Characterization of the acidic properties of mesoporous aluminosilicates synthesized from leached saponite with additional aluminum incorporation

The acidic properties of hexagonal mesoporous aluminosilicates synthesized via a new successful short time synthesis route using leached saponite and a low concentration of surfactant are thoroughly investigated. The resulting aluminosilicate mesoporous materials with high Si/Al ratios of around 11 have a maximal surface area of 1130 m(2)/g, a pore volume of 0.92 cm(3)/g, and a narrow pore size distribution at around 3 nm. The replacement of the sodium ions, present as counterions in the synthesized aluminosilicates, with protons imparts useful catalytic acidity. This acidity is extensively studied with FTIR spectroscopy after adsorption of ammonia and cyclohexylamine, while deuterated acetonitrile differentiates between Bronsted and Lewis acidity. Al-27 NMR spectroscopy determined the coordination of the aluminum in the FSM materials. Simultaneously the effect of an additional Al incorporation, utilizing sodium aluminate, aluminum nitrate, and aluminum isopropoxide is studied. From an acidic point of view, the incorporation with Al(NO3)(3) appears to be the most optimal, as the sample has a very high amount of acid sites (1.3 mmol/g). Investigating the nature of the acid sites it is found that in all samples except the one incorporated with Al(NO3)(3), more Bronsted than Lewis sites are present, both sites being quite acidic as they resist desorption temperatures up to 300 degreesC. Probing the coordination and location of the Al atoms, all the catalysts appeared to have mostly tetrahedral aluminum, up to 95% of the total Al amount for the proton exchanged AI(NO3)(3) incorporated sample.

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.

Effect of pore packing defects in 2-D ordered mesoporous carbons on ionic transport

Ordered mesoporous materials show great importance in energy, environmental, and chemical engineering. The diffusion of guest species in mesoporous networks plays an important role in these applications, especially for energy storage, such as supercapacitors based on ordered mesoporous carbons ( OMCs). The ion diffusion behavior in two different 2-D hexagonal OMCs was investigated by using cyclic voltametry and electrochemical impedance spectroscopy. In addition, transmission electron microscopy, small-angle X-ray diffraction, and nitrogen cryosorption methods were used to study the pore structure variations of these two OMCs. It was found that, for the OMC with defective pore channels ( termed as pore packing defects), the gravimetric capacitance was greatly decayed when the voltage scan rate was increased. The experimental results suggest that, for the ion diffusion in 2-D hexagonal OMCs with similar mesopore size distribution, the pore packing defect is a dominant dynamic factor.

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.

Preparation and characterization of mesoporous Ni/Zr-laponite for the catalytic deoxygenation of vegetable oils into liquid hydrocarbons

The deoxygenation of vegetable oils was studied over a Ni/Zr-laponite catalyst in various nickel loading composition. Stearic acid has been used as a model compounds. The liquid and gas products were analyzed using gas chromatograph equipped with thermal conductivity detector and flame ionization detector. From product distribution it was determined the effect of catalyst composition on reaction conditions

Hydrofluoric acid pre-treatment for improving 13C CPMAS NMR spectral quality of forest soils in south-east Queensland, Australia

Hydrofluoric acid (HF) was used to pre-treat forest soils of south-east Queensland for assessing the effectiveness of iron (Fe) removal, carbon (C) composition using C-13 cross-polarisation (CP) with magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) before and after the HF pre-treatment, and the improvement of C-13 CPMAS NMR spectra. Soil samples were collected from 4 experimental sites of different soil types, harvest residue management or prescribed burning, and tree species. More than 86% of Fe was in all soil types removed by the HF treatment. The C-13 NMR spectral quality was improved with increased resolution, especially in the alkyl C and O-alkyl C regions, and reduced NMR run-time (1-5 h per sample compared with >20 h per sample without the pre-treatment). The C composition appeared to alter slightly after the pre-treatment, but this might be largely due to improved spectrometer conditions and increased resolution leading to more accurate NMR spectral integration. Organic C recovery after HF pre-treatment varied with soil types and forest management, and soluble soil organic matter (SOM) could be lost during the pre-treatment. The Fourier Transform-Infrared (FT-IR) spectra of HF extracts indicated the preferential removal of carboxylic C groups during the pre-treatment, but this could also be due to adsorbed water on the mineral matter. The NMR spectra revealed some changes in C composition and quality due to residue management and decomposition. Overall, the HF treatment was a useful pre-treatment for obtaining semi-quantitative C-13 CPMAS NMR spectra of subtropical Australian forest soils.

