Effect of Particle Size and Phase Composition of Titanium Dioxide Nanoparticles on the Photocatalytic Properties

Titanium dioxide (TiO₂) nanoparticles were prepared by the oxidation of titanium tetrachloride (TiCl₄) in a diffusion flame reactor. The average diameter of particles was 15–30 nm and mass fraction of anatase ranged from 40% to 80%. Effects of particle size and phase composition of those TiO₂ nanoparticles on photocatalytic properties such as decomposition of methylene blue, bacteria and ammonia gas were investigated. The degree of decomposition of methylene blue by the TiO₂ nanoparticles under the illumination of the black light was directly proportional to the anatase mass fraction, but inversely to the particle size. The decomposition of bacteria and ammonia gas by the TiO₂ nanoparticles under the illumination of the fluorescent light showed the same trend as in the case of the methylene blue.     

金-二氧化钛（Au-TiO_2）复合薄膜的制备及局域表面等离子体共振（LSPR）效应

利用溶胶凝胶法在玻璃衬底上制备了金-二氧化钛（Au-TiO2）复合纳米薄膜,研究了热处理温度对复合薄膜表面纳米颗粒沉积的影响。利用原子力显微镜对样品进行了形貌表征,结果显示：复合薄膜是由纳米微晶组成的致密膜,温度越高越有利于Au粒子的形成。在550℃的热处理温度下,薄膜表面沉积的纳米微晶的粒径约为100nm。利用紫外-可见分光光度计测量了反射谱线,结果表明：由于局域表面等离子体共振（LSPR）的产生,在不同的热处理温度下,第一个反射峰（短波长处）不发生变化,第二个反射峰（长波长处）发生漂移（红移）。     

TiO2及其掺Fe材料的制备和EPR谱的研究

以钛酸四丁酯、无水乙醇、冰醋酸为原料,在室温下用溶胶-凝胶法制备得到二氧化钛及其掺Fe样品的湿凝胶,室温放置2天后,100 ℃干燥得到干凝胶,在500 ℃下焙烧得到二氧化钛及其掺Fe的粉末状样品. 利用X射线衍射、电子顺磁共振等测试手段对样品进行分析,结果显示所得样品均为锐钛矿,Fe被引入了二氧化钛晶格中,Ti³⁺氧化中心信号强度随Fe掺杂量的增加而增强,峰值向磁场减小方向小幅偏移. 在不同测试温度下, 含Fe量为0.1%的Fe-TiO₂样品中Ti³⁺氧化中心信号强度随温度升高而增强,峰值也向磁场减小方向小幅偏移. 根据电子顺磁共振理论以及二氧化钛在空气中与O₂的反应解释了这些现象.     

In Vitro Analyses of Effect of Light on Toxicity of Titanium Dioxide Nanoparticles to Tetrahymena pyriformis Using Fourier Transform Infrared Spectra

ABSTRACT

The wide application of titanium dioxide nanoparticles (TiO₂ NPs) has caused a large number of TiO₂ NPs to be released into the water environment without treatment, which would inevitably result in unexpected toxic damage to aquatic animals. The objects of this research were to discuss the toxic effects of TiO₂ NPs to Tetrahymena pyriformis (T. pyriformis) under dark and light conditions. The Fourier transform infrared (FTIR) spectra were utilized to investigate the biochemical constituent changes of T. pyriformis under the exposure of TiO₂ NPs. The results showed that illumination had little effect on the cell numbers of T. pyriformis after 24 hr exposure at 5 mg/L of TiO₂ concentration. However, the cell viability of TiO₂ NP–exposed T. pyriformis under light illumination (81.4%) decreased compared with that in the dark environment (96.1%). The FTIR results showed that the typical absorption band of the CH₂ asymmetric stretching vibration shifted from 2924.64 to 2925.49 cm^?1 in the dark, which indicated an increase in membrane fluidity without illumination. A decreased intensity (p < 0.05) was observed in amide I and amide II from 98.57 ± 9.62 and 41.88 ± 3.63 to 75.65 ± 4.07 and 25.25 ± 1.12 in the irradiated T. pyriformis, respectively, which suggested that the coexistence of TiO₂ NPs and light could induce an obvious decrease of protein. In the light condition, the overproduction of ROS led to the breakdown of balance of the oxidative/antioxidative system, resulting in the lipid peroxidation and the death of cells. The results further reveal that TiO₂ NPs under light conditions are more toxic than in the dark.     

