Preparation of Crack-Free Nanocomposite Ceramic Membrane Intermediate Layers on α-alumina Tubular Supports

The objective of this work was to develop a crack-free membrane intermediate layer on tubular ceramic supports via dip-coating. TiO₂ submicron powder, Boehmite as a coupling agent, and SiO2 nanopowder as low melting-point sintering aid were used to deposit a thin and crack-free nanocomposite layer onto α-Al₂O₃ supports. Effects of key parameters such as solid content, number of coated layers, the presence of coupling agent, and a low melting point nanopowder on physicochemical properties like the thickness, microstructure, pore size, pure water flux, and gas permeance of the final modified ceramic supports were investigated. The obtained results showed that after twice coating of support in 3 wt.% bidispersed TiO₂-Boehmite suspension, the pore size of the alumina substrate, ～0.6 micron, was reduced to ～0.1 by the uniform membrane intermediate layers with low permeation resistance could be prepared. Moreover, by adding SiO₂ nanopowder, sintering temperature of intermediate layers decreases considerably (1000 to 700°C).     

The effect of TiO2 particle size on the characteristics of Au–Pd/TiO2 catalysts

The nanocrystalline TiO₂ materials with average crystallite sizes of 9 and 15 nm were synthesized by the solvothermal method and employed as the supports for preparation of bimetallic Au/Pd/TiO₂ catalysts. The average size of Au–Pd alloy particles increased slightly from sub-nano (< 1 nm) to 2–3 nm with increasing TiO₂ crystallite size from 9 to 15 nm. The catalyst performances were evaluated in the liquid-phase selective hydrogenation of 1-heptyne under mild reaction conditions (H₂ 1 bar, 30 °C). The exertion of electronic modification of Pd by Au–Pd alloy formation depended on the TiO₂ crystallite size in which it was more pronounced for Au/Pd on the larger TiO₂ (15 nm) than on the smaller one (9 nm), resulting in higher hydrogenation activity and lower selectivity to 1-heptene on the former catalyst.     

Photodegradation of Molasses Wastewater Using TiO2–ZnO Nanohybrid Photocatalyst Supported on Activated Carbon

Molasses wastewater (MWW) is characterized by high organic loading and a recalcitrant dark brown color. A study was carried out to determine the photocatalytic efficiency of TiO₂–ZnO nanohybrid supported onto activated carbon (AC) for the remediation of MWW. Immobilization of ZnO onto TiO₂ formed TiO₂–ZnO, which was then supported onto AC forming TiO₂–ZnO–AC composite. X-ray diffraction (XRD), scanning electron (SEM), energy-dispersive X-ray (EDX) and Fourier transform infrared (FTIR) spectroscopies, and transmission electron (TEM) microscopy revealed the successful hybridization of TiO₂ and ZnO, and the subsequent support of the hybrid onto AC. Photoluminescence (PL) spectroscopy further revealed a restrained electron-hole pair recombination resulting from both the successful formation of a heterojunction, and the introduction of electron accepting AC support. Photodegradation process was monitored by color and total organic carbon (TOC) reductions. It was observed that TiO₂–ZnO (ratio 3:1) supported onto AC (30% loading) had a higher adsorptive capacity and catalytic activity than bare TiO₂–ZnO resulting in a 14% increment in overall color reduction. UV-photodegradation was found to be very effective for color as compared to TOC reduction, with 96% and 9% reductions, respectively, after 1 hour of irradiation. A pH of 5 was found to be optimum for photodegradation.     

Studies on Permeation of Nd (III) through Supported Liquid Membrane Using DNPPA + TOPO as Carrier

