Mesoporous materials characterization

Direct incorporation of Al in SBA mesoporous materials characterization, stability and catalytic activity... 

Martin Hartmann, Stefan Ernst, A.M. Prakash and Larry Kevan Direct Incorporation of A1 in SBA Mesoporous Materials Characterization, 209... 

This chapter discusses the synthesis, characterization and applications of a very unique mesoporous material, TUD-1. This amorphous material possesses three-dimensional intercoimecting pores with narrow pore size distribution and excellent thermal and hydrothermal stabilities. The basic material is Si-TUD-1 however, many versions of TUD-1 using different metal variants have been prepared, characterized, and evaluated for a wide variety of hydrocarbon processing applications. Also, zeolitic material can be incorporated into the mesoporous TUD-1 to take the advantage of its mesopores to facilitate the reaction of large molecules, and enhance the mass transfer of reactants, intermediates and products. Examples of preparation and application of many different TUD-1 are described in this chapter. 

Since the discovery by researchers at Mobil of a new family of crystalline mesoporous materials (1), a large effort has been expended on synthesis, characterization, and catalytic evalrration (2). MCM-41 is a one-dimerrsiorral, hexagonal structure. MCM-48 is a cubic structine with two, norrintersecting pore systems (3). MCM-50 is a layered stractme with silica sheets between the layers (4). Many scientists also looked into other mesoporous materials, of note the HMS (Hexagonal Molecular Sieve) family (5) and SBA-15 (acronym derived from Santa Barbara University) (6), bnt to date few materials have been both catalytically significant and inexpensive to synthesize. 

Carotenoid radical intermediates generated electrochemically, chemically, and photochemically in solutions, on oxide surfaces, and in mesoporous materials have been studied by a variety of advanced EPR techniques such as pulsed EPR, ESEEM, ENDOR, HYSCORE, and a multifrequency high-held EPR combined with EPR spin trapping and DFT calculations. EPR spectroscopy is a powerful tool to characterize carotenoid radicals to resolve -anisotropy (HF-EPR), anisotropic coupling constants due to a-protons (CW, pulsed ENDOR, HYSCORE), to determine distances between carotenoid radical and electron acceptor site (ESEEM, relaxation enhancement). 

With the combined methods of 29Si NMR spectroscopy, X-ray diffraction, HRTEM and SAED we were able to characterize the Ti-Beta particle growth. 29Si NMR spectroscopy gave us an opportunity to see the formation of nanoparticles even before they were detectable with other techniques such as XRD. The above mentioned techniques enabled us to obtain sufficient knowledge to prepare Ti-Beta nanoparticles which were than successfully incorporated in novel micro/mesoporous materials [1],... 

Acidic micro- and mesoporous materials, and in particular USY type zeolites, are widely used in petroleum refinery and petrochemical industry. Dealumination treatment of Y type zeolites referred to as ultrastabilisation is carried out to tune acidity, porosity and stability of these materials [1]. Dealumination by high temperature treatment in presence of steam creates a secondary mesoporous network inside individual zeolite crystals. In view of catalytic applications, it is essential to characterize those mesopores and to distinguish mesopores connected to the external surface of the zeolite crystal from mesopores present as cavities accessible via micropores only [2]. Externally accessible mesopores increase catalytic effectiveness by lifting diffusion limitation and facilitating desorption of reaction products [3], The aim of this paper is to characterize those mesopores by means of catalytic test reaction and liquid phase breakthrough experiments. 

Thommes, M. 2004. Physical adsorption characterization of ordered and amorphous mesoporous materials. In Nanoporous Materials Science and Engineering, edited by Lu, G. Q. Zhao, X. S. Imperial College Press, London, pp. 317-364. 

The analytical methods for the characterization of catalysts are described extensively in other chapters of this book. Here, only a brief overview on methods of predominant importance for the investigation of micro- and mesoporous materials will be given... 

Gas adsorption (physisorption) is one of the most frequently used characterization methods for micro- and mesoporous materials. It provides information on the pore volume, the specific surface area, the pore size distribution, and heat of adsorption of a given material. The basic principle of the methods is simple interaction of molecules in a gas phase (adsorptive) with the surface of a sohd phase (adsorbent). Owing to van der Waals (London) forces, a film of adsorbed molecules (adsorbate) forms on the surface of the solid upon incremental increase of the partial pressure of the gas. The amount of gas molecules that are adsorbed by the solid is detected. This allows the analysis of surface and pore properties. Knowing the space occupied by one adsorbed molecule, Ag, and the number of gas molecules in the adsorbed layer next to the surface of the solid, (monolayer capacity of a given mass of adsorbent) allows for the calculation of the specific surface area, As, of the solid by simply multiplying the number of the adsorbed molecules per weight unit of solid with the space required by one gas molecule ... 

