Sonochemical fabrication of fluorinated mesoporous titanium dioxide microspheres

A sonochemical-hydrothermal method for preparing fluorinated mesoporous TiO₂ microspheres was developed. Formation of mesoporous TiO₂ and doping of fluorine was achieved by sonication and then hydrothermal treatment of a solution containing titanium isopropoxide, template, and sodium fluoride. The as-synthesized TiO₂ microspheres were characterized by X-ray diffraction (XRD), Fourier translation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX) spectroscopy, photoluminescence spectroscopy (PL), and BET surface areas. The P123 template was removed completely during the hydrothermal and washing steps, which was different from the conventional calcination treatment. The as- synthesized TiO₂ microspheres had good crystallinity and high stability. Results from the photocatalytic degradation of methylene blue (MB) showed that fluorination could remarkably improve the photocatalytic activity of titanium dioxide.     

Macroporous ordered titanium dioxide (TiO2) inverse opal as a new label-free immunosensor

Photonic crystal sensing materials have been validated that they are very sensitive to refractive index changes. Herein, three-dimensionally ordered macroporous (3DOM) (>50 nm) TiO₂ inverse opal film has been fabricated by the self-assembly technique. Based on the TiO₂ inverse opal film, the optical spectrometer was established for label-free immunosensor. The sensing performance of the 3DOM TiO₂ was investigated using human IgG/goat anti-human IgG couple, which showed that the sensitivity of 3DOM TiO₂ inverse opal film could reach to 1 μg mL⁻¹ (equivalent to 1.5 pg mm⁻²) of protein concentration detection limit. The 3DOM TiO₂ inverse opal has a large internal surface area, low fluorescence background and unique optical properties. These characteristics indicated the feasibility of 3DOM TiO₂ inverse opal in label-free immunoassay.     

Low-temperature synthesis of photocatalytic TiO2 thin film from aqueous anatase precursor sols

Anatase TiO₂ sols (RS) were synthesized by peptizing the hydrolysis of titanyl sulfate in abundant hydrogen peroxide solution and subsequent reflux to enhance crystallization. The influences of various reflux time on crystallinity, morphology, and size of the obtained TiO₂ sol and dried TiO₂ film particles were investigated. At room temperature, crystalline TiO₂ thin film was deposited on glass silde from the as prepared TiO₂ sol by dip-coating method. No further thermal posttreatment was required to eliminate organics from the film or to induce titania crystallization. TiO₂ thin film on substrates could be thickened by means of consecutive dip-coating process. Titania film thus obtained was transparent and showed proper adherence. The photocatalytic activities of the TiO₂ thin film was assessed by the degradation of methyl orange in aqueous solution. The preparation process of photocatalytic TiO₂ thin film was quite simple and a low-temperature route.     

Selective extraction of phospholipids from dairy products by micro-solid phase extraction based on titanium dioxide microcolumns followed by MALDI-TOF-MS analysis

A new micro-solid phase extraction (μ-SPE) procedure based on titanium dioxide microcolumns was developed for the selective extraction of phospholipids (PLs) from dairy products before matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) analysis. All the extraction steps (loading, washing, and elution) have been optimized using a synthetic mixture of PLs standard and the procedure was subsequently applied to food samples such as milk, chocolate milk and butter. The whole method demonstrated to be simpler than traditional approaches and it appears very promising for a rapid PLs screening and characterization also in biological matrices.     

A novel acrylate carrying a hindered phenol moiety as monomer and terminator in radical polymerization

Radical polymerizations of methyl methacrylate (MMA), styrene (St), and vinyl acetate (VAc) were carried out in the presence of a novel phenyl acrylate derivative bearing a hindered phenol moiety (HPA). It has been clarified that HPA acts as a retarder and inhibitor for the polymerizations of MMA and VAc, respectively, and that in the polymerization of St it behaves as a monomer to give a copolymer. These additive effects were interpreted in terms of intramolecular transfer of the phenolic hydrogen in competition with propagation of the HPA radical to monomers. © 1994 John Wiley & Sons, Inc.     

