Formation and size control of titanium particles by cathode discharge electrolysis of molten chloride

Cathode discharge electrolysis of LiCl–KCl–K₂TiF₆ has been conducted under 1 atm of Ar. Near spherical particles consisting of metallic or partially oxidized titanium in the core and TiO₂ in the surface layer were obtained. The Ti particles are originally formed in the melt by reduction of Ti ions, and a surface TiO₂ layer is formed when the Ti particles are exposed to air or water. The particle sizes were in the range 10–400 nm, and were strongly dependent on electrolytic conditions, such as quantity of electricity, K₂TiF₆ concentration, bath temperature and current per melt volume. The particle growth mechanism was also investigated, and it was confirmed that reduction of ions at particle surfaces is involved in particle growth.     

Preparation and characterization of multicomponent porous materials prepared by the sol-gel process

An experimental strategy was developed to obtain transparent Si-Al-Ti-Ni-Mo and Si-Zr-Ti-Ni-Mo sols via the sol-gel process. The sol was prepared from Si(OEt)₄ (TEOS), Al(OBu^s)₃ (OBu^s: C₂H₅CH(CH₃)O), Ti(OEt)₄ (OEt: OCH₂CH₃), Zr(OPrⁿ)₄ (OPrⁿ: OCH₂CH₂CH₃). In both cases nickel nitrate hexahydrate (Ni(NO₃)₂ · 6H₂O) and ammonium heptamolybdate tetrahydrate ((NH₄)₆Mo₇O₂₄ · 4H₂O) were the Ni and Mo sources, respectively. The sols were characterized by Fourier Transform Infrared Spectroscopy (FTIR). Assignments of the simultaneous formation of the Si-O-Al, Si-O-Ti, Si-O-Ni, and Si-O-Zr bonds were done. The sols were polymerized at room temperature (293 K) to obtain gels, and these were dried at 423 K and calcined at 573, 853 and 893 K in air. The characterization techniques used were small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), scanning electron microscopy (SEM), and ²⁹Si and ²⁷Al magic angle spinning nuclear magnetic resonance (MAS NMR). The density of the solids was measured following ASTM method D-4892 and the porosity and surface area were determined by N₂ adsorption/desorption isotherms. The corresponding average pore diameters were evaluated using the BJH, HK, and DA methods.     

Preparation and magnetic properties of iron titanium oxide nanotube arrays

FeTi alloy was prepared by a vacuum smelting method, iron titanium oxide nanotube arrays have been made directly by anodization of the FeTi alloy. Morphologies and microstructures of the samples were characterized by scanning electron microscope, transmission electron microscope, and X-ray diffractometer. Influences of temperature and H₂O concentration on the morphologies of the nanotube arrays have been discussed in detail. Magnetic properties of the samples have also been investigated. The as-prepared samples were amorphous. When annealed at 500 °C and 550 °C, pesudobrookite Fe₂TiO₅ was obtained. At 600 °C, there were mixed Fe₂TiO₅, rutile TiO₂, and α-Fe₂O₃. Magnetic performance of the nanotube arrays exhibited high sensitivity to temperature and changed interestingly upon annealing. The values of the coercivity and remanence were 340 Oe and 0.061 emu/g respectively for the sample annealed at 550 °C.     

Preparation of porous TiO2 by a novel freeze casting

Highly porous and open interconnected pore structural TiO₂ were prepared by a novel freeze casting method. In the experiment, the well-dispersed aqueous slurries were first frozen, and then dried at a reduced vacuum. Since the sublimation of ice crystals developed in the freezing process, the green bodies with highly porous were obtained. The phase composition and the microstructure of the sintered samples were characterized by XRD, SEM, porosity and the pore size distribution was measured by mercury porosimetry. The results demonstrated that the PVA concentration in the slurries remarkably affect the microstructure of TiO₂ ceramics. The pore morphology of TiO₂ ceramics with 3 wt.% polyvinyl alcohol (PVA) addition was dendritic, and however, the pore morphology of TiO₂ ceramics with 6 wt.% PVA addition changed into columnar. The reason for the variation of the pore morphology was ascribed to the effect of the PVA gelation on the growth behavior of the ice crystals.     

