纳米SiOx改性不饱和聚酯树脂

用纳米SiOx粒子对298#不饱和聚脂(UPR)进行增强、增韧改性，发现随粒子用量增加，树脂凝胶时间、粘度增大；粒子用量为0．5％时树脂有脆韧转变现象；用量为3％时，拉伸强度和断裂延伸率分别提高约33％和60％。用KH-570偶联剂进行表面处理有助于提高纳米SiOx粒子在UPR中的均匀分散。     

含钛介孔SiO2 催化剂的合成及其催化性能

分别以廉价硅酸钠与正硅酸乙酯为硅源,通过复合模板剂制备了介孔二氧化硅,并利用吸附相反应技术合成了TiO2/SiO2复合催化剂。用X射线衍射(XRD)、红外谱图分析(FT-IR)等手段对其结构进行了表征,通过苯酚的羟基化反应考察了催化剂的催化性能。     

Surface chemistry and kinetics of the hydrolysis of isocyanic acid on anatase

In order to meet the stricter NO_x and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO₂. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 °C the reaction was in the intrinsic kinetic regime (E_A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH₃ and NO₂, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO₂ were most effective in blocking cations and anions of TiO₂. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO₂ forms Ti–NCO and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH₃ and NO₂ retards hydrolysis leading to the appearance of isocyanate species on the surface.     

Maya crude hydrodemetallization and hydrodesulfurization catalysts: An effect of TiO2 incorporation in Al2O3

Hydrotreating of Maya heavy crude oil over high specific surface area CoMo/TiO₂–Al₂O₃ oxide supported catalysts was studied in an integral reactor close to industrial practice. Activity studies were carried out with Maya crude hydrodesulfurization (HDS), hydrodemetallization (HDM), hydrodenitrogenation (HDN), and hydrodeasphaltenization (HDAs) reactions. The effect of support composition, the method of TiO₂ incorporation, and the catalyst deactivation are examined. Supported catalysts are characterized by BET specific surface area (SSA), pore volume (PV), pore size distribution (PSD), and atomic absorption. It has been found that sulfided catalysts showed a wide range of activity variation with TiO₂ incorporation into the alumina, which confirmed that molybdenum sulfided active phases strongly depend on the nature of support. The pore diameter and nature of the active site for HDS, HDM, HDN, and HDAs account for the influence of the large reactant molecules restricted diffusion into the pore, and/or the decrease in the number of active sites due to the MoS₂ phases buried with time-on-stream. The textural properties and hysteresis loop area of supported and spent catalysts indicated that catalysts were deactivated at the pore mouth due to the metal and carbon depositions. The atomic absorption results agreed well regarding the textural properties of spent catalysts. Thus, incorporation of TiO₂ with γ-Al₂O₃ alters the nature of active metal interaction with support, which may facilitate the dispersion of active phases on the support surface. Therefore, the TiO₂ counterpart plays a promoting role to HDS activity due to the favorable morphology of MoS₂ phases and metal support interaction.     

The tribological behavior of micrometer and nanometer TiO2 particle‐filled poly(phthalazine ether sulfone ketone) composites

Micrometer and nanometer TiO₂ particle‐filled poly(phthalazine ether sulfone ketone) (PPESK) composites with various filler volume fractions from 0.5 to 7.5 vol % were prepared by heating compression molding. The friction and wear behaviors of the PPESK composites were evaluated using the block‐on‐ring test rig by sliding PPESK‐based composite blocks against a mild carbon steel ring under dry friction conditions. The wear debris and the worn surfaces of the PPESK composites filled with micrometer and nanometer TiO₂ particles were investigated by using a scanning electron microscope (SEM), while the structures of PPESK composites and wear debris were analyzed with IR spectra. Experimental results show that antiwear properties of the PPESK composites can be improved greatly by filling nanometer TiO₂ particles, and the friction coefficient decreases when the filler volume fraction is below 2.5%, but when the filler volume fraction is above 2.5% the friction coefficient increases gradually with increasing filler volume fraction. In the case of micrometer TiO₂ filler, wear rates increase with increasing filler volume fractions under identical test conditions, and the friction coefficients are less sensitive to the filler volume fraction. It was also found that the wear mechanism of micrometer TiO₂ particle‐filled PPESK is mainly severe adhesion and abrasive wear, while that of nanometer TiO₂ particle‐filled PPESK is mainly slight abrasive wear. In the former case, there are no transfer film formed on the surface of the counterpart steel, and wear debris are in the form of long and large ribbon. While in the latter case, the wear debris was granule and their size was about 10 μm. In case of 1 vol % nanometer TiO₂ particle‐filled PPESK composites, the transfer film was fairly thinner and smoother, and the transfer film provided better coverage on the surface of steel ring, while that of 7.5 vol % was thicker and discrete. These account for the different friction and wear behavior of micrometer and nanometer TiO₂ particle‐filled PPESK composite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 906–914, 2004     

