Silicalite preparation

At higher Si/Ti ratios, the total acidity decreases and acid strength distribution shortens in all the titanium silicalites prepared. 

The ionic conductivities of the Sn-ferrierites and Sn-silicalites, prepared by treatment of H-zeolite with tin chloride dihydrate, were mentioned in literatrrre [93K1]. The ac birlk corrductivity of Sn-ferrierite is higher than that of H-ferrierite and depends on the water content - Fig. 57. The bulk conductivities are almost indeperrdeirt on temperature in the range between 298 and 388 K. 

The zeolite nanocrystals have attracted the considerable attention of many researchers [1-5]. The syntheses of several types of zeolites with different nanometer sizes, such as silicalite-1, ZSM-5, A-type and Y-type, have been reported. Recently, micellar solutions or surfactant-containing solutions have been used for the preparation of zeolite nanoerystals [4,5], We have also successMIy prepared silicalite nanoerystals via hydrothermal synthesis using surfactants. In this study, we demonstrate a method for preparing mono-dispersed silicalite nanoerystals in a solution consisting of surfiictants, organic solvents and water. 

Mono-dispersed silicalite and ZSM-5 type zeolite nanocrystals with a diameter of 80-120 nm were successfully prepared in a surfactant-oil-water solution. The ionicity of the surfactants used in the preparation affected the crystallinity and structure of the silicalite crystals, and silicalite nanocrystals could he obtained when using a nonionic sur ctant. By adding an A1 source into the synthetic solution, ZSM-5 type zeolite nanocrystals with strong acid sites could be obtained. 

The silicalite-alumina membrane was prepared after adding a solution containing the silicalite precursor (i e silica + template) to the above-mentioned porous tube (hereafter called support) and a specific hydrothermal treatment performed [8], under the chosen conditions no material is formed in the absence of the porous support. The tube is then calcined at 673 K for removing the template. 

After the calcination step, experimental data (XRD, 29 i maSNMR) show that a zeolite with the silicalite structure has been formed. 29 i MASNMR indicates for the zeolite material a Si/Al ratio depending on the sample prepared it has been observed that both the natures of the silicon source and of the alumina supports may originate these fluctuations. 

Although the complete mechanism for each of the previously described reactions is not known, substantial details have been worked out. First, it is clear that Ti is incorporated into the framework of the silicalite structure. Too much Ti (more than about 2.5%) in the preparation steps forms nonframework TiOz crystallites, which decompose H202. Second, the rate enhancement due to methanol suggests a tight association at the Ti active site as shown in Fig. 6.8.37,38 This is supported by the fact that methanol oxidizes much more slowly than other alcohols.47 This tight coordination of methanol is proposed to increase the electrophilicity of the Ti-coordinated H202 and facilitate oxygen transfer to the alkene.31... 

Beyer and Belenykaia (27) have investigated the sorption properties of DAY zeolites prepared from Y zeolite and SiCl vapors. They reported a very low adsorption capacity for water and ammonia, similar to that of the almost aluminum-free silicalite (49). The low adsorption capacity for water is indicative of a hydrophobic zeolite surface. The adsorption isotherms for n-butane, benzene and n-hexane obtained on the aluminum-deficient zeolite have a shape similar to those obtained on NaY zeolite and are characteristic for micropore structures. They show the absence of secondary pores in this DAY zeolite. 

Jia and coworkers prepared thin-film composite zeolite-filled silicone rubber membranes by a dip-coating method [82]. The membranes have a thin silicalite-1/ silicone rubber mixed-matrix selective layer on top of a porous polyetherimide support. 

Chen, H Li, Y and Yang, W. (2007) Preparation of silicalite-1 membrane by solution-filling method and its alcohol extraction properties. J. Membr. Sci., 296, 122-130. 

The atom-planting method for the preparation of several metallosilicates with MFI structure was studied. By the treatment of silicalite or ZSM-5 type zeolite with metal chloride vapor at elevated temperatures, metal atom could be introduced into the zeolite framework. From the results of alumination of silicalite it is estimated that the metal atoms are inserted into defect sites, such as hydroxyl nests in zeolite framework. The metallosilicate prepared had both Bronsted and Lewis acid sites with specific acid strength corresponding to the kind of metal element. 

