Photocatalytic characterization of silica coated titania nanoparticles with tunable coatings

Photocatalytic experiments were conducted using the silica coated titania nanoparticles with tunable coatings to photocatalytically degrade methyl orange in water solutions. When the silica loading on titania nanoparticles was 4.67 wt%, the silica coating layer was incomplete and the photocatalytic activity of coated nanoparticles was higher than titania nanoparticles. However, when the silica loading on titania nanoparticles increased to 9.33 wt%, the thickness of silica coatings was 1.5 nm and the photocatalytic activity of coated nanoparticles sharply decreased. When the silica loading on titania nanoparticles increased to 25.19 wt%, the coated nanoparticles still exhibited a certain photacatalytic activity due to the porosity of silica coatings. The change of the effective tiania surface area available for methyl orange caused by silica coatings and the dispersion stability were used to explain the difference in photocatalytic activity.     

Synthesis and characterization of silica—titania core—shell particles

Abstract Nearly monodispersed particles of silica were prepared and coated with uniform layers of titanium dioxide in anatase phase by hydrolysis and condensation of titanium butoxide. The coating thickness could be altered by adjusting the concentration of reactants (titanium butoxide and water) and the amount of added silica particles. Different coating thicknesses were deposited and studied using optical absorption spectroscopy, electron microscopy and Fourier transform infra-red spectroscopy. It was found that silica particles of size 170 ±5 nm were coated with 23±5 nm thick layer of titanium dioxide. Alternatively titania particles of size 340±5 nm were synthesized by controlled hydrolysis of titanium ethoxide in the presence of sodium chloride. These particles were further coated with 135±5 nm thick layer of silica to investigate changes in properties after changing the shell material     

Formation mechanisms of colloidal silica via sodium silicate

Colloidal silica is formed by titrating active silicic acid into a heated KOH with seed solution. The colloidal silica formation mechanisms are investigated by sampling the heated solution during titration. In the initial stage, the added seeds were dissolved. This might due to the dilution of seed concentration, the addition of potassium hydroxide (KOH) and the heating at 100°C. Homogenous nucleation and surface growth occur simultaneously in the second stage of colloidal silica formation. Homogenous nucleation is more important when the seed concentration is relatively low. On the other hand, surface growth plays an important role when the seed concentration is increased. In the middle seed concentration, the seed particles grow up and some new small particles are born by the homogenous nucleation process to form a bimodal size distribution product. As the titrating volume of active silicic acid exceeds a specific value in the last stage the particle size increases rapidly and the particle number decreases, which may be caused by the aggregation of particles. The intervals between each stage were varied with the seed concentration. Increasing the seed concentration led to the formation of uniform particle size colloidal silica.     

Tin-Platinum catalysts interactions on titania and silica

Pt-Sn was supported on titania and silica, and the resulting interactions between the components in prepared samples and the resulting interactions between the components before and after treatment with hydrogen were characterized by Mössbauer spectroscopy, X-ray diffraction, Rietveld refinement, high-resolution transmission electron microscopy (HRTEM) and catalytic tests data. Results show the presence of Pt and SnO₂ after calcinations, and Pt₃Sn, PtSn and PtSn₃ after reduction. Rietveld analysis shows that some Ti⁴⁺ are replaced by Sn⁴⁺ atoms in the titania structure. Finally, HRTEM and the practically absence of activity observed confirms that metallic platinum is encapsulated.     

Self-cleaning performance of polycarbonate surfaces coated with titania nanoparticles

The effect of NaOH-etching and UVC-irradiation on the mechanical stability of TiO₂ nanoparticles on polycarbonate (PC) slides was investigated. TiO₂ nanoparticles were found to adhere more strongly on UVC-treated PC than NaOH-etched PC, caused by the increase in the hydroxyl and carboxyl groups on the UVC-treated PC. Although a mechanically strong TiO₂ film was developed on UVC-treated PC, the sheet-like wetting effect and antifogging behaviour were only observed with the film coated on NaOH-etched PC. It was also detected that the film coated onto NaOH-etched PC exhibited a more superior performance in degrading methylene blue than that in the UVC-treated PC system. Evidences from the FTIR and AFM analyses indicated that the performance of TiO₂ films was strongly depended on the leaching rate of PEG.     

Growth and characterization of Fe3O4 nanoparticles in silica matrix

Nano-magnetic Fe₃O₄ particles coated with silica are synthesized. The study of structural and magnetic properties was carried out using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometer (VSM) techniques. The VSM results show that these kinds of composite particles exhibit superparamagnetic behavior with zero coercivity and remanence. The magnetic spheroid alumina carriers containing these magnetic composite particles were prepared by an internal gelation process. The SiO₂ coatings prevent the reaction between Fe₃O₄ and Al₂O₃ during the sintering process and maintain the superparamagnetic behavior of the catalyst carriers.     

