In the current investigation we have used the hydrogenation of ethylene and crotonaldehyde as probe reactions in an attempt to follow any changes in catalytic behavior induced by supporting nickel on different types of graphite nanofiber support materials. The hydrogenation of the α,β-unsaturated aldehyde to the desired product, crotyl alcohol, is a particularly difficult task since there is a strong tendency to hydrogenate both the C=C and C=O in the reactant molecule. This study is designed to compare the catalytic behavior of the metal particles when dispersed on three types of nanofibers, where the orientation of the graphite platelets within the structures is significantly different in each case. The metal crystallites are located in such a manner that the majority of particles are in direct contact with graphite edge regions. For comparison purposes, the same set of hydrogenation reactions were carried out under similar conditions over γ-Al2O3 supported nickel particles.

Carbon nanotubes were prepared by the dc arc-discharge method under a controlled helium pressure ranging from 10 to 80 kPa and subsequently purified by oxidation in air. The purified carbon nanotubes were observed by transmission electron microscopy. The room temperature electron spin resonance (ESR) spectra of the purified nanotubes were measured. The variations in the ESR line shape, g-value, linewidth and relative spin density of the purified nanotubes on helium pressure were studied and discussed.

Several approaches for achieving reversible hydrogen uptake by carbon are considered, including intercalation, adsorption by a graphite surface, hydrogenation of fullerenes, and the filling of carbon nanotubes. Most scenarios suggest that it is difficult to achieve an atomic uptake [H/C] ratio exceeding unity. Evidence for H2 uptake by various carbon materials is reviewed.

A method was developed for the production of macroporous oxide materials by using the droplets of a nonaqueous emulsion as the templates around which material is deposited through a sol-gel process. Moreover, uniform pores arranged in regular arrays can be obtained by starting with an emulsion of uniform droplets. These droplets first self-assemble into a colloidal crystal after which gelation of the suspending sol-gel mixture captures the ordered structure. After drying and calcination pellets are obtained which contain ordered arrays of spherical pores left behind by the emulsion droplets. The method can be used to make uniform pores in the range from 0.05–5 micrometers in many different materials. We demonstrate the process for titania, silica, and zirconia.

The hydrothermal reaction of vanadium pentoxide with methylamine leads to a series of new layered vanadium oxides by using different acids to adjust the initial pH. The structure of these layered vanadium oxides was established by X-ray single crystal and powder diffraction. The new phases were also characterized by TGA and FTIR. The oxidation state of vanadium was determined. These materials are expected to exhibit catalytic activity and may be of interest as cathode materials for secondary lithium batteries.

Hybrid catalysts with the external configuration for the cocatalyst showed enhanced product diffusion rates in the n-octane hydrocracking, only if the reaction was carried out at relatively high temperatures. In the n-heptane isomerization, direct incorporation of the Al species into the HY zeolite micropores produced sorption sites which positively affected the selectivity to liquid isomers. Such as internal hybrid configuration resulted in a more important increase in the liquid isomer selectivity than that given by the external hybrid configuration, both systems being designed for better product outward-diffusion.

Mixed Metal Phospho-Sulfates were prepared and evaluated for use as acid catalysts via 2-methyl-2-pentene isomerization and o-xylene isomerization. Particular members of this class of materials exhibit greater levels of activity than sulfated zirconia as well as lower rates and magnitudes of deactivation. 31P MAS NMR has been used to examine the role of phosphorous in contributing to the activity and deactivation behavior of these materials, while powder X-ray diffraction, BET surface area, IR, and elemental analysis were used to characterize the bulk catalysts.

The relationship between the chemical composition, bulk real structure, surface properties and catalytic activity of dispersed complex framework zirconium phosphates with a NASICON-type structure is considered. For both crystalline and amorphous samples, a model of their bulk structure is suggested. The Lewis and Bröensted acidity was shown to vary broadly and be dependent upon the composition and preparation procedure, which is important for catalysts of hydro-carbons activation. Selective catalytic reduction of NOx by methane in excess oxygen appears to be one of the application areas for these systems.

The synthesis of aluminum oxide grafted on silica gel surface was carried out by the reaction of a suitable aluminum precursor with the surface hydrolysis of the oxide support. The chemical and physical properties of the attached oxide, SiO2/ Al2O3, can be quite different than those found for bulk Al2O3. The advantage of this preparation method, compared to the conventional ones (impregnation, precipitation and calcination), is that the oxide is highly dispersed on the surface (monolayer or submonolayer). We characterized the surface oxides treated at the temperature range of 423 to 1573 K employing X-ray photoelectron spectroscopy (XPS), solid state nuclear magnetic resonance spectroscopy (NMR), and diffuse reflectance spectroscopy (DRS). XPS was used to identify the oxidation states and atomic ratios. Al27 NMR detected two species for samples heated up to 1023 K, and another one above this temperature. DRS, using pyridine as a molecular probe, showed that both Lewis and Brönsted acid sites are stable up to 1023 K. We concluded that the aluminum oxide is highly dispersed on the silica gel surface and it remains stable up to 1023 K.

