Generalized synthesis of periodic surfactant/inorganic composite materials

THE recent synthesis of silica-based mesoporous materials1,2 by the cooperative assembly of periodic inorganic and surfactant-based structures has attracted great interest because it extends the range of molecular-sieve materials into the very-large-pore regime. If the synthetic approach can be generalized to transition-metal oxide mesostructures, the resulting nanocomposite materials might find applications in electrochromic or solid-electrolyte devices3,4, as high-surface-area redox catalysts5 and as substrates for biochemical separations. We have proposed recently6 that the matching of charge density at the surfactant/inorganic interfaces governs the assembly process; such co-organizatio…

Surfactant controlled preparation of mesostructured transition-metal oxide compounds

The use of surfactants as templates allows the synthesis of mesostructured transition-metal oxides by a cooperative, interface controlled condensation process.

Organization of Organic Molecules with Inorganic Molecular Species into Nanocomposite Biphase Arrays

Dry synthesis of B-MFI, MTN- and MTW-type materials

Abstract B-MFI and MTN-type materials were synthesized via the fluoride route from dry powders in the complete absence of a solution phase. Amorphous precursors obtained by drying SiO 2 · Al 2 O 3 gels at 700°C were transformed into MTN-type material in the presence of dried NH 4 F and TMACl. Amorphous precursors obtained by drying SiO 2 gels at 700°C were transformed into B-MFI in the presence of dried NH 4 F, B 2 O 3 and TPABr. Water is formed as a reaction product. However, the water vapor pressure is appreciably below the water vapor saturation pressure under the given reaction conditions. In addition, syntheses using seed crystals were carried out successfully.

TEMPLATE-FREE AND ALKALI-FREE SYNTHESIZED SILICATES WITH MFI-STRUCTURE -A COMPARATIVE STUDY

ABSTRACT Zeolites and gallosilicates with an MFI-structure which were crystallized from inorganic reaction systems and from alkali-free, tetrapropylammonlumbromide (TPABr) containing systems are compared. The strength, nature and distribution of the acidic sites were determined by FTIR-spectroscopy, TPD, electron microprobing, 29 si, 27 Al and 1 H MAS NMR spectroscopy. The influences of the different trivalent elements as well as the strength, type and distribution of the acidic sites on the catalytic performance of the different MFI-silicates are discussed.

Factors affecting the UV-Transparency of Molecular Sieves

The optical properties in the UV-region of several types of molecular sieves were studied. The initial onset of absorption around 280 nm which was observed for basically all samles synthesized without special precautions is not due to an early onset of band gap absorption, but might be correlated to the crystal size as well as structural defects within the crystals, e.g. E'-center or peroxy-radical. Using template free synthesis procedures which lead to small crystals containing few defect sites, we were able to synthesize molevular sieves which were almost completely transparent down to 200 nm. Such crystals can become very important in the development of technical luminophores.

Formation of a Porous Zirconium Oxo Phosphate with a High Surface Area by a Surfactant-Assisted Synthesis

Influence of synthesis conditions on the morphology of Dodecasil 1H

Abstract The synthesis of Dodecasil 1H was studied in the system SiO2/1-adamantylamin/NH3/water with the objective of controlling the particle size and the morphology of the crystals. Since nucleation occurs in a very early stage of the synthesis, the heating rate to the final temperature and/or holding points during heat up have a strong influence on both parameters. Crystals smaller than 150 μm could only be obtained by the use of seed crystals, which are completely consumed in the synthesis with subsequent new nucleation. Using seed crystals, the expensive template 1-adamantylamine can be substituted with cheaper reagents such as sodium dodecyl sulfate or trimethylethylammonium bromide a…

Ein poröses Zirconiumoxophosphat sehr hoher Oberfläche durch eine tensidunterstützte Synthese

Polarized IR Spectra of p-Nitroaniline-Loaded AlPO4-5 Single Crystals

Controlling the spatial distribution of aluminum in ZSM-5 crystals

Abstract The spatial distribution of aluminum over ZSM-5 crystals was systematically studied using electron microprobing on polished crystals. Crystals synthesized with TPABr as template exhibit a pronounced enrichment of aluminum in the crystal rim, essentially irrespective of the aluminum source employed, although aluminum sources with organic anions are favoring less inhomogeneous profiles. With 1,6-hexanediol or from totally inorganic reaction gels, crystals with completely homogeneous aluminum profiles are obtained, even if the crystals grow larger than 50 μm. In the 1,6-hexanediol system the homogeneous profiles could be changed to profiles similar to the TPABr system by addition of K…

