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DOI: 10.1039/A808726A (Paper) Reference Section for: J. Mater. Chem., 1999, 9, 1185-1189

Hydrothermal synthesis and ab initio structure determination from powder data of a new three-dimensional mixed valence oxyfluorinated titanium phosphate with an open structure: TiIIITiIVF(PO4)2·2H2O or MIL-15

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Christian Serre, Nathalie Guillou and Gérard Ferey

Abstract

TiIIITiIVF(PO4)2·2H2O (MIL-15) has been prepared hydrothermally (3 days, 483 K, autogenous pressure) in the presence of an organic base (diazabicyclo[2.2.2]octane). The structure of this compound has been determined ab initio from powder diffraction data and has been refined in the monoclinic space group: P21/n (no. 14); the unit cell is a=10.935(1), b=14.447(1), c=5.105(1) Å, β=90.50(1)° and V=806.5(1) Å3, Z=4. Its three-dimensional network, built up from corner sharing TiX6 octahedra (X=F, O, H2O) and tetrahedral PO4 groups, delimits seven-membered ring channels along the c-axis. The two crystallographically independent titanium atoms have different oxidation states (+III and +IV) and are connected via fluorine atoms while two water molecules are bound to the trivalent titanium atoms. Thermal decomposition of MIL-15 in two steps is described. Structural correlations with other titanium phosphates are presented.

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