Diffusion of n-decane in mesoporous MCM-41 silicas

We investigate here the diffusion of n-decane in nanoporous MCM-41 silicas with pore diameters between 3.0 and 4.3 nm, and at various temperatures and purge flow rates, by the Zero Length Column method. A complete-time-range analysis of desorption curves is used to derive the diffusion coefficient, and the effect of pore size, purge flow rate and temperature on the diffusion character is systematically studied. The results show that the calculated low-coverage diffusivity values are strongly dependent on temperature but only weakly dependent on pore size. The study reveals that transport is controlled by intracrystalline diffusion and dominated by sorbate-sorbent interaction, with the experimental isosteric heat matching the potential energy of flat-lying n-decane molecules on the surface, determined using a united atom model. The diffusion activation energy and adsorption isosteric heat at zero loading for the different pore size MCM-41 samples vary in a narrow range respectively, and their ratio is essentially constant over the pore size range studied. The study shows that the ZLC method is an effective tool to investigate the diffusion kinetics of hydrocarbons in mesoporous MCM-41 materials. (c) 2005 Elsevier Inc. All rights reserved.

Immobilization of aluminum chloride on MCM-41 as a new catalyst system for liquid-phase isopropylation of naphthalene

A great deal of effort has been made at searching for alternative catalysts to replace conventional Lewis acid catalyst aluminum trichloride (AlCl3). In this paper, immobilization of AlCl3 on mesoporous MCM-41 silica with and without modification was carried out. The catalytic properties of the immobilized catalyst systems for liquid-phase isopropylation of naphthalene were studied and compared with those of H/MCM-41 and H/mordenite. The structures of the surface-immobilized aluminum chloride catalysts were studied and identified by using solid-state magic angle spinning nuclear magnetic resonance (MAS NMR), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption, and X-ray diffraction (XRD) techniques. The catalytic activity of the immobilized catalysts was found to be similar to that of acidic mordenite zeolite. A significant enhancement in the selectivity of 2,6-diisopropylnaphthalene (2,6-DIPN) was observed over the immobilized aluminum chloride catalysts. Immobilization of aluminum chloride on mesoporous silica coupled with surface silylation is a promising way of developing alternative catalyst system for liquid-phase Friedel-Crafts alkylation reactions. (C) 2002 Elsevier Science B.V. All rights reserved.

Comparison of nitrogen adsorption at 77 K on non-porous silica and pore wall of MCM-41 materials by means of density functional theory

Nitrogen adsorption on a surface of a non-porous reference material is widely used in the characterization. Traditionally, the enhancement of solid-fluid potential in a porous solid is accounted for by incorporating the surface curvature into the solid-fluid Potential of the flat reference surface. However, this calculation procedure has not been justified experimentally. In this paper, we derive the solid-fluid potential of mesoporous MCM-41 solid by using solely the adsorption isotherm of that solid. This solid-fluid potential is then compared with that of the non-porous reference surface. In derivation of the solid-fluid potential for both reference surface and mesoporous MCM-41 silica (diameter ranging front 3 to 6.5 nm) we employ the nonlocal density functional theory developed for amorphous solids. It is found that, to out, surprise, the solid-fluid potential of a porous solid is practically the same as that for the reference surface, indicating that there is no enhancement due to Surface curvature. This requires further investigations to explain this unusual departure from our conventional wisdom of curvature-induced enhancement. Accepting the curvature-independent solid-fluid potential derived from the non-porous reference surface, we analyze the hysteresis features of a series of MCM-41 samples. (c) 2005 Elsevier Inc. All rights reserved.

Catalytic properties of heteropolyacids supported on MCM-41 mesoporous silica for hydrocarbon cracting reactions

It is known that MCM-41 structures have very weak acid sites because of the lack of the bridging hydroxyl groups present in zeolites. Strong acidity however is required for the potential use of these materials in some specific applications such as: cracking and hydrotreating of heavy residue molecules, cracking of waste plastic, etc. The acidity enhancement of the MCM-41 materials was assessed using the n-hexane and polyethylene cracking reactions. MCM-41 samples were impregnated using heteropolyacid (HPA) such as tungestophospheric acid. The catalyst samples were characterized also by x-ray diffraction and benzene adsorption.