Refined method of potential enhancement in the equilibria characterization of activated carbon. Comparison with GCMC and DFT

In this paper, we present a technique for equilibria characterization of activated carbon having slit-shaped pores. This method was first developed by Do (Do, D. D. A new method for the characterisation of micro-mesoporous materials. Presented at the International Symposium on New Trends in Colloid and Interface Science, September 24-26, 1998 Chiba, Japan) and applied by his group and other groups for characterization of pore size distribution (PSD) as well as adsorption equilibria determination of a wide range of hydrocarbons. It is refined in this paper and compared with the grand canonical Monte Carlo (GCMG) simulation and density functional theory (DFT). The refined theory results in a good agreement between the pore filling pressure versus pore width and those obtained by GCMG and DFT. Furthermore, our local isotherms are qualitatively in good agreement with those obtained by the GCMC simulations. The main advantage of this method is that it is about 4 orders of magnitude faster than the GCMC simulations, making it suitable for optimization studies and design purposes. Finally, we apply our method and the GCMG in the derivation of the PSD of a commercial activated carbon. It was found that the PSD derived from our method is comparable to that derived from the GCMG simulations.

Absorption and fluorescence spectroscopy of rhodamine 6G in titanium dioxide nanocomposites

A comparison has been made between the spectroscopic properties of the laser dye rhodamine 6G (R6G) in mesostructured titanium dioxide (TiO2) and in ethanol. Steady-state excitation and emission techniques have been used to probe the dye-matrix interactions. We show that the TiO2-nanocomposite studied is a good host for R6G, as it allows high dye concentrations, while keeping dye molecules isolated, and preventing aggregation. Our findings have important implications in the context of solid state dye-lasers and microphotonic device applications. (C) 2003 Elsevier B.V. All rights reserved.

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.

Formation of mesostructured titania thin films using iospropoxide precursors

Mesostructured titania thin films were prepared by an evaporation-induced self-assembly process. The highly acidic sot precursors contained titanium(IV) tetraisopropoxide (TTIP) as a titanium source, a tri-block copolymer Pluronic P123 as a template, and acetylacetonate and HCl as hydrolysis inhibitors. Characteristics of the resultant titania thin films were studied using X-ray diffraction (XRD) analysis, N-2-adsorption/desorption analysis, and transmission electron microscopy (TEM). XRD and TEM investigations on the as-synthesised films revealed the appearance of cubic-like, pseudohexagonal, and lamellar mesophases; depending on the amount of water in the sols of film precursors. Template removal by a calcination process yields high surface area (320-360 m(2)/g) mesoporous materials with crystalline anatase frameworks. Water content also influences the degree of anatase crystallinity of the calcined films. Higher water content resulted in improved anatase crystallinity. These nanostructured materials are of interest for photocatalysts, pbotoelectrochemical solar cells and other photonic devices. (C) 2003 Elsevier B.V. All rights reserved.

Control of ordered structure and morphology of large-pore periodic mesoporous organosilicas by inorganic salt

Highly ordered rodlike periodic mesoporous organosilicas (PMO) were successfully synthesized using 1.2-bis(trimethoxysilyl)ethane as an precursor and triblock copolymer P123 as a template at low acid concentration and in the presence of inorganic salts (KCl). The role of acid and salt as well as the effects of synthesis temperature and reactant mole ratio in the control of morphology and the formation of ordered mesostructure was systematically examined. It was found that the addition of inorganic salt can dramatically expand the range of the synthesis parameters to produce highly ordered PMO structure and improve the quality of PMO materials. The morphology of PMOs was significantly dependent on the induction time for precipitation. The uniform PMO rods can only be synthesized in a narrow range of acid and salt concentrations. The results also show that the optimized salt concentration (I M) and low acidity (0.167 M) were beneficial to the formation of not only highly ordered mesostructure but also rodlike morphology. Increasing acidity resulted in fast hydrolysis reaction and short rod or plate-like particles. Highly ordered rod can also be prepared at low temperature (35 degrees C) with high salt amount (1.5 M) or high temperature (45 degrees C) with low salt amount (0.5 M). Optimum reactant molar composition at 40 degrees C is 0.035P123:8KCl:1.34HCI:444H(2)O:1.0bis(trimethoxysilyl)ethane. Lower or higher SiO2/PI23 ratio led to the formation of uniform meso-macropores or pore-blocking effect. (c) 2005 Elsevier Inc. All rights reserved.

