Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

Alumina-supported catalysts for propane oxidative dehydrogenation from mixed VXM(6−X)O19 (M=W, Mo) hexametalate precursors

γ-Al₂O₃ supported vanadium oxides were modified by tungsten and molybdenum oxides in order to improve dispersion and selectivity towards olefins in propane oxidative dehydrogenation (ODH). Both vanadium–tungsten and vanadium–molybdenum catalysts were obtained by adsorption of mixed isopolyanions (VW₅O₁₉⁵⁻, V₂W₄O₁₉⁴⁻, VMo₅O₁₉⁵⁻ and V₂Mo₄O₁₉⁴⁻) from aqueous solutions. The isopolyanion solutions were characterized by UV-Vis and ⁵¹V NMR spectroscopy. Vanadium, vanadium–tungsten and vanadium–molybdenum precursors and catalysts were also characterized by UV-Vis (diffuse reflectance) and solid state ⁵¹V NMR spectroscopy. An improved selectivity to propene in the presence of tungsten and molybdenum in VO_x/γ-Al₂O₃ was observed and attributed to dilution of vanadium by tungsten or molybdenum oxides on the γ-Al₂O₃ surface.     

Catalytic dehydrogenation of ethylbenzene with carbon dioxide: promotional effect of antimony in supported vanadium–antimony oxide catalyst

Alumina-supported vanadium oxide, VO_x/Al₂O₃, and binary vanadium–antimony oxides, VSbO_x/Al₂O₃, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by S_BET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO₂ pulse methods. VSbO_x/Al₂O₃ exhibited enhanced catalytic activity and especially on-stream stability compared to VO_x/Al₂O₃ catalyst. Incorporation of antimony into VO_x/Al₂O₃ increased dispersion of active VO_x species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V_0.43Sb_0.57O_x/Al₂O₃ system.     

Preparation and characterisation of vanadium catalysts supported over alumina-pillared clays

Supported vanadium-containing catalysts were prepared by impregnation of Al-pillared clays with NaVO₃ precursor aqueous solutions. A montmorillonite and a saponite, both natural as well as previously pillared with Al₁₃-Keggin polycations, were used as supports, being impregnated with solutions of the precursor by means of the incipient wetness technique. The layered structure of the supports is maintained after impregnation, and even after calcination of the impregnated solids at 500 °C, although with a significant worsening of the textural properties of the solids, in particular, a loss of specific surface area. Three crystalline vanadium-containing phases were identified in the impregnated solids, namely, NaV₃O₈, AlVO₄ and V₂O₅ (shcherbinaite). The reduction of these phases to V³⁺ species was observed as wide processes in the 450–750 °C range, all of them centred at ca. 600 °C.     

Effects of CSCW on organizations

We consider the potential impact of Computer Supported Cooperative Work, with special reference to large technically advanced projects involving several organizations. It is vital that such projects are managed efficiently, without delays, since a product that reaches the market a few months earlier than its competitors enjoys a great advantage. Traditional methods of coordinating large projects, based on hierarchical communication, tend to produce delays, since technicians at remote sites are obliged to solve coordination problems by passing them up the hierachy. It would be better if such problems were solved by improvising conferences among the technicians; Computer Supported Cooperative Work will provide the technical means of implementing this heterarchical style of management without losing control of the project. The use of computers as a social medium raises methodological and ethical issues which are discussed in the final section.     

Vanadium species in new catalysts for the selective oxidation of methane to formaldehyde: Activation of the catalytic sites

New vanadium oxide supported on mesoporous silica catalysts for the oxidation of methane to formaldehyde were investigated by infrared and Raman spectroscopies to identify and characterize the molecular structure of the most active and selective catalytic sites. In situ and operando experiments have been conducted in order to understand the redox and hydroxylation/dehydroxylation processes of the vanadium species. (SiO)₂VO(OH) species were identified in these catalysts in reaction conditions and shown to undergo a deprotonation at 580 °C under vacuum, leading to a site giving a photoluminescence band at 550 nm attributed to reverse radiative decay from the excited triplet state:

(V⁴⁺–O⁻)^*  (V⁵⁺O²⁻). An activation mechanism of vanadium monomeric species with electrophilic oxygen species is proposed.     

Ring hydrogenation of naphthalene and 1-naphthol over supported metal catalysts in supercritical carbon dioxide solvent

Catalytic ring hydrogenations of naphthalene and 1-naphthol were studied over several supported metal catalysts in supercritical carbon dioxide solvent at low temperature. Higher concentration of hydrogen in supercritical carbon dioxide and lower reaction temperature were responsible for higher catalyst activity and selectivities to the desired partial ring hydrogenated products as compared with those observed in organic solvent for the same catalyst.     

Aerobic selective oxidation of (hetero)aromatic primary alcohols to aldehydes or carboxylic acids over carbon supported platinum

The synthesis of substituted benzaldehydes, benzoic acids, heterocyclic aromatic aldehydes and acids has been studied via the oxidation of the aromatic alcohols with air under mild pressure (<20 bar) at 100 °C, in the presence of a 1.95 wt.% Pt/C catalyst. The solvent was found to play the most important role in determining the selectivity of the oxidation products. Changing the solvent enabled tuning the reaction either to the aldehyde (pure dioxane), or the carboxylic acid (dioxane/aqueous solution without or with addition of sodium hydroxide). This oxidation method allowed to effectively oxidize many substituted benzylalcohols with various electron-releasing or -attracting groups (NO₂, Me, OMe, Cl, Br, OH, phenyl, …) and heterocyclic alcohols including nitrogen and sulphur atoms (2-thiophenemethanol, 2- and 4-pyridine methanol compounds).     

Effects of the boundary layer and interfacial reaction on the time lag in supported liquid membranes

A mathematical model is proposed to describe the effects of boundary layer resistance and interfacial reaction on the time lag in supported liquid membranes for metal ion separation. The model shows that the presence of boundary layer resistance and interfacial reaction delays the time-lag, compared with the limiting case that rapid equilibrium at the interfaces and negligible boundary layer resistance are assumed. Calculated result describes the expected trend and the model equation allows one to predict the lumped parameters which represent the ratios of the diffusion time in the membrane to the characteristic time for boundary layer transfer and interfacial reactions.     

A comprehensive assessment of supported titania photocatalysts in a fluidized bed photoreactor: Photocatalytic activity and adherence stability

Titania (TiO₂) was immobilized onto hydroxylated glass beads (HGB) via the thermal bonding and sol–gel coating methods. The photocatalytic activity and adherence stability of the prepared supported photocatalysts were studied in a fluidized bed photoreactor. P25 thermally bonded HGB was found to be more active than sol–gel coated HGB prepared with the same immobilization conditions, while both of them exhibited poor adherence stability, i.e., large amounts of immobilized TiO₂ detached from HGB during the degradation. The adherence stability was improved with limited extents by increasing the calcination temperature or reducing the coverage of TiO₂ on HGB, but either of these approaches resulted in lower activity. The poor adherence stability was ascribed to the fluid shear force and particle friction in fluidized bed, as well as the insufficient bonding between TiO₂ and HGB in terms of the bonding mechanism.

Hydroxylated quartz sands (HQS) and silica gel beads (SGB) were further studied and used as supports. Results have shown that the adherence stability was significantly improved with SGB but only slightly improved with HQS. Characterizations results showed that a coarser surface and more surface Si–OH groups could improve the adherence stability of supported TiO₂ photocatalysts.