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.

Synthesis and stabilization of nanocrystalline zirconia with MSU mesostructure

In the presence of nonionic block-copolymer surfactant, nanocrystalline zirconia particles with MSU mesostrucmre were synthesized by a novel solid-state reaction route. The zirconia particles possess a nanocrystalline pore wall, which renders higher thermal stability compared to an amorphous framework. To further enhance its stability, laponite, a synthetic clay, was introduced. Laponite acts as an inhibitor to crystal a growth and also as a hard template for the mesostructure. High surface area and ordered pore structure were observed in the stabilized zirconia. The results show that the formation of the MSU structure is attributed to reverse hexagonal micelles, which are the products of the cooperative self-assembly of organic and inorganic species in the solid-state synthesis system with crystalline water and hygroscopic water present.

Synthesis of wormlike nanoporous nickel oxide with nanocrystalline framework for electrochemical energy storage

In this work, nanoporous nickel oxide was synthesized using anionic surfactant assembly method. Structure characterizations show that this nickel oxide possesses partly-ordered mesoporous structure with nanocrystalline pore wall. The formation mechanism of wormlike nanoporous structure is ascribed to the quasi-reverse micelle system formed by ternary phases of SDS (sodium dodecyl sulfate)/urea/water. Cyclic voltammetry shows that these nickel oxide samples possess both good capacitive behavior due to its unique nanoporous structure and very high specific capacitance due to its high surface area with electrochemical activity.

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.

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.

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.

Synthesis and characterization of turbostratic carbons prepared by catalytic chemical vapour decomposition of acetylene

The turbostratic mesoporous carbon blacks were prepared by catalytic chemical vapour decomposition (CCVD) of acetylene using Ni/MgO catalysts prepared by co-precipitation. The relationship between deposition conditions and the nanostructures of resultant carbon black materials was investigated. It was found that the turbostratic and textural structures of carbon blacks are dependent on the deposition temperature and nickel catalyst loading. Higher deposition temperature increases the carbon crystallite unit volume V-nano and reduces the surface area of carbon samples. Moreover, a smaller V-nano is produced by a higher Ni loading at the same deposition temperature. In addition of the pore structure and the active metal surface area of the catalyst, the graphitic degree or electronic conductivity of the carbon support is also a key issue to the activity of the supported catalyst. V-nano is a very useful parameter to describe the effect of the crystalline structure of carbon blacks on the reactivity of carbon blacks in oxygen-carbon reaction and the catalytic activity of carbon-supported catalyst in ammonia decomposition semi-quantitatively. (C) 2006 Elsevier B.V. All rights reserved.

Nanoassembly of biocompatible microcapsules for urease encapsulation and their use as biomimetic reactors

Biocompatible polypeptide capsules with high enzyme loading and activity prepared by templating mesoporous silica spheres were used as biomimetic reactors for performing CaCO3 synthesis exclusively inside the capsule interior via urease-catalyzed urea hydrolysis.

Characterization of sugar cane waste biomass derived chars from pressurized gasification

There is interest in the use of sugar cane waste biomass for electricity cogeneration, by integrated gasification combined cycle (IGCC) processes. This paper describes one aspect of an overall investigation into the reactivity of cane wastes under pressurized IGGC conditions, for input into process design. There is currently a gap in understanding the morphological transformations experienced by cane waste biomass undergoing conversion to char during pressurized gasification, which is addressed by this work. Char residuals remaining after pressurized pyrolysis and carbon dioxide gasification were analysed by optical microscope, nitrogen (BET) adsorption analysis, SEM/EDS, TEM/EDS and XPS techniques. The amorphous cane plant silica structures were found to remain physically intact during entrained flow gasification, but chemically altered in the presence of other inorganic species. The resulting crystalline silicates were mesoporous (with surface areas of the order of 20 m(2) g(-1)) and contributed to much of the otherwise limited pore volume present in the residual chars. Coke deposition and intimate blending of the carbonaceous and inorganic species was identified. Progressive sintering of the silicates appeared to trap coke deposits in the pore network. As a result ash residuals showed significant organic contents, even after extensive additional oxidation in air. The implications of the findings are that full conversion of cane trash materials under pressurized IGCC conditions may be significantly hampered by the silica structures inherent in these biomass materials and that further research of the contributing phenomena is recommended.

Synthesis and structure characterization of chromium oxide prepared by solid thermal decomposition reaction

Mesoporous chromium oxide (Cr2O3) nanocrystals were first synthesized by the thermal decomposition reaction of Cr(NO3)(3)(circle)9H(2)O using citric acid monohydrate (CA) as the mesoporous template agent. The texture and chemistry of chromium oxide nanocrystals were characterized by N-2 adsorption-desorption isotherms, FTIR, X-ray diffraction (XRD), UV-vis, and thermoanalytical methods. It was shown that the hydrate water and CA are the crucial factors in influencing the formation of mesoporous Cr2O3 nanocrystals in the mixture system. The decomposition of CA results in the formation of a mesoporous structure with wormlike pores. The hydrate water of the mixture provides surface hydroxyls that act as binders, making the nanocrystals aggregate. The pore structures and phases of chromium oxide are affected by the ratio of precursor-to-CA, thermal temperature, and time.

Role of nanosized zirconia on the properties of Cu/Ga2O3/ZrO2 catalysts for methanol synthesis

The introduction of mesoporous nanosize zirconia to the catalyst for methanol synthesis dedicates the nanosized catalyst and mesoporous duplicated properties. The catalyst bears the larger surface area, larger mesoporous volume and more uniform diameter, more surface metal atoms and oxygen vacancies than the catalyst prepared with the conventional coprecipitation method. The modification of microstructure and electronic effect could result in the change of the reduced chemical state and decrease of reducuction temperature of copper, donating the higher activity and methanol selectivity to the catalyst. The results of methanol synthesis demonstrate that the Cu+ is the optimum active site. Also, the interaction between the copper and zirconia shows the synergistic effect to fulfil the methanol synthesis.

Comparisons of the structural and catalytic properties of Ti-HMS synthesized using the hydrothermal and molecular designed dispersion methods

Titanium containing wormhole-like mesoporous silicas, denoted Ti-HMS, synthesized both via the hydrothermal synthesis route and the post synthesis grafting technique, known as molecular designed dispersion, have been successfully applied in the gas phase oxidation of Toluene to CO and CO2. Selectivity towards CO2 for all catalysts, at temperatures between 400-600degreesC, was above 80%. Benzene and benzaldehyde were observed at temperatures above 450degreesC, but in very low concentrations. The conversion of toluene was shown to increase significantly when the V-TEX/N-MESO ratios were increased from 0.07 to 0.84. No significant difference in catalytic activity was observed for catalysts prepared via the different synthesis techniques. The catalytic activity also depends on the concentration of tetrahedrally coordinated titanium atoms and not on the total concentration of titanium in the catalyst.

On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus:evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

Cu and Fe oxides dispersed on SBA-15:a Fenton type bimetallic catalyst for N,N-diethyl-p-phenyl diamine degradation

A bimetallic oxidation catalyst has been synthesized via wet impregnation of copper and iron over a mesoporous SBA-15 silica support. Physicochemical properties of the resulting material were characterized by XRD, N2 physisorption, DRUVS, FTIR, Raman, SEM and HRTEM, revealing the structural integrity of the parent SBA-15, and presence of highly dispersed Cu and Fe species present as CuO and Fe2O3. The CuFe/SBA-15 bimetallic catalyst was subsequently utilized for the oxidative degradation of N,N-diethyl-p-phenyl diamine (DPD) employing a H2O2 oxidant in aqueous solution.