Al_2O_3负载TiO_2光催化氧化剂的制备与性能试验

以钛酸四丁酯为钛源、Al2O3为载体,采用浸渍法制备了一系列TiO2/Al2O3复合氧化物光催化剂。以光催化降解甲醛为探针反应,考察了催化剂的光催化活性。并采用XRD、SEM技术对催化剂进行了表征。考察了催化剂的焙烧温度、钛含量、反应温度等因素对甲醛光催化降解率的影响。结果表明:400℃是制备TiO2/Al2O3光催化剂的最佳焙烧温度;在TiO2负载质量为5.0%的复合氧化物光催化剂催化效果最好,甲醛的降解率达到58.4%。随着反应温度的升高,复合氧化物光催化剂的催化性能下降,由25℃时的58.4%的甲醛降解率下降到50℃时的4.8%。     

纳米稀土复合固体超强酸催化合成乙酸苄酯

采用共沉淀法制备了纳米稀土复合固体超强酸SO4^2-／ZrO2-2％Nd2O3催化剂，电镜分析表明，催化剂颗粒直径在25nm左右，比表面积测定：71．03m^2／g。酸强度-12．70〈Ho〈-11．99。并对合成乙酸苄酯的最佳反应条件进行了研究。研究表明：当苯甲醇与乙酸的物质的量比为1：2，反应时间为5h，反应温度为120℃，催化剂用量为6％苯甲醇的质量时，酯化率可达92．04％。研究发现，该催化剂可重复使用并可活化再生。     

Corrosion protection of magnesium ZM 21 alloy with polyaniline–TiO2 composite containing coatings

A polyaniline–TiO₂ composite (PTC) was prepared by oxidative polymerization of aniline in phosphoric acid with ammonium persulphate, in the presence of TiO₂. The composite was characterized by spectroscopic methods. An acrylic paint containing the PTC was prepared and the coating formed on magnesium alloy was evaluated by electrochemical impedance spectroscopy after exposure to salt spray test for a period of 250 h. The coating containing the PTC was found to protect the magnesium alloy more efficiently than the coating containing polyaniline.     

Decolorization of organic dyes on Pilkington Activ™ photocatalytic glass

The air–solid photocatalytic degradation of organic dye films Acid Blue 9 (AB9) and Reactive Black 5 (RBk5) is studied on Pilkington Activ™ glass. The Activ™ glass comprises of a colorless TiO₂ layer deposited on clear glass. The Activ™ glass is characterized using atomic force microscopy (AFM) and X-ray diffraction (XRD). Using AFM, the TiO₂ average agglomerate particle size is 95 nm, with an apparent TiO₂ thickness of 12 nm. The XRD results indicate the anatase phase of TiO₂, with a calculated crystallite size of 18 nm.

Dyes AB9 and RBk5 are deposited in a liquid film and dried on the Activ™ glass to test for photodecolorization in air, using eight UVA blacklight-blue fluorescent lamps with an average UVA irradiance of 1.4 mW/cm². A novel horizontal coat method is used for dye deposition, minimizing the amount of solution used while forming a fairly uniform dye layer. About 35–75 monolayers of dye are placed on the Activ™ glass, with a covered area of 7–10 cm². Dye degradation is observed visually and via UV–vis spectroscopy.

The kinetics of photodecolorization satisfactorily fit a two-step series reaction model, indicating that the dye degrades to a single colored intermediate compound before reaching its final colorless product(s). Each reaction step follows a simple irreversible first-order reaction rate form. The average k₁ is 0.017 and 0.021 min⁻¹ for AB9 and RBk5, respectively, and the corresponding average k₂ is 2.0 × 10⁻³ and 1.5 × 10⁻³ min⁻¹. Variable light intensity experiments reveal a p = 0.44 ± 0.02 exponent dependency of initial decolorization rate on the UV irradiance. Solar experiments are conducted outdoors with an average temperature, water vapor density, and UVA irradiance of 30.8 °C, 6.4 g water/m³ dry air, and 1.5 mW/cm², respectively. For AB9, the average solar k₁ is 0.041 min⁻¹ and k₂ is 5.7 × 10⁻³ min⁻¹.     

紫外光原位还原法制备Pt/TiO_2及其光催化性能研究

以TiO2纳米粒子为载体,采用紫外光原位还原法制备了Pt/TiO2纳米光催化剂,并用TEM和EDS对其进行了表征。结果表明:纳米Pt负载到TiO2纳米粒子表面;Pt/TiO2的光催化活性是未处理纳米TiO2光催化活性的3~4倍。