Recently, the preparation of metallosilicates with MFI structure, which are composed of silicone oxide and metal oxide substituted isomorphously to aluminium oxide, has been studied actively [1,2]. It is expected that acid sites of different strength from those of aluminosilicate are generated when some tri-valent elements other than aluminium are introduced into the framework of silicalite. The Bronsted acid sites of metallosilicates must be Si(0H)Me, so the facility of heterogeneous rupture of the OH bond should be due to the properties of the metal element. Therefore, the acidity of metallosilicate could be controlled by choosing the metal element. Moreover, the transition-metal elements introduced into the zeolite framework play specific catalytic roles. For example, Ti-silicate with MFI structure has the high activity and selectivity for the hydroxylation of phenol to produce catechol and hydroquinon [3],... 

It has been reported that aluminium can be introduced into the framework of silicalite with MFI structure by the treatment with AICI3 vapor at elevated temperatures [4-8]. By such treatment, not only Bronsted acid sites but Lewis acid sites are also generated, because aluminium atoms are introduced not only into the framework sites but alkso into the non-framework sites [6-8]. It is expected that this method can be applied to prepare some metallosilicates with MFI structure. Namely, by treating silicalite with metal chloride vapor at... 

The incorporation of vanadium(V) into the framework positions of silicalite-2 has been reported by Hari Prasad Rao and Ramaswamy . With this heterogeneons oxidation catalyst the aromatic hydroxylation of benzene to phenol and to a mixtnre of hydroqninone and catechol conld be promoted. A heterogeneons ZrS-1 catalyst, which has been prepared by incorporation of zirconinm into a silicalite framework and which catalyzes the aromatic oxidation of benzene to phenol with hydrogen peroxide, is known as well in the literature. However, activity and selectivity were lower than observed with the analogous TS-1 catalyst. 

V-containing silicalite (Al- and Na-free) samples were prepared hydrothermally and then treated with an ammonium acetate solution at room temperature in order to remove extralattice vanadium. Three samples with Si02A 203 ratios of 117, 237 and 545, respectively, were prepared. Hereinafter these samples will be referred to as follows V-SH117, V-SU237 and V-SH545. Details on the preparation procedure, and characterization of the samples have been reported previously (7,2). 

In addition to the three principal polymorphs of silica, three high pressure phases have been prepared keatite [17679-64-0], coesite, and stishovite. The pressure—temperature diagram in Figure 5 shows the approximate stability relationships of coesite, quartz, tridymite, and cristobalite. A number of other phases, eg, silica O, silica X, silicalite, and a cubic form derived from the mineral melanophlogite, have been identified (9), along with a structurally unique fibrous form, silica W. 

A unique titanium(IV)-silica catalyst prepared by impregnating silica with TiCLt or organotitanium compounds exhibits excellent properties with selectivities comparable to the best homogeneous molybdenum catalysts.285 The new zeolite-like catalyst titanium silicalite (TS-1) featuring isomorphous substitution of Si(IV) with Ti(IV) is a very efficient heterogeneous catalyst for selective oxidations with H2C>2.184,185 It exhibits remarkable activities and selectivities in epoxidation of simple olefins.188,304-306 Propylene, for instance, was epoxidized304 with 97% selectivity at 90% conversion at 40°C. Shape-selective epoxidation of 1- and 2-hexenes was observed with this system that failed to catalyze the transformation of cyclohexene.306 Surface peroxotitanate 13 is suggested to be the active spe-... 

Figure 1 shows XRD patterns of MCM-41 and silicalite-1 prepared by microwave irradiation. The material prepared at 120-100°C for 40 min by microwave irradiation exhibits... 

Niobium- and tantalum-containing mesoporous molecular sieves MCM-41 have been studied by X-ray powder diffraction, 29Si MAS NMR, electron spin resonance, nitrogen adsorption and UV-Vis spectroscopy and compared with niobium- and tantalum-containing silicalite-1. The results of the physical characterization indicate that it is possible to prepare niobium- and tantalum-containing MCM-41 and silicalite-1, where isolated Nb(V) or Ta(V) species are connected to framework defect sites via formation of Nb-O-Si and Ta-O-Si bonds. The results of this study allow the preparation of microporous and mesoporous molecular sieves with remarkable redox properties (as revealed by ESR), making them potential catalysts for oxidation reactions. 

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