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      Interrupted Chalcogenide-Based Zeolite-Analogue Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties

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          Colossal cages in zeolitic imidazolate frameworks as selective carbon dioxide reservoirs.

          Zeolitic imidazolate frameworks (ZIFs) are porous crystalline materials with tetrahedral networks that resemble those of zeolites: transition metals (Zn, Co) replace tetrahedrally coordinated atoms (for example, Si), and imidazolate links replace oxygen bridges. A striking feature of these materials is that the structure adopted by a given ZIF is determined by link-link interactions, rather than by the structure directing agents used in zeolite synthesis. As a result, systematic variations of linker substituents have yielded many different ZIFs that exhibit known or predicted zeolite topologies. The materials are chemically and thermally stable, yet have the long-sought-after design flexibility offered by functionalized organic links and a high density of transition metal ions. Here we report the synthesis and characterization of two porous ZIFs-ZIF-95 and ZIF-100-with structures of a scale and complexity previously unknown in zeolites. The materials have complex cages that contain up to 264 vertices, and are constructed from as many as 7,524 atoms. As expected from the adsorption selectivity recently documented for other members of this materials family, both ZIFs selectively capture carbon dioxide from several different gas mixtures at room temperature, with ZIF-100 capable of storing 28 litres per litre of material at standard temperature and pressure. These characteristics, combined with their high thermal and chemical stability and ease of fabrication, make ZIFs promising candidate materials for strategies aimed at ameliorating increasing atmospheric carbon dioxide levels.
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            Conduction and Valence Band Positions of Ta2O5, TaON, and Ta3N5by UPS and Electrochemical Methods

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              Supertetrahedral sulfide crystals with giant cavities and channels

               Laine,  O'Keeffe,  Yaghi (1999)
              Although aluminosilicates and metal phosphates can form porous open-framework materials such as zeolites, sulfide analogs usually form high-density phases because of the relatively small tetrahedral angle at sulfur atoms. One strategy to overcome this limitation is to use tetrahedral clusters as the building blocks to achieve porous sulfide-based networks. The preparation and crystal structures of two indium sulfide open frameworks (ASU-31 and ASU-32) built of supertetrahedral clusters around organic template and water guests are described. ASU-31, based on the sodalite-tetrahedrite network, contains cavities 25.6 angstroms in diameter, and ASU-32, based on the tetragonal CrB4 network, contains channels with a minimum diameter of 14.7 angstroms. The organic cations can be completely exchanged with sodium ions in aqueous solution at room temperature without degradation of the crystals.
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                Author and article information

                Journal
                Angewandte Chemie International Edition
                Angew. Chem. Int. Ed.
                Wiley
                14337851
                April 20 2015
                April 20 2015
                February 26 2015
                : 54
                : 17
                : 5103-5107
                Article
                10.1002/anie.201500659
                © 2015
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