A model for adsorption of condensable vapors on nonporous materials

A new isotherm is proposed here for adsorption of condensable vapors and gases on nonporous materials having type II isotherms according to the Brunauer-Deming-Deming-Teller (BDDH) classification. The isotherm combines the recent molecular-continuum model in the multilayer region, with other widely used models for sub-monolayer coverage, some of which satisfy the requirement of a Henry's law asymptote. The model is successfully tested using isotherm data for nitrogen adsorption on nonporous silica, carbon and alumina, as well as benzene and hexane adsorption on nonporous carbon. Based on the data fits, out of several different alternative choices of model for the monolayer region, the Freundlich and the Unilan models are found to be the most successful when combined with the multilayer model to predict the whole isotherm. The hybrid model is consequently applicable over a wide pressure range. (C) 2000 Elsevier Science B.V. All rights reserved.

Characterization of the structural and surface properties of chemically modified MCM-41 material

Mesoporous Mobil catalytic materials of number 41 (MCM-41) silica was chemically modified using both inorganic and organic precursors and characterized using the techniques, XRD, XPS, MAS NMR, FTIR, W-Vis, and physical adsorption of nitrogen, hydrocarbons (hexane, benzene, acetone, and methanol) and water vapor. Modification using organic reagents was found to result in a significant loss in porosity and a shape change of surface properties (increased hydrophobicity and decreased acidity). With inorganic modifying reagents, the decrease in porosity was also observed while the surface properties were not significantly altered as reflected by the adsorption isotherms of organics and water vapors. Chemical modifications can greatly improve the hydrothermal stability of MCM-41 material because of the enhanced surface hydrophobicity (with organic modifiers) or increased pore wall thickness (with inorganic modifiers). (C) 2000 Elsevier Science B.V. All rights reserved.

Aluminophosphate-based mesoporous molecular sieves: synthesis and characterization of TAPOs

Mesoporous Ti-substituted aluminophosphates (AlPOs) with a hexagonal, cubic and lamellar pore structure, characteristic of MCM-41, MCM-48. and MCM-50, respectively, were synthesized. The stability of these mesophases upon template removal was studied. The pore structures, surface properties, and local atom environments of Al, P, and Ti of the hexagonal and cubic Ti-containing mesoporous products were extensively characterized using X-ray diffraction, magic angle spinning nuclear magnetic resonance, AAS, XPS, ultraviolet-visible, and adsorption of nitrogen and water vapor techniques while the lamellar mesophase was not further characterized due to its very poor thermal stability. Ti-containing mesoporous AlPO materials show a reasonable thermal stability upon template removal, a hydrophilic surface property, and high porosity showing application potentials in catalytic oxidation of hydrocarbons. (C) 2001 Elsevier Science B,V. All rights reserved.

Aluminophosphate-based mesoporous molecular sieves: Synthesis and characterization of TAPOs

Mesoporous Ti-substituted aluminophosphates (AlPOs) with a hexagonal, cubic and lamellar pore structure, characteristic of MCM-41, MCM-48, and MCM-50, respectively, were synthesized. The stability of these mesophases upon template removal was studied. The pore structures, surface properties, and local atom environments of Al, P, and Ti of the hexagonal and cubic Ti-containing mesoporous products were extensively characterized using X-ray diffraction, magic angle spinning nuclear magnetic resonance, AAS, XPS, ultraviolet–visible, and adsorption of nitrogen and water vapor techniques while the lamellar mesophase was not further characterized due to its very poor thermal stability. Ti-containing mesoporous AlPO materials show a reasonable thermal stability upon template removal, a hydrophilic surface property, and high porosity showing application potentials in catalytic oxidation of hydrocarbons.