Abstract
TITANIUM occurs widely in the Earth's crust, traces of it being present in most rocks, soils and clays. It is estimated that titanosilicate minerals alone number more than 100; but, remarkably, in only one of these does the Ti(IV) ion take up fivefold coordination. This is in fresnoite1 (Ba2TiSi2O8), which contains square-pyramidal TiO5 polyhedra. In the course of a programme2–11 to produce new microporous and mesoporous solid catalysts, we have discovered an unusual non-centrosymmetric, tetragonal layered solid (Na4Ti2Si8O22·4H2O), designated JDF-L1, which promises to have interesting applications in materials chemistry. This material contains five-coordinate Ti(IV) ions in the form of TiO5 square pyramids in which each of the vertices of the base is linked to SiO4 tetrahedra [TiO·O4(SiO3)4] to form continuous sheets. The structure was solved by applying ab initio methods to data obtained by X-ray absorption spectroscopy and powder X-ray diffraction. The interlamellar Na+ ions of JDF-L1 are replaceable by protonated amines, and after treatment with a mixture of dilute acid and hydrogen peroxide the parent solid selectively oxidizes phenol to quinone. These results indicate that the material should have useful catalytic, intercalation and ion-exchange properties analogous to those of aluminosilicate clays.
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Roberts, M., Sankar, G., Thomas, J. et al. Synthesis and structure of a layered titanosilicate catalyst with five-coordinate titanium. Nature 381, 401–404 (1996). https://doi.org/10.1038/381401a0
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DOI: https://doi.org/10.1038/381401a0
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