Synthesis of ZSM‐5 Films and Monoliths with Bimodal Micro/Mesoscopic Structures

A route to synthesize ZSM‐5 crystals with a bimodal micro/mesoscopic pore system has been developed in this study; the successful incorporation of the mesopores within the ZSM‐5 structure was performed using tetrapropylammonium hydroxide (TPAOH)‐impregnated mesoporous materials containing carbon nanotubes in the pores, which were encapsulated in the ZSM‐5 crystals during a solid rearrangement process within the framework. Such mesoporous ZSM‐5 zeolites can be readily obtained as powders, thin films, or monoliths.     

Effects of surfactant/silica and silica/cerium ratios on the characteristics of mesoporous Ce-MCM-41

Using the surfactant CTMABr (cetyltrimethyl ammonium bromide) and cerium(IV) sulfate, mesoporous Ce-MCM-41 molecular sieves were produced under a hydrothermal condition with various surfactant/silica (surfactant/Si) and silica/cerium (Si/Ce) ratios. Changes to the structural traits caused by changing the molar ratios of both surfactant/Si and Si/Ce were investigated. XRD (X-ray diffraction), FT-IR (fourier transform infrared spectroscopy), and SEM (scanning electro microscopy) were used for the characterization of prepared mesoporous samples. Among the tested molar ratios, surfactant/Si ratio of 0.5 and 0.2 showed highest values of d_1 0 0 and intensity, respectively, for the Si-MCM-41. XRD analysis also identified a quintessential hexagonal structure of Ce-MCM-41 for the Si/Ce molar ratio higher than 40 (maintaining the surfactant/Si ratio at 0.2). When cerium content was increased to have the Si/Ce molar ratio of 20, the hexagonal structure of Ce-MCM-41 was collapsed due to the structural stress of substituted cerium. FT-IR results confirmed calcination of Ce-MCM-41 and the incorporation of Ce⁴⁺ ions of cerium sulfate into the silica surface with proper removal of the surfactant. Rod-like shape with rounded edges of the prepared Ce-MCM-41 samples was identified by SEM. These results suggest surfactant/Si ratio of 0.2 and Si/Ce ratio of 40 for the production of Ce-MCM-41 with the highest level of crystallinity.     

Advances in Microporous and Mesoporous Solids—Highlights of Recent Progress

This report highlights developments in the fields of microporous and mesoporous materials that were published mostly during the year 2002. Selected examples are provided to illustrate new zeolite structures, porous coordination materials, mesoporous solids with new compositions, controlled morphologies, and increased hydrothermal and thermal stabilities, as well as porous solids with tunable pore openings or other structural features that can be dynamically modified. A number of applications are discussed, including stabilization of reactive guests, separations, electronic materials, and sensors.     

A Silicon–Silica Nanocomposite Material

The synthesis and characterization of a novel silicon–silica nanocomposite material are reported. A self‐assembly method allows the encapsulation of silicon nanoclusters within the channels of a periodic mesoporous silica thin film. The result is the formation of a silicon–silica nanocomposite film with bright, room‐temperature photoluminescence in the visible range, and a nanosecond luminescence lifetime. The properties of the nanocomposite material have been studied by several analytical techniques, which collectively show the existence within the channels of non‐diamondoid‐structure‐type silicon nanoclusters with various hydrogenated silicon sites. It is estimated that the silicon nanoclusters in the silica mesoporous films occupy up to 39 % of the accessible pore volume. The nanocomposite film shows improved resistance to air oxidation compared to crystalline silicon. The high loading and chemical stability to oxidation under ambient conditions are important advantages in terms of the development of silicon‐based light‐emitting diodes from this class of materials.     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Facile synthesis of ordered nanocrystalline alumina thin films with tunable mesopore structures

Mesoporous alumina layers have attracted attention for their potential use in ultrafiltration of salts, as a heterogeneous catalyst support, an adsorbent in environmental cleanup, and in petroleum refinement. The ability to control the fast hydrolysis rate of the inorganic precursors using simple and inexpensive routes is important for that potential to be realized. Herein, we introduce a novel and facile route to synthesize mesoporous alumina thin films from the combination of inexpensive and commercially available copolymer with aluminum chloride or nitrate (salts) in an EtOH–surfactant–NH₃ · H₂O–salts (EsNs) system through the evaporation-induced self-assembly (EISA) method. Mesoporous alumina layers obtained utilizing the EsNs system have ordered and tunable pore structures. The ability to easily control the mesophases of the alumina layers within a short time provides distinct advantages over previously reported synthesis procedures. Most importantly, we demonstrate that the binding of surfactant and NH₃ · H₂O for the formation of hydrogen bond between them in the EsNs system controls the fast hydrolysis rate of the inorganic species. This allows for the synthesis of nanocrystalline alumina layers via the aluminum oxo-clusters’ assembly with the surfactant. Such simple route may be applied in the synthesis of other non-silica mesostructured oxides.     