Analysis of Active-Site Distribution in ZSM-5 Crystals by Infrared Microscopy

Abstract The acid Site distribution over large ZSM-5 crystals was analyzed using FTIR microscopy. Results of the analysis of the OH-stretching vibrations and of vibrations of pyridine adsorbed on Bronsted and Lewis acid sites were found to be in good agreement. The resolution which can be obtained using this novel technique is about 10-20 μm. This limits the application to large crystals as analyzed in this study. Comparison of the results of IR microscopy with aluminum distributions obtained by electron microprobe analysis revealed that IR microscopy cannot resolve inhomogeneities on a scale smaller than the above-stated limits. The results of both methods on a larger scale, however. are i…

Synthesis And Sorptive Properties Of Dodecasil 1 H With An Acessible Pore System

Abstract The synthesis of Dodecasil 1H was studied in the system SiO2/1-adamantylamine/NH3/water with the objective of controlling the particle size and the morphology of the crystals. Since nucleation occurs in a very early stage of the synthesis, the heating rate to the final temperature have a strong influence on both parameters. Using seed crystals and such a heating programme, the expensive template 1-adamantylamine can be reduced to so small amounts, that a nearly template free pore system is achieved. The emptiness of the pore system was demonstrated from adsorption measurement using He and H2.

Oscillatory Reactions in Heterogeneous Catalysis

Publisher Summary This chapter focuses on the oscillatory reactions in heterogeneous catalysis. Oscillations are possible on all levels in a catalytic reactor, from the single-crystal plane to the crystallite to the catalyst pellet to the packed-bed reactor, and each level adds another degree of complexity. So, it is necessary to isolate the major influences at each level and to separate the characteristics of the oscillations on one level from the effects caused by coupling with other levels. Only when each level is well understood is it possible to fully understand the overall oscillatory behavior. Oscillations in heterogeneous catalysis, therefore, remain an intriguing and demanding prob…

Capillary Hysteresis in Nanopores: Theoretical and Experimental Studies of Nitrogen Adsorption on MCM-41

Capillary hysteresis in cylindrical nanopores has been studied using MCM-41 as the prime example of a mesoporous material. These materials, due to their regular pore structure, can be considered to be candidates for reference adsorbents for standardizing adsorption measurements and methods for characterization of porous solids. They provide a unique opportunity for verification of theoretical models employed for predicting phase equilibrium in confined geometry. Three samples with monodisperse pore channels have been synthesized and examined using X-ray diffraction (XRD). Nitrogen adsorption isotherms were modeled using nonlocal density functional theory (NLDFT) in a wide range of pore size…

Critical Appraisal of the Pore Structure of MCM-41

Purely siliceous and aluminosilicate types of MCM-41 were synthesized and characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen sorption (NS) and size exclusion chromatography (SEC).

Photoluminescence of chromium(III)-doped silicoaluminophosphate with AFI structure

Theoretical and Experimental Studies of Capillary Hysteresis in MCM-41

Mesoporous materials of MCM-41 type are considered to be reference model adsorbents due to their regular pore structure. Nitrogen adsorption isotherms on MCM-41 are modeled using the Non-Local Density Functional Theory (NLDFT). The thermal dependence of the thermodynamic hysteresis predicted by the NLDFT is confirmed by experimental measurements. The nitrogen hysteresis on MCM-41 at temperatures below 77.4 K or in pores greater than 4 nm is associated with the metastability of the adsorption branch of the isotherm. In the hysteresis regime, the desorption branch is likely to be thermodynamically stable and is recommended for calculating pore size distributions.

