Catalytic combustion of methane on Co/MgO: characterisation of active cobalt sites

A series of Co/MgO catalysts with 3–12 wt.% Co were prepared by impregnation and calcined at 1073 K for 10 h. The catalytic behaviour of these samples toward CH4 combustion was found to increase with cobalt loading, though a plateau was reached at ca. 9 wt.% Co content. Bulk characterisation was carried out using XRD, TPR and Raman spectroscopy, and showed that the solids were made up of a CoO–MgO solid solution and a MgO phase. A detailed examination of their surfaces was achieved through FTIR spectroscopy of adsorbed CO probe molecules, which indicated that at low cobalt loadings only a small proportion of the Co going into the solid solution was present on exposed faces as either Co2+ oxo-species or pentacoordinated Co2+. However, as the cobalt content of the samples increased, a larger amount was exposed on the surface. This effect levelled off at 9 wt.% Co, after which the increase in exposed Co2+ sites was countered by the masking effect of islands of MgO. In addition, at high cobalt loadings (9 and 12 wt.%) Co formed small clusters which showed bulk CoO-like behaviour. Consequently, the benefit of having surface Co2+ species was balanced by the clustering effect of these species and the presence of MgO islands, negating their contribution to the overall catalytic activity of the samples.Fil: Ulla, Maria Alicia del H.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Spretz, R.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Lombardo, Eduardo Agustin. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Investigaciones en Catálisis y Petroquímica ; ArgentinaFil: Daniell, W.. Ludwig Maximilians Universitat; AlemaniaFil: Knözinger, H.. Ludwig Maximilians Universitat; Alemani

Adsorption and reaction of CO on (Pd–)Al2O3 and (Pd–)ZrO2: vibrational spectroscopy of carbonate formation

γ-Alumina is widely used as an oxide support in catalysis, and palladium nanoparticles supported by alumina represent one of the most frequently used dispersed metals. The surface sites of the catalysts are often probed via FTIR spectroscopy upon CO adsorption, which may result in the formation of surface carbonate species. We have examined this process in detail utilizing FTIR to monitor carbonate formation on γ-alumina and zirconia upon exposure to isotopically labelled and unlabelled CO and CO2. The same was carried out for well-defined Pd nanoparticles supported on Al2O3 or ZrO2. A water gas shift reaction of CO with surface hydroxyls was detected, which requires surface defect sites and adjacent OH groups. Furthermore, we have studied the effect of Cl synthesis residues, leading to strongly reduced carbonate formation and changes in the OH region (isolated OH groups were partly replaced or were even absent). To corroborate this finding, samples were deliberately poisoned with Cl to an extent comparable to that of synthesis residues, as confirmed by Auger electron spectroscopy. For catalysts prepared from Cl-containing precursors a new CO band at 2164 cm−1 was observed in the carbonyl region, which was ascribed to Pd interacting with Cl. Finally, the FTIR measurements were complemented by quantification of the amount of carbonates formed via chemisorption, which provides a tool to determine the concentration of reactive defect sites on the alumina surface

n-Heptane hydroconversion over nickel-loaded aluminum- and/or boron-containing BEA zeolites prepared by recrystallization of magadiite varieties

Phase-pure [Al]BEA and [Al,B]BEA zeolites, prepared by solid-state recrystallization of synthetic aluminum-containing magadiites and conventionally synthesized [B]BEA, were tested, after ion exchange with nickel, as bifunctional catalysts for hydroconversion of n-heptane. The reducibility of nickel ions incorporated into BEA zeolites by ion exchange was investigated by temperature-programmed reduction (TPR). The acidity of the samples was characterized with strong (pyridine (Py), ammonia (NH3)) and weak (nitrogen) bases. The adsorbed bases were studied by transmission FT-IR (Py), diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy (N2), and temperature-programmed ammonia evolution (TPAE, NH3). Over Ni/H-[B]BEA the reactants were completely converted via fast hydrogenolysis, whereas this reaction pathway plays only a negligible role in the hydroconversion over Ni/H-[Al]BEA and Ni/H-[Al,B]BEA zeolites. Boron-containing BEA zeolites were less active catalysts than the boron-free catalyst in the principal unimolecular hydroconversion reactions. However, incorporation of boron into the framework of BEA zeolite results in a considerable selectivity shift towards isomerization. Results suggest that the acid strength of bridged hydroxyls, probed with weak (N2) and strong basis (pyridine), was found to be similar in the boron-free and boron-containing BEA samples. The decrease in the isomerization rate and the increase of the apparent activation energy upon incorporation of boron may be attributed to the decrease in the heat of n-heptane adsorption