Discovering the Determining Parameters for the Photocatalytic Activity of TiO2 Colloids Based on an Anomalous Dependence on the Specific Surface Area

The photocatalytic (PC) performance of titanium dioxide (TiO₂) nanoparticles strongly depends on their specific surface, the presence of crystal defects, their crystal phase, and the exposed crystal facets. In order to understand which of these factors contributes most significantly to the PC activity of TiO₂ colloids, all of them have to be individually analyzed. This study entails the synthesis of five anatase nanocrystal samples. By maintaining the same reactant ratios as well as hydrothermal sol–gel synthesis route and only varying the autoclaving time or temperature, different crystallite sizes are obtained under comparable experimental conditions. A decrease in PC performance with increase in specific surface area is found. Such an unexpected counterintuitive result establishes the basis for a better understanding of the crucial factors that ultimately determine the PC activity. These are investigated by studying nanocrystals bulk and surface structure and morphology using a selection of complementary analysis methods (X‐ray photoelectron spectroscopy (XPS), X‐ray absorption fine structure (XAFS), X‐ray diffraction (XRD)…). It is found that a change in the nanocrystal morphology from an equilibrium state truncated tetragonal bipyramid to a more elongated rod‐like structure accompanied by an increase in oxygen vacancies is responsible for an augmented PC activity of the TiO₂ nanocrystals.     

The Effect of Boundary Conditions on Gas-phase Synthesised Silver Nanoparticles

We have prepared spherical non-agglomerated silver nanoparticles by an evaporation–condensation–dilution/cooling technique. Silver was evaporated from a crucible in a tubular flow reactor. A porous tube diluter was used to quench the carrier gas at the outlet of the reactor to enhance the formation of small particles and to suppress agglomeration and other particle growth mechanisms. The number size distribution of the prepared particles was measured with a differential mobility analyser–condensation nucleus counter combination and the size and the shape of the particles were analysed with transmission electron microscope. The system was modelled using a sectional aerosol dynamics computer code to estimate the importance of different aerosol processes. In all conditions the particles obtained were non-agglomerated and spherical. The mean particle diameter varied from 4 to 10-nm depending on boundary conditions. From the modelling studies it can be concluded that the nucleation rate is the most important parameter controlling the final particle size.     

镧掺杂介孔TiO2光催化剂的制备、表征及其光催化性能

以钛酸四正丁酯和硝酸镧为原料, 以P123为模板剂,采用模板法合成了La掺杂型介孔TiO₂光催化剂, 借助TGA-DSC、BET、XRD及UV-Vis等测试手段对样品进行了表征,并以苯酚为模型污染物考察了镧掺杂量对样品光催化活性的影响．结果表明: La掺杂介孔TiO₂光催化剂孔径分布较均匀(～10 nm),比表面积可达165 m²/g．与纯介孔TiO₂相比,经掺杂改性后的样品在紫外光区及可见光区的吸收显著增强,对光具有更高的利用率,La掺杂可显著提高介孔TiO₂的光催化活性.     

纳米二氧化钛的红外辐照相变

以四氯化钛为原料 ,采用溶胶凝胶法技术合成路线 ,可以获得平均粒径在 30到 4 0纳米的二氧化钛粉末。在X—射线衍射 (XRD)和拉曼散射 (Raman)测试技术下 ,分析得到红外干燥方式下可使锐钛矿向金红石相转化 ,同时由于TiO2 纳米晶粒的尺寸效应以及弱的结晶性和局部格点不完善 ,使得Raman光谱特征峰向低波数移动。此外 ,随着反应温度的提高 ,逐步有金红石相产生 ,而 4 48cm- 1Eg 活性模对温度的依赖性体现了反斯托克斯现象。     

Details of Structure Formation During the Induction Period of Spinodal-Type Polymer Crystallization

An unexpected type of primary crystal nucleation is described, involving spinodal decomposition (SD) type microphase separation due to the orientation fluctuations of rigid segments prior to crystal nucleation. This type of mechanism was found by the present authors about 10 years ago, and recently, it was theoretically revealed by Olmsted et al. to be one of three types of primary crystal nucleation: the well-known homogeneous crystal nucleation directly from the liquid–crystal coexistence domain, which occurs at higher temperatures above the binodal temperature T _b , crystal nucleation after binodal microphase separation between T _b and spinodal temperature T _s , and that after SD below T _s . The detailed experimental results for the spinodal-type crystal nucleation, especially the temperature dependence of characteristic wavelength in SD, are explained as well.     

