Characterization of vanadium and titanium oxide supported SBA-15

Supported vanadium and titanium oxide catalysts were prepared by adsorption and subsequent calcination of the vanadyl and titanyl acetylacetonate complexes, respectively, on mesoporous SBA-15 by the molecular designed dispersion (MDD) method. Liquid and gas phase depositions at different temperatures were carried out with vanadyl acetylacetonate, and the different results together with those of titanyl acetylacetonate in the liquid phase deposition were discussed. The bonding mechanism, the influence of the metal interaction with the support material, and differences due to the way of deposition and the temperature were investigated by TGA, chemical analysis, FTIR, and Raman spectroscopy. Elevated dissolving temperatures in the liquid phase led to higher final loadings on the SBA-15 without the formation of clusters, even at high loadings. The decomposition of the anchored vanadium and titanium complexes, their thermal stability, and the conversion to the covalently bound VO(x) and TiO(x) species on SBA-15 were studied and investigated by in situ transmission IR spectroscopy. In general, the titanium complex is more reactive than the vanadium complex toward the surface of SBA-15 and has a higher thermal stability. The MDD method of the VO(acac)2 and TiO(acac)2 enables to create a dispersed surface of supported VO(x) and TiO(x), respectively. The structure configurations of VO(x) and TiO(x) oxide catalysts obtained at different metal loadings were studied by Raman spectroscopy. Pore size distributions, XRD, and N2 sorption confirmed the structural stability of these materials after grafting. VO(x)/SBA-15 and TiO(x)/SBA-15 samples, with different metal loadings, were also catalytically tested for the selective catalytic reduction (SCR) of NO with ammonia.     

Waste water analysis by purge and trap capillary GC-FTIR spectrometry

Gas chromatography with Fourier transform infra-red spectroscopic detection (GC-FTIR) is used for the analysis of waste water samples. Compared to GC-MS, this technique offers a more complete identification of organic compounds. Lower concentrations of organic volatiles however require preconcentration techniques such as a Purge and Trap (P&T) preconcentrator. Using this combination, concentrations of organic volatiles in the ppb range can be detected and positively identified.     

Centred TVD schemes for hyperbolic conservation laws

New first- and high-order centred methods for conservation lawsare presented. Convenient TVD conditions for constructing centredTVD schemes are then formulated and some useful results areproved. Two families of centred TVD schemes are constructedand extended to nonlinear systems. Some numerical results arealso presented.     

Chemical Surface Coating: Synthesis and Characterization of a Silicon Oxynitride Coated Silica Sel

Mesoporous silica gel has been coated with a thin silicon oxynitridefilm via chemical surface coating. In the first part of the synthesis, achemically bound preceramic polysilazane coating is formed layer by layer onthe pore walls at low temperature, using SiCl₄ andNH₃ as reagents. In the second part of the synthesis, thepolysilazane coated silica gel is pyrolysed, yielding a chemically bound,thin oxynitride coating.During the synthesis, the evolution of the chemical and morphologicalcomposition has been investigated with several elemental and spectroscopicanalysis techniques as well as with nitrogen porosimetry.     

FTIR-PAS analysis of silica gel modified with amines for the treatment of natural gases contaminated with sulphur compounds

The quantitative analysis of organic microsamples [vinylite (PVC-PVA) cellulose-nitrate and polyamide] on Al-foils was performed with good precision (rel. standard deviation 1.04% to 12.1%) after calibration of their main IR-bands with relative conductometric techniques. It was shown that the lower detection limit using the 15×Cassegrain objective was 1m and that the linear range of the calibration curves was limited by a deviation of Beer's law atA>1.2 due to the reststrahlen-effect.     

Synthesis, spectroscopy and catalysis of

Chromium acetyl acetonate [Cr(acac)3] complexes have been grafted onto the surface of two mesoporous crystalline materials; pure silica MCM-41 (SiMCM-41) and Al-containing silica MCM-41 with an Si:Al ratio of 27 (AlMCM-41). The materials were characterized with X-ray diffraction, N2 adsorption, thermogravimetrical analysis, diffuse reflectance spectroscopy in the UV-Vis-NIR region (DRS), electron spin resonance (ESR) and Fourier transform infrared spectroscopy. Hydrogen bonding between surface hydroxyls and the acetylacetonate (acac) ligands is the only type of interaction between [Cr(acac)3] complexes and SiMCM-41, while the deposition of [Cr(acac)3] onto the surface of AlMCM-41 takes place through either a ligand exchange reaction or a hydrogen-bonding mechanism. In the as-synthesized materials, Cr3+ is present as a surface species in pseudo-octahedral coordination. This species is characterized by high zero-field ESR parameters D and E, indicating a strong distortion from O(h), symmetry. After calcination, Cr3+ is almost completely oxidized to Cr6+, which is anchored onto the surface as dichromate, some chromate and traces of small amorphous Cr2O3 clusters and square pyramidal Cr5+ ions. These materials are active in the gas-phase and slurry-phase polymerization of ethylene at 100 degrees C. The polymerization activity is dependent on the Cr loading, precalcination temperature and the support characteristics: a 1 wt % [Cr(acac)3]-AlMCM-41 catalyst pretreated at high temperatures was found to be the most active material with a polymerization rate of 14000 g polyethylene per gram of Cr per hour. Combined DRS-ESR spectroscopies were used to monitor the reduction process of Cr(6+/5+) and the oxidation and coordination environment of Cr(n+) species during catalytic action. It will be shown that the polymer chains initially produced within the mesopores of the Cr-MCM-41 material form nanofibres of polyethylene with a length of several microns and a diameter of 50 to 100 nanometers. These nanofibres (partially) cover the outer surface of the MCM-41 material. The catalyst particles also gradually break up during ethylene polymerization resulting in the formation of crystalline and amorphous polyethylene with a low bulk density and a melt flow index between 0.56 and 1.38g per 10 min; this indicates the very high molecular weight of the polymer.     