The transport behavior of Nd (III) through a supported liquid membrane (SLM) containing PTFE as support with organophosphorus extractant dinonyl phenyl phosphoric acid (DNPPA) carrier has been studied. The effect of neutral donors such as TOPO (tri-n-octyl phosphine oxide) TBP (tri-n-butyl phosphate), TEHP (tris 2-ethylhexyl phosphate) and Cyanex 923 (a mixture of four trialkyl phosphine oxides) in combination with DNPPA on transport of Nd (III) from HCl across SLM has been examined and the following trend was observed: TOPO > Cyanex 923 > TBP > TEHP. The effect of experimental variables such as feed acidity (0.5 to 5 M HCl), neodymium metal ion concentration (6.94 × 10^?4 to 6.94 × 10^?3 M), DNPPA concentration (0.2 to 0.6 M), stripping reagents in the receiving phase on Nd (III) transport across SLM were investigated. The percentage transport of Nd (III) was 97% after 6 hr run with 0.6 MDNPPA + 0.13 MTOPO as carrier. The permeability of Nd (III) decreased with increase in HCl and Nd (III) concentration in the feed solution. The transport of Nd (III) decreased with increase in membrane thickness as well as with decrease in pore size. Under optimized conditions transport behavior of other rare earths was also investigated independently, the trend observed was: La > Pr ≥ Nd > Sm > Eu > Gd > Tb > Dy > Ho > Er > Tm > Lu ≥ Y.     

Relationship Between the Synthesis and Structure of Ceramic Precursors of the TiO2–CeO2–ZrO2 System

Refractories and Industrial Ceramics - Tetragonal solid solutions based on the TiO2–CeO2–ZrO2 system stable up to 1,350°C were obtained. A method of pH titration of the initial...     

Kinetic Study of Formic Acid Oxidation on Highly Dispersed Carbon Supported Pd–TiO2 Electrocatalyst

The highly dispersed carbon supported Pd–TiO₂ catalyst was prepared by a liquid phase reduction method with intermittent microwave irradiation. The kinetic parameters, such as the charge transfer parameter (α) and the apparent diffusion coefficient (D) of formic acid electrooxidation on a carbon supported Palladium Titanium dioxide (Pd–TiO₂/C) electrode were obtained under the quasi steady-state conditions. The dependence on temperature of the formic oxidation at a Pd–TiO₂/C electrode was also investigated and the activation energy (E _a) at different potentials was obtained.     

Heterogeneous Photocatalytic Degradation of Ibuprofen Over TiO2–Ag Supported on Activated Carbon from Waste Tire Rubber

In recent years it has been discovered that some common use medicines, such as ibuprofen and other nonsteroidal anti-inflammatory drugs, are found in water sources in concentrations that have the potential to affect aquatic organisms. On the other hand, waste used tires are a massive problem for the environment due to the leaching of toxic compounds to soils and water. Also, the exposition to environmental conditions can make them sources of vectors like mosquitoes. In this work, three activated carbon (AC) catalysts derived from waste tire rubber, titanium dioxide and silver were synthesized using the sol–gel method. Morphological characterizations such as SEM and TEM were performed in which, the agglomeration of titanium particles and silver crystals on the surface of the AC is evident. In the XRD analysis, the presence of elemental silver nanoparticles was detected. In the diffuse reflectance spectroscopy analysis, the decrease in the titanium band gap, as well as activity in the visible spectrum, was observed. The photocatalytic tests were performed at pH 3 and 7 in the presence of UV/Vis radiation. These tests show that there are differences between the catalyst in both, UV and visible regions. Adsorption is a major phenomenon for the removal of ibuprofen, followed by photolytic decomposition. In visible spectra, the catalysts show a good performance for the removal of ibuprofen.

     

Vapor Permeation and Pervaporation of Aqueous 2‐Propanol Solutions through the Torlon® Poly(amide imide) Membrane

Abstract

In the present study, vapor permeation and pervaporation of aqueous 2‐propanol mixtures were investigated using Torlon^® poly(amide imide) as a membrane material. Torlon membranes preferentially permeated H₂O from aqueous 2‐PrOH mixtures both by vapor permeation and pervaporation. Diffusion experiments led to the conclusion that both solubility selectivity and diffusivity selectivity showed a preference for H₂O. Solubility selectivity is by far the dominant factor governing permselectivity, and as a result, Torlon membranes showed permselectivity toward water in vapor permeation and pervaporation. The present study showed that Torlon^® poly(amide imide) is a membrane material potentially applicable to the dehydration of water miscible organics.     

