RESUMO
Terephthalate-intercalated nickel-aluminum layered double hydroxides (LDHs) were prepared by a co-precipitation method, with nominal x values in the general formula Ni((1-x))Al(x)(OH)(2)(C(8)H(4)O(4))(x/2) in the range 0.3-0.8. The materials were characterized by X-ray diffraction, X-ray fluorescence spectroscopy, CHN analysis, thermogravimetric analysis, FTIR spectroscopy, EXAFS at the Ni edge and (27)Al NMR spectroscopy. A combination of XRD, XRF and CHN analysis indicated that crystalline LDHs with true x values up to 0.5 were obtained, along with increasing segregation of an aluminum hydroxide phase with increasing aluminum content. The EXAFS analysis indicated an upper limit of ca. 0.6 for the atomic fraction of aluminum at the second nickel coordination sphere. The (27)Al NMR analysis suggested that a phase containing octahedrally co-ordinated Al(3+) is segregated for nominal x values from 0.6 upwards.
RESUMO
With the aim of obtaining materials with properties for use as catalysts, two new trimetallic oxides containing Co or Ni and Mo and W were synthesized by a hydrothermal method, using milder conditions than those normally used for wolframite type solids. They were characterized by X-ray diffraction, Fourier transformed infrared spectroscopy, laser Raman spectroscopy, temperature-programmed reduction and atomic absorption spectroscopy, indicating that pure wolframite phases were formed. The X-ray diffraction studies confirmed the formation of the structure in the monoclinic system with cell parameters similar to nickel tungsten wolframite. The laser Raman and infrared spectra showed differences among the samples, mainly due to the incorporation of molybdenum atoms in the wolframite structure. Incorporation of molybdenum in the catalysts improved catalytic activity for propane oxidative dehydrogenation, and lower reaction temperatures were required in order to obtain similar propene yields as in bimetallic tungsten wolframites.
RESUMO
Carburized molybdenum catalysts supported on a dealuminated NaH-Y zeolite were prepared by carburization under a 20% methane in hydrogen flow of two precursors obtained by adsorption of molybdenum hexacarbonyl, one containing 5 wt % and the other 10 wt % Mo, and a third one was prepared by impregnation with aqueous ammonium heptamolybdate, containing 5 wt % Mo. The three catalysts displayed very distinct behaviors in the benzene hydrogenation reaction at atmospheric pressure and 363 K. By using XANES spectroscopy at the molybdenum L edge, EXAFS and XANES spectroscopy at the molybdenum K edge, and 27Al solid-state NMR spectroscopy, it was shown that different carburized molybdenum species exist in each sample. In the catalyst containing 10 wt % Mo, formation of molybdenum carbide nanoparticles was observed, with an estimated diameter of 1.8 nm. In the catalyst containing 5 wt % Mo and prepared by carburization of adsorbed molybdenum hexacarbonyl, formation of molybdenum oxycarbide dimers is proposed. In the latter case, density functional theory calculations have led to a dimer structure which is compatible with EXAFS results. In the catalyst prepared by impregnation with ammonium heptamolybdate solution followed by carburization, the molybdenum seems to interact with extraframework alumina to produce highly disordered mixed molybdenum-aluminum oxycarbides.