Investigation of the morphology of the mesoporous SBA-16 and SBA-15 materials

Mesoporous SBA-16 and SBA-15 were studied in order to control their possible morphologies. SBA-16 is synthesized using a silicon source (tetraethoxysilane, TEOS) and a ternary system consisting of surfactant F127 (EO106PO70EO106), water, and butanol. The same ternary system, with higher butanol concentration, is used to form SBA-15 material as well. An increase of the TEOS concentration results in a morphology shift of SBA-16 from micron-sized spheres, over randomly shaped aggregated particles, to macrospheres with a size of 15 mm. An identical increase in TEOS concentration also results in the formation of SBA-15 macrospheres, which can be controlled in size. Micron-sized spheres of SBA-15 were formed using a quaternary system of surfactant P123 (EO20PO70EO20), cetyltrimethylammonium bromide (CTAB), ethanol, and water. All mesoporous silica materials were characterized using SEM, XRD, and N2 sorption techniques.     

Modification of MCM-48-, SBA-15-, MCF-, and MSU-type mesoporous silicas with transition metal oxides using the molecular designed dispersion method

Four various mesoporous silicas (MCM-48, SBA-15, MCF, and MSU) were modified by the molecular designed dispersion method using Fe(acac)3, Cr(acac)3, and Cu(acac)2 complexes. The deposition was performed at the same concentration of the metal acetylacetonate (acac) complex in a toluene solution. All as-synthesized samples were investigated by diffuse reflectance infrared Fourier transform spectroscopy, Fourier transform infrared photoacoustic spectroscopy, and thermogravimetric analysis. The calcined materials were studied with respect to their textural properties (Brunauer-Emmett-Teller adsorption isotherm) and chemical composition (electron microprobe analysis). It allowed elucidation of the mechanism of interaction between the acac complex and the silanol groups. For the MCM-48, SBA-15, and MCF materials, the formation of hydrogen bonding was found for the chromium- and copper-modified samples, whereas the Fe-containing materials showed the ligand exchange mechanism. The strong interaction of the MSU support and the different acetylacetonate complexes, resulting in a loss of at least one acac ligand, was observed. The mesoporous silicas modified with transition metal oxides were studied by UV-vis-DR spectroscopy. The different metal dispersions were found for the samples containing various transition metal oxides.     

Laser microprobe mass analysis of N,N-dimethylaniline and catalytic oxidation products adsorbed on asbestos fiber surfaces

Summary The adsorption behaviour of different asbestos varieties for N,N-dimethylaniline and its catalytically formed oxidation products e. g. Methyl Violet is studied using laser microprobe mass analysis (LAMMA) in laser desorption conditions. The results prove that amosite and chrysotile adsorb more easily than crocidolite, whereas anthophyllite does not give rise to a detectable adsorption. In the presence of hydrogen peroxide, the method developed shows potential for the investigation of the surface reactivity of pure and industrially transformed asbestos and other fibrous materials.

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Laser-Mikro-Massenspektrometrie von N,N-Dimethylanilin und dessen Oxydationsprodukten auf der Oberfläche von Asbestfasern

Zusammenfassung Das Adsorptionsverhalten verschiedener Asbestarten gegenüber N,N-Dimethylanilin und seinen katalytisch hergestellten Oxydationsprodukten, z. B. Methylviolett, wurde mit der Laser-Mikro-Massenspektrometrie (LAMMA) studiert. Mittels laserinduzierter Desorption konnte festgestellt werden, daß Amosit und Chrysotil eine höhere Adsorptionsfähigkeit als Krokidolit zeigen. Bei Anthophyllit konnte keine Adsorption von DMA festgestellt werden. In Gegenwart von H₂O₂ kann die entwickelte Methode für die Untersuchung der Reaktivität von reinen und behandelten Oberflächen von Asbest und anderen faserförmigen Stoffen eingesetzt werden.