Ultrasonic-assisted de-agglomeration and power draw characterization of silica nanoparticles

Breakage of nanoparticle cluster require high-intensity devices for stable and uniform distribution of aggregates. The ultra-sonication process is a high energy-intensive technique that produces cavitation effect to break the aggregates. In the present study, ultra-sonication is used for the de-agglomeration of fumed silica nanoparticles in low to high viscosity liquids. Water- and glycerol-based dispersion has been investigated at different solid loadings (up to 10 wt% for water-based dispersion and 5 wt% in glycerol-based dispersion) and viscosity of continuous phase (1–100 mPa.s). Breakup mechanism and kinetics have been studied at optimized operating conditions and no significant effect is found at different solid loadings on breakup mechanism. Particle size measurements are reported and found that volume of fine generation increased with an increase in sonication time. Further, it is observed that the stability of dispersion in the liquid is very high even at high concentration of solid used. Larger agglomerates are found at high viscosity of continuous phase and a lag is also observed for 100 mPa.s glycerol solution even at low solid loading (1 wt%). From, rheological characterizations it is found that the behavior of dispersed solution changed with time, temperature and solid loading. Erosion is found to be the breakup mechanism and further, validated with scattering light characterization. Furthermore, power draw increased with an increase in the viscosity of continuous phase, however, no significant effect of solid loading is observed. It is also observed that process is more energy-efficient at higher solid loading as the volume of fine produced is more as compared to low solid loading. Therefore, it can be concluded that the stable and uniform dispersion of nanoparticles can be achieved using an ultra-sonication device at high solid loading in viscous liquids.     

Preparation, characterization and MRI application of carboxymethyl dextran coated magnetic nanoparticles

Superparamagnetic nanoparticles functionalized with carboxymethyl dextran (CM-dextran) were synthesized by a two-step method. First, the magnetic nanoparticles (MNPs) coated with dextran (M_w ≈ 20000) were prepared by co-precipitation of Fe²⁺ and Fe³⁺ ions. Then, dextran on the surface of MNPs reacted with monochloroacetic acid (MCA) in alkaline condition. The influences of temperature and reactant concentration on the amount of -COOH on the surface of nanoparticles were systematically studied. The obtained MNPs coated with CM-dextran were stable over the entire range of pH and NaCl concentration. The MRI experiment indicated that the CM-dextran MNPs could potentially be used as MRI contrast agents for magnetic resonance molecular imaging.     

Type of lattice strain alteration,the reducing agent of activation energy of titania loading on the silica matrix than that of pure titania

Nanosized titania and silica-supported titania (SST) were prepared by the sol–gel method using titanium tetrachloride as a titania precursor. An opposite behavior was observed in the lattice strain of titania and SST before and after transition onset point (TOP). The effect of the changes of the lattice strain on the size of nanocrystallites, the TOP, and activation energy of phase transformation from anatase to rutile is investigated. It is shown that under identical synthesis conditions, the average size of nanocrystallites in SST was less than that of pure titania. Moreover, TOP of titania was lower in pure titania sample than that of SST due to the tensile strain of pure titania vs. the compressive strain of SST at low calcination temperature. However, the activation energy of pure titania due to the compressive strain and the exponential leap of the tensile strain of SST, after TOP, was higher than that of SST.     

Visible-light-driven titania/silica photocatalyst co-doped with boron and ferrum

The sol-gel route was employed to prepare a titania/silica photocatalyst co-doped with boron and ferrum. The microstructure and the optical property of the photocatalyst were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV-vis diffusive reflectance spectroscopy (DRS), Fourier transform infrared spectroscopy (FT-IR), and N₂ adsorption-desorption isotherm. The decomposition of phenol under visible light irradiation was used as probe reaction to evaluate the photocatalytic activity. The results revealed that the dopants could inhibit phase transformation of TiO₂, and that there were intimate molecule-level interactions between titania and silica. The doping boron led to the response to visible light. The doping ferrum, which existed in the form of Fe₂O₃ and dispersed on the surface of TiO₂, increased photoquantum efficiency and resulted in the enhancement of catalytic performance. The photocatalytic activity related to the annealing temperature and component. The synergistic effects of co-doping and intimate interaction between titania and silica were responsible for the increase of photoactivity.     

Preparation and characterization of titania based nanowires

A new method for preparation of titania nanowires with diameter around 10 nm and length up to 2–3 μm is described. The precursor was prepared from sodium titanate by adding ethylene glycole (EG) and heating at temperature of 198°C for 6 h under reflux. The sodium titanate glycolate formed by this way aggregated into 1D nanostructures and was subsequently transformed into titania glycolate during a chemical treatment with 98% sulfuric acid. Titania nanowires with variable amount of anatase and rutile were prepared by heating to temperatures in the range 350–1000°C. The precursor as well as titania based samples were characterized by X-ray diffraction, Infrared spectroscopy, Scanning electron microscopy, High resolution transmission microscopy, Thermogravimetry, Differential thermal analysis, Evolved gas analysis and Emanation thermal analysis. The nitrogen adsorption/desorption was used for surface area and porosity determination. The photoactivity of the prepared titania samples was assessed by the photocatalytic decomposition of 4-chlorophenol in an aqueous slurry under UV irradiation of 365 nm wavelength.     