High Electrochemical Performance and Stability of Co-Deposited Pd–Au on Phase-Pure Tungsten Carbide for Hydrogen Oxidation

Co-deposited Pd and Au nanoparticles were loaded on phase-pure tungsten mono-carbide (WC) prepared by a polymer-induced carburization method. Among the electrocatalysts, Pd₃Au/WC displayed an excellent electrochemical activity for the hydrogen oxidation reaction comparable to the state-of-the-art Pt/C catalyst both in half-cell tests and single cell tests under proton exchange membrane fuel cell (PEMFC) conditions. This unique and strong synergistic effect was not observed on the carbon support, and thus the crucial role of WC was demonstrated as a strongly interacting support as well as an active component of the electrocatalyst. Dissolution of Pd observed on the carbon support was suppressed in this Pd₃Au/WC electrocatalyst, which showed good stability in a continuous operation for 3,000?min. Thus the proposed electrocatalyst could be a potential alternative anode catalyst of lower cost for PEMFC replacing Pt/C.     

Room Temperature Photocatalytic Oxidation of Carbon Monoxide Over Pd/TiO2–SiO2 Catalysts

The photocatalytic oxidation of carbon monoxide over TiO₂–SiO₂ and Pd/TiO₂–SiO₂ catalysts was studied. The catalyst samples were synthesized by using sol–gel technique coupled with hydrothermal treatment and all samples were hydrothermally treated before calcination in air. The catalyst samples were characterized by XRD, BET and DRIFTS techniques. The photocatalytic activity of the samples was determined by using circulated batch photoreactor coupled with in line gas transmission FTIR cell charged with 2,000 ppm carbon monoxide in air initially over 0.5 g of catalyst sample under 33 W (254 nm) irradiation power. XRD and BET results confirmed the presence of anatase phase and the decrease on the crystallite size of TiO₂ with SiO₂ addition which yield higher surface area and better dispersion of TiO₂ over mesoporous SiO₂. DRIFTS results indicated the presence of surface hydroxyls coordinated to Ti⁴⁺ and Si–O–Ti sites. All samples containing 10–90 % TiO₂ over SiO₂ exhibited significant photo oxidation activity at room temperature. The photocatalytic oxidation rate of carbon monoxide is favored by SiO₂ addition due to high surface area, better dispersion of TiO₂ particles and higher surface defects. The addition of PdO improves the photocatalytic activity significantly and the synergy between the TiO₂ and PdO phases.     

Synthesis of SiC–TiO2 hybrid aerogel via supercritical drying combined PDCs route

The SiC-TiO₂ hybrid aerogels were obtained from polycarbosilane (PCS) and tetrabutyltitanate (TBT) as precursors using supercritical drying and polymer derived ceramics route. The polymer to ceramic conversion and the crystallization behavior were studied by X-ray diffraction (XRD) and transmission electron microscopy (TEM), suggesting the preceramic aerogels converted to the SiC-TiO₂ ceramic aerogels through pyrolysis process at different temperatures. At 1200 °C, the ceramic aerogels were homogeneous with well-distributed element components, composed of rutile TiO₂ and the β-SiC crystalline phases. The results show that the SiC-TiO₂ ceramic aerogels with netwoks structure have 23.36 nm average pore size, high surface area (58 m²/g) and pore volume (0.22 cm³/g).     

Effects of hydrophobicity on the epoxidation of cyclohexene by tert-butyl hydroperoxide on TiO2–SiO2 mixed oxides

The effects of the addition of water to the reaction medium have been investigated for the epoxidation of cyclohexene by tert-butyl hydroperoxide catalysed by a series of TiO₂–SiO₂ mixed oxides prepared by a sol–gel procedure in which a fraction F of tetraethoxysilane is substituted by phenyltriethoxysilane. Infrared spectrometry gives a direct evidence of the retention of Si–C bonds by the solid. The substitution of OH groups by phenyls modifies the catalytic properties: for F=0, the solid is hydrophilic, inhibited by water and catalyses the hydrolysis of TBHP as competitive side reaction, whereas the solid obtained for F=0.2 is hydrophobic and not sensitive to a water/TBHP ratio as large as 1. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of addition of TiO2 on reaction sintered MgO–Al2O3 spinels

Three different spinel compositions with MgO:Al₂O₃ molar ratios 2:1, 1:1 and 1:2 were studied using TiO₂ as an additive up to 2 wt.%. Solid state reaction sintering technique was employed for all the compositions in the temperature range of 1550–1650°C. Attrition milling was done for the reduction of particle size. Sintered products were characterised in terms of densification and shrinkage studies, phase analysis, strength evaluation both at ambient temperature and at elevated temperature, strength retention after different number of thermal cycles at 1000°C, quantitative elemental analysis and microstructural studies.     