Preparation of nanometer dispersed polypropylene/polystyrene interpenetrating network using supercritical CO2 as a swelling agent

Nanometer dispersed polypropylene/polystyrene (PP/PS) interpenetrating networks (IPNs) have been prepared by the radical polymerization and crosslinking of styrene (St) within supercritical (SC) CO₂-swollen PP substrates. In this method, monomer St, crosslinking agent divinyl benzene (DVB), and the initiator benzoyl peroxide were first impregnated into PP matrix using SC CO₂ as a solvent and swelling agent at 35.0 °C, and then the polymerization and crosslinking were carried out at 120 °C. The composition of the IPNs can be controlled by SC CO₂ pressure, concentrations of St and DVB in the fluid phase. Transmission electron microscopy shows that the PS is homogeneously dispersed in the IPNs and its phase size is in the range of 20-30 nm. The impact strength, tensile strength, and elongation-at-break of the PP/PS IPNs increase with increasing PS percentage in the IPNs.     

Photocatalysis of methylene blue on titanium dioxide nanoparticles synthesized by modified sol-hydrothermal process of TiCl4

Titanium dioxide nanoparticles were synthesized by the hydrolysis and condensation of TiCl₄, an economic titanium precursor, in a mixed solvent of iso-propyl alcohol and water. As-prepared powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), energy filtering transmission electron microscopy (EF-TEM). To examine the photocatalytic activity of the as-prepared TiO₂, the photodegradation of MB which is a typical dye resistant to biodegradation has been investigated on TiO₂ powders in aqueous heterogeneous suspensions. The photocatalytic activity of TiO₂ powders prepared by the hydrolysis of TiCl₄ in the mixed solutions of iso-PrOH/H₂O exceeded that of commercial TiO₂ powders. The apparent first order rate constants (k _app) for the photodegradation of methylene blue (MB) showed a good correlation with the absorbance area obtained by UV-VIS DRS on wavelength in the limits of used lamp emission 300∼420 nm.     

The growth of interfacial compounds between titanium dioxide and bismuth oxide

The growth of interfacial compounds between TiO₂ and Bi₂O₃ during transient liquid phase bonding at 900, 1000 and 1100 °C for various times was investigated. The microstructures and compositions of compounds in joints were analyzed by means of SEM and EPMA. It was found that the compound Bi₄Ti₃O₁₂ forms initially and replaces the Bi₂O₃ interlayer. Bi₂Ti₄O₁₁ then arises at the interface between Bi₄Ti₃O₁₂ and TiO₂ and the metastable Bi₂Ti₂O₇ phase appears last at the interface between Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁. The modes and activation energies of the growth of Bi₄Ti₃O₁₂ and Bi₂Ti₄O₁₁ were determined respectively. Holes in the middle of the joint heated at 1100 °C for 24 h were also found.     

Alkylation of aldehydes with methanol over titanium oxide catalysts

The methylation of various aldehydes, such as acetaldehyde, propionaldehyde, and phenylacetaldehyde over titanium oxidesupported vanadium oxide was studied under atmospheric pressure and temperatures of 250–400°C. The catalyst properties of titanium oxide can be enhanced only by addition of a fairly small amount of vanadium. High-temperature treatment transforms titanium oxide, the support, from anatase to rutile, which causes the catalysts to lose their catalytic properties. The reactivity of these can be ranked in the following order: acetaldehyde > propionaldehyde > phenylacetaldehyde. The steric effect of the substituted groups in propionaldehyde or phenylacetaldehyde may prevent self-condensation to form oligomers and to give a high selectivity of alkylated products.     

An aqueous synthesis of photocatalyst by selective dissolution of titanium oxide/hydroxyapatite composite

A novel synthesis method of a highly active photocatalyst was proposed. Titanium dioxide (TiO₂) nano-particles were prepared by three-step procedure, precipitation of hydroxyapatite (HAp) on TiO₂ particles, heat treatment of the TiO₂/HAp composites, and acid treatment in hydrochloric acid. The unique point of this procedure is the selective dissolution of HAp to obtain exposed TiO₂ surfaces. The HAp precipitation was achieved by stirring TiO₂ powders in the mixtures of Ca(NO₃)₂ and NH₄H₂PO₄ aqueous solutions at pH 8.5. Then, the heat-treated TiO₂/HAp composites were treated with hydrochloric acid. The precipitated HAp avoided the direct contact of TiO₂ particles and suppressed the phase transformation from anatase-to-rutile >200 °C. The HAp also suppressed a decrease of specific surface area of TiO₂ during the heat treatment. The photocatalytic activities were evaluated from an absorbance decrease of methylene blue (MB) under ultraviolet (UV) irradiation. The MB photodecomposition was approximated to the first-order reaction and the reaction rate constants of the obtained TiO₂ powders heated at various temperatures were higher than those of conventional TiO₂ powders heated at same temperatures. The enhanced photocatalytic activity is attributed to the suppression effects for the phase transformation to rutile phase and the decreasing of specific surface area in the heat treatment.     