荧光素-纳米二氧化钛表面复合及光诱导电子转移

本文研究了中性条件下TiO2纳米粒子与双阴离子态荧光素F2-的结合能力,发现所形成的复合物与文献报道的强酸性条件下TiO2-质子化荧光素H3F+复合物相比,结构与性能均很不同,F2--TiO2复合物吸收光谱红移30 nm以上且发射荧光。用UV-vis吸收光谱测定了复合物的结合常数、用稳态和瞬态荧光光谱测定了复合物的荧光效率和寿命分别为0.14和1.08 ns,与相应自由态F2-的测定值0.92和4.68 ns相比,复合物荧光效率和寿命都有很大的降低,这是由于复合物内部光诱导电子转移所致,因这一电子转移是热力学上非常有利的过程,其自由能变化达1.1 eV。光致电子转移的速率常数为7.1×108s-1,是其它竞争过程的3倍以上,复合物内光诱导电子转移效率达77%。     

Titanium dioxide plasma treatment

After a review of the literature on titanium production under plasma conditions, the main parameters controlling the reactions (residence time, type and relative quantity of reducer, reaction temperature, etc.) are emphasized. The controlled-atmosphere chamber where the rutile or anatase particles are heated and partly reduced in a crucible by a d.c. plasma torch with Ar-H₂ as plasma gas is described. Study of the temperature dependence of the Gibbs free energy allows one to explain, at least qualitatively, the experimental results obtained which correspond at best to 10% (weight) of TiO₂ reduced to TiO by carbon.     

Catalytic oxidation of no to NO2 over Cr/TiO2 and Cu/TiO2 under oxidizing atmosphere

The catalytic activity of Cr/TiO₂ and Cu/TiO₂ for the oxidation of NO under an oxidizing atmosphere has been examined. Both catalysts had excellent ability for the oxidation of NO to NO₂ in the temperature range of 350–400°C.     

p-Aminophenylacetic acid-mediated synthesis of monodispersed titanium oxide hybrid microspheres in ethanol solution

Monodispersed TiO₂ hybrid microspheres were prepared via the hydrolysis of titanium isopropoxide (TTIP) in ethanol solution containing p-aminophenylacetic acid (APA). The effects of the APA:TTIP molar ratio, water content, reaction time and reaction temperature on the morphology of the resultant spheres were investigated. The products were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and X-ray diffraction. It was demonstrated that the diameters of the resultant TiO₂ spheres could be tuned in the range of 380–800 nm by changing the APA:TTIP molar ratio (1:3 to 3:1) and water content (1–3 v/v%) in the reaction medium, and that increasing the APA:TTIP molar ratio led to larger TiO₂ hybrid spheres while increasing the water content decreased their size. The loading content of APA in the hybrid spheres could reach 20 wt.% as they were prepared with the APA:TTIP ratio of 3:1. The possible formation mechanism of the hybrid spheres was also investigated. It was found that APA slowed down the hydrolysis rate of the titanium precursor so that resulted in the formation of the TiO₂ spheres. In addition, the APA present in TiO₂ spheres acted as a reducing agent to in situ convert HAuCl₄ into metallic Au on the surface of the TiO₂ spheres. The catalytic activity of the resultant Au/APA–TiO₂ composite was examined using transfer hydrogenation of phenylacetone with 2-propanol, and it was indicated that the catalyst displayed high efficiency for this reaction.     

Low temperature CO oxidation on Au/TiO2 sol-gel catalysts

A comparative study on Au/TiO₂catalysts prepared by impregnation with HAuCl₄of commercial TiO₂ or by impregnation of sol-gel derived TiO₂has been carried out during CO oxidation. Specific surface areas and mean Au particle of 49 and 74 m²/g and 35 and 25 Å were obtained for impregnated commercial TiO₂ and sol-gel preparations, respectively. XRD patterns shown that in sol-gel derived TiO₂ only anatase phase was identified, while in commercial TiO₂ anatase and rutile phases co-exist. Titania support effect on Au activity for the oxidation of CO has been observed. The light-off during the reaction on Au/TiO₂initiates at 50°C, whereas for commercial impregnated TiO₂ catalyst the light-off initiates at 200°C.     

Electrocatalytic oxidation of nitric oxide at nano-TiO2/Nafion composite film modified glassy carbon electrode

A novel nanocrystalline TiO₂ (nano-TiO₂) and Nafion composite film modified glassy carbon electrode has been developed for the determination of nitric oxide (NO) radical in an aqueous solution. This modified electrode can be employed as a NO sensor with a low detection limit, fast response, high sensitivity and selectivity. Two apparent anodic peaks were observed at 0.67 and 0.95 V at the nano-TiO₂ modified glassy carbon electrode by differential pulse voltammetry (DPV). After further modification with a thin film of Nafion, which was capable of preventing some anionic interference such as nitrite and ascorbic acid, only one peak appeared and the peak current enhanced greatly. The chronocoulometric experimental results showed NO was oxidized by one-electron transfer reaction at the composite film modified electrode. The amperometric responses increased linearly with the concentrations of NO ranging from 3.6×10⁻⁷ mol/L to 5.4×10⁻⁵ mol/L. The detection limit was estimated to be 5.4×10⁻⁸ mol/L. In this sensor system, the modification film provides complete selectivity for NO over nitrite anions (NO₂⁻).     

