Designing the synthesis of catalytically active Ti-β by using various new templates in the presence of fluoride anion.

Crystallization of large-pore Ti-β by using a variety of diquaternary ammonium derivatives of dibromoalkane and amines such as triethylamine, 1,4-diazabicyclo[2,2,2]octane (DABCO), and quinuclidine as structure-directing agents (SDA) is described. The size of hydrophobic bridging alkyl-chain length of the template [R(3)N(+)-(CH(2))(x)-N(+)R(3)](OH(-))(2) directs the final crystalline product: Ti-β, Ti-ZSM-12, Ti-nonasil or Ti-ZSM-5, as x gradually changes from 6 to 1, in the fluoride medium under hydrothermal conditions. A dense phase such as Ti-nonasil (clathrasil type) is crystallized as the size of hydrophobic bridging alkyl-chain length decreases. The use of F(-) anions as a mineralizer and Ti(4+) as a heteroatom in the synthesis gel also influences the selectivity of final crystalline product. The phase purity and incorporation of Ti(4+) into the lattice of β (BEA) and ZSM-12 frameworks are confirmed using XRD, UV-visible, FT-IR, (29)Si NMR spectroscopes, elemental analysis (ICP), surface area measurements and catalytic test reactions. The morphology of Ti-β samples is dependent on the nature of the structure-directing agent as revealed by the scanning electron microscopic (SEM) observations. The catalytic activity in the epoxidation of 4-vinyl-1-cyclohexene is increased with the amount of tetrahedral Ti(4+) atoms in the framework. The new templates can be effectively used for preparation of catalytically active Ti-β with the minimum number of framework defect sites.