Transmission electron microscopy (TEM) can provide detailed stmcture of zeolites. I use the word characterize or characterization for stmctural study on a unit cell scale, such as various kind of stmctural defects and basic stmctural units, and determine or determination for obtaining atomic coordinates within the unit cell for all the atoms of a crystal. A simple text or reviews for stmctural characterization of porous materials can be found in a book or review articles [1-6]. Now, we are in a new era, that is, we can determine new stmctures of micro- and mesoporous materials only by electron microscopy(EM), an area called electron crystallography (EC) [7-11]. 

Coluccia, S., Marchese, k., and Martra, G. (2000) Molecular probes for the characterization of adsorption sites in micro-and mesoporous materials, in Photofunctional Zeolites (ed. M. Anpo), NOVA Science, New York, pp. 39-74. 

In the following section, we restrict our discussion to templated mesoporous solids that are of potential interest as battery electrodes, including many transition-metal oxides and carbon. This slice of the literature still points the interested reader to many articles on the synthesis and physical characterization of relevant mesoporous materials. A much smaller number of electrochemical studies with templated mesoporous electrodes have been published, and these studies in particular will be noted. 

The acidity of thermally stable mesoporous aluminophosphates (AlPO) and sili-coaluminophosphates (SAPO) has also been stndied by microcalorimetry [245]. By contrast with microporous crystalline alnminophosphate molecnlar sieves, mesoporous compounds are amorphous and characterized by Al/P ratios greater than 1. These particularities are responsible for a strong Lewis acidity, making these mesoporous materials more acidic than the microporons analognes, with an amonnt of strong acid sites that increases with the silicon content. 

Polyacrylic acid Hybrid organic/inorganic network polymers were formed via the reaction of polyacrylic acid with tin(IV). titanium(IV), and silicon (IV) alkoxides and subsequent hydrolysis to form mesoporous materials. Treatment by nitric acid removed the polyacrylate template and produced microporous inorganic hydrous metal oxides Surface areas characterized by BET measurements 130... 

To further characterize the effect of the ammonia hydrothermal treatment, we compared elemental analysis data and 1R spectra before and after ammonia hydrothermal treatment to quantitatively disclose the role of counterion between the silica framework and surfactants. In Table 2, the N/C molar ratio of the mesoporous materials prior to the ammonia hydrothermal treatment is nearly twice of that after the treatment. Moreover, the IR band at 1383 cm 1, which arises from the N03 stretch bending mode, completely disappears after ammonia hydrothermal treatment [20], These results verify that the existence of nitrate counterion (the nitrate/surfactant 1) between surfactant molecules and silica framework in the acid-made mesoporous materials. The bridging counterion N03 was completely removed after ammonia hydrothermal treatment. 

The synthesis and characterization of the structural defects within aluminosilicate mesoporous materials were provided. We further discussed the fascinating adsorption-desorption hysteresis behaviors and the influencing factors in the formation of the structural defects. However, mesoporous MCM-41 can act as catalyst support for many catalytic reactions, especially involve bulk oiganic molecules, due to its large surface area and pore size. The ability to synthetically control the connectivity of the mesoporous materials may have important applications in catalysis. 

The samples obtained by this procedure, containing various ratios of zeolite and mesoporous materials, were tested in 100% steam for 5 hours at temperatures of 650 and 815°C, respectively, in a fixed bed reactor. Prior to the tests the samples were calcined at 550°C in N2 (1 hour) and dry air (4 hours). Synthesis and characterization data for the most interesting samples with regard to improved hydrothermal stability are listed in Tables 1 and 2. 

Since the first synthesis of mesoporous materials MCM-41 at Mobile Coporation,1 most work carried out in this area has focused on the preparation, characterization and applications of silica-based compounds. Recently, the synthesis of metal oxide-based mesostructured materials has attracted research attention due to their catalytic, electric, magnetic and optical properties.2 5 Although metal sulfides have found widespread applications as semiconductors, electro-optical materials and catalysts, to just name a few, only a few attempts have been reported on the synthesis of metal sulfide-based mesostructured materials. Thus far, mesostructured tin sulfides have proven to be most synthetically accessible in aqueous solution at ambient temperatures.6-7 Physical property studies showed that such materials may have potential to be used as semiconducting liquid crystals in electro-optical displays and chemical sensing applications. In addition, mesostructured thiogermanates8-10 and zinc sulfide with textured mesoporosity after surfactant removal11 have been prepared under hydrothermal conditions. 

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