Orientation of the acidity probes benzene, acetonitrile and pyridine in SAPO-5 and GaAPO-5 molecular sieves: an FTIR microscopy study

The adsorption and desorption behaviour of benzene, acetonitrile (CD3CN) and pyridine for large crystals of SAPO-5 and GaAPO-5 is studied using FTIR microscopy with polarised IR radiation. From the analysis of the polarised adsorption bands it is concluded that the adsorbates are ordered in the molecular sieves at 373 K. The orientation of molecules interacting with Bronsted or Lewis acid sites and of physisorbed molecules are discussed. Benzene adsorbed at Bronsted sites is oriented with the aromatic ring parallel to the crystallographic c-axis of the molecular sieve, whereas physisorbed benzene is oriented with the aromatic ring parallel to the crystallographic a,bplane. Acetonitrile can …

Cooperative formation of inorganic-organic interfaces in the synthesis of silicate mesostructures.

A model is presented to explain the formation and morphologies of surfactant-silicate mesostructures. Three processes are identified: multidentate binding of silicate oligomers to the cationic surfactant, preferential silicate polymerization in the interface region, and charge density matching between the surfactant and the silicate. The model explains present experimental data, including the transformation between lamellar and hexagonal mesophases, and provides a guide for predicting conditions that favor the formation of lamellar, hexagonal, or cubic mesostructures. Model Q(230) proposed by Mariani and his co-workers satisfactorily fits the x-ray data collected on the cubic mesostructure …

Anthraquinones formation on zeolites with BEA structure

Publisher Summary Zeolites with BEA structure are in focus mainly in the field of conversion of hydrocarbons. However, their unique physico-chemical properties let to suppose that these systems can be successfully used in reactions of organic synthesis. Such zeolites can be used as catalysts for the synthesis of large organic molecules. The interaction of phthalic anhydride with aromatic hydrocarbons is a subject for investigation, both for science purposes and for industrial applications. The use of zeolites in this reaction is an example of the acylation of aromatics on solid-acid catalysts; on the other hand, such a study creates the possibilities of developing more appropriate technolog…

MCM-41 and related materials as media for controlled polymerization processes

The synthesis of mesoporous MCM-41 type materials based on transition metal oxides and the polymerization of several monomers within MCM-41 is presented with the aim to specifically investigate the effects of the interface and confinement on host-guest interactions. In addition to standard MCM-41, material based on transition metal oxides is obtained although template removal has been unsuccessful for such compounds until now. In situ polymerization of styrene, methyl methacrylate and vinyl acetate is possible within the mesopore system. The properties of some of the encapsulated polymers differ markedly with those obtained in the bulk.

Transition Metal Compound Oxide Catalysts for Lowering the Light Off-Temperature of Particles from Diesel Exhaust

Publisher Summary It has been realized that particle emissions from diesel engines are a severe environmental problem, which is difficult to solve by engine modifications alone. Even if the combustion occurs in a high excess of air, appreciable amounts of soot particles are found. Cracking processes, dehydrogenation, and polymerization play an important role in the formation of soot. To reduce soot fraction, several methods have been developed in the past, but most of them have fundamental disadvantages. Thus, a new procedure based on the catalytic burning of the soot in the exhaust gas is becoming important. This chapter describes the effect of several compound oxides. Further investigatio…

Aluminum-27 double-rotation NMR investigations of SAPO-5 with variable silicon content

Summary Double-rotation NMR (DOR) studies of 27 Al species in SAPO-5, a silicon aluminophosphate molecular sieve with a one dimensional channel system, have revealed a minimum of three aluminum sites resulting from the synthesis. The DOR technique was used specifically to increase the spectral resolution by removing the broadening influences from second-order quadrupolar interactions associated with the spin 5/2 27 Al nuclei. The DOR investigations of SAPO-5 crystals with variable Si/Al ratios resulted in the identification of three aluminum species, two consistent with the reported isotropic shift values for AlPO 4 -5; however, these two resonances are only observable when small quantities…

Is the formation of a zeolite from a dry powder via a gas phase transport process possible?

Abstract ZSM-5 was synthesized by four methods with a gradually decreasing water content ending in a reaction mixture with absolutely dry reagents in the form of a powder in the complete absence of a solution phase. Amorphous precursors obtained by drying SiO2·A2O3 gels at 650°C were transformed into zeolites in the presence of dried NH4F and TPABr. Some water is probably formed as a reaction product, but the maximum water pressure is appreciably below the saturation pressure under the given reaction conditions. To explain the formation of a zeolite, we suggest a vapor phase mass transfer process with SiF4 as the mobile species between the solid phase, which contains the amorphous Si/Al pre…