Analysis of preparation of TiO<Subscript>2</Subscript> particles by diffusion flame reactor for photodegradation of phenol and toluene

TiO₂ nanoparticles were produced in the diffusion flame reactor, and the size and anatase/rutile content of TiO₂ were examined by a Particle Size Analyzer and X-ray diffraction, respectively. Increase in fuel/O₂ ratio, initial concentration of TiCl₄ or total gas flow rate causes the larger particle size and the higher rutile composition. The photocatalytic activities of TiO₂ powders were tested on the decompositions of phenol and toluene in the aqueous solution under UV irradiation. The degradation rate increases as the TiO₂ particle size decreases and as the initial concentration of phenol or toluene increases. The photodegradation rate of phenol by TiO₂ particles is higher than that of toluene at the same process conditions. The computational method was used to simulate the gas temperature, velocity and species mass fractions inside the diffusion flame reactor during synthesis of TiO₂ nanoparticles. The measured and simulated temperature results were compared on several positions above the burner and both of them show good agreements. The typical contours of TiCl₄, TiO₂ mass fractions and gas velocities in flame reactor were presented.     

Mechanical and thermal properties of nanosized titanium dioxide filled rigid poly(vinyl chloride)

Nano-sized rod-like titanium dioxide (TiO2) filled rigid poly(vinyl chloride) (PVC) nanocomposites were prepared by using injection-molding method. Vicat, Charpy impact and tensile tests as well as thermogravimetric and dynamic mechanical analyses were used to characterize the structure and properties of the nanocomposites. The results showed that nano-TiO2 could improve Vicat softening temperature and also improve thermal stability of PVC during the stages of dehydrochlorination and formation of carbonaceous conjugated polyene sequences, which can be ascribed to restriction of the nanoparticles on the segmental relaxation as being evidenced by raises in glass transition and β-relaxation temperatures of PVC upon filling TiO2. Addition of TiO2 nanoparticles less than 40 phr (parts per hundreds of resin) could significantly improve impact strength of the composites while the TiO2 agglomeration at high contents leads to a reduction in impact toughness.     

Structural characterization of Th-doped TiO2 photocatalyst and its extension of response to solar light for photocatalytic oxidation of oryzalin pesticide: a comparative study

The degradation efficiency of Th-doped TiO₂ / TiO₂ photocatalysts were investigated under UV and solar light illumination. The model compound chosen for the study was Oryzalin (OZ). Doping of inner transition metal ion Th was intended to modify the electronic properties of TiO₂. The Th-doped TiO₂ were synthesized by incorporating 0.02, 0.04, 0.06, and 0.1 atom percentage of Th into the TiO₂ lattice by solid-state reaction. The stochiometry of the prepared samples is Ti_1−xTh_xO₂, where ‘x’ is the percentage of Th. The samples were characterized by UV-Visible absorption, UV-Visible -Diffused reflectance spectra, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Analysis (EDX) and X-ray Diffraction (XRD). The pore size and surface area of these samples were studied by Brunauer, Emmett and Teller (BET) adsorption method. It was found that metal ion doping at various percentage compositions enables a large shift in the absorption band of the TiO₂ towards visible light region. This is due to the formation of various mid band gaps at 2.84 eV, 2.804 eV, 2.66 eV, and 2.55 eV. The extent of degradation of the pesticide was followed by UV-Visible spectroscopy and GC-MS methods. Based on the spectral analysis, the probable degradation reaction mechanism for OZ is proposed. These results indicate that Th-doped TiO₂ with the modified electronic properties is a good catalyst under solar light irradiation. But these particles show marginal variation in rates under UV-illumination. All the photodegradation reactions follow the first order kinetics.      

Comparison of decomposition procedures for analysis of titanium dioxide using inductively coupled plasma optical emission spectrometry

The determination of impurities in titanium dioxide pigments, such as Al, Cd, Cr, Fe, Mn, P, Zn and Zr, is relevant because trace elements affect pigment properties. The critical step in the analysis of this pigment is the conversion of the solid sample to a representative solution. This study compared four acid decomposition procedures for TiO₂ for the determination of Al, P and trace impurities using inductively coupled plasma optical emission spectrometry. The decomposition procedures investigated involved acid digestion with: (i) (NH₄)₂SO₄/H₂SO₄; (ii) HF/H₂SO₄; (iii) H₃PO₄; and (iv) HCl/HNO₃/HF. This latter mixture was tested in a microwave-assisted procedure with closed vessels. Comparing the procedures using conventional conductive heating, the procedure using (NH₄)₂SO₄/H₂SO₄ was the most suitable for complete decomposition of TiO₂ samples, requiring approximately 30 min. Applying a paired t-test, it was shown that all strategies led to results in agreement at a 95% confidence level with those obtained using X-ray fluorescence. The accuracy for Cr, Fe, P and Zr was also checked using a certified reference material, and again all results were in agreement at a 95% confidence level. The performance of two ICP-OESs, one based on a mini-torch using a radial view configuration, and the other based on an axial view configuration, were compared. Both plasmas are intensely affected by matrix constituents. The mini-torch plasma is less able to cope with high amounts of solids; however this parameter also negatively affects the background level when using axial-viewed ICP-OES.     