Impedance model of electrolyte-insulator-semiconductor structure with porous silicon semiconductor

We present a generic impedance model for the porous silicon|electrolyte structure that is valid for a range of interfacial layers and bias in these structures. The model is validated using three widely different porous structures: short irregular silicon columns and pores, long cylindrical silicon columns and pores; and branched interconnected silicon microchannels and voids in a mesh structure. The model incorporates appropriate RC or constant phase elements for the different parts of the porous structure, namely, the top of the silicon columns (channels)|electrolyte, the column (channel) walls|electrolyte in the pores/channels, and the electrolyte|semiconductor interface at the base of the pores/channels. This physical model underscores the effects of column/channel depletion and accumulation, either due to applied bias or change of surface charge, to the impedance spectra of the device. The model helps to explain why the porosity needs to be optimized for specific applications and helps as a measurement tool for optimization.     

Photocatalytic activity of porous titania nanocrystals prepared by nanoscale permeation process in supercritical CO2: Effects of supercritical conditions

Porous TiO₂ nanocrystals (PTN) were synthesized using activated carbon templates with supercritical CO₂ by using the nanoscale permeation (NP) process. The photoactivity of PTN was tested by methylene blue (MB) degradation. Compared with the commercially available P-25, all PTN exhibited significant photocatalytic degradation of MB mainly due to their porous structure with high surface area, high hydroxy concentration and small crystalline size. The optimum temperature and pressure are found to be 60 °C and 26 MPa, under which obtained PTN-1 shows the highest photoactivity and slow deactivation for MB degradation after 15 trials.     

Optimization of atrazine removal from synthetic groundwater by electrooxidation process using titanium dioxide and graphite electrodes

ABSTRACT

Atrazine is used in agriculture and is known for its high toxicity. It therefore poses a risk to surface and ground waters, and human life. In this study, an electrochemical method was optimized for atrazine removal from SGW using TiO₂ and graphite electrodes. A comparison between one factor at a time period optimization and Box-Behnken design (BBD) optimization using RSM was carried out to select the optimum conditions. The results show excellent atrazine removal efficiency (99.70%) and close optimum conditions for both applied methods (pH 7 and 7.4; current 2.5 and 2 A and time 14 and 12.12 min, respectively).     

Low temperature deposition of titanium oxide containing thin films in trench features from titanium diisopropoxide bis(dipivaloylmethanate) in supercritical CO2

We studied supercritical carbon dioxide fluid deposition of titanium oxide (TiO₂) in trench features on Si substrates using a flow-type deposition apparatus from titanium diisopropoxide bis(dipivaloylmethanate), aiming at fabricating conformal films at a relatively low temperature. We investigated the deposition rate and step coverage under a fluid temperature from 40 to 60 °C, a pressure from 8.0 to 10.0 MPa, and a substrate temperature from 80 to 120 °C. They were dependent on the fluid density, indicating that the solubility difference between the bulk fluid and the neighborhood of the substrate surface plays a decisive role for the deposition. An excellent conformal filling of the trench features was achieved from the fluid of 60 °C under 8 MPa on the substrate kept at 80–100 °C. The XPS spectra of the deposited film suggested partial formation of TiO₂, and the XRD spectra showed the existence of some crystalline TiO₂ (anatase).     

Photocatalytic degradation of methylene blue and acetaldehyde by TiO<Subscript>2</Subscript>/glaze coated porous red clay tile

Nanosized TiO₂ sol synthesized by sol-gel method was successfully coated on the porous red clay tile (PRC tile) with micrometer sized pores. PRC tile was first coated with a low-firing glaze (glaze-coated PRC tile) and then TiO₂ sol was coated on the glaze layer. A low-fired glaze was prepared at various blending ratios with frit and feldspar, and a blending ratio glazed at 700 °C was selected as an optimum condition. Then TiO₂ sol synthesized from TTIP was dip-coated on the glazed layer (TiO₂/glaze-coated PRC tile), and it was calcined again at 500 °C. Here, these optimum calcination temperatures were selected to derive a strong bonding by a partial sintering between TiO₂ sol particles and glaze layer. Photocatalytic activity on the TiO₂/glaze-coated PRC tile was evaluated by the extent of photocatalytic degradation of methylene blue and acetaldehyde. Methylene blue with the high concentration of 150 mg/l on the surface of TiO₂/glaze-coated PRC tile was almost photodegraded within 5 hours under the condition of average UV intensity of 0.275 mW/cm₂, while no photodegradation reaction of methylene blue occurred on the glaze-coated PRC tile without TiO₂. Another photocatalytic activity was also evaluated by measuring the extent of photocatalytic degradation of gaseous acetaldehyde. The photodegradation efficiency in TiO₂/glaze-coated PRC tile showed about 77% photocatalytic degradation of acetaldehyde from 45,480 mg/l to 10,536 mg/l after the UV irradiation of 14 hours, but only about 16% in the case of the glaze-coated PRC tile.     