Oil-Water Interface Templating of Mesoporous Macroscale Structures

Ordered mesostructured porous silicas that are also macroscopically structured were created by control of the interface on two different length scales simultaneously. Micellar arrays controlled the nanometer-scale assembly, and at the static boundary between an aqueous phase and an organic phase, control was achieved on the micrometer to centimeter scale. Acid-prepared mesostructures of silica were made with the p6, Pm3n, and the P63/mmc structures in the form of porous fibers 50 to 1000 micrometers in length, hollow spheres with diameters of 1 to 100 micrometers, and thin sheets up to 10 centimeters in diameter and about 10 to 500 micrometers in thickness. These results might have implicat…

Water Sorption on Mesoporous Aluminosilicate MCM-41

Characterization of the interaction of water with the highly ordered mesoporous solid MCM-41 (pore diameter ∼2.5 nm) is undertaken with the aid of several techniques (adsorption gravimetry, X-ray diffraction, Fourier transform infrared spectroscopy, and controlled rate-evolved gas analysis). The relatively complex water-MCM-41 interactions are characterized by a type V isotherm indicating an initial repulsive character followed by a capillary condensation step of the adsorbate. This highlights both hydrophobic and hydrophilic properties of this potential model mesoporous adsorbent.

FTIR Microscopy with Polarized Radiation for the Analysis of Adsorption Processes in Molecular Sieves

FTIR Microscopy with polarized light was used to study the orientation of different molecules in Silicalite I, SAPO-5 and AlPO 4 -5 molecular sieves during the adsorption process and in their equilibrium positions. While the uptake and the equilibrium positions of p-xylene are essentially not influenced by the the framework charge, large differences between AlPO 4 -5 and SAPO-5 are observed with the strongly basic p-nitroaniline molecule.

Pore Size Analysis of MCM-41 Type Adsorbents by Means of Nitrogen and Argon Adsorption

Methods of nonlocal density functional theory (NLDFT), proposed recently for predictions of adsorption equilibrium and calculations of pore size distributions in micro- and mesoporous materials, were tested on reference MCM-41 materials. Five newly synthesized MCM-41 adsorbents with presumably uniform pore channels varying from 32 to 45 Å were characterized by X-ray diffraction (XRD), nitrogen adsorption at 77 K, and argon adsorption at 77 and 87 K. New sets of intermolecular interaction parameters of the NLDFT model for N2 and Ar adsorption on MCM-41 were determined. The parameters were specified to reproduce the bulk liquid-gas equilibrium densities and pressures, liquid-gas interfacial t…

Improvement of Raman Spectra of SAPO-5 by Chromium(III)-Induced Luminescence Quenching

Surfactant based synthesis of oxidic catalysts and catalyst supports

The preparation of mesostructured metal oxides based on the surfactant controlledsynthesis of MCM-41 is presented. It can be expected that the new metal oxide materials will exhibit a high surface area of nearly 1000 m 2 /g and could have a possible use as catalysts, especially in partial oxidation reactions and as hosts for quantum sized material, if the surfactant can be removed without destroying the structure.

Polarized Fourier transform infrared microscopy as a tool for structural analysis of adsorbates in molecular sieves

Using FTIR microscopy with polarized IR radiation on silicalite I single crystals fully loaded with p-xylene, the existence of an ordered adsorbate could be proven for the first time by IR spectroscopy. By analyzing the polarized absorption bands the orientation of the p-xylene molecules relative to the host structure could be determined. The results agree well with structural data obtained from X-ray diffraction experiments. These first results suggest that polarized IR microscopy could develop into a powerful tool for the analysis of adsorbate structures, assisting in complete structure resolution by diffraction techniques

The synthesis of zeolites from dry powders

Summary ZSM-5 was synthesized by different methods with a gradually decreasing water content ending in a reaction mixture with absolutely dry reagents in form of a powder in the complete absence of a solution phase. Amorphous precursors obtained by drying SiO 2 * Al 2 O 3 gels at 650°C were transformed into zeolites in the presence of dried NH 4 F and TPABr. The reaction products were characterized by XRD, REM, TG/DTA, MAS NMR and Electron Micropobe. Pure ZSM-5 or Silicalite-1 was obtained in all cases. Some water is probably formed as a reaction product, but the maximum water pressure is appreciably below the saturation pressure at the given reaction conditions. To explain the formation of…