Vanadium species in new catalysts for the selective oxidation of methane to formaldehyde: Activation of the catalytic sites

New vanadium oxide supported on mesoporous silica catalysts for the oxidation of methane to formaldehyde were investigated by infrared and Raman spectroscopies to identify and characterize the molecular structure of the most active and selective catalytic sites. In situ and operando experiments have been conducted in order to understand the redox and hydroxylation/dehydroxylation processes of the vanadium species. (SiO)₂VO(OH) species were identified in these catalysts in reaction conditions and shown to undergo a deprotonation at 580 °C under vacuum, leading to a site giving a photoluminescence band at 550 nm attributed to reverse radiative decay from the excited triplet state:

(V⁴⁺–O⁻)^*  (V⁵⁺O²⁻). An activation mechanism of vanadium monomeric species with electrophilic oxygen species is proposed.     

Cu/SBA-15 as adsorbent for propane/propylene separation

Samples of mesoporous silica SBA-15 were prepared under hydrothermal conditions where Cu cations were incorporated to the structure by impregnation in order to compare the adsorption behavior in the presence and absence of this element. The adsorption/desorption equilibrium isotherms of propylene, propane, and N₂ were measured to evaluate their usefulness in the propane/propylene separation. All the adsorption isotherms of SBA-15 measured in the absence of Cu cations were described by the Freundlich equation, while the adsorption isotherms of propane on Cu/SBA-15 were better represented by the Henry equation and those of propylene were satisfactorily described by the Langmuir model in the range P < 100 Torr. The adsorption uptake of propylene increased and that of propane decreased in Cu/SBA-15 as compared to the amounts observed in the SBA-15 sample. The presence of Cu atoms in the adsorbent lattice increased the selectivity towards propylene. Under some working conditions the adsorbed amount of propylene in Cu/SBA-15 sample was totally reversible and the propane uptake, negligible.     

Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications

SBA15–TiO₂ samples prepared by introducing titanium with a grafting method and having TiO₂ loadings below 15 wt.% have been characterized by XRF, XRD, IR, porosimetry, SEM, HRTEM, and UV–Visible diffuse reflectance. Differently from the samples reported in the literature characterized by a high TiO₂ loading, no evidences have been found for the presence of titania particles inside or outside the mesopores of SBA-15. Three different titanium species were instead evidenced to be present. The first two derive from the reaction of titanium with silanol groups in the corona area of inner SBA-15 walls leading to the formation of either TiO₄ tetrahedral sites (by reaction by hydroxyl nests of surface defect sites) and/or pseudo-octahedral surface sites anchored by two (or more) Si or Ti ions through bridging oxygens. The third species derives from the reaction of titanium in the regions with high sylanol density, e.g. in the micropores located in the corona of SBA-15 channels, leading to the formation of TiO₂-like nanoareas (probably Si-doped) with dimensions of around 1–2 nm maximum. The potential interest of these materials as photocatalysts, for the presence of a TiO₂-like nanoareas highly accessible by reactants, is discussed.     

Halogen-free acylation of toluene over FeSBA-1 molecular sieves

Three-dimensional cage type iron substituted mesoporous silica with different iron contents (FeSBA-1) was synthesized in a highly acidic media using cetyltriethylammonium bromide and tetraethylorthosilicate as a template and a silica source, respectively. Acylation of toluene with acetic anhydride (AA) was carried out over FeSBA-1 mesoporous catalysts with different n_Si/n_Fe ratios in the temperature range 80–180 °C for a time-on-stream of 1–6 h under liquid phase conditions. The important factors affecting the conversion and the selectivity of the reaction, such as the reaction temperature, feed ratio, catalyst weight and time-on-stream were studied and the results are discussed in detail. The reaction conditions were optimized and the n_AA/n_Toluene ratio of 2 and catalyst weight of 0.1 g (3.3 wt% of total reaction mixture) were maintained for all catalytic runs. It was found that the catalytic activity is strongly influenced by the amount of tetrahedral iron in the catalysts. Among the catalysts used in the present study, FeSBA-1(36) showed a high toluene conversion and selectivity to p-methylacetophenone (p-MAP) under the optimized reaction conditions. It was also found that the selectivity for p-MAP was always higher than m-MAP and o-MAP for all the catalysts and the activity of the catalysts changes in the following order: FeSBA-1(36) > FeSBA-1(90) > FeSBA-1(120).