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.

Diffusion of linear paraffins in nanoporous silica

The diffusion of hexane, heptane, octane, and decane in nanoporous MCM-41 silica at various temperatures is investigated by the zero-length-column method. The diffusion coefficients are derived by a complete-time-range analysis of desorption curves at different purge flow rates and temperatures. The results show that the calculated low-coverage diffusivity values decrease monotonically, and the derived Henry's law constants increase, as the carbon number of paraffins increases. The study reveals that transport is strongly influenced by intracrystalline diffusion and dominated by the sorbate-sorbent interaction. The diffusion activation energy and adsorption isosteric heat at zero loading increase monotonically with the carbon number of linear paraffins, but their ratio is essentially constant for each adsorbate compound.

Application of density functional theory to equilibrium adsorption of argon and nitrogen on amorphous silica surface

We present a new version of non-local density functional theory (NL-DFT) adapted to description of vapor adsorption isotherms on amorphous materials like non-porous silica. The novel feature of this approach is that it accounts for the roughness of adsorbent surface. The solid–fluid interaction is described in the same framework as in the case of fluid–fluid interactions, using the Weeks–Chandler–Andersen (WCA) scheme and the Carnahan–Starling (CS) equation for attractive and repulsive parts of the Helmholtz free energy, respectively. Application to nitrogen and argon adsorption isotherms on non-porous silica LiChrospher Si-1000 at their boiling points, recently published by Jaroniec and co-workers, has shown an excellent correlative ability of our approach over the complete range of pressures, which suggests that the surface roughness is mostly the reason for the observed behavior of adsorption isotherms. From the analysis of these data, we found that in the case of nitrogen adsorption short-range interactions between oxygen atoms on the silica surface and quadrupole of nitrogen molecules play an important role. The approach presented in this paper may be further used in quantitative analysis of adsorption and desorption isotherms in cylindrical pores such as MCM-41 and carbon nanotubes.

Capillary phenomena in the framework of the two-dimensional density functional theory

We present results of application of the density functional theory (DFT) to adsorption and desorption in finite and infinite cylindrical pores accounting for the density distribution in radial and axial directions. Capillary condensation via formation of bridges is considered using canonical and grand canonical versions of the 2D DFT. The potential barrier of nucleation is determined as a function of the bulk pressure and the pore diameter. In the framework of the conventional assumptions on intermolecular interactions both 1D and 2D DFT versions lead to the same results and confirm the classical scenario of condensation and evaporation: the condensation occurs at the vapor-like spinodal point, and the evaporation corresponds to the equilibrium transition pressure. The analysis of experimental data on argon and nitrogen adsorption on MCM-41 samples seems to not completely corroborate this scenario, with adsorption branch being better described by the equilibrium pressure - diameter dependence. This points to the necessity of the further development of basic representations on the hysteresis phenomena.

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.

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.

Modeling of adsorption and nucleation in infinite cylindrical pores by two-dimensional density functional theory

In this paper, we present an analysis of argon adsorption in cylindrical pores having amorphous silica structure by means of a nonlocal density functional theory (NLDFT). In the modeling, we account for the radial and longitudinal density distributions, which allow us to consider the interface between the liquidlike and vaporlike fluids separated by a hemispherical meniscus in the canonical ensemble. The Helmholtz free energy of the meniscus was determined as a function of pore diameter. The canonical NLDFT simulations show the details of density rearrangement at the vaporlike and liquidlike spinodal points. The limits of stability of the smallest bridge and the smallest bubble were also determined with the canonical NLDFT. The energy of nucleation as a function of the bulk pressure and the pore diameter was determined with the grand canonical NLDFT using an additional external potential field. It was shown that the experimentally observed reversibility of argon adsorption isotherms at its boiling point up to the pore diameter of 4 nm is possible if the potential barrier of 22kT is overcome due to density fluctuations.

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.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

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.

