Investigation of the Deactivation Phenomena Occurring in the Cyclohexane Photocatalytic Oxidative Dehydrogenation on MoOx/TiO2 through Gas Phase and in situ DRIFTS Analyses

In this work, the results of gas phase cyclohexane photocatalytic oxidative dehydrogenation on MoOx/SO4/TiO2 catalysts with DRIFTS analysis are presented. Analysis of products in the gas-phase discharge of a fixed bed photoreactor was coupled with in situ monitoring of the photocatalyst surface during irradiation with an IR probe. An interaction between cyclohexane and surface sulfates was found by DRIFTS analysis in the absence of UV irradiation, showing evidence of the formation of an organo-sulfur compound. In particular, in the absence of irradiation, sulfate species initiate a redox reaction through hydrogen abstraction of cyclohexane and formation of sulfate (IV) species. In previous studies, it was concluded that reduction of the sulfate (IV) species via hydrogen abstraction during UV irradiation may produce gas phase SO2 and thereby loss of surface sulfur species. Gas phase analysis showed that the presence of MoOx species, at same sulfate loading, changes the selectivity of the photoreaction, promoting the formation of benzene. The amount of surface sulfate influenced benzene yield, which decreases when the sulfate coverage is lower. During irradiation, a strong deactivation was observed due to the poisoning of the surface by carbon deposits strongly adsorbed on catalyst surface

Enhanced visible-light-driven photodegradation of Acid Orange 7 azo dye in aqueous solution using Fe-N co-doped TiO2

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Controlled growth of CNT in mesoporous AAO through optimized conditions for membrane preparation and CVD operation

Anodic aluminium oxide (RAAO) membranes with a mesoporous structure were prepared under strictly controlling experimental process conditions, and physically and chemically characterized by a wide range of experimental techniques. Commercial anodic aluminium oxide (CAAO) membranes were also investigated for comparison. We demonstrated that RAAO membranes have lower content of both water and phosphorus and showed better porosity shape than CAAO. The RAAO membranes were used for template growth of carbon nanotubes (CNT) inside its pores by ethylene chemical vapour deposition (CVD) in the absence of a catalyst. A composite material, containing one nanotube for each channel, having the same length as the membrane thickness and an external diameter close to the diameter of the membrane holes, was obtained. Yield, selectivity and quality of CNTs in terms of diameter, length and arrangement (i.e. number of tubes for each channel) were optimized by investigating the effect of changing the experimental conditions for the CVD process. We showed that upon thermal treatment RAAO membranes were made up of crystallized allotropic alumina phases, which govern the subsequent CNT growth, because of their catalytic activity, likely due to their Lewis acidity. The strict control of experimental conditions for membrane preparation and CNT growth allowed us to enhance the carbon structural order, which is a critical requisite for CNT application as a substitute for copper in novel nano-interconnects

Improved Performances of a Fluidized Bed Photoreactor by a Microscale Illumination System

The performances of a gas-solid two-dimensional fluidized bed reactor in photocatalytic selective oxidation reactions, irradiated with traditional UV lamps or with a microscale illumination system based on UV emitting diodes (UVA-LEDs), have been compared. In the photocatalytic oxidative dehydrogenation of cyclohexane to benzene on catalyst the use of UVA-LEDs modules allowed to achieve a cyclohexane conversion and benzene yield higher than those obtained with traditional UV lamps. The better performances with UVA-LEDs are due to the UVA-LEDs small dimensions and small-angle emittance, which allow photons beam be directed towards the photoreactor windows, reducing the dispersion outside of photoreactor or the optical path length. As a consequence, the effectively illuminated mass of catalyst is greater. We have found that this illumination system is efficient for photo-oxidative dehydrogenation of cyclohexane to cyclohexene on sulphated and ethanol to acetaldehyde on

In situ sulphated CuOx/ZrO2 and CuOx/sulphated-ZrO2 as catalysts for the reduction of NOx with NH3 in the presence of excess O2

Sulphated catalysts containing the same amount of sulphates (2.6 SO4 nm2) and a different amount of copper (0.3–3.9 Cu atoms nm2), Cu/SZ, were prepared by impregnation of sulphated-ZrO2 with toluene solutions of Cu(acetylacetonate)2. Sulphated catalysts containing the same amount of copper (0.3 or 2.5 atoms nm2) and a different amount of sulphates (up to 4.9 SO2 nm2), Cu/ZSg, were prepared by sulphation of CuOx/ZrO2 (Cu/Z) via the gas-phase. Samples were characterised by Fourier transformed IR spectroscopy. The selective catalytic reduction of NO with NH3 in the presence of excess O2 (SCR reaction), the NH3 + O2 and the NO + O2 reactions were studied in a flow apparatus. Activity and selectivity did not depend on the sulphation method used for catalyst preparation but depended on the amount of copper and sulphate, particularly on the sulphate/copper ratio. As on Cu/Z, on Cu/SZ CuII was active for both SCR and NH3 + O2 reactions. The presence of covalent sulphates caused lower reducibility of CuII to CuI and higher Lewis acid strength of CuI in Cu/SZ than in Cu/Z. For (i) SCR, (ii) NH3 + O2 and (iii) NO + O2, Cu/ZSg were less active than the parent Cu/Z. As the sulphate content in Cu/ZSg increased, the NO yield in the NH3 + O2 reaction markedly decreased, thus accounting for the increased selectivity in the SCR reaction. In CuOx/ sulphated-ZrO2 copper ions were less prone reversibly to undergo the redox process CuII/CuI. These findings provide new information on the role of copper and sulphate in determining the activity and selectivity for the SCR with NH

Photocatalytic removal of patent blue V dye on Au-TiO2 and Pt-TiO2 catalysts

In this work it was studied the efficiency of a photocatalytic process for the removal of patent blue V. This dye is very difficult to remove by conventional treatments such as adsorption or coagulation therefore the photocatalytic process is a very interesting alternative for the removal this dye mainly because it does not require expensive oxidants and it can be carried out at mild temperatures and pressures. In this work it was tested the efficiency of Au-TiO2 and Pt-TiO2 photocatalysts in the Patent blue V removal. The Au-TiO2 catalysts were prepared by two different methods: chemical reduction and photochemical deposition; Pt-TiO2 catalysts were obtained only by photochemical deposition. In the synthesis of the catalysts prepared by photochemical deposition, it was evaluated the influence of some parameters, such as deposition time and the intensity of the light source over the physicochemical properties and photocatalytic activity of the materials obtained. An analysis of the effect of the catalyst dosage and initial patent blue V concentration over the dye degradation efficiency was also attempted. In general, it was observed that the presence of Au or Pt on TiO2 enhances the patent blue V photodegradation; it was found that noble metal particle size and distribution on TiO2 surface are important factors influencing the dye removal. The highest dye degradation was obtained over the Au-TiO2 catalyst prepared by photochemical deposition, using high light intensity and 15 min of deposition time during the synthesis. A discoloration and a total organic carbon (TOC) removal of 93 and 67% respectively, were obtained over this material after 180 min of UV irradiation. These values are higher than that the obtained on S-TiO2 (discoloration and TOC removal of about 25% and 3%, respectively)