Substructure of Titanium Dioxide Agglomerates from Dry Ball-milling Experiments

The calciner discharge of TiO₂ white pigments from the sulphate process is ground batchwise in a planetary ball mill, varying the energy of comminution between 0 and 5.1 times the earth's gravitational constant. Particle sizes and specific surfaces of the ground products reveal that the calciner discharge consists of aggregates of 430nm diameter built from 160–210nm TiO₂ crystals. The contact area of a primary particle in an aggregate is about 15% of its surface. The success in comminution of aggregates as a function of grinding energy follows Kick's law. The theory by Rose and Weichert is used to quantify the mechanical strength of the aggregates. Ca. 20% of the aggregates are further agglomerated to granules of ca. 35µm. At all energy levels above a certain threshold, agglomerates break directly into aggregates.     

羧酸型聚芴/二氧化钛杂化材料的制备及其荧光猝灭行为

通过Suzuki偶合反应合成了聚[9,9-二辛基芴-9,9-双(丙酸基)芴](PF8COOH),并采用溶胶-凝胶法制备了羧酸型聚芴/二氧化钛(TiO₂)杂化材料。通过核磁共振氢谱(¹H NMR)、凝胶渗透色谱(GPC)、紫外-可见吸收光谱(UV-Vis)、X射线衍射(XRD)和荧光发射光谱对聚合物及其杂化材料进行了表征,并研究了杂化材料的荧光猝灭行为。结果表明,所合成的PF8COOH数均分子量为19 600,PF8COOH的紫外-可见吸收和荧光发射光谱较聚(9,9-二辛基芴)(PF8)均发生红移。通过溶胶-凝胶法制得了PF8COOH/TiO₂杂化材料,其中TiO₂主要为金红石型。杂化材料出现明显的荧光猝灭现象,TiO₂含量越大则杂化材料的荧光猝灭现象越明显。羧基的引入可使聚芴与TiO₂之间的相互作用增强,电子更容易从聚芴向TiO₂转移,因而PF8COOH/TiO₂杂化材料的荧光猝灭现象比PF8/TiO₂杂化材料更明显。     

基于银/二氧化钛复合膜的表面等离子共振气体传感器

表面等离子体共振是一种免标记的传感技术,当介质周围的介电常数发生改变时,则SPR谐振光谱特性也会随之改变.因此表面等离子体共振传感技术已广泛应用于生物化学和环境监测等领域.由于二氧化钛(TiO2)覆盖层不仅可以保护金属层,还能调谐SPR谐振的光谱强度和谐振波长于近红外波段,应用于1550 nm的光纤传感,其氧化还原反应...     

Titanium Dioxide/Carbon Fabric Prepared by a Controlled Pyrolysis Method

Titanium dioxide/carbon fabrics were prepared through pyrolysis of cellulosic fabrics in the presence of titanium ions. The influence of sintering temperature on the characteristics of the TiO₂/carbon fabrics was investigated. The properties of the samples were characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The photocatalytic efficiency was evaluated by degradation of methylene blue (MB) solution. The results showed that the sample sintered at 300°C exhibits high photocatalytic efficiency.     

Oriented Crystallization of Polyethylene in Compatible Blends with Polyamide 11

The oriented crystallization of polyethylene (PE) in uniaxially oriented films of compatible blends with polyamide 11 (PA11) was studied. The PE sample used was a random copolymer of PE with methacrylic acid (MAA), poly(ethylene-co-methacrylic acid) (PEMAA), with 4wt% MAA units. Oriented films of PA11/PEMAA blends were prepared by uniaxial drawing of the melt-mixed blends. The drawn films with fixed lengths were heat-treated at 120°C for 3min to melt the PE component, followed by cooling the sample to room temperature at a rate of 2°C/min to recrystallize the PE (designated slowly crystallized sample). The PE component crystallized in elongated domains of PEMAA with diameters of 0.5–2 μ m and lengths of 5–10 μ m for the PA11/PEMAA = 80/20 blend, resulting in the oriented crystallization of PE crystals. The crystal b-axis of PE was highly oriented in the direction perpendicular to drawing, while the crystal a-axis was weakly oriented in the drawing direction in the slowly crystallized sample of the PA11/PEMAA = 80/20 blend. The a-axis orientation of PE crystals in the PA11/PEMAA = 80/20 blend contributes to the improvement of mechanical properties in the direction perpendicular to drawing.     