氮掺杂TiO2的冲击合成及可见光催化活性研究

 冲击相变及冲击诱导化学反应可导致材料的物理、化学性能发生显著改变。采用炸药爆轰驱动飞片高速碰撞产生冲击波的方法,对富氮掺杂物双氰胺（C₂N₄H₄）与P25 TiO₂或偏钛酸（H₂TiO₃）的粉末混合物进行冲击加载,对回收产物进行X射线粉末衍射、透射电子显微镜、X光电子能谱、比表面积及紫外-可见漫反射光谱表征,通过亚甲基蓝和罗丹明B评价了回收产物的可见光催化降解活性。结果表明：以P25 TiO₂为原料的冲击氮掺杂浓度可达8.88%,掺杂样品具有明显的可见光吸收,能带宽度减小到1.75 eV,样品中形成了少量Srilankite高压相;而以偏钛酸为原料的冲击氮掺杂浓度为3%～4%,能带宽度变化较小,但是由于其独特的冲击脱水膨胀机理,比表面积剧增。冲击氮掺杂样品对亚甲基蓝和罗丹明B染料有较好的吸附和可见光催化降解作用,其中高飞片速度处理的样品有更高的光催化降解活性。     

Fluorescence lifetime measurements to determine the core-shell nanostructure of FITC-doped silica nanoparticles: An optical approach to evaluate nanoparticle photostability

In this paper, we described a novel fluorescence lifetime-based approach to determine the core-shell nanostructure of FITC-(fluorescein isothiocyanate, isomer I) doped fluorescent silica nanoparticles (FSNPs). Because of phase homogeneity between the core and the shell, electron microscopic technique could not be used to characterize such core-shell nanostructure. Our optical approach not only revealed the core-shell nanostructure of FSNPs but also evaluated photobleaching of FSNPs both in the solvated and non-solvated (dry) states. The FSNPs were produced via Stöber's method by hydrolysis and co-condensation reaction of tetraethylorthosilicate (TEOS) and fluorescein linked (3-aminopropyl)triethoxysilane (FITC-APTS conjugate) in the presence of ammonium hydroxide catalyst. To obtain a pure silica surface coating, FSNPs were then post-coated with TEOS. The average particle size was 135 nm as determined by TEM (transmission electron microscope) measurements. Fluorescence excitation and emission spectral data demonstrated successful doping of FITC dye molecules in FSNPs. Fluorescence lifetime data revealed that approximately 62% of dye molecules remained in the solvated silica shell, while 38% of dye molecules remained in the non-solvated (dry) silica core. Photobleaching experiments of FSNPs were conducted both in DI water (solution state) and in air (dry state). Severe photobleaching of FSNPs was observed in air. However, FSNPs were moderately photostable in the solution state. Photostability of FSNPs in both solution and dry states was explained on the basis of fluorescence lifetime data.     

Sonochemical synthesis, photocatalytic activity and optical properties of silica coated ZnO nanoparticles

In this paper, we report the synthesis of silica coated ZnO nanoparticles by ultrasound irradiation of a mixture of dispersion of ZnO, tetraethoxysilane (TEOS), and ammonia in an ethanol-water solution medium. The silica coating layer formed at the initial TEOS/ZnO loading of 0.8 for 60 min ultrasonic irradiation was uniform and extended up to 3 nm from the ZnO surface as revealed from HR-TEM images. Silica coated ZnO nanoparticles demonstrated a significant inhibition of photocatalytic activity against photodegradation of methylene blue dye in aqueous solution. The effects of silica coating on the UV blocking property of ZnO nanoparticles were also studied.     

Subsurface defect characterization and laser-induced damage performance of fused silica optics polished with colloidal silica and ceria

This paper mainly focuses on the influence of colloidal silica polishing on the damage performance of fused silica optics. In this paper, nanometer sized colloidal silica and micron sized ceria are used to polish fused silica optics. The colloidal silica polished samples and ceria polished samples exhibit that the root-mean-squared(RMS) average surface roughness values are 0.7 nm and 1.0 nm, respectively. The subsurface defects and damage performance of the polished optics are analyzed and discussed. It is revealed that colloidal silica polishing will introduce much fewer absorptive contaminant elements and subsurface damages especially no trailing indentation fracture. The 355-nm laser damage test reveals that each of the fused silica samples polished with colloidal silica has a much higher damage threshold and lower damage density than ceria polished samples. Colloidal silica polishing is potential in manufacturing high power laser optics.     

