Mesoporous molecular sieves properties

Dispersion of POMs onto inert solid supports with high surface areas is very important for catalytic application because the surface areas of unsupported POMs are usually very low (—10 m2g). Another advantage of dispersion of POMs onto inert supports is improvement of the stability. Therefore, immobilization of POMs on a number of supports has been extensively studied. Silica and active carbon are the representative supports [25], Basic supports such as MgO tend to decompose POMs [101-104], Certain kinds of active carbons firmly entrap POMs [105,106], The maximum loading level of POMs on active carbons is 14 wt% [107], Dispersion of POMs onto other supports such as zeolites, mesoporous molecular sieves, and apatites, is of considerable interest because of their high surface areas, unique pore systems, and possibility to modify their compositions, morphologies, and sorption properties. However, a simple impregnation of POM compounds on inert supports often results in leaching of POMs. 

In this current work, cerium-modified MCM-41 mesoporous molecular sieve was synthesized using heptahydrated cerium chloride, colloidal fumed-silica, sodium hydroxide, cethyltrimethylammonium bromide and water. The incorporation of cerium to MCM-41 improved the quality, stability and acid properties of the resulting ordered mesoporous material. Its surface and structural properties were extensively studied by nitrogen adsorption and high-resolution thermogravimetry. 

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. 

The AlSBA mesoporous molecular sieves can be obtained easily by direct synthesis. These novel mesoporous materials retain the hexagonal order and physical properties of AlMCM-41... 

In the present work the synthesis of highly dispersed niobium or titanium containing mesoporous molecular sieves catalyst by direct grafting of different niobium and titanium compounds is reported. Grafting is achieved by anchoring the desired compounds on the surface hydroxyl groups located on the inner and outer surface of siliceous MCM-41 and MCM-48 mesoporous molecular sieves. Catalytic activity was evaluated in the liquid phase epoxidation of a-pinene with hydrogen peroxide as oxidant and the results are compared with widely studied titanium silicalites. The emphasis is directed mainly on catalytic applications of niobium or titanium anchored material to add a more detailed view on their structural physicochemical properties. 

Diffuse reflectance UV-spectra showed the framework incorporation of titanium and niobium in the all sample studied. The detailed characterisation of the materials will be presented in the subsequent paper. The catalytic properties are studied by the epoxidation of a-pinene, using H20, as an oxidizing agent. The framework 2.0wt % Ti-MCM-41 and 2.0wt % Ti-MCM-48 mesoporous molecular sieves samples synthesized by direct hydrothermal route,... 

Table 1 shows the structural properties of the titanium-incorporated mesoporous molecular sieves. The surface areas of all samples were over 750 m2/g, being typical of M41S group materials. After grafting, surface area and total pore volume decreased [8],... 

Table 2. Catalytic and adsorption properties of mesoporous molecular sieves...

Physico-chemical and catalytic properties of MCM-41 mesoporous molecular sieves containing transition metals (Cu, Ni, and Nb)... 

Since the first synthesis of siliceous mesoporous molecular sieves described in the literature in 1992 [1], several mesoporous materials possessing various T atoms together with Si in the lattice have been prepared. The synthesis and properties of niobium- and siliceous-containing mesoporous sieves of MCM-41 type were first time described by our group [2,3] and almost parallely, Nb-doped mesoporous sieves were synthesized by Zhang and Ying [4]. 

The potential catalytic application of mesoporous molecular sieves is addressed to the adsorption and transformation of bulky compounds which are not capable of diffusing in the micropores of zeolites. In the case of Nb-containing mesoporous molecular sieves, their unique oxidizing properties [S] make them interesting also for the reactions of smaller molecules. 

Catalytic properties of mesoporous molecular sieves 3.3.1 The catalytic decomposition of NO... 

Zeolites and related materials, pillared clays, and mesoporous molecular sieves (MMSs) are the most important acid catalysts. In this section, the catalytic properties of these materials are explained [12-22],... 

A common and well-known method to prepare silica membranes with molecular sieving properties is sol-gel coating [3-5], With this technique, microporous silica layers with a pore-size of about 0.5 nm are dip-coated on top of supported y-alumina membranes. The supports are porous a-alumina disks with pore diameters in the range from 100-200 nm. On top of these macroporous supports a 3 pm thick mesoporous y-alumina layer is coated, with a pore size of 3 nm. 

Review of literature concerning the photochemistry of inorganic compounds shows us that a substantial progress was achieved during the past two decades in understanding the photophysical and photochemical properties of nanometer semiconductor particles [1-4] and structurally organized semiconductor materials, including the nanostructured semiconductor films, mesoporous molecular sieves [5 - 10] etc., and, also in the elaboration of physical and chemical techniques for their synthesis and examination of their photocatalytic activity in various chemical and electrochemical redox-processes. 

All these aspects were thoroughly discussed by lecturers and participants during the round table organized during the Poitiers School on The Future Trends in Zeolite Applications . Special emphasis was placed on the role played by the sites at the external surface (pockets, etc.) or at the pore mouth, by mesopores, extraframework aluminum species, as well as by the polarity of reactant and product molecules. Other important topics dealt with the remarkable catalytic properties of BEA zeolites for fine chemical synthesis, the potential of mesoporous molecular sieves, zeolitic membranes and the role of combinatorial catalysis in the development of zeolite catalysts. It is our hope that the fruits of these discussions will appear in the literature or even better as new and environmentally friendly products or processes. 

Christopher JCW, Tsuji K, Takewaki T, Beck LW, and Davis ME. Tailoring molecular sieve properties during SDA removal via solvent extraction. Micropor Mesopor Mater 2001 48 57-64. 

Copper and zinc containing mesoporous molecular sieves AIMCM-41 have been studied by MAS NMR, electron spin resonance, nitrogen and carbon monoxide adsorption and temperature programmed reduction. AlMCM-41 materials with ns,/nAi = 15, 30 and x have been synthesized in the presence of copper and zinc Carbon monoxide adsorption shows the presence of Cu ions after mild activation, but Zn ions have not been detected indicating that only a ZnO phase is formed Temperature programmed reduction reveals the presence of CuO clusters of various size depending on the on the ns./n ij ratio and the zinc concentration The results of this study allow the preparation of mesoporous molecular sieves with remarkable redox properties, which are potential model catalyst for methanol synthesis... 

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