Characterization of the structures of size-selected TiO2 nanoparticles using X-ray absorption spectroscopy

To investigate the relationship between the size and structure of TiO(2) nanoparticles, three size-selected samples of TiO(2) nanoparticles were prepared via a hydrolysis method that uses Ti[OCH(CH(3))(2)](4) as the starting material. The structures of the nanoparticles were characterized using powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray absorption spectroscopy (XAS). Analysis of the XRD patterns and of the TEM images showed that the samples were dispersed, with an average particle size of approximately 30 nm (sample A), approximately 12 nm (sample B), and approximately 7 nm (sample C). Their X-ray absorption spectra indicate that samples A and B have an anatase structure, whereas sample C has a structure very similar to that of the TiO( 2) II phase, which generally arises only under high-pressure conditions. This difference can be attributed to size-induced radial pressure within the smaller nanoparticles, which plays an important role in the phase of TiO(2) nanoparticles in sample C.     

Synthesis and dye-sensitized solar cell performance of nanorods/nanoparticles TiO2 from high surface area nanosheet TiO2

High surface area nanosheet TiO2 with mesoporous structure were synthesized by hydrothermal method at 130 degrees C for 12 h. The samples characterized by XRD, SEM, TEM, SAED, and BET surface area. The nanosheet structure was slightly curved and approximately 50-100 nm in width and several nanometers in thickness. The as-synthesized nanosheet TiO2 had average pore diameter about 3-4 nm. The BET surface area and pore volume of the sample were about 642 m(2)/g and 0.774 cm(3)/g, respectively. The nanosheet structure after calcinations were changed into nanorods/nanoparticles composite with anatase TiO2 structure at 300-500 degrees C (10-15 nm in rods diameter and about 5-10 nm in particles diameter). The solar energy conversion efficiency (eta) of the cell using nanorods/nanoparticles TiO2 (from the nanosheet calcined at 450 degrees C for 2 h) with mesoporous structure was about 7.08% with Jsc of 16.35 mA/cm(2), Voc of 0.703 V and ff of 0.627; while eta of the cell using P-25 reached 5.82% with Jsc of 12.74 mA/cm(2), Voc of 0.704 V, and ff of 0.649.     

Small-sized titanium dioxide nanoparticles mediate immune toxicity in rat pulmonary alveolar macrophages in vivo

Small-sized titanium dioxide (TiO2) nanoparticles (< 10 nm) are widely used in both industry and daily life due to their enhanced thermomagnetic and photocatalytic properties and surface activity. However, their increasing use increases the health risk of people exposed to these particles, either occupationally or environmentally. This study was performed to evaluate the effect of small-sized TiO2 nanoparticles on the immune function of rat pulmonary alveolar macrophages in vivo. Forty-two rats were intra-tracheally instilled with 0.5, 5 or 50 mg/kg of NP-1 and F-1 TiO2 primary particles with a median size of 5 nm and 200 nm, respectively. Rat pulmonary alveolar macrophages were obtained from lung lavage fluids using a closed chest technique. Cells were assessed for morphology, phagocytic ability and chemotactic ability, Fc receptor expression, MHC-class II molecule expression, and expression of nitric oxide (NO) and tumor necrosis factor-alpha (TNF-alpha). The result showed that the inhalation of NP-1 TiO2 particles induced the membrane and ultrastructure damage of PAMs. The phagocytic ability of the macrophages increased when they were exposed to low dose of NP-1 TiO2 and decreased when they were exposed to high dose of NP-1 TiO2. Exposure to NP-1 TiO2 also decreased the chemotactic ability of the macrophages as well as decreasing the expression of Fc receptors and MHC-class II on the cell surface. The mechanism responsible for these changes was mediated via altering NO and TNF-alpha expression by the PAMs. The amount of NO and TNF-alpha secreted by macrophages gradually increased as the dosage of TiO2 nanoparticles increased. Small-sized TiO2 nanoparticles (but not the fine counterpart) elicited stronger NO and TNF-alpha production. The present study suggests that both damage to the cell structure and pulmonary alveolar macrophage dysfunction may occur, leading to a reduction in both non-specific and specific immune responses in individuals exposed to small-sized TiO2 nanoparticles.     