The Adsorption of H2O on TiO2 and SnO2(110) Studied by First-Principles Calculations

First-principles calculations based on density functional theory and the pseudopotential method have been used to investigate the energetics of H$_2$O adsorption on the (110) surface of TiO$_2$ and SnO$_2$. Full relaxation of all atomic positions is performed on slab systems with periodic boundary conditions, and the cases of full and half coverage are studied. Both molecular and dissociative (H$_2$O $\rightarrow$ OH$^-$ + H$^+$) adsorption are treated, and allowance is made for relaxation of the adsorbed species to unsymmetrical configurations. It is found that for both TiO$_2$ and SnO$_2$ an unsymmetrical dissociated configuration is the most stable. The symmetrical molecularly adsorbed configuration is unstable with respect to lowering of symmetry, and is separated from the fully dissociated configuration by at most a very small energy barrier. The calculated dissociative adsorption energies for TiO$_2$ and SnO$_2$ are in reasonable agreement with the results of thermal desorption experiments. Calculated total and local electronic densities of states for dissociatively and molecularly adsorbed configurations are presented and their relation with experimental UPS spectra is discussed

Effect of carbon fiber crystallite size on the formation of hafnium carbide coating and the mechanism of the reaction of hafnium with carbon fibers

The effect of carbon source crystallite size on the formation of hafnium carbide (HfC) coating was investigated via direct reaction of hafnium powders with mesophase pitch-based carbon fibers (CFs) heat-treated at various temperatures. X-ray diffraction, scanning electron microscopy and energy dispersive X-ray spectroscopy analyses reveal that uniform and dense HfC coatings are preferentially formed on CFs containing larger and more ordered graphite crystallites. The carbide synthesis temperature and the sizes of crystallites in the CFs have a remarkable influence on the integrity and thickness of the coatings. The formation the HfC coatings can be attributed to the surface diffusion of hafnium and the bi-directional diffusion of hafnium and carbon sources inside the HfC coating. The reaction of HfC coated carbon fibers with zirconium powders leads to the growth of ZrC on the HfC coating and this has been shown to occur by the diffusion of carbon from the carbon fiber core through the carbide coating to its surface

On the Synergistic Catalytic Properties of Bimetallic Mesoporous Materials Containing Aluminum and Zirconium: The Prins Cyclisation of Citronellal

Bimetallic three-dimensional amorphous mesoporous materials, Al-Zr-TUD-1 materials, were synthesised by using a surfactant-free, one-pot procedure employing triethanolamine (TEA) as a complexing reagent. The amount of aluminium and zirconium was varied in order to study the effect of these metals on the Brønsted and Lewis acidity, as well as on the resulting catalytic activity of the material. The materials were characterised by various techniques, including elemental analysis, X-ray diffraction, high-resolution TEM, N2 physisorption, temperature-programmed desorption (TPD) of NH3, and 27Al MAS NMR, XPS and FT-IR spectroscopy using pyridine and CO as probe molecules. Al-Zr-TUD-1 materials are mesoporous with surface areas ranging from 700–900 m2 g−1, an average pore size of around 4 nm and a pore volume of around 0.70 cm3 g−1. The synthesised Al-Zr-TUD-1 materials were tested as catalyst materials in the Lewis acid catalysed Meerwein–Ponndorf–Verley reduction of 4-tert-butylcyclohexanone, the intermolecular Prins synthesis of nopol and in the intramolecular Prins cyclisation of citronellal. Although Al-Zr-TUD-1 catalysts possess a lower amount of acid sites than their monometallic counterparts, according to TPD of NH3, these materials outperformed those of the monometallic Al-TUD-1 as well as Zr-TUD-1 in the Prins cyclisation of citronellal. This proves the existence of synergistic properties of Al-Zr-TUD-1. Due to the intramolecular nature of the Prins cyclisation of citronellal, the hydrophilic surface of the catalyst as well as the presence of both Brønsted and Lewis acid sites synergy could be obtained with bimetallic Al-Zr-TUD-1. Besides spectroscopic investigation of the active sites of the catalyst material a thorough testing of the catalyst in different types of reactions is crucial in identifying its specific active sites