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      Tailored crystalline microporous materials by post-synthesis modification.

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          Abstract

          Crystalline microporous solids are an important class of inorganic materials with uses in different areas impacting our everyday lives, namely as catalysts, adsorbents, and ion exchangers. Advancements in synthesis have been invaluable in expanding the classical aluminosilicate zeolites to new unique framework types and compositions, motivating innovative developments. However, the inexhaustible post-synthetic options to tailor zeolite properties have been and will continue to be indispensable to realize emerging and to improve conventional applications. Starting from the routine drying and template removal processes that every zeolite must experience prior to use, a wide spectrum of treatments exists to alter individual or collective characteristics of these materials for optimal performance. This review documents the toolbox of post-synthetic strategies available to tune the properties of zeolitic materials for specific functions. The categorisation is based on the scale at which the alteration is aimed at, including the atomic structure (e.g. the introduction, dislodgment, or replacement of framework atoms), the micropore level (e.g. template removal and functionalisation by inorganic and organic species), and the crystal and particle levels (e.g. the introduction of auxiliary porosity). Through examples in the recent literature, it is shown that the combination of post-synthetic methods enables rational zeolite design, extending the characteristics of these materials way beyond those imposed by the synthesis conditions.

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          Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism

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            A new family of mesoporous molecular sieves prepared with liquid crystal templates

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              A homochiral metal-organic porous material for enantioselective separation and catalysis

              Seo, Whang, Lee (2000)
              Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.
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                Author and article information

                Journal
                Chem Soc Rev
                Chemical Society reviews
                Royal Society of Chemistry (RSC)
                1460-4744
                0306-0012
                Jan 07 2013
                : 42
                : 1
                Affiliations
                [1 ] Laboratoire Catalyse et Spectrochimie, ENSICAEN - Université de Caen - CNRS, 6 Bd du Maréchal Juin, 14050 Caen, France. valentin.valtchev@ensicaen.fr
                Article
                10.1039/c2cs35196j
                22996351
                2771a754-1cba-4590-b232-5006a18eaa6f
                History

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