Improvement of the Derjaguin-Broekhoff-de Boer theory for capillary condensation/evaporation of nitrogen in mesoporous systems and its implications for pore size analysis of MCM-41 silicas and related materials

In this work, we propose an improvement of the classical Derjaguin-Broekhoff-de Boer (DBdB) theory for capillary condensation/evaporation in mesoporous systems. The primary idea of this improvement is to employ the Gibbs-Tolman-Koenig-Buff equation to predict the surface tension changes in mesopores. In addition, the statistical film thickness (so-called t-curve) evaluated accurately on the basis of the adsorption isotherms measured for the MCM-41 materials is used instead of the originally proposed t-curve (to take into account the excess of the chemical potential due to the surface forces). It is shown that the aforementioned modifications of the original DBdB theory have significant implications for the pore size analysis of mesoporous solids. To verify our improvement of the DBdB pore size analysis method (IDBdB), a series of the calcined MCM-41 samples, which are well-defined materials with hexagonally ordered cylindrical mesopores, were used for the evaluation of the pore size distributions. The correlation of the IDBdB method with the empirically calibrated Kruk-Jaroniec-Sayari (KJS) relationship is very good in the range of small mesopores. So, a major advantage of the IDBdB method is its applicability for small mesopores as well as for the mesopore range beyond that established by the KJS calibration, i.e., for mesopore radii greater than similar to4.5 nm. The comparison of the IDBdB results with experimental data reported by Kruk and Jaroniec for capillary condensation/evaporation as well as with the results from nonlocal density functional theory developed by Neimark et al. clearly justifies our approach. Note that the proposed improvement of the classical DBdB method preserves its original simplicity and simultaneously ensures a significant improvement of the pore size analysis, which is confirmed by the independent estimation of the mean pore size by the powder X-ray diffraction method.

Study of hexane adsorption in nanoporous MCM-41 silica

We study here the adsorption of hexane on nanoporous MCM-41 silica at 303, 313, and 323 K, for various pore diameters between 2.40 and 4.24 nm. Adsorption equilibria, measured thermogravimetrically, show that all the isotherms, that are somewhat akin to those of type V, exhibit remarkably sharp capillary adsorption phase transition steps and are reversible. The position of the phase transition step gradually shifts from low to high relative pressure with an increase in the temperature as well as the pore sizes. The isosteric heats of adsorption derived from the equilibrium information using the Clapeyron equation reveal a gradual decrease with increasing adsorbed amount because of the surface heterogeneity but approach a constant value near the phase transition. A decrease in the pore size results in an increase in the isosteric heat of adsorption because of the increased dispersion forces. A simple strategy, based on the Broekhoff and De Boer adsorption theory, successfully interprets the hexane adsorption isotherms for the different pore size MCM-41 samples. The parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting the monolayer region prior to capillary condensation and the experimental phase transition simultaneously, for some pore sizes. Subsequently, the parameters are used to predict the adsorption isotherm on other pore size samples, which showed good agreement with experimental data.

Adsorption of argon and nitrogen in cylindrical pores of MCM-41 materials: application of density functional theory

Adsorption of argon and nitrogen at their respective boiling points in cylindrical pores of MCM-41 type silica-like adsorbents is studied by means of a non-local density functional theory (NLDFT), which is modified to deal with amorphous solids. By matching the theoretical results of the pore filling pressure versus pore diameter against the experimental data, we arrive at a conclusion that the adsorption branch (rather than desorption) corresponds to the true thermodynamic equilibrium. If this is accepted, we derive the optimal values for the solid–fluid molecular parameters for the system amorphous silica–Ar and amorphous silica–N2, and at the same time we could derive reliably the specific surface area of non-porous and mesoporous silica-like adsorbents, without a recourse to the BET method. This method is then logically extended to describe the local adsorption isotherms of argon and nitrogen in silica-like pores, which are then used as the bases (kernel) to determine the pore size distribution. We test this with a number of adsorption isotherms on the MCM-41 samples, and the results are quite realistic and in excellent agreement with the XRD results, justifying the approach adopted in this paper.

