Two-dimensional zeolitic materials have drawn increasing attention because of their structural diversity, high accessible surface areas, and potential as precursors to form novel three-dimensional (3D) structures. Here we report a new layered fluoroaluminophosphate, denoted as EMM-9 (ExxonMobil Material #9), synthesized in the same synthesis system as that for a previously reported 3D framework structure EMM-8 (framework-type code: SFO) using an F– medium and 4-(dimethylamino)pyridine (DMAP) as the organic structure-directing agent. The structure of EMM-9 was solved from rotation electron diffraction data and refined against synchrotron powder X-ray diffraction data. The fluoroaluminophosphate layer of EMM-9 is composed of sti composite building units. The DMAP cations are located between the layers. π–π interactions between the DMAP cations and hydrogen bonding between the DMAP cations and layers were identified. The layered EMM-9 structure is closely related to the 3D framework structure of EMM-8 and ca...

Synthesis and Structure of a Layered Fluoroaluminophosphate and Its Transformation to a Three-Dimensional Zeotype Framework.

Here we describe the synthesis and structure of PST-18, a novel open-framework silicogermanate with Si/Ge ∼ 0.6, which contains a three-dimensional pore system consisting of large cuboid-shaped cavities with 8-ring windows, as well as with 7-rings interrupted by one OH group. Synchrotron single-crystal X-ray diffraction reveals that the structure of PST-18, synthesized using only tetramethylammonium fluoride as a structure-directing agent, is built up of natrolite zeolite chains and Ge9O18(OH)4 clusters in a fully ordered manner. The discovery of such a hybrid structure of zeolitic building units and non-zeolitic oxide clusters provides a new direction for expanding the structural regime of inorganic microporous crystalline materials.

An open-framework silicogermanate regularly constructed from natrolite zeolite chains and Ge9O18(OH)4 clusters.

Two zinc-diphosphonates driven by 4,4'-bipyridine (4,4'-bipy), [Zn4(HEDP)2(4,4'-bipy)2]·4.5(H2O) (1) and (H2-4,4'-bipy)0.5·[Zn3(HEDP)(H2EDP)(H2O)]·1.5(H2O) (2), were solvothermally prepared (HEDP = CH3C(OH)(PO3)2, 1-hydroxyethylidenediphosphonate). Compound 1 features a layered structure with the Zn-HEDP chains as supramolecular units and 4,4'-bipy as interchain linkers. Compound 2 possesses a Zn-HEDP layer with protonated 4,4'-bipy as template. The structure differences between the two compounds are mainly ascribed to the distinct role of 4,4'-bipy in the process of in situ assembly. In compound 1, the 4,4'-bipy moiety acts as coordinative unit to participate in the formation of the resulting architecture. However, in compound 2, the protonated 4,4'-bipy serves as template to direct the formation of the final structure. The luminescence and proton conduction of the two compounds were investigated. Compounds 1 and 2 exhibit intense blue fluorescence; compound 2 has a proton conductivity of 2.61 × 10-4 S cm-1 at 100% relative humidity and 70 °C.

Bipyridine-triggered modulation of structure and properties of zinc-diphosphonates: coordination role vs. template rule.

Zeolites are crystalline porous materials with important industrial applications, including uses in catalytic and adsorption-separation processes. Access into and out of their inner confined space, where adsorption and reactions occur, is limited by their pore apertures. Stable multidimensional zeolites with larger pores able to process larger molecules are in demand in the fine chemical industry and for the oil processing on which the world still relies for fuels. Currently known extra-large-pore zeolites display poor stability and/or lack pore multidimensionality, limiting their usefulness. We report ZEO-1, a robust, fully connected aluminosilicate zeolite with mutually intersecting three-dimensional extra-large plus three-dimensional large pores. ZEO-1 is stable up to 1000°C, has an extraordinary specific surface area (1000 square meters per gram), and shows potential as a catalytic cracking catalyst.

A Stable Aluminosilicate Zeolite with Intersecting Three-Dimensional Extra-Large Pores.

Silicogermanate (JU110) with an interrupted open-framework has been synthesized by using a hydrothermal method using 1,1′-(1,4-phenylenebis(methylene))bis(1-methylpyrrolidin-1-ium) hydroxide as an organic structure-directing agent (OSDA). Silicon and fluoride anions were introduced to the concentrated-gel synthesis system, and different synthetic parameters influencing the synthesis were discussed. The structure of JU110 was characterised by using rotation electron diffraction (RED) and high-resolution powder X-ray diffraction. JU110 crystallizes in the space group Fm2m (No. 42) with a = 13.9117(2) A, b = 18.2980(3) A and c = 32.7800(6) A. The structure is constructed by the sti layers found in the STI framework that are pillared by D4R/Ge7 units to form a large cavity, showing 10-ring openings along [100] and 9-ring openings along [110]. Thermal stability studies showed that the framework was maintained with the loss of water molecules, but collapsed with the removal of charge-compensating cations.

Interrupted silicogermanate with 10-ring channels: synthesis and structure determination by combining rotation electron diffraction and powder X-ray diffraction

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Interrupted silicogermanate with 10-ring channels: synthesis and structure determination by combining rotation electron diffraction and powder X-ray diffraction