Effect of TiO<Subscript>2</Subscript> loading on the activity of V/TiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the catalytic oxidehydrogenation of ethylbenzene with carbon dioxide

TiO₂-Al₂O₃ mixed oxides with different compositions ranging from 40wt-% to 95wt-% of TiO₂ were prepared by sol-gel method and impregnated with different amounts of VO _x . Supports and catalysts were characterized by X-ray diffraction (XRD), physisorption, temperature preprogrammed reduction (H₂-TPR), and ammonia temperature programmed desorption (NH₃-TPD). TiO₂ content in the support had obvious effect on the crystal structure, texture characteristic, acid property, and catalytic activity in dehydrogenation of ethylbenzene (EB) with carbon dioxide. The highest catalytic activity was acquired when the TiO₂ content was 50 wt-%.     

Preparation and characterization of mesoporous TiO<Subscript>2</Subscript> thin film

Ordered hexagonal mesoporous TiO₂ thin film was prepared by the evaporation-induced self-assembly (EISA) method using triblock copolymer (Pluronic P123) and tetrabutyl orthotitanate (Ti(OBu ⁿ )₄, TBOT) in 1-methoxy-2-propanol (C₄H₁₀O₂, PGME) solvent. The arrangement of mesopores was identified by small-angle X-ray diffraction and transmission electron microscopy (TEM). The well-ordered hexagonal mesoporous TiO₂ had a high specific surface area of 239 m²/g and an average pore size of 6.3 nm. The structure of mesoporous TiO₂ thin film was anatase with a 5.1 nm crystallite. The absorption band shift of the mesoporous TiO₂ toward longer wavelengths as calcined at 350 °C due to the residual carbon.     

CeO<Subscript>2</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript>/ZSM-5 sorbents for high-temperature H<Subscript>2</Subscript>S removal

Performance of CeO₂-La₂O₃/ZSM-5 sorbents for sulfur removal was examined at temperature ranging from 500 oC to 700 oC. The sulfur capacity of 5Ce5La/ZSM-5 was much bigger than that of CeO₂/ZSM-5. H₂ had a negative impact on the sulfidation; however, CO had little influence on sulfur removal. The characterization results showed that CeO₂ and La₂O₃ were well dispersed on ZSM-5 because of the intimate admixing of La₂O₃ and CeO₂, the major sulfidation products were Ce₂O₂S and La₂O₂S, the XRD and SEM results revealed that ZSM-5 structure could remain intact during preparation and sulfidation process, the H₂-TPR showed that the reducibility of CeO₂ can be remarkably enhanced by addition of La.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hollow spheres and their activity in methylene blue photodecomposition

PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO₂ hollow spheres preparation. TiO₂-doped SiO₂ hollow spheres were obtained by using the appropriate amount of Ti(SO₄)₂ solution on SiO₂ hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO₂-doped SiO₂ hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO₂-doped SiO₂ hollow sphere has shown higher surface area in comparison with pure TiO₂ hollow spheres. The 40 wt% TiO₂-doped SiO₂ hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m²g⁻¹. The photodegradation rate of MB using the TiO₂-doped SiO₂ catalyst was much higher than that of pure TiO₂ hollow spheres.     

Preparation of hydrophobic SiO<Subscript>2</Subscript>@(TiO<Subscript>2</Subscript>/MoS<Subscript>2</Subscript>) composite film and its self-cleaning properties

TiO₂/MoS₂ composite was encapsulated by hydrophobic SiO₂ nanoparticles using a sol–gel hydrothermal method with methyltriethoxysilane (MTES), titanium tetrachloride (TiCl₄), and molybdenum disulfide (MoS₂) as raw materials. Then, a novel dual functional composite film with hydrophobicity and photocatalytic activity was fabricated on a glass substrates via the combination of polydimethylsiloxane adhesives and hydrophobic SiO₂@(TiO₂/MoS₂) composite particles. The influence of the mole ratios of MTES to TiO₂/MoS₂ (M:T) on the wettability and photocatalytic activity of the composite film was discussed. The surface morphology, chemical compositions, and hydrophobicity of the composite film on the glass substrate were investigated by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and water contact angle (water CA) measurements. The results indicated that the composite film exhibited stable superhydrophobicity and excellent photocatalytic activity for degradation of methyl orange (MO) even after five continuous cycles of photocatalytic reaction when M/T was 7:1. The water CA and degradation efficiency for MO remained at 154° and 94%, respectively. Further, the composite film showed a good non-sticking characteristic with the water sliding angle (SA) at about 4°. The SiO₂@(TiO₂/MoS₂) composite consisting of hydrophobic SiO₂ nanoparticles and TiO₂/MoS₂ heterostructure could provide synergistic effects for maintaining long-term self-cleaning performance.     