Simultaneous speciation of inorganic arsenic and antimony in natural waters by dimercaptosuccinic acid modified mesoporous titanium dioxide micro-column on-line separation and inductively coupled plasma optical emission spectrometry determination

A novel absorbent was prepared by dimercaptosuccinic acid chemically modifying mesoporous titanium dioxide and was employed as the micro-column packing material for simultaneous separation/preconcentration of inorganic arsenic and antimony species. It was found that both trivalent and pentavalent of inorganic As and Sb species could be adsorbed quantitatively on dimercaptosuccinic acid modified TiO₂ within a pH range of 4–7, and only As(III) and Sb(III) could be quantitatively retained on the micro-column within a pH range of 10–11 while As(V) and Sb(V) were passed through the micro-column without the retention. Based on this fact, a new method of flow injection on-line micro-column separation/preconcentration coupled to inductively coupled plasma optical emission spectrometry was developed for simultaneous speciation of trace inorganic arsenic and antimony in natural waters. Under the optimized conditions, an enrichment factor of 10 and sampling frequency of 10 h^− 1 were obtained with on-line mode. The detection limits of As(III), As(V), Sb(III), and Sb(V) are 0.53, 0.49, 0.77 and 0.71 ng mL^− 1 for on-line mode and as low as 0.11, 0.10, 0.15 and 0.13 ng mL^− 1 for off-line mode due to its higher enrichment factor (50), respectively. The relative standard deviations of two modes are less than 6.7% (C = 20 ng mL^− 1, n = 7). The concentration ratio of lower oxidation states/higher oxidation states changing from 1:10 to 10:1 has no obvious effect on the recoveries of As(III) and Sb(III). In order to validate the developed method, two certified reference materials of GSBZ5004-88 and GBW(E)080545 water sample were analyzed and the determined values are in good agreement with the certified values. The proposed method was successfully applied to the simultaneous speciation of inorganic arsenic and antimony in natural waters.     

Titania supported copper catalysts for methanol synthesis from carbon dioxide

The effect of co-catalyst (ZnO or ZrO₂) has been tested for hydrogenation of CO₂ on CuO/TiO₂ and CuO/Al₂O₃. CuO−ZnO/TiO₂ catalyst showed the highest activity for methanol synthesis. Kinetic parameters were also determined.     

Photocatalytic cleavage of C-F bond in pentafluorobenzoic acid with titanium dioxide-P25

The photocatalytic C-F bond cleavage in pentafluorobenzoic acid (PFBA) with TiO₂-P25 using UV-C light has been investigated under different conditions. Complete cleavage of C-F is observed with TiO₂-P25 under UV-C light irradiation. Oxidants such as IO₄⁻, BrO₃⁻, S₂O₈²⁻, H₂O₂ and ClO₃⁻ ions enhance the defluoridation of PFBA. The order of their activities is IO₄⁻ > H₂O₂ > S₂O₈²⁻ ≈ BrO₃⁻ > ClO₃⁻. C-F cleavage is also influenced by the addition of inorganic anions and metal ions. The defluoridation intermediates were analyzed by GC-MS technique.     

核壳结构TiO2@SiO2催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯

以反相微乳液法和沉淀法相结合制备了核壳结构TiO₂@SiO₂,首次用于碳酸二甲酯与苯酚酯交换合成碳酸二苯酯反应,显示较好的催化活性. 采用200 ℃焙烧的TiO₂@SiO₂,用量0.20 g,反应9 h,苯酚转化率达41.8%,酯交换选择性为100%. 透射电镜显示TiO₂@SiO₂核厚壳薄,TiO₂核直径220-300 nm,SiO₂壳厚度40-60 nm,具有介孔结构. TiO₂@SiO₂对碳酸二甲酯与苯酚酯交换反应有好的重复使用性,使用4次苯酚转化率仍保持在40%以上. TiO₂与SiO₂发生相互作用,Ti进入骨架形成Ti-O-Si键,骨架Ti的形成提高了TiO₂@SiO₂的催化性能.     

Friedel-Crafts alkylation of indoles with epoxides catalyzed by nanocrystalline titanium(IV) oxide

Friedel-Crafts alkylation of indoles with epoxides to afford 3-alkyl indole derivatives at room temperature with moderate to good yields and high regioselectivity using nanocrystalline titanium(IV) oxide catalyst is described.