纳米TiO2的光催化作用及其应用研究进展

纳米TiO2 是一种宽禁带半导体光催化剂 ,可用于污水处理、空气净化、灭菌消毒、医疗、化学合成、贵金属提取冶金、能源材料等多个领域 ,未来的研究发展重点应是实用化纳米TiO2 光催化剂的开发及高效光反应器的研制。     

Ultrasonic properties of hexagonal ZnS at nanoscale

Higher order elastic constants have been calculated in ZnS at 300 K and 500 K following the interaction potential model. Ultrasonic attenuation, velocity and other related parameters have been calculated using the higher order elastic constants for the different size of the material at 500 K. The size dependency of the ultrasonic properties is discussed in correlation with elastic, thermal and electrical properties. It has been found that the thermal conductivity is the main contributor to the behaviour of the ultrasonic attenuation as a function of the size and the responsible cause of attenuation is phonon-phonon interaction. The semiconducting nature of ZnS film has been achieved with the study of size variation of thermal relaxation time and ultrasonic attenuation.     

Preparations of nanosized TiO2 in reverse microemulsion and their photocatalytic activity

Nanosized titania sol has been produced by the controlled hydrolysis of titanium tetraisopropoxide (TTIP) in sodium bis(2-ethylhexyl)sulfosuccinate (AOT) reverse micelles. The physical properties, such as surface area, crystallite size and crystallinity according to R and W₀ ratio, have been investigated by TEM, XRD, BET, FT–IR, TGA and DTA. In addition, the photocatalytic decomposition of p-nitrophenol has been studied by using a batch reactor in the presence of UV light in order to compare the photocatalytic activity of prepared nanosized titania. It is shown that the anatase structure appears in the 300–600 °C calcination temperature range and the transformation of anatase into rutile starts above 700 °C. The crystallite size increases with increasing R and W₀ ratio but W₀ ratio shows a stronger effect on the crystallite size than R ratio. In the photocatalytic decomposition of p-nitrophenol, the photocatalytic activity is mainly determined by the crystallinity of titania. In addition, the titania calcined at 500 °C shows the highest activity on the photocatalytic decomposition of p-nitrophenol() and the pure anatase structure.     

Catalytic wall reactor: Catalytic coatings of stainless steel by VOx/TiO2 and Co/SiO2 catalysts

Catalytic wall (structured) reactors and structured supports are suitable to study the catalytic properties of nanosized materials. The coating of metallic (aluminum and stainless steel) plates by thin layers of active phase is presented in two cases, VO_x/TiO₂ and Co/SiO₂, catalysts used in the oxidative dehydrogenation (ODH) of propane and in Fischer–Tropsch synthesis (FTS) of clean fuels, respectively. The preparation of coated plates and their characterisation by various methods of physicochemical analysis are described. Both chemical and physical methods were used for coating. VO_x/TiO₂ layers were obtained by grafting of Ti (on Al or stainless-steel plates) and V (on TiO₂) alkoxides and use of sol–gel media or suspension. A silica primer was deposited (on stainless-steel plate) by plasma-assisted chemical vapour deposition (PACVD) onto which Co oxide and silica were coprecipitated from sol–gel. The catalytic experiments in the respective reactions were carried out in special plate reactors and compared with those of catalytic powders. The study shows that the coating of a metallic substrate by a catalyst is not straightforward and requires specific studies dealing with both chemistry (chemical affinity between substrate and catalytic layers) and catalytic engineering (catalytic performance in taylor-made reactors).     

Semi-continuous emulsion copolymerization of butyl methacrylate with polymerizable anionic surfactants

Two polymerizable anionic surfactants sodium 4-(ω-acryloyloxyalkyl)oxy benzene sulfonate (SABS-n, n=8 or 10) have been successfully used in the semi-continuous emulsion copolymerization with butyl methacrylate (BMA). After generating seeding particles in an emulsion consisting SABS-8 or SABS-10 and small amount of BMA using a redox initiator ammonium persulfate (APS)/tetramethylethylenediamine (TMEDA) at room temperature, most of BMA was added drop-wise to the polymerizing emulsion system during a period of 4-8 h. These emulsion copolymerizations produced nanosized latexes with high polymer/surfactant weight ratios up to about 12/1 and nearly monodisperse particles ranging from 18 to 33 nm in diameter. X-ray photoelectron spectroscopy results showed that SABS-n was significantly enriched on the surface of latex particles. The effects of concentrations of SABS-n, BMA, and APS/TMEDA and the latex characteristics during the continuous addition of monomer were studied. A possible polymerization mechanism was proposed.     