Synthesis, characterization and photocatalytic H2 generation over ternary indium titanate nanoparticles

A low temperature surfactant-free solution-phase method has been successfully developed for the synthesis of ternary In2TiO5, nanoparticles using a solvothermal route. The mechanistic aspects of synthesis of In2TiO5 nanoparticles from precursors, In(acac)3 and Ti(IV) isopropoxide in benzyl alcohol at 220 degrees C under solvothermal conditions, were investigated by GC-MS and 13C{1H} NMR analysis. The N2-BET surface area of the 5-8 nm sized In2TiO5 nanoparticles was found to be 60 m2 g(-1), which decreased with increase in calcination temperature; 38 m2 g(-1) at 800 degrees C; 5 m2 g(-1) at 1200 degrees C. The High resolution transmission electron microscopy (HR-TEM) shows well-developed lattice fringes of the crystalline nanoparticles, and selected area electron diffraction (SAED), pattern was indexed to be orthorhombic In2TiO5. The nanoparticles show better photocatalytic hydrogen generation from water-methanol mixtures over bulk In2TiO5, anatase TiO2 nanoparticles prepared by identical route and commercial TiO2 photocatalyst (Degussa, P25) under UV-visible irradiation (16% UV + 84% visible). Photocatalytic properties as a function of crystallinity and surface area of indium titanate nanoparticles have also been investigated. The high photoactivity obtained is correlated with the electronic and crystal structure of In2TiO5.     

Synthesis of SnS nanoparticles by SILAR method for quantum dot-sensitized solar cells

SnS-sensitized TiO2 electrodes were applied in quantum dot-sensitized solar cells (QDSSCs) which are environmentally more favorable than conventional Cd or Pb-chalcogenide-sensitized electrodes. SnS nanoparticles were well-distributed over the surface of TiO2 nanoparticles by the successive ionic layer adsorption and reaction (SILAR) method. Deposited SnS nanoparticles had diameter about 3 nm. Under AM1.5 irradiation with 100 mW/cm2 light intensity (at 1 sun), the energy conversion efficiency of obtained cells reached a value of 0.21% (0.25 cm2) at SILAR coating cycles of 5. In addition, the photovoltaic performance was improved by additional ZnS coating on the surface of SnS-sensitized TiO2 electrodes.     

TiO2 nanoparticles co-doped with silver and nitrogen for antibacterial application

We have prepared a series of TiO2 nanoparticles for antibacterial applications. These TiO2 nanoparticles were prepared by the hydrolysis precipitation method with Ti(OBu)4, silver nitrate and ammonia. Crystal structure, particle size, interfacial structure and UV-visible light response of the prepared nanoparticles were characterized by X-ray diffraction measurements (XRD), Transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR) and UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRs). The XRD spectra showed that all samples were anatase structure calcined at 450 degrees C for 3 hours. The Ag doping made the peak of diffraction wider. The results of TEM showed that the nanoparticles of TiO2, N-TiO2 and 1% Ag-N-TiO2 were all spherical in shape and well distributed with a mean size of 19.8 nm, 39.2 nm and 20.7 nm, respectively. N doping caused the nanoparticle size to increase, while, when the doped amount of Ag+ increased, the TiO2 particle size decreased. The FTIR revealed that Ag and N doping of TiO2 appeared to have strong absorption by -OH group and showed the characteristic absorption band of NH4+ and Ag. The UV-Vis-DRs indicated that the absorption band of Ag-N co-doped TiO2 had red shift and that the optical absorption response (between 400 nm and 700 nm) had obvious enhancement. The antibacterial properties of nanoparticles were investigated by agar diffusion method toward Escherichia coli and Bacillus subtilis. The results indicated that both Ag- and N-doped TiO2 could increase the antibacterial properties of TiO2 nanoparticles under fluorescent light irradiation. A 1% Ag-N-TiO2 had the highest antibacterial activity with a clear antibacterial circle of 33.0 mm toward Escherichia coli and 22.8 mm toward Bacillus subtilis after cultivation for 24 hours.     