Electrocatalytic activity of Pt nanoparticles deposited on porous TiO2 supports toward methanol oxidation

Porous TiO₂ thin films were prepared on the Si substrate by hydrothermal method, and used as the Pt electrocatalyst support for methanol oxidation study. Well-dispersed Pt nanoparticles with a particle size of 5–7 nm were pulse-electrodeposited on the porous TiO₂ support, which was mainly composed of the anatase phase after an annealing at 600 °C in vacuum. Cyclic voltammetry (CV) and CO stripping measurements showed that the Pt/TiO₂ electrode had a high electrocatalytic activity toward methanol oxidation and an excellent CO tolerance. The excellent electrocatalytic performance of the electrode is ascribed to the synergistic effect of Pt nanoparticles and the porous TiO₂ support on CO oxidation. The strong electronic interaction between Pt and the TiO₂ support may modify CO chemisorption properties on Pt nanoparticles, thereby facilitating CO oxidation on Pt nanoparticles via the bifunctional mechanism and thus improving the electrocatalytic activity of the Pt catalyst toward methanol oxidation.     

Evaluating the effectiveness of photocatalysts based on titanium dioxide in the degradation of the dye Ponceau 4R

The performance of different titanium dioxide (TiO₂) catalysts and a composite based on the association between TiO₂ P25 and Zinc Phthalocyanine (TiO₂/ZnPc 1.6%) was evaluated in the photocatalytic degradation of the dye Ponceau 4R (C.I. 16255). The results show that the composite presents a better performance than the other, reaching about 50% mineralization of the dye in 120 min of reaction, around three times higher than that observed under the action of pure TiO₂ P25, although this catalyst presents a quantum yield of hydroxyl radical generation about three times higher than that estimated for the composite. This result seems to be a consequence of the synergism between the electronically excited ZnPc aggregates and the TiO₂ surface.A parallel study, based on methods from quantum mechanics also suggested the most feasible routes for the photodegradation of the dye in the absence of the catalyst.     

Preparation and performance of anatase-loaded porous carbons for water purification

Fine particles of photoactive anatase-type TiO₂ were loaded on activated carbon and carbon spheres through the hydrolysis of titanium oxysulfate under autogenous hydrothermal conditions. Their photoactivity and adsorptivity were evaluated separately by the measurements of relative concentration of methylene blue (MB) and iminoctadine triacetate (IT) remained in the solution either in the dark or under UV irradiation. Activated carbon could adsorb a large amount of MB but only a small amount of IT, and carbon spheres could adsorb only a small amount of MB. Loading of anatase under hydrothermal conditions was found to occur preferentially at the entrance of pores on the surface of substrate carbon in the beginning of deposition and to result in the reduction of specific surface area and consequently of the adsorption rate of MB. Further hydrothermal treatment was found to give homogeneous coverage of the surface of activated carbon by anatase fine particles. By UV irradiation after the saturation of adsorption in the dark, a marked decrease in concentration of MB and IT was observed, which recovered a high adsorptivity of activated carbon. Through repetitive measurements of concentration decrease in the solution in the dark and under UV irradiation, it was proved that MB and IT, which were adsorbed in the dark, could be decomposed under UV irradiation.     

Preparation of nano-TiO2/polyurethane emulsions via in situ RAFT polymerization

Stable nano-TiO₂/polyurethane (PU) emulsions were prepared via in situ reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of 2-hydroxyethyl acrylate (HEA)-capped PU macromonomer, using azobisisobutyronitrile (AIBN) as a radical initiator and 2-{[(butylsulfanyl)carbonothioyl]sulfanyl} propanoic acid (BCSPA) anchored onto TiO₂ nanoparticles (TiO₂-BCSPA) as a RAFT agent. When the molar ratio of AIBN to TiO₂-BCSPA was changed from 1:3 to 1:10, the polydispersity index (PDI) of polymers in the emulsions decreased from 1.83 to 1.06, due to more effective RAFT polymerization in the emulsions. The TiO₂ nanofillers were well-dispersed throughout the polymer films. The tensile strengths of the nanocomposite films were significantly enhanced due to coordination bonding between the TiO₂ nanofillers and the –COOH end groups of the polymers, as evidenced by the FT-IR spectral data.