A poled ferroelectric material of a LiNbO3 single crystal and a polycrystalline lead strontium zirconium titanate(PSZT) disc were employed as a catalyst substrate, on which various metals such as Pd, Ag, Ni and Pt and a WO3 oxide were deposited as a thin film catalyst. The effects of acoustic waves generated by rf power upon catalyst activation and reaction selectivity have been examined. The activity for CO oxidation of a Pt/PSZT catalyst increased by a factor of 3.9 with a thickness-extensional(TE) mode of resonance oscillation(RO) and 2.9 with a radial-extensional (RE) mode. The activation energy of the reaction was larger for the TE mode( 38 kJmol−1) than that for the RE mode(24 kJmol−1). The polarization axis-dependent changes in surface potential occurred with the TE mode, but not with the RE mode. With the TE mode, the activation energy of ethanol oxidation over a Ni/LiNbO3 and a Ag/LiNbO3 catalyst decreased from 36 to 19 kJmol−1 and from 76 to 30 kJmol−1, respectively, and the TE mode had a larger effect on the reaction with a higher activation energy. In ethanol dehydrogenation and dehydration on a WO3 / LiNbO3 catalyst, the TE mode increased remarkably the selectivity for ethylene production without giving a significant change to acetaldehyde production. The effects of acoustic wave excitations on the catalysts are discussed.

Thin films of (001) and (100) oriented rutile phase TiO2, undoped or doped with Ga or Nb, have been grown using the MOCVD technique on sapphire substrates for use in studies of the effects of humidity on the electrical properties of rutile, lbe crystallographic and microstructural quality of the films decreases with increasing Ga and Nb concentrations. Heteroepitaxy is, however, maintained with Ga or Nb concentrations up to 4.5 at% for the (001) orientation and to 0.5 at% Ga for the (100) orientation. The electrical properties of the (001) oriented rutile films have been characterized from room temperature to 225 °C in dry and humid, N2 and air atmospheres. At constant temperature in dry atmospheres, the conductance of the Nb-doped rutile films is greater than that of the undoped, which is greater than the conductance of the Ga-doped films. The activation energies for conduction in die Nb-doped and undoped rutile films in dry atmospheres are similar (∼0.1 eV), whereas the activation energy in Ga-doped films is much greater (∼0.8 eV). The effects of humidity in reducing the resistance of rutile is greatest in the Ga-doped and very min (∼150 Å) undoped films. Humidity is observed to have similar effects on both the (001) and (100) oriented 0.5 at% Ga-doped films.

Molecular simulation methods provide a means for carrying out systematic studies of the factors affecting adsorption phenomena. For selective adsorption, the selectivity is strongly affected by the interaction energy with the pore walls, molecular size and shape, site specific interactions, entropie effects, differences in diffusion rates, and networking effects. Two recent studies of site specific selectivity will be described. The first is an investigation of the effect of oxygenated surface sites on the adsorption of water vapor on activated carbons. Hydrogen-bonding sites are modeled using off-center square well interactions for both water and wall sites; wall sites are placed at the edges of the graphite micro-crystals. New experimental results for water adsorption at low pressures on carefully characterized activated carbons are reported, and are found to be in good agreement with the simulations. In the second application, we consider the separation of alkene/alkane mixtures using aluminas whose surfaces have been doped with metal ions, π-complexation between these metal ions and the alkenes can produce a highly selective separation. The simulations are found to be in good agreement with the available experimental data, and have been used to predict separations for other conditions not yet studied in the laboratory.

Catalysts containing tungsten and nickel oxides are important in hydrodesulfurization (HDS), hydrogénation (HY), and steam reforming of hydrocarbons. A series of W/Ni/Al2O3 catalysts was prepared by two different methods: (1) coprecipitation of nickel and aluminium hydroxicarbonate from their nitrates, followed by calcination and impregnation of tungsten; (2) precipitation of boehmite from aluminium nitrate, followed by impregnations of nickel, firstly, and tungsten. The nickel content was kept constant, while the amount of tungsten varied from 2.5 to 15.5 wt-%. The resulting oxides were characterized by inductively coupled plasma spectroscopy (ICP), atomic absorption spectroscopy (AAS), X-ray diffraction (XRD), temperature programmed reduction (TPR), and X-ray photoelectron spectroscopy (XPS). ICP and AAS were used to determine the W, Ni, and Al concentrations. XRD detected two phases: NiO and NiAl2O4 (no phase containing metallic tungsten was detected). Increasing the amount of W, the quantity of NiAl2O4 rose, the quantity of NiO decreased, and the particle size of NiO enlarged. The TPR profiles presented three peaks: one at about 1000 °C, associated to a very stable phase; for the samples prepared by coprecipitation, the other two peaks corresponded to “free NiO” and a nonstoichiometric aluminate. For the samples prepared by impregnation, those peaks corresponded to NiO and NiAl2O4. XPS identified Al2O3, NiAl2O4, and Al2(WO4)3 for both preparation methods. Increasing the amount of tungsten in the impregnated samples, NiWO4 was also observed.