漆酚醛缩聚物/丙烯酸树脂/TiO2复合涂料的制备及性能

采用Sol-Gel法制备了漆酚缩甲醛聚合物/多羟基丙烯酸树脂/TiO2纳米复合涂料(UFP/MPA/TiO2),并用透射电镜、动态机械热分析、红外光谱和其它手段对复合涂膜进行测试。结果表明,TiO2以40 nm~80 nm的粒子均匀地分布于m(UFP)∶m(MPA)=5∶2的UFP/MPA聚合物基体中,且纳米TiO2粒子和聚合物间存在着较强的氢键。纳米TiO2粒子的引入,使得该复合涂膜具有比UFP或UFP/MPA涂膜更好的抗紫外线性能、常规物理力学性能和动态力学性能。     

TiO2纳米微粒的溶胶-凝胶法制备及XRD分析

本文采用溶胶 凝胶法制备二氧化钛纳米微粒。用XRD分析了二氧化钛胶体经不同温度热处理后的晶粒粒径。分析表明温度在 4 73K时TiO2 微粒呈锐钛矿结构 ,粒径约为 5 5nm。在 6 73K以上TiO2 粒径迅速增大 ,微粒出现锐钛相与金红石相混晶结构。 973K时TiO2 微粒完全转化为金红石相。用晶界结构弛豫的观点解释粒径随热处理温度变化关系     

Preparation and characterization of the transparent hybrids of silicone epoxy resin and titanium dioxide nanoparticles via sol-gel reactions

In order to prepare transparent hybrid films of high refractive index, nanoparticles of TiO2 were prepared and dispersed in a silicone epoxy (SE) resin synthesized from diphenyl silane diol and [2-(3,4-epoxycyclohexyl)ethyl] trimethoxysilane by sol-gel reactions. It was found that amorphous TiO2 nanoparticles of about 5 nm modified with hexahydro-4-methyl phthalic anhydride [HMPA] were dispersed in the SE resin without agglomerations. The refractive index of the hybrids increased linearly with increasing the TiO2 contents. The hybrid containing 30 wt% of the TiO2 particles showed light transmittance of 94% at 450 nm and refractive index of 1.63. The fine dispersion of the TiO2 nanoparticles was attributable to the sol-gel reactions between the SE resin and TiO2 nanoparticles and the modification of the TiO2 particles with HMPA.     

TiO2--Ta2O5 composite thin films deposited by radio frequency ion-beam sputtering

TiO2--Ta2O5 composite films were prepared by a radio frequency ion-beam sputtering deposition process, and the refractive indices and extinction coefficients of the composite films were found to be between those of the TiO2 and Ta2O5 films. The structure of the as-deposited films was amorphous, and the surface roughness was approximately 0.1 nm. The residual stress of the composite films was less than that of pure TiO2 film. The structure of the composite films after annealing was amorphous, with low surface roughness and slightly increased residual stress. The film containing 6.3% TiO2 displayed better properties than either the pure TiO2 or the pure Ta2O5 film.     

Photocatalytic degradation of rhodamine B by anchored TiO2 nanowires

Rutile TiO2 nanowires anchored on silica were fabricated by annealing TiO2 nanoparticles dispersed on silicon or quartz substrate by means of a polystyrene nanosphere monolayer template at 1000 degrees C for 1 h without any catalyst. The diameter and length of the nanowires were 30-80 nm and 1-3 microm, respectively. The growth direction of the nanowires is [112]. The photocatalytic activities of TiO2 nanoparticles and anchored nanowires were evaluated. TiO2 nanowires had higher photocatalytic activity for rhodamine B than TiO2 nanoparticles.     

