Use of titanium dioxide photocatalysis on the remediation of model textile wastewaters containing azo dyes

The photocatalytic degradation of two commercial textile azo dyes, namely C.I Reactive Black 5 and C.I Reactive Red 239, has been studied. TiO(2) P25 Degussa was used as catalyst and photodegradation was carried out in aqueous solution under artificial irradiation with a 125 W mercury vapor lamp. The effects of the amount of TiO(2) used, UV-light irradiation time, pH of the solution under treatment, initial concentration of the azo dye and addition of different concentrations of hydrogen peroxide were investigated. The effect of the simultaneous photodegradation of the two azo dyes was also investigated and we observed that the degradation rates achieved in mono and bi-component systems were identical. The repeatability of photocatalytic activity of the photocatalyst was also tested. After five cycles of TiO(2) reuse the rate of colour lost was still 77% of the initial rate. The degradation was followed monitoring the change of azo dye concentration by UV-Vis spectroscopy. Results show that the use of an efficient photocatalyst and the adequate selection of optimal operational parameters may easily lead to a complete decolorization of the aqueous solutions of both azo dyes.     

Bactericidal mode of titanium dioxide photocatalysis

When exposed to near-UV light, titanium dioxide (TiO₂) exhibits a strong bactericidal activity. However, the killing mechanism(s) underlying the TiO₂ photocatalytic reaction is not yet well understood. The aim of the present study is to investigate the cellular damage sites and their contribution to cell death. A sensitive approach using o-nitrophenol β- galactopyranosideside (ONPG) as the probe and Escherichia coli as model cells has been developed. This approach is used to illustrate damages to both the cell envelope and intracellular components caused by TiO₂ photocatalytic reaction. Treatment of E. coli with TiO₂ and near-UV light resulted in an immediate increase in permeability to small molecules such as ONPG, and the leakage of large molecules such as β- galactosidase after 20 min. Kinetic data showed that cell wall damage took place in less than 20 min, followed by a progressive damage of cytoplasmic membrane and intracellular components. The results from the ONPG assay correlated well with the loss of cell viability. Cell wall damage followed by cytoplasmic membrane damage leading to a direct intracellular attack has therefore been proposed as the sequence of events when microorganisms undergo TiO₂ photocatalytic attack. It has been found that smaller TiO₂ particles cause quicker intracellular damage. Evidence has been obtained that indicated that the TiO₂ photocatalytic reaction results in continued bactericidal activity after the UV illumination terminates.     

Thick titanium dioxide films for semiconductor photocatalysis

Thick paste TiO₂ films are prepared and tested for photocatalytic and photoinduced superhydrophilic (PSH) activity. The films are effective photocatalysts for the destruction of stearic acid using near or far UV and all the sol–gel films tested exhibited a quantum yield for this process of typically 0.15%. These quantum yields are significantly greater (4–8-fold) than those for titania films produced by an APCVD technique, including the commercial self-cleaning glass product Activ™. The films are mechanically robust and optically clear and, as photocatalysts for stearic acid removal, are photochemically stable and reproducible. The kinetics of stearic acid photomineralisation are zero order with an activation energy of ca. 2.5 kJ mol⁻¹. All titania films tested, including those produced by APCVD, exhibit PSH. The light-induced fall, and dark recovery, in the water droplet contact angle made with titania paste films are similar in profile shape to those described by others for thin titania films produced by a traditional sol–gel route.     

Enhancement of titanium dioxide photocatalysis by water-soluble fullerenes

Fullerenes are known for their unique electronic properties including high electron affinity. Although use of fullerenes for scavenging photo-generated electrons from titanium dioxide particles has been demonstrated, no attempts have been made to utilize the unique properties of fullerenes to increase the efficacy of photocatalysis. The present study has demonstrated that a mixture of water-soluble polyhydroxy fullerenes (PHF) and titanium dioxide (anatase polymorph) enhances photocatalytic degradation of organic dye. The PHF molecules adsorbed to the surface of titanium dioxide due to electrostatic forces, with adsorption density being higher at lower pH values. The surface coverage of titanium dioxide nanoparticles by PHF molecules determined the extent of enhancement, with an optimum dosed weight ratio of PHF to titanium dioxide at 0.001. Hydroxylation and concomitant solubilization of fullerenes allow their unique electronic properties to be harnessed for photocatalysis.     

Modeling titanium dioxide nanostructures for photocatalysis and photovoltaics

Heterogenous photocatalysis is regarded as a holy grail in relation to the energy and environmental issues with which our society is currently struggling. In this context, the characterization of titanium dioxide nanostructures and the relationships between structural/electronic parameters and chemical/physical–chemical properties is a primary target, whose achievement is in high demand. Theoretical simulations can strongly support experiments to reach this goal. While the bulk and surface properties of TiO₂ materials are quite well understood, the field of nanostructures still presents a few unexplored areas. Here we consider possible approaches for the modeling of reduced and extended TiO₂ nanostructures, and we review the main outcomes of the investigation of the structural, electronic, and optical properties of TiO₂ nanoparticles and their relationships with the size, morphology, and shape of the particles. Further investigations are highly desired to fill the gaps still remaining and to allow improvements in the efficiencies of these materials for photocatalytic and photovoltaic applications.

The latest findings from theoretical investigations into TiO₂ nanoparticles are reviewed, including both realistic models from a bottom-up approach (1–3 nm diameter) and cut from bulk models (>3 nm diameter) in a top-down approach.     

Effect of silicon dioxide on the formation of the phase composition and pore structure of titanium dioxide with the anatase structure

The formation of the structure of titanium dioxide modified with silicon dioxide, which was introduced as tetraethyl orthosilicate, was studied. It was found that the formation of the nanocrystalline structure of TiO₂ occurred upon the modification of titanium dioxide with silicon dioxide. This nanocrystalline structure of TiO₂ was formed by highly dispersed anatase particles of size 6–10 nm stabilized by silicon oxide layers, which were formed upon the decomposition of tetraethyl orthosilicate. An increase in the modifier concentration resulted in a deceleration of the growth of anatase particles and an increase in the temperature of the phase transition of anatase to rutile. It was found that the anatase phase in the samples containing 5–15 wt % SiO₂ was stable up to