纳米二氧化钛光催化材料研究新进展

纳米级TiO2作为一种光催化材料，在环境保护、光能转换、纺织建筑、工业催化等领域有着极为广泛的用途，其制备方法也得到了深入系统的研究。文章简要介绍了近年来纳米二氧化钛的制备方法、掺杂改性途径以及在卫生保健、废水处理、有机气体降解、新型材料制备等应用中的最新进展，并展望纳米二氧化钛今后的研究方向。     

Effect of heat treatment on crystal phase and photocatalytic activity of Tm doped TiO2 nanoparticles

Abstract

Abstract

Tm doped TiO₂ nanoparticles have been synthesised by hydrolysis-precipitation method. The effect of heat treatment on the crystal phase and photocatalytic activity of Tm doped TiO₂ nanoparticles has been studied. The prepared samples were characterised by transmission electron microscopy, X-ray diffraction, Fourier transformed infrared and diffuse reflection spectrum analysis. The results show that Tm³⁺ doping can effectively inhibit the phase transformation from antase to rutile and decrease the crystallite size of nano-TiO₂ particles. There is an optimal Tm doping (1·4?mol.-%) after calcination at 550°C for the photocatalytic activity of methylene blue degradation.     

Nanosized zeolite films for vapor-sensing applications

Colloidal zeolites LTA and BEA sized below 100 nm were synthesized as building blocks for the controlled growth of thin microporous films on piezoelectric sensor devices (quartz crystal microbalance, QCM). The zeolite films were prepared on pre-seeded gold substrates on QCM devices. Initially, a layer of colloidal particles was deposited on the support through chemical bonding with a silane coupling agent, followed by hydrothermal growth. BEA- and LTA-type zeolite films with thicknesses of 250 and 450 nm, respectively, were prepared by optimizing the synthesis conditions. The application of these zeolite films in microsensors for water and organic compounds is presented. The importance of the zeolite structure type with respect to the sensitivity towards different organic and water vapors at various concentrations is discussed. Both zeolites are thermally stable and show reproducible responses during long-term experiments. Based on these results, it was concluded that both zeolite films could be used effectively as humidity sensor materials for water vapor sensing purposes. High sensitivity, good reversibility and long life were demonstrated for this type of zeolite film at low water concentrations. In comparison to LTA, the BEA films show a higher sorption capacity towards water vapor and no rejection of pentane, hexane and cyclohexane, due to the larger pore size of the BEA structure.     

Synthesis of functional nanocrystallites through reactive thermal plasma processing

A method of synthesizing functional nanostructured powders through reactive thermal plasma processing has been developed. The synthesis of nanosized titanium oxide powders was performed by the oxidation of solid and liquid precursors. Quench gases, either injected from the shoulder of the reactor or injected counter to the plasma plume from the bottom of the reactor, were used to vary the quench rate, and therefore the particle size, of the resultant powders. The experimental results are well supported by numerical analysis on the effects of the quench gas on the flow pattern and temperature field of the thermal plasma as well as on the trajectory and temperature history of the particles. The plasma-synthesized TiO₂ nanoparticles showed phase preferences different from those synthesized by conventional wet-chemical processes. Nanosized particles of high crystallinity and nonequilibrium chemical composition were formed in one step via reactive thermal plasma processing.     

Transformation of amorphous silica colloids to nanosized MEL zeolite

Si-MEL molecular sieve is prepared from aged colloidal precursor solutions under hydrothermal treatment (HT) at 90 °C. In situ dynamic light scattering (DLS) investigations of the precursor solutions and the crystalline Si-MEL sols are performed with the original concentrations. Sub-colloidal particles with a mean radius of about 1 nm and colloidal aggregates with a radius of 10 nm are detected in the precursor colloidal solutions after 5 h aging at room temperature. Consumption of the sub-colloidal particles with time and an increase of the colloidal fraction of 10 nm particles after 48 h aging is observed. After heating of the aged precursor solution at 90 °C for 30 h, three particle populations of 1, 10, and 100 nm radius are formed. Complete transformation from amorphous to crystalline colloidal particles is observed after 68 h extended HT of the aged precursor solution. The mean hydrodynamic radius of the crystalline Si-MEL particles is about 100 nm based on the DLS measurements. The size of the MEL crystals was also confirmed with SEM. Additional time-dependent ²⁹Si NMR measurements of the aged precursor colloidal solutions prior to further crystal growth show that the amount of Q⁰ species (δ=−71.2) decreases, while signals of high intensity in the range between δ=−88.6 and −98.9 indicating the formation of Q³₆ and Q³₈ silicon species appear. IR data reveal that with aging of the precursor colloidal solutions at room temperature, an increased ordering of the silica species similar to those found in the final MEL product is observed.