Preparation and characterization of mesoporous TiO<Subscript>2</Subscript>-pillared titanate photocatalyst

Mesoporous anatase TiO₂-pillared titanate has been successfully prepared by the exfoliation-restacking route. The resulting nanocomposite was characterized by powder X-ray diffraction, scanning electron microscope, thermogravimetric analysis, IR and UV–Vis spectroscopy, specific surface area and porosity measurements. It was revealed that the present nanocomposite exhibits greatly expanded specific surface area (~200 m² g⁻¹) with 2.8- and 6.6-nm-in-diameter mesopore structure, and that there exists an electronic coupling between the host titanate sheets and the guest anatase TiO₂ nanoparticles in the pillared system. The results of degradation of methylene blue under ultraviolet and visible radiation show that the present nanocomposite exhibits much higher photocatalytic activities than that of TiO₂ nanoparticles or layered titanate alone, which are based on the bandgap excitation and the dye sensitization.     

Preparation and Characterization of Mesoporous MoO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> Composite with High Surface Area by Self-Supporting and Ammonia Method

Abstract  

A mesoporous MoO₃/TiO₂ composite was prepared from titanate derivative by consecutive self-supporting and ammonia method. All samples were characterized by X-ray Diffraction, N₂ adsorption–desorption, Raman Spectra and Field-Emission Scanning Electron Microscopy. The results showed that mesoporous MoO₃/TiO₂ composite had a higher surface area (173 m²/g) and a better MoO₃ dispersion than that prepared by traditional impregnation (90 m²/g). As for hydrodesulfurization tests, mesoporous MoO₃/TiO₂ composite in this case presented a better catalytic performance, attributed to its high surface area and good dispersion of MoO₃. It can be found that self-supporting played a key role in preparing mesoporous MoO₃/TiO₂ composite with high surface area. Additionally, aqueous ammonia could effectively dissolve excess MoO₃, which helped to obtain mesoporous MoO₃/TiO₂ composite with better dispersion of MoO₃.     

Phase evolution during mechanochemical coreduction of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and TiO<Subscript>2</Subscript> with A

The direct preparation of V-Ti solid solution alloy by coreduction of V₂O₅ and TiO₂ with Al in an attritor mill was investigated. The reduction of V₂O₅ with Al is highly exothermic, whereas reduction of TiO₂ with Al is not sufficiently exothermic for a self-sustaining reaction. A range of compositions of a mixture of V₂O₅ and TiO₂ can be so chosen as to make the overall reduction of V₂O₅ and TiO₂ with Al sufficiently exothermic for a self-sustaining reaction. Initial studies were done to identify the reaction products obtained by reducing V₂O₅ with Al. The reaction yielded the intermetallic phase (Al₃V), V, and Al₂O₃. SEM images indicated melting and solidification of the phases, leading to agglomeration. Further experiments involved mixing appropriate amounts of TiO₂ with V₂O₅ and reducing the mixture with Al. XRD data for products showed the presence of V, V₅Al₈, and Al₂O₃. X-Ray Florescence (XRF) analysis and energy dispersive analyzer (EDAX) of SEM sample images indicated the formation of V-Ti solid solution. Microstructure of the milled charges taken out prior to reaction initiation indicated morphology change in Al powder and agglomeration/segregation of reactants. As a result, the reaction of V₂O₅ with the excess Al at certain regions also promoted the formation of vanadium aluminide.     

