Michihiro Miyake

Syntheses of ferrierite, ZSM-48, and ZSM-5 in glycerol solvent

Abstract The mixtures of SiO 2 , Al 2 O 3 , and Na 2 O with various batch compositions have been allowed to react in glycerol solvent at 210°C for 7–14 d. Consequently, the crystallization fields of three kinds of zeolites of ferrierite, ZSM-48, and ZSM-5 in addition to sodalite were newly discovered. Ferrierite was obtained at lower molar percentages of Al 2 O 3 and Na 2 O than was sodalite. ZSM-48 and ZSM-5 were obtained at much lower molar percentages of Al 2 O 3 than was ferrierite. Glycerol was found to act as both a solvent and a template from the fact that these zeolites encapsulated glycerol molecules in their framework. The comparison with the crystallization of zeolitic phases in aqueous solvent without using organic templates suggested the availability of glycerol for the syntheses of ferrierite, ZSM-48, and sodalite.

Molecular structures and charge-transfer complexes of cis-dibenzo[c,h]-1,6-disilabicyclo[4.4.0]deca-3,8-dienes and bi(benzo[c]silacyclopent-3-ene-1-yl)s

The reaction of the di-Grignard reagent of α,α′-dichloro-o-xylene with Cl2RSiSiRCl2(R  iPr and Me) produced cis-dibenzo[c,h-1,6-dialkyl-1,6-disilabicyclo[4.4.O]deca-3,8-diene (1) and bi(benzo[c]-1-alkylsilacyclopent-3-ene-1-yl) (2). The structures of 1a (R  iPr) and 2a (R  iPr) were determined by X-ray crystallography. Crystal data for 1a: orthorhombic, Pbca, a = 14.816(1), b = 16.263(1), c = 17.257(1) A, V = 4158.1(3) A3, Z = 8, R = 0.040, Rw = 0.050 for 2008 reflections. Crystal data for 2a: triclinic, P1, a = 8.179(2), b = 10.389(3), c = 6.605(2) A, α = 100.39(2)°, β = 98.29(2), γ = 106.75(2)°, V = 517.0(3) A3, Z = 1, R = 0.042, Rw = 0.051 for 1167 reflections. Compounds 1 and 2 have relatively low oxidation potentials (1.24–1.59 V vs. SCE, in acetonitrile) and form charge-transfer complexes with tetracyanoethylene (TCNE). In the case of 2a, the charge-transfer complex was isolated as red crystals and the structure was determined by X-ray crystallography. Crystal data for the 2a-TCNE complex: triclinic, P1, a = 6.8399(8), b = 8.2836(6), c = 12.868(1) A, α = 84.142(6)°, β = 88.737(6)°, γ = 66.801(8)°, V = 666.5(1) A3, Z = 1, R = 0.038, Rw = 0.042 for 1554 reflections.

Si,Al solid solution in sodalite: synthesis, 29Si NMR and X-ray structure

A formation of complete solid solution series of Si,Al in the sodalite framework is tried in a non aqueous solution. The formation of two types of solid solutions, type A and type B, are successfully confirmed, which are separated at two discontinuous points of 1.4 and 2.0 in the Si/Al ratio. The characteristic X-ray powder diffraction patterns, crystal structure, thermoanalysis and 29 Si MAS NMR data are shown.

Encapsulation of pyrrole into AlPO4 molecular sieves with chromium ions

Encapsulation of pyrrole in one-dimensional channels of AlPO4-5 and AlPO4-11 with chromium ions was attempted by a gas diffusion process and investigated by means of thermoanalytic, spectroscopic and conductivity methods. From the results, it was found that conducting polypyrrole was synthesized in channels of AlPO4-5 with chromium ions which acted as oxidizing agents. Polypyrrole, however, could not be occluded in channels of AlPO4-11 with chromium ions.