Preparation of CoFe alloy nanoparticles with tunable electromagnetic wave absorption performance

CoFe alloy nanoparticles with different particle sizes were successfully prepared by hydrogen-thermal reduction of CoFe₂O₄ microspheres at different temperatures. It was found that the real part of the permeability of the CoFe alloy nanoparticles increased with the decrease of the particle size, and accordingly the reflection loss (RL) peak moved towards the low-frequency region. The maximum RL of the coating based on CoFe alloy nanoparticles exceeded −23 dB, and a wide effective absorption band width (RL≤−10 dB) of about 6 GHz was simultaneously achieved. The EMA performance was confirmed to be tunable by the control of the absorber's particle size, and thus a new clue for the design of the EMA applications was supplied.     

Nanostructured Silica-Gel Doped with TiO2 for Mercury Vapor Control

A novel high surface area SiO₂–TiO₂ composite has been developed for elemental mercury vapor removal from combustion sources. The composite exhibits synergistic adsorption and photocatalytic oxidation. Mercury vapor in the gas stream is adsorbed, oxidized and stays on the composite. The composite has demonstrated a high mercury capacity (1512ug/g) although in its current 3-mm pellet form only the outer layer is effectively utilized. The loading of 13% TiO₂ shows the best removal, both with and without UV irradiation. Increasing TiO₂ loading beyond this level does not enhance the removal further. It has also been observed that the composite after being 'activated' by photocatalytic oxidation has better performance, probably due to the change of surface functional groups. The examination of the effects of flow velocity reveals that mass transfer is the rate limiting step. Relative humidity has been found to impede adsorption therefore decreasing the overall removal efficiency. By rinsing with acid, both the deposited mercury and composite can be regenerated.     

Spontaneous formation of large-area monolayers of well-ordered nanoparticles via a wet-coating process

Monolayers of well-ordered close-packed silica nanoparticles (NPs) with a diameter of 25 nm were spontaneously formed on silicon substrates over a large area and at a high rate via a wet-coating process using a capillary coater. The effects of zeta potential, dispersion solvent, and substrate friction on the NP self-assembly induced by the solvent evaporation were investigated. Experimental results showed that the solvent and the substrate had a larger impact on the order of formed monolayers than the zeta potential did, which are discussed from the viewpoint of the Derjaguin-Landau-Verwey-Overbeek (DLVO) and non-DLVO theories. Based on the above studies, we proposed a solution to fabrication of well-ordered NP monolayers without boundary defects at the surface coverage of 1 via the wet-coating process.     

Raman spectroscopy and support vector machines for quick toxicological evaluation of titania nanoparticles

With the rapid development of nanotechnology products, there is a significant concern on the adverse effects that might be associated with them. Traditional biological assays are typically used to asses the toxicity in vitro. There are, however, questions regarding the suitability of these assays for this purpose, mainly due to the potential interaction of the particles with the utilized dyes. In addition, this process can be costly and time consuming, as a large number of different assays have to be used. To address some of these issues, Raman spectroscopy is used in this study to investigate the particle‐cell interactions. The spectrum of a living cell is a very complex and rich collection of data directly related to its chemical composition. To enhance the data resolution and make the detection of toxicity more robust, data‐mining techniques have been deployed. Furthermore, data‐mining techniques enable full automation of the entire process, minimizing user input. The Raman spectroscopy successfully evaluated the toxicity of TiO₂ nanoparticles by both the peak‐by‐peak analysis and with the implementation of support vector machines. The particles were found to display cytotoxicity after 36 h of exposure. The results were confirmed by MTT (3‐(4,5‐Dimethylthiazol‐2‐Yl)‐2,5‐Diphenyltetrazolium Bromide) assay and are in agreement with the existing literature on the subject. Overall, Raman spectroscopy appears to be among the very few techniques that exhibit low levels of interferences (obscuration, fluorescence, emission, etc.) from the particle addition. Since it does not rely on biomarkers, it can be used in situ for an extended period with minimal effects on the cellular biochemistry. Copyright © 2011 John Wiley & Sons, Ltd.     

氧化锌纳米粉体的制备及其光催化性能研究

采用溶胶-凝胶法制备了氧化锌光催化剂,分别利用XRD、TG、FT-IR对所制粉体进行了表征。结果表明ZnO为六方晶系纤锌矿型,粒子大小约为27nm。粉体的IR光谱表明,热处理后NH基团和单乙酸锌的吸收峰消失,在470cm-1附近出现Zn-O伸缩振动。纳米粉体的光催化降解水杨酸实验结果显示出,焙烧后所得的纤锌矿型ZnO粉体具有较高的光催化活性,以310nm波长光照射16小时可降解水杨酸95.1%。