Preparation of Phase-Pure M1 MoVTeNb Oxide Catalysts by Hydrothermal Synthesis—Influence of Reaction Parameters on Structure and Morphology

This work presents a detailed investigation of the preparation of MoVTeNbO _x catalysts by hydrothermal synthesis. Phase-pure synthesis of M1 has been achieved applying the metals in a molar ratio Mo/V/Te/Nb = 1/0.25/0.23/0.12. Raman, UV/Vis spectroscopy, and SEM/EDX analysis show that the elements are inhomogeneously distributed in the initial suspension that is formed after mixing the metal salts in an aqueous medium. Iso- and heteropoly anions of molybdenum, free telluric acid as well as supra-molecular polyoxometalate clusters are observed in the solution, whereas all metals have been found in the precipitate. Complete rearrangement of molecular building blocks under hydrothermal conditions is essential for formation of phase-pure materials. Optimized synthesis conditions with respect to temperature and time result in the formation of a precursor consisting of nano-structured M1 characterized by an extended periodic organization in the [001] direction and a fairly homogeneous distribution of the elements. Residual ammonium containing supra-molecular species in the precursor result in the formation of phase mixtures during the subsequent crystallization by heat treatment in inert gas. Phase-pure M1 exhibits a distinct degree of flexibility with respect to the chemical composition that becomes obvious by incorporating Nb not exclusively into pentagonal bi-pyramidal units, but also into octahedral coordinated positions as shown by EXAFS. Anisotropic growth of the needle-like M1 crystals has been observed during the final heat treatment performed at 873–923 K in inert atmosphere disclosing a potential method to control the catalytic properties of MoVTeNbO _x catalysts.     

Fullerene-based ruthenium catalysts: a novel approach for anchoring metal to carbonaceous supports. I. Structure

The influence of fullerenes and related support materials on the structural and catalytic properties of ruthenium was investigated. Catalysts based on C₆₀, raw fullerene black, extracted fullerene black, cathode deposit and graphite were prepared by an impregnation/activation procedure with Ru₃CO₁₂. The local co-ordination sphere of the resulting highly dispersed X-ray amorphous ruthenium was investigated by means of EXAFS. The dominating role of the presence of non-six-membered carbon rings on the structure and the stability of the Ru particles will be illustrated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Surface and subsurface products of the interaction of O2 with Ag under catalytic conditions

Polycrystalline Ag treated with O₂ at pressures up to 1 bar and at temperatures up to 920 K was examined by TDS. It was found that the peak commonly observed at 595±25 K and assigned to adsorbed atomic oxygen (O_a) is shifted to higher desorption temperatures with rising dosing temperatures. Since saturation of the uptake was not possible either, this peak was identified as dissolved atomic oxygen (O_d). The existence of a maximum for the O₂ uptake after exposure at 820 K was found. Hence, under conditions of formaldehyde synthesis ( 920 K) the ability of the catalyst to dissolve oxygen is near its maximum.     

Use of mesoporous SBA-15 for nanostructuring titania for photocatalytic applications

SBA15–TiO₂ samples prepared by introducing titanium with a grafting method and having TiO₂ loadings below 15 wt.% have been characterized by XRF, XRD, IR, porosimetry, SEM, HRTEM, and UV–Visible diffuse reflectance. Differently from the samples reported in the literature characterized by a high TiO₂ loading, no evidences have been found for the presence of titania particles inside or outside the mesopores of SBA-15. Three different titanium species were instead evidenced to be present. The first two derive from the reaction of titanium with silanol groups in the corona area of inner SBA-15 walls leading to the formation of either TiO₄ tetrahedral sites (by reaction by hydroxyl nests of surface defect sites) and/or pseudo-octahedral surface sites anchored by two (or more) Si or Ti ions through bridging oxygens. The third species derives from the reaction of titanium in the regions with high sylanol density, e.g. in the micropores located in the corona of SBA-15 channels, leading to the formation of TiO₂-like nanoareas (probably Si-doped) with dimensions of around 1–2 nm maximum. The potential interest of these materials as photocatalysts, for the presence of a TiO₂-like nanoareas highly accessible by reactants, is discussed.     

Activity and Selectivity of a Nanostructured CuO/ZrO2 Catalyst in the Steam Reforming of Methanol

Steam reforming of methanol for production of hydrogen can be carried out over copper based catalyst. In the work presented here, the catalytic properties of a CuO/ZrO₂ catalyst (8.5wt%) synthesised by a templating technique were investigated with respect to activity, long term stability, CO formation, and response to oxygen addition to the feed. The results were obtained using a fixed bed reactor and compared to a commercial methanol synthesis catalyst CuO/ZnO/Al₂O₃. It is shown that, depending on the time on stream, the temporary addition of oxygen to the feed has a beneficial effect on the activity of the CuO/ZrO₂ catalyst. After activation, the CuO/ZrO₂ catalyst is found to be more active (per copper mass) than the CuO/ZnO/Al₂O₃ system, more stable during time on stream (measured up to 250h), and to produce less CO. Structural characterisation by means of X-ray powder diffraction (XRD) and X-ray absorption spectroscopy (XAS) reveals that the catalyst (as prepared) consists of crystalline, tetragonal zirconia with small domain sizes (about 60Å) and small/disordered crystallites of CuO.     

Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.     

Preparation of Vanadium and Vanadium Oxide Clusters by Means of Inert Gas Aggregation

Vanadium clusters were prepared by the inert gas aggregation technique by evaporating V of high purity. Structural characterization was performed by high-resolution transmission electron microscopy. Apart from vanadium clusters of bcc structures in different orientations, crystalline VO clusters of NaCl structures were observed, which was attributed to the reaction with free oxygen present on the amorphous carbon substrates. The latter could be detected by electron energy-loss spectroscopy. The exposure of the samples to air caused a change to amorphous structures, which re-crystallized under the electron beam. This effect was interpreted as a reaction with water present in the air.     

Identification of the state of palladium in various hydrogenation catalysts by XPS

Various commercial supported palladium hydrogenation catalysts were studied by XPS and treated at ambient pressure with hydrogen and air. Unused catalysts exhibit a significant fraction of divalent Pd (oxide) which is reduced by hydrogen treatment at room temperature. Exposure to air in systems with carbonate, alumina, silica or active carbon as support causes the formation of a solid solution of oxygen in Pd characterized by a Pd 3d chemical shift of ca. + 0.4 eV. The absolute binding energy of Pd depends strongly on the matrix, indicating a significant contribution of extra-atomic screening, which prevents a direct comparison of reference samples and supported catalysts. Using the oxidation of CO to CO₂ at 300 K as in situ chemical probe it was confirmed that Pd supported on carbonate, silica and alumina exists in the same metallic state which could be activated for the test reaction irrespective of the variation in XPS binding energies.     

Preparation and characterization of a model system for the study of monolayers and multilayers of vanadia supported on titania

A model system for the study of structural and chemical properties of monolayers and multilayers of vanadium oxide immobilized on titania is presented. Investigation of the planar oxide-oxide interface by XP, UV and IS spectroscopy indicated that vanadium immobilized by a single impregnation step exists as an incomplete heterogeneous layer containing well dispersed V⁴⁺ species. Increase of the vanadia loading by multiple impregnations led to vanadia agglomerates with higher apparent oxidation state of the vanadium. TD spectroscopy with O₂ and CO₂ as probe molecules revealed that the chemical reactivity of the vanadia surface species depends on their structure. The surface containing well-dispersed vanadia species exchanged oxygen more easily and showed pronounced interactions with CO₂.