Hydrogen Production from Aqueous Solutions of Glycerol on TiO<Subscript>2</Subscript>/Ru-MCM-41 Photocatalysts Using Solar Light

Ru-MCM-41 molecular sieves were prepared (Si/Ru atomic ratio?=?50 or 100) by a hydrothermal method and impregnated with TiO₂. The materials were characterized by XRD, N₂ physisorption, DRS, SEM and TEM. Their potential application to hydrogen production by photolysis of water using solar light was tested in a batch reactor using mixtures of water and glycerol (0–6.85 mol L^?1) at pH varying from 1 to 11. The photocatalytic efficiency under simultaneous UV (0.05 μW cm^?2) and visible light (90.07 W m^?2) irradiation was compared to the activity of TiO₂/MCM-41 (i.e., no Ru incorporated) and commercial Degussa TiO₂ P25. The most active material was 20%TiO₂/Ru-MCM-41(100) whose performance (220.6 µmol g_Ti ^?1 H₂) was approximately 47 times higher than TiO₂ P25. Characterization results showed the deposition of TiO₂ and revealed the formation of RuO₂ on the surface. Hydrogen generation was improved due to higher charge separation at the TiO₂/RuO₂ heterojunction and to the enhancement of visible light absorption caused by surface plasmon resonance (SPR). Hydrogen production increased with glycerol concentration, tending to stabilize around 40.3 µmol h^?1 g_Ti ^?1 above 4 mol L^?1 of glycerol. Hydrogen generation reached its maximum at extreme values of pH (1 and 11).     

Degradation kinetics of recalcitrant organic compounds in a decontamination process with UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> and UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> processes

In this study, degradation aspects and kinetics of organics in a decontamination process were considered in the degradation experiments of advanced oxidation processes (AOP),i.e., UV, UV/H₂O, and UV/H₂O,/TiO₂ systems. In the oxalic acid degradation with different H₂O₂ concentrations, it was found that oxalic acid was degraded with the first order reaction and the highest degradation rate was observed at 0.1 M of hydrogen peroxide. Degradation rate of oxalic acid was much higher than that of citric acid, irrespective of degradation methods, assuming that degradation aspects are related to chemical structures. Of methods, the TiO₂ mediated photocatalysis showed the highest rate constant for oxalic acid and citric acid degradation. It was clearly showed that advanced oxidation processes were effective means to degrade recalcitrant organic compounds existing in a decontamination process.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Combustion of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript>/Al thermit mixtures in steel tubes

Explored was the combustion of Fe₂O₃/TiO₂/Al thermit mixtures in steel tubes upon variation in green composition and with special emphasis on the dependence of combustion temperature T _c and burning velocity U on reaction heat Q. Special attention was given to incompleteness of combustion for compositions with low Q.     

Synergism Between Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Au/TiO<Subscript>2</Subscript> in the Low Temperature Oxidation of Propene

CO impedes the low temperature (<170 °C) oxidation of C₃H₆ on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO₂ to Pt/Al₂O₃ either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T ₅₀) for C₃H₆ oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C₃H₆, 14% O₂, 2% H₂O.     

Effect of La as Promoter in the Photoreduction of CO<Subscript>2</Subscript> Over TiO<Subscript>2</Subscript> Catalysts

In this work, TiO₂ has been modified by treating it thermally together with different proportions (0.5–15 wt%) of La₂O₃. The resulting materials have been extensively characterized by XRD, TEM, N₂ adsorption isotherms, temperature-programmed CO₂ desorption, Raman, UV–Vis photoluminescence and X-ray photoelectron spectroscopies. The activity tests of these materials for the gas-phase photocatalytic reduction of carbon dioxide show that the main products of the reaction are in all cases CO and CH₄, together with H₂ from the parallel reduction of water. After the preparation procedure, La phases are best described as oxycarbonates, and lead to improved activity with respect to TiO₂ with La contents up to 5 wt%. Higher loadings do not, however, lead to further enhanced activity. Retarded electron–hole recombination and enhanced CO₂ adsorption are invoked as the key factors contributing to this activity improvement, which is optimized in the case of 0.5 wt% La leading to higher productions of CO and CH₄ and increased quantum efficiency with respect to titania.