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.     

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%。     

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。     

TiO2/NiO复合纳米纤维制备及光催化性能研究

通过溶胶一凝胶过程,采用静电纺丝技术,以聚乙烯吡略烷酮(PVP,Mn=900 000)和钛酸正丁酯为前驱物,制备了PVP/Ti(OPr)./Ni(CH3COO)2复合一维纳米纤维材料.经控温缓慢氧化分解,在600℃的条件下成功制备了直径50～100 nmTiO2/NiO纳米纤维.采用扫描电镜、红外光谱、X射线粉末衍射、拉曼等分析手段对样品进行了表征,系统地介绍了TiO2光催化作用机理并在紫外灯下使用样品对罗丹明B溶液进行降解实验.结果显示,0.5%TiO2/NiO复合纳米纤维具有良好的光催化活性.     

过氧钛酸溶胶TiO_2薄膜及其亲水性研究

通过过氧钛酸溶胶凝胶法在不锈钢基底上制备锐钛矿型的纳米TiO2薄膜,采用XRD、EDXA和AFM对其进行了晶体结构、元素成分及形貌的表征。结果表明:在300~600℃热处理温度下,500℃处理的TiO2薄膜光诱导超亲水性较好;在热处理温度为500℃的条件下,与双氧水浓度为12%的前躯体溶液相比,双氧水浓度为3%的前躯体溶液制备的TiO2薄膜具有较好的光诱导超亲水性能。     

沉积Ag的TiO_2纳米管的制备及其光催化性能的研究

采用电化学阳极氧化法制备了管长约为1.48μm,管径约为87 nm的Ti O2纳米管,然后采用光还原沉积法在不同浓度的AgNO3溶液中制备了沉积单质Ag的Ti O2纳米管.利用SEM,XRD和XPS对Ag-Ti O2纳米管进行了表征,并以罗丹明B溶液为目标降解物评价了其光催化活性.结果表明:Ag微粒是以稳定的单质形式存在,Ag-Ti O2纳米管的光催化活性随着AgNO3溶液浓度的增大而呈增大的趋势,当AgNO3浓度达到0.08 mol/L时其活性达到最大值,而后随着浓度的增大活性反而下降.     

La~（3＋）/Ce~（4＋）掺杂对TiO_2光催化活性的影响

以钛酸四丁酯为前驱体,采用溶胶-凝胶法制备纯的及掺杂稀土的TiO2,重点考察了退火温度对纳米颗粒晶相转变的影响。通过光催化降解实验,探讨了退火温度、退火时间、稀土离子掺杂浓度等因素对TiO2光催化活性的影响。结果表明,TiO2粉末在400℃下为锐钛矿型,具有很高的光催化活性;掺杂的TiO2纳米样品在短时间内降解均较未掺杂TiO2纳米样品的催化活性高;掺La3＋最佳摩尔分数为0.05,掺Ce4＋最佳摩尔分数为0.20,最佳退火温度为400℃,退火时间为9 h。掺La3＋量相对较少时催化活性高,而掺Ce4＋的纳米粉体在相对较高的浓度下可达到完全降解。