Electrochemiluminescence cell fabrication using TiO2 nanotube produced by anodic oxidation

Electrochemiluminescence (ECL) cell using the electrode of TiO2 nanotube (NT) and Ru(ll) complex Ru(bpy)3(PF6)2 as a luminacence substance was fabricated. TiO2 NT were produced from the membrane of TiO2 NT arrays fabricated by anodic oxidation of approximately 100 microm thick Ti-plate. TiO2 NT arrays inject increasing number of electrons to the Ru(II) complex at the interface of TiO2 NTs. It allows the increasing exergonic oxidation/reduction reaction of Ru(II) complex. The ECL cell emits approximately 600 nm light in orange color. The cell structure is composed of a glass/F-doped SnO2(FTO)/TiO2 NT/Ru(II) complex in propylene carbonate/FTO/glass. The ECL efficiency of the cell consisting of the layer of TiO2 NT was approximately 255 cd/m2 at a bias of 4 V. The use of TiO2 NT increases ECL intensities by 5 times compared to the typical ECL cell without the use of TiO2 NT.     

The glass transition and thermodynamics of liquid and amorphous TiO(2) nanoparticles

The glass transition and thermodynamics of spherical liquid TiO(2) nanoparticles, with different sizes ranging from 2 to 5?nm, have been studied in a model under non-periodic boundary conditions. We use the pairwise interatomic potentials proposed by Matsui and Akaogi. Models have been obtained by cooling from the melt via molecular dynamics (MD) simulation. The structural properties of liquid nanoparticles at 3500?K have been analyzed in detail through the partial radial distribution functions (PRDFs), coordination number distributions, bond-angle distributions and interatomic distances. Moreover, we also show the radial density profile in nanoparticles. Calculations show that size effects on the structure of a model are significant and that liquid TiO(2) nanoparticles have a distorted pentahedral network structure with the mean coordination numbers Z(Ti-O)≈5.0 and Z(O-Ti)≈2.5, while amorphous TiO(2) nanoparticles have an octahedral network structure. The temperature dependence of the surface structure and surface energy of the nanoparticles has been obtained and is presented. In addition, the size dependence of the glass transition temperature and the temperature dependence of the diffusion constant of atomic species have been found and are discussed.     

A composite photocatalyst of cdS nanoparticles deposited on TiO2 nanosheets

A nanocomposite photocatalyst consisting of deposited CdS nanoparticles on TiO2 nanosheets was fabricated by a simple one-pot method. The contact between two phases was maximized by making a composite structure of TiO2 nanosheet decorated with CdS nanoparticles. The composite photocatalyst showed higher photoactivity for hydrogen production from aqueous Na2S/Na2SO3 solution and decomposition of methylene blue under visible light irradiation (lamda > or =420 nm) compared with single component CdS nanoparticles or a physical mixture of CdS nanoparticles and TiO2 nanorods. The intentional formation of nanoscale heterojunctions between two phases appears beneficial for inducing an efficient electron-hole separation.     

Shape transformation and relaxation dynamics of photoexcited TiO2/Ag nanocomposites

The laser-induced sintering of TiO2 nanoparticles into larger nanospheres is accelerated by adsorbed silver particles. For the same weight fraction of silver, silver nanoparticles of 5 nm in diameter modify TiO2 nanoparticles more effectively than those of 1.5 nm do, suggesting that the photocatalysis of TiO2 nanoparticles as well as their stability is highly dependent on the sizes, the shapes, and the distribution of adsorbed metal nanoparticles. The photoexcited electrons of TiO2 nanoparticles are quenched at trap sites and surface states by transfer to the conduction band of silver, implying that the presence of adsorbed silver nanoparticles enhances the photocatalytic effect of TiO2.     

微乳液化学剪裁制备纳米钛酸钡和二氧化钛

以钛酸丁酯、氢氧化钡和正己醇制备凝胶,用吐温-80/正已醇／环己烷／水制成w／O型微乳液在25℃下进行化学剪裁,将前驱物在550℃下煅烧,分别制备出了纳米钛酸钡和纳米二氧化钛．对产物进行X-射线粉末衍射（XRD）、透射电镜（TEM）、红外（IR）和差热（DTA）分析,研究了煅烧温度对BaTi03和Ti02纳米质点粒径和组成的影响．结果表明,最好的煅烧温度是550℃．所得纳米钛酸钡为具有较好晶型的六方晶体,粒径在30～42nm之间,钡钛摩尔比为1：1;纳米二氧化钛为单一的锐钛矿型八面体结构,平均粒径小于50nm．实验表明,通过凝胶．微乳液法合成的纳米物质可以有效地减少团聚,控制微粒的组成和粒径,且操作简单,成本低．     