Fast pyrolysis of cassava rhizome in the presence of catalysts

Cassava rhizome was catalytically pyrolysed at 500 °C using analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to investigate the effect of catalysts on bio-oil properties. The catalysts studied were zeolite ZSM-5, two aluminosilicate mesoporous materials Al-MCM-41 and Al-MSU-F, and a proprietary commercial catalyst alumina-stabilised ceria MI-575. The influence of catalysts on pyrolysis products was observed through the yields of aromatic hydrocarbons, phenols, lignin-derived compounds, carbonyls, methanol and acetic acid. Results showed that all the catalysts produced aromatic hydrocarbons and reduced oxygenated lignin derivatives, thus indicating an improvement of bio-oil heating value and viscosity. Among the catalysts, ZSM-5 was the most active to all the changes in pyrolysis products. In addition, all the catalysts with the exception of MI-575 enhanced the formation of acetic acid. This is clearly a disadvantage with respect to the level of pH in the liquid bio-fuel.

Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis

Rhizome of cassava plants (Manihot esculenta Crantz) was catalytically pyrolysed at 500 °C using analytical pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) method in order to investigate the relative effect of various catalysts on pyrolysis products. Selected catalysts expected to affect bio-oil properties were used in this study. These include zeolites and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F type), metal oxides (zinc oxide, zirconium (IV) oxide, cerium (IV) oxide and copper chromite) catalysts, proprietary commercial catalysts (Criterion-534 and alumina-stabilised ceria-MI-575) and natural catalysts (slate, char and ashes derived from char and biomass). The pyrolysis product distributions were monitored using models in principal components analysis (PCA) technique. The results showed that the zeolites, proprietary commercial catalysts, copper chromite and biomass-derived ash were selective to the reduction of most oxygenated lignin derivatives. The use of ZSM-5, Criterion-534 and Al-MSU-F catalysts enhanced the formation of aromatic hydrocarbons and phenols. No single catalyst was found to selectively reduce all carbonyl products. Instead, most of the carbonyl compounds containing hydroxyl group were reduced by zeolite and related materials, proprietary catalysts and copper chromite. The PCA model for carboxylic acids showed that zeolite ZSM-5 and Al-MSU-F tend to produce significant amounts of acetic and formic acids.

Catalytic pyrolysis of agricultural residues for bio-oil production

Agricultural residues from Thailand, namely stalk and rhizome of cassava plants, were employed as raw materials for bio-oil production via fast pyrolysis technology. There were two main objectives of this project. The first one was to determine the optimum pyrolysis temperature for maximising the organics yield and to investigate the properties of the bio-oils produced. To achieve this objective, pyrolysis experiments were conducted using a bench-scale (150 g/h) reactor system, followed by bio-oil analysis. It was found that the reactor bed temperature that could give the highest organics yield for both materials was 490±15ºC. At all temperatures studied, the rhizome gave about 2-4% higher organics yields than the stalk. The bio-oil derived from the rhizome had lower oxygen content, higher calorific value and better stability, thus indicating better quality than that produced from the stalk. The second objective was to improve the bio-oil properties in terms of heating value, viscosity and storage stability by the incorporation of catalyst into the pyrolysis process. Catalytic pyrolysis was initially performed in a micro-scale reactor to screen a large number of catalysts. Subsequently, seven catalysts were selected for experiments with larger-scale (150 g/h) pyrolysis unit. The catalysts were zeolite and related materials (ZSM-5, Al-MCM-41 and Al-MSU-F), commercial catalysts (Criterion-534 and MI-575), copper chromite and ash. Additionally, the combination of two catalysts in series was investigated. These were Criterion-534/ZSM-5 and Al-MSU-F/ZSM-5. The results showed that all catalysts could improve the bio-oils properties as they enhanced cracking and deoxygenation reactions and in some cases such as ZSM-5, Criterion-534 and Criterion-534/ZSM-5, valuable chemicals like hydrocarbons and light phenols were produced. The highest concentration of these compounds was obtained with Criterion-534/ZSM-5.