Molecular sieves, pore structure characterization

Recent progress in the theory of adsorption on porous solids, in general, and in the adsorption methods of pore structure characterization, in particular, has been related, to a large extent, to the application of the density functional theory (DFT) of Inhomogeneous fluids [1]. DFT has helped qualitatively describe and classify the specifics of adsorption and capillary condensation in pores of different geometries [2-4]. Moreover, it has been shown that the non-local density functional theory (NLDFT) with suitably chosen parameters of fluid-fluid and fluid-solid interactions quantitatively predicts the positions of capillary condensation and desorption transitions of argon and nitrogen in cylindrical pores of ordered mesoporous molecular sieves of MCM-41 and SBA-15 types [5,6]. NLDFT methods have been already commercialized by the producers of adsorption equipment for the interpretation of experimental data and the calculation of pore size distributions from adsorption isotherms [7-9]. 

Under the mineralogical name zeolite such sieves occur naturally. For technical purposes due to their higher uniformity only synthetic zeolites are used [10], In the empirical formula Me is an exchangeable cation of the valence n (zeolites are cation exchangers). Molecular sieves have a very regular and orderly crystal structure, which is characterized by a three-dimensional system of cavities with a diameter of 11 A. These cavities are interconnected by pores with a constant diameter. The value of this diameter depends on the type of the exchangeable cation Me. It is 5 A, if in the above formula Me stands for 75% Na+ and 25% Ca2+. 

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. 

The purpose of the present work is to incorporate aluminum into the framework of SBA-15 during the synthesis in order to create acid sites on the surface of the material directly and to enhance its activity in acid-catalyzed reactions and to study the stability of SBA and AlSBA molecular sieves under various treatments. The influence of these treatments on the pore size, wall thickness and the environment of Al in these materials are investigated in detail. X-ray diffraction (XRD), Electron Microscopy (TEM) and N2 adsorption were used to characterize the structure, the porosity and the stability of these materials. 27Al MAS NMR was used to ascertain the nature and environment of Al, cumene cracking to test the catalytic activity of parent materials and ammonia chemisorption to probe their surface acidity. 

Specifically, this volume focuses on the synthesis, processing, and structural tailoring of nanocrystalline and nanoporous materials. Nanocrystalline materials possess unique hybrid properties characteristic of neither the molecular nor the bulk solid-state limits and may be confined in nanometersized domains in one, two, or three dimensions for unusual size-dependent behavior. Nanoporous materials, characterized by well-defined pores or cavities in the nanometer size regime and controlled pore diameter and structure, give rise to unique molecular sieving capabilities and ultrahigh internal surface areas. Nanoporous structures also act as hosts and templates for the fabrication of quantum dots and quantum wires. 

If we define in that way the phenomena taking place on the molecular sieves surface, the first step to characterize the type of separation mechanism of a specific gas mixture should be determination of the pore sizes. However, selection of the measurement method for characterization of porous structures also has to take into account these mechanisms. 

The aim of this review is to describe the most interesting results characterizing the skeletal isomerization of n-butenes catalyzed by zeolitic and nonzeolitic molecular sieves and to discuss the state of the art of the isomerization mechanism, the nature and location of the active sites responsible for the selectivity for isobutylene, and the influence of the pore dimensions and pore structures of the molecular sieves. 

TTus paper is concerned with the particular class of molecular sieves having periodic mesoporous structure with pore sizes in the range of 2 to 10 nm. They are comprised of the M41S mesoporous molecular sieves and solids with related structures. In the first part, the preparation methods and characterization techniques will be reviewed and discussed. Silicate-based materials and non-silicate materials will be dealt with separately. In the second part of this review particular emphasis will be put on potential applications reported in both the patent and the open literature. Early progress in tWs field has been presented in the previous Summer School by Casci [37]. Potential catalytic applications of M41S were also reviewed rprPTitlv 1381... 

Molecular sieves (e g. zeolites, alumino-phosphates) are interesting as catalytic materials and are characterized by a very narrow pore size distribution in the micropore region and by a crystalline structure. 

Preoxidation of the coal generates in low activated chars a microporous structure characterized by a narrow size distribution (domination of micropores accessible for benzene but inaccessible for cyclohexane, i.e., with widths between 0.41 and 0.54 nm). The molecular sieve properties of these chars are however not accompanied by sufficiently high pore volumes within the indicated pore widths region. Figures 6 and 7... 

M. Yoshikawa, P. Wagner, M. Lovallo, K. Tsuji, T. Takewaki, C. Chen, L.W. Beck, C. Jones, M. Tsapatsis, S.I. Zones, andM.E. Davis, Synthesis, Characterization, and Structure Solution of CIT-5, a New, High-silica, Extra-large-pore Molecular Sieve. J. Phys. Chem. B, 1998,102, 7139-7147. 

Since carbon molecular sieves are amorphous materials, the dimensions of their pore structures must be measured phenomenologically by the adsorption of small probe molecules with different critical dimensions. There is insufficient long range order to utilize standard x-Ray diffraction methods for characterization. The earliest reports of molecular sieving carbons dealt primarily with coals and charcoals. Sorption of helium, water, methanol, n-hexane, and benzene was measured and related to the porosity of the carbon. Pore-sizes were estimated to be two to six angstroms (3-6). In a classic paper P.H. Emmett described methods for tailoring the adsorptive properties and pore size distributions of carbon Whetlerites. 

As far as shape selective catalysis is concerned, the structure characteristic of greatest interest is the pore/channel system of these molecular sieves. As we know, depending on the largest channel, zeolites are characterized as small, medium or large pore if they contain apertures made by rings of 8, 10 or 12 linked tetrahedra. 

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