Hydroformylation of 1-Hexene on Silicalite-1 Zeolite Membrane Coated Pd–Co/A.C. Catalyst

A core–shell-like encapsulated catalyst was designed where Pd–Co/activated carbon (A.C.) catalyst was enwrapped by silicalite-1 zeolite membrane, which greatly improved normal to iso ratio of aldehyde products during hydroformylation of 1-hexene with syngas (CO + H₂), due to its spatial confined structure and shape selective property derived from zeolite membrane.     

Influence of precursors on formation of TiO2–CrTaO4 rutile solid solutions

Abstract

Rutile solid solutions Cr_x Ti_1-2xTa_xO₂ (0 < x < 0·5) have been synthesised by: firing mixtures of Cr₂O₃ , Ta₂O₅ , and TiO₂ (anatase); firing colloidal gels obtained from TiCl₄ , TaCl₅ , and CrCl₃ . 6H₂O; and firing polymeric gels prepared from Ti⁴⁺ isopropoxide, Ta⁵⁺ethoxide, and Cr³⁺ acetylacetonate at 300–1300°C. Samples were characterised by XRD, differential thermal and thermogravimetric analysis, UV visible spectroscopy, Cielab colour parameter measurements, and electron microscopy. In samples synthesised from oxide mixtures, CrTaO₄ (rutile structure) appeared as an intermediate phase in the formation of the solid solutions and a positive departure from Vegard's law was observed. Ta₂O₅ segregation in gel samples seems to prevent the formation of material consisting only of rutile. The distortion of MO₆ octahedra varies as x increases. The chemical, structural, and thermal stability, and the colouration obtained on glazes containing 3 wt-%samples, indicate their potential for use as ceramic pigments. Under the experimental conditions used, the materials prepared by sol–gel synthesis were not found to be better than those prepared from oxide mixtures.     

Production of middle distillate through hydrocracking of paraffin wax over Pd/SiO2–Al2O3 catalysts

Pd/SiO₂–Al₂O₃ catalysts (Pd/SA-X) with different SiO₂ contents (X, wt%) were prepared for use in the production of middle distillate (C₁₀–C₂₀) through hydrocracking of paraffin wax. The effect of SiO₂ content of Pd/SA-X catalysts on their physicochemical properties and catalytic performance in the hydrocracking of paraffin wax was investigated. High surface area and well-developed mesopores of Pd/SA-X catalysts improved the dispersion of Pd species on the SiO₂–Al₂O₃ support. Acidity of Pd/SA-X catalysts determined by NH₃-TPD experiments showed a volcano-shaped trend with respect to SiO₂ content. Conversion of paraffin wax increased with increasing acidity of the catalyst, while selectivity for middle distillate decreased with increasing acidity of the catalyst. Yield for middle distillate showed a volcano-shaped curve with respect to acidity of the catalyst. This indicates that acidity of Pd/SA-X catalysts played an important role in determining the catalytic performance in the hydrocraking of paraffin wax. Among the catalyst tested, Pd/SA-69 with moderate acidity showed the highest yield for middle distillate.     

Structural Effect of Pincer Pd(II)–ONO Complexes Modified with Acylthiourea on Sizes of the In Situ Generated Pd Nanoparticles During Heck Coupling Reaction

Catalysis Letters - The Pd nanoparticles generated in situ from Pd–pincer complexes catalyzed Heck coupling reaction. For this purpose, new Pd(II)–ONO pincer complexes (1–4)...     

Anatase–rutile transformation of TiO2 sol–gel coatings deposited on different substrates

Titanium dioxide is widely used in a lot of applications. The properties of TiO₂ strongly depend on its phase composition. The transformation temperature between phases is influenced by a lot of factors. One of them is a type of substrate under the TiO₂ film. In presented work, thin films of TiO₂ were deposited by the sol–gel method on silicon, stainless steel (304 L) and Co–Cr–Mo alloy (Vitallium). The process of anatase–rutile phase transformation was investigated by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) studies of deposited coatings. The results were compared with anatase–rutile transformations temperature of TiO₂ powders obtained by analogous sol–gel process. The temperature of anatase–rutile phase transformation changed in the range of 700–1000 °C and strongly depends on a kind of substrate. It was found that anatase–rutile transformation of TiO₂ coating proceeded at a higher temperature than rutilization of titania powders.