Raman Spectroscopic Study of Nanophase Titanium Dioxide

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Surface Stabilization of Nano-sized Titanium Dioxide: Improving the Colloidal Stability and the Sintering Morphology

We have developed a simple surface modification technique to avoid irreversible agglomeration of titanium dioxide nanoparticles. The technique is based on hydrolysis-precipitation procedure, using TiOSO₄ as a precursor and water as a hydrolyser and a preparation medium. Diethylene glycol monomethyl ether is used as a surface modifier. Using a variety of characterization techniques, including XRD, SEM, TEM, TGA, DTA, AES, XPS, ELS and DLS, the resulting powders and the mechanism of surface stabilization were investigated. According to the proposed mechanism, hydroxyl-terminated ether molecules react with the surface of nanoparticles and then chemically adsorbed there. The layer of adsorbed molecules prevents the strong irreversible agglomeration during precipitation from the sol. The obtained anatase powder remains within the nanometric scale under heat-treatment up to 760 °C. The powders can be re-dispersed in water by ultrasound treatment, resulting in relatively stable aqueous dispersions. In addition, the morphology of sintered bodies made of these powders is significantly improved as compared to non-stabilized powders, due to less agglomeration in the initial sintering stage.     

Characterization of TiO2 Smoke Prepared Using Gas‐Phase Hydrolysis of TiCl4

The formation of submicron TiO₂ smoke (a gas‐phase suspension) from titanium tetrachloride in a low‐pressure hydrolysis reaction in a simple reactor configuration has been studied. Particle size distribution, particle morphology and degree of crystallinity have been characterized as a function of reaction conditions. Highly crystalline anatase TiO₂ particles with narrow size distribution and smaller particle size were formed at high reactor temperature, while larger, amorphous particles were found at lower reactor temperatures. These results are consistent with literature studies. At 817 °C, small (450 nm), spherical, unagglomerated particles could be produced. A gas‐phase dispersion of these particles is intended for use as seeds in subsequent kinetic studies of titanium dioxide formation reactions involving a rapid compression methodology.     

Evaluation of Morphology and Size Distribution of Silicon and Titanium Oxide Nanoparticles Generated by Laser Ablation

Nanometer-sized particles of silicon and titanium oxide were generated by irradiating solid targets using a nanosecond pulsed-Nd : YAG laser in a low pressure atmosphere. A low pressure differential mobility analyzer (LP-DMA) was used to classify the size of the generated particles. The LP-DMA and electron microscopes (SEM and TEM) were used to measure the change in the size distribution and morphology of the generated particles with laser power density and system pressure. The size distribution of both silicon and titanium oxide ranged from two to one hundred nanometers in diameter depending on the laser power density and pressure. From the high resolution TEM observation and electron diffraction, it was found that the generated titanium oxide nanoparticles were composed of a core of faceted metallic single crystals with an oxide layer 'shell.     

Crystal Phases of TiO2 Ultrafine Particles Prepared by Laser Ablation of Solid Rods

Titanium dioxide ultrafine particles (UFPs) are produced by pulsed laser ablation of titanium or titanium dioxide (anatase and rutile) rods in an atmosphere of He or O₂/He mixture. The collected UFPs on cellulose membrane filters at the exit of the ablation chamber are analyzed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The TiO₂ particles produced are composed of very small particles (diameter: 10–50nm) that are completely anatase, irrespective of the rod material, and relatively large particles (diameter: 100nm–1m) that are a mixture of anatase and rutile. The large particles consist of the direct strip-off fragments coming from the rod surface. The particles obtained from the laser ablation on TiO₂ rods in an atmosphere of He contains gray particles that are supposed to be amorphous TiO₂ (x < 2). In the presence of O₂ in the ablation chamber, these oxygen defects in amorphous TiO₂ are stabilized and anatase UFPs are formed. These results suggest that the crystal phase of the products can be controlled by adjusting the rod material and the gases used in the ablation process.     

Influence of Hollow Glass Microspheres Modified by a Rare-Earth/Titanium Coupling Agent on the Nonisothermal Crystallization of Polypropylene

Hollow glass microspheres (HGMs) were surface modified by a rare-earth/titanium coupling agent. Then polypropylene/HGMs composites were prepared by the method of melt blending. The nonisothermal crystallization of the polypropylene (PP) and its composites were investigated by differential scanning calorimetry. The results showed the modified HGMs caused a decrease in the peak crystallization temperature and onset crystallization temperature. Further analysis of the nonisothermal crystallization kinetics, by using the Jeziorny and Mo equations, showed that the crystallization rate rose with increasing cooling rate. Moreover, the presence of the modified HGMs slightly increased the crystallization rates of PP.