Pore size characterization of mesoporous materials by a thermodynamic approach: A curvature-dependent solid-fluid potential

A thermodynamic analysis of nitrogen adsorption in cylindrical pores of MCM-41 and SBA-15 samples at 77 K is presented within the framework of the Broekhoff and de Boer (BdB) theory. We accounted for the effect of the solid surface curvature on the potential exerted by the pore walls. The developed model is in quantitative agreement with the non-local density functional theory (NLDFT) for pores larger than 2 tun. This modified BdB theory accounting for the Curvature Dependent Potential (CDP-BdB) was applied to determine the pore size distribution (PSD) of a number of MCM-41 and SBA-15 samples on the basis of matching the equilibrium theoretical isotherm against the adsorption branch of the experimental isotherm. In all cases investigated the PSDs determined with the new approach are very similar to those determined with the non-local density functional theory also using the same basis of matching of theoretical isotherm against the experimental adsorption branch. The developed continuum theory is very simple in its utilization, suggesting that CDP-BdB could be used as an alternative tool to obtain PSD for mesoporous solids from the analysis of adsorption branch of adsorption isotherms of any sub-critical fluids.

Comparative Analysis of Structural and Morphological Properties of Large-Pore Periodic Mesoporous Organosilicas and Pure Silicas

A systematic study on the structural properties and external morphologies of large-pore mesoporous organosilicas synthesized using triblock copolymer EO20PO70EO20 as a template under low-acid conditions was carried out. By employing the characterization techniques of SAXS, FE-SEM, and physical adsorption of N-2 in combination with alpha(s)-plot method, the structural properties and external morphologies of large-pore mesoporous organosilicas were critically examined and compared with that of their pure-silica counterparts synthesized under similar conditions. It has been observed that unlike mesoporous pure silicas, the structural and morphological properties of mesoporous organosilicas are highly acid-sensitive. High-quality mesoporous organosilicas can only be obtained from synthesis gels with the molar ratios of HCl/H2O between 7.08 x 10(-4) and 6.33 x 10(-3), whereas mesoporous pure silicas with well-ordered structure can be obtained in a wider range of acid concentration. Simply by adjusting the HCl/H2O molar ratios, the micro-, meso-, and macroporosities of the organosilica materials can be finely tuned without obvious effect on their structural order. Such a behavior is closely related to their acid-controlled morphological evolution: from necklacelike fibers to cobweb-supported pearl-like particles and to nanosized particulates.

Application of a generalized thermodynamic approach to characterize mesoporous materials

Equilibrium adsorption and desorption in mesoporous adsorbents is considered on the basis of rigorous thermodynamic analysis, in which the curvature-dependent solid-fluid potential and the compressibility of the adsorbed phase are accounted for. The compressibility of the adsorbed phase is considered for the first time in the literature in the framework of a rigorous thermodynamic approach. Our model is a further development of continuum thermodynamic approaches proposed by Derjaguin and Broekhoff and de Boer, and it is based on a reference isotherm of a non-porous material having the same chemical structure as that of the pore wall. In this improved thermodynamic model, we incorporated a prescription for transforming the solid-fluid potential exerted by the flat reference surface to the potential inside cylindrical and spherical pores. We relax the assumption that the adsorbed film density is constant and equal to that of the saturated liquid. Instead, the density of the adsorbed fluid is allowed to vary over the adsorbed film thickness and is calculated by an equation of state. As a result, the model is capable to describe the adsorption-desorption reversibility in cylindrical pores having diameter less than 2 nm. The generalized thermodynamic model may be applied to the pore size characterization of mesoporous materials instead of much more time-consuming molecular approaches. (c) 2005 Elsevier B.V. All rights reserved.