Effect of niobium on the structure and photoactivity of anatase (TiO2) nanoparticles

Anatase-type TiO2 nanoparticles doped with 0-30 mol% niobium were directly formed from precursor solutions of TiOSO4 and NbCl5 under mild hydrothermal conditions at 120-180 degrees C for 5 h using the hydrolysis of urea. When the niobium content increased from 0 to 30 mol%, the crystallite size of anatase increased from 8.5 to 19 nm. The band gap of anatase was slightly decreased by making solid solutions with niobium. Their photocatalytic activity and adsorptivity were evaluated separately by the measurement of the concentration of methylene blue (MB) remained in the solution after maintained in the dark or under UV-light irradiation. To form anatase-type solid solutions by doping 5-15 mol% niobium into TiO2 was effective for improvement of the photoactivity of TiO2. The photocatalytic activity (the photooxidation rate) and the adsorption amount of MB for the sample containing 15 mol% niobium became more than approximately nine times and six times as much as those of the hydrothermal anatase-type pure TiO2, respectively.     

One step synthesis of rutile TiO2 nanoparticles at low temperature

Sphere-like rutile TiO2 nanocrystals have been synthesized by sol-gel method followed by hydrolysis of titanium tetrachloride in deionized water in the presence of ammonium hydroxide as hydrolysis catalyst. The as-prepared TiO2 nanoparticles have single rutile phase with average diameter approximately 26.4 nm. The results show that the temperature has a great influence on the particle size distribution and also crystalline phase (rutile) of TiO2 nanoparticles is consistent with the temperature. Characterization of the as-prepared nanocrystalline powder was carried out by different techniques such as powder X-ray diffraction (XRD), field emission transmission electron microscopy (FE-TEM) and Raman spectroscopy.     

Layer-by-Layer assembly of TiO2 nanoparticles for stable hydrophilic biocompatible coatings

Stable, super-hydrophilic (water contact angle approximately equal to 0 degrees) titanium dioxide nanoparticle thin films have been obtained on substrates with different initial wettability such as glass, poly(methyl methacrylate) and poly(dimethyl siloxane) using layer-by-layer nano-assembly method. Titanium dioxide nanoparticles were alternated with poly(styrene sulfonate) to form films of thickness ranging from 11 nm to 220 nm. The hydrophilicity of these thin films increases with increasing number of deposited PSS/TiO2 bilayers. It was found that 2, 5 and 20 layers were needed to form super-hydrophilic TiO2 coating on glass, PMMA and PDMS respectively. Oxygen plasma treatment of substrate surfaces enhanced the formation of homogeneous TiO2 films and accelerated the formation of hydrophilic layers. Super-hydrophilicity has been shown to be unique to PSS/TiO2 films as compared with other polyelectrolyte/nanoparticle layers, and UV irradiation may restore hydrophilicity even after months of storing of the samples. Biocompatibility of TiO2 nanoparticle films has been demonstrated by the successful cell culture of human dermal fibroblast.     

A polyol-mediated synthesis of titania-based nanoparticles and their electrochemical properties

Ti-based nanoparticles were prepared in polyol mediums of EG (ethylene glycol) and TEG (triethylene glycol), with heating treatment. Ti-based materials of dried power and heated samples showed average sizes of 4, 10, 3, and 8 nm with spherical shapes and monodispersed state, respectively. The XRD patterns of TiO2 and Li4Ti5O12 materials of dried powder and heated samples were indexed to anatase phase TiO2 (space group: I4(1)/amd) and the spinel phase (space group: Fd3m) except for the dried powder sample of Li4Ti5O12, which was corresponded with amorphous-like characteristics from the X-ray diffraction and electron diffraction pattern of Field emission-TEM analysis. The TiO2 and Li4Ti5O12 samples after heat-treated at 500 degrees C exhibited excellent high rate capabilities at a current density of 0.4 mA/cm2 during extended cycles due to their electrochemically beneficial highly crystalline characteristics, nano-sized (approximately 10 nm), and uniform distributions state.