrication of novel biomaterials through molecular self-assembly.

          Two complementary strategies can be used in the fabrication of molecular biomaterials. In the 'top-down' approach, biomaterials are generated by stripping down a complex entity into its component parts (for example, paring a virus particle down to its capsid to form a viral cage). This contrasts with the 'bottom-up' approach, in which materials are assembled molecule by molecule (and in some cases even atom by atom) to produce novel supramolecular architectures. The latter approach is likely to become an integral part of nanomaterials manufacture and requires a deep understanding of individual molecular building blocks and their structures, assembly properties and dynamic behaviors. Two key elements in molecular fabrication are chemical complementarity and structural compatibility, both of which confer the weak and noncovalent interactions that bind building blocks together during self-assembly. Using natural processes as a guide, substantial advances have been achieved at the interface of nanomaterials and biology, including the fabrication of nanofiber materials for three-dimensional cell culture and tissue engineering, the assembly of peptide or protein nanotubes and helical ribbons, the creation of living microlenses, the synthesis of metal nanowires on DNA templates, the fabrication of peptide, protein and lipid scaffolds, the assembly of electronic materials by bacterial phage selection, and the use of radiofrequency to regulate molecular behaviors.
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            Metal-organic frameworks.

            Metal-organic frameworks are a recently-identified class of porous polymeric material, consisting of metal ions linked together by organic bridging ligands, and are a new development on the interface between molecular coordination chemistry and materials science. A range of novel structures has been prepared which feature amongst the largest pores known for crystalline compounds, very high sorption capacities and complex sorption behaviour not seen in aluminosilicate zeolites. The development of synthetic approaches to these materials and investigations of their properties are reviewed.
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              From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry.

              Supramolecular chemistry has developed over the last forty years as chemistry beyond the molecule. Starting with the investigation of the basis of molecular recognition, it has explored the implementation of molecular information in the programming of chemical systems towards self-organisation processes, that may occur either on the basis of design or with selection of their components. Supramolecular entities are by nature constitutionally dynamic by virtue of the lability of non-covalent interactions. Importing such features into molecular chemistry, through the introduction of reversible bonds into molecules, leads to the emergence of a constitutional dynamic chemistry, covering both the molecular and supramolecular levels. It considers chemical objects and systems capable of responding to external solicitations by modification of their constitution through component exchange or reorganisation. It thus opens the way towards an adaptive and evolutive chemistry, a further step towards the chemistry of complex matter.
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                Author and article information

                Journal
                CSTAGD
                Catalysis Science & Technology
                Catal. Sci. Technol.
                Royal Society of Chemistry (RSC)
                2044-4753
                2044-4761
                2018
                2018
                : 8
                : 19
                : 4834-4857
                Affiliations
                [1 ]Department of Organic Chemistry
                [2 ]Biochemistry and Catalysis
                [3 ]Faculty of Chemistry
                [4 ]University of Bucharest
                [5 ]Bucharest 030016
                [6 ]Instituto Universitario de Tecnología Química Consejo Superior de Investigaciones Científicas-Universitat Politecnica de Valencia
                [7 ]Universitat Politecnica de Valencia
                [8 ]46022 Valencia
                [9 ]Spain
                Article
                10.1039/C8CY01295D
                0fa9c723-3cee-40f6-af5b-a849bfbe1360
                © 2018

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

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