Effect of the preparation technique on the catalytic properties of mesoporous V-HMS for the oxidation of toluene

Various mesoporous catalysts with vanadium loadings between 0.5 and 6 V wt.% and surface areas around 1300 m(2)/g were synthesized using the isomorphous substitution (IS) and molecular designed dispersion (MDD) techniques. Their catalytic properties were tested using toluene as a model VOC in a fixed bed reactor at temperatures between 300 and 550 degrees C. It was found that during the oxidation of toluene, over V-HMS synthesized via IS, conversion of toluene mainly results in carbon oxides, benzene, benzaldehyde and water. Total conversion is greatly improved when the vanadium content is increased from around 1.5 to 3.0 wt.%, but an increase in the textural porosity (V-TEX/V-MESO) from 0.3 to 0.6 had no discernable effect on the conversion. This can be explained by the fact that a V-TEX/V-MESO as low as 0.3 is sufficient to facilitate the access of toluene into the framework confined mesopores without any molecular transport limitations. However, when using V-HMS synthesized by MDD, conversion of toluene is greatly improved when the V-TEX/ V-MESO ratio is increased from 0.1 to 0.6. This is because the diffusion limitations are minimized by this increase. V-HMS synthesized via MDD does not exhibit selectivity to benzaldehyde, favoring total oxidation to CO and CO2. This different oxidation mechanism can be explained in terms of location, accessibility and number of active species on the surface of the HMS support. (c) 2005 Elsevier Inc. All rights reserved.

Modeling nitrogen adsorption in spherical pores of siliceous materials by density functional theory

Adsorption of nitrogen in spherical pores of FDU-1 silica at 77 K is considered by means of a nonlocal density functional theory (NLDFT) accounting for a disordered structure of pore walls. Pore size distribution analysis of various FDU-1 samples subject to different temperatures of calcination revealed three distinct groups of pores. The principal group of pores is identified as ordered spherical mesopores connected with each other by smaller interconnecting pores and irregular micropores present in the mesopore walls. To account for the entrances (connecting pores) into spherical mesopores, a concept of solid mass distribution with respect to the apparent density was introduced. It is shown that the introduction of the aforementioned distribution was sufficient to quantitatively describe experimental adsorption isotherms over the entire range of relative pressures spanning six decades.

Equilibrium adsorption in cylindrical mesopores: A modified Broekhoff and de boer theory versus density functional theory

This paper presents a thermodynamic analysis of capillary condensation phenomena in cylindrical pores. Here, we modified the Broekhoff and de Boer (BdB) model for cylindrical pores accounting for the effect of the pore radius on the potential exerted by the pore walls. The new approach incorporates the recently published standard nitrogen and argon adsorption isotherm on nonporous silica LiChrospher Si-1000. The developed model is tested against the nonlocal density functional theory (NLDFT), and the criterion for this comparison is the condensation/evaporation pressure versus the pore diameter. The quantitative agreement between the NLDFT and the refined version of the BdB theory is ascertained for pores larger than 2 nm. The modified BdB theory was applied to the experimental adsorption branch of adsorption isotherms of a number of MCM-41 samples to determine their pore size distributions (PSDs). It was found that the PSDs determined with the new BdB approach coincide with those determined with the NLDFT (also using the experimental adsorption branch). As opposed to the NLDFT, the modified BdB theory is very simple in its utilization and therefore can be used as a convenient tool to obtain PSDs of all mesoporous solids from the analysis of the adsorption branch of adsorption isotherms of any subcritical fluids.

Application of density functional theory to capillary phenomena in cylindrical mesopores with radial and longitudinal density distributions

In this paper, we applied a version of the nonlocal density functional theory (NLDFT) accounting radial and longitudinal density distributions to study the adsorption and desorption of argon in finite as well as infinite cylindrical nanopores at 87.3 K. Features that have not been observed before with one-dimensional NLDFT are observed in the analysis of an inhomogeneous fluid along the axis of a finite cylindrical pore using the two-dimensional version of the NLDFT. The phase transition in pore is not strictly vapor-liquid transition as assumed and observed in the conventional version, but rather it exhibits a much elaborated feature with phase transition being complicated by the formation of solid phase. Depending on the pore size, there are more than one phase transition in the adsorption-desorption isotherm. The solid formation in finite pore has been found to be initiated by the presence of the meniscus. Details of the analysis of the extended version of NLDFT will be discussed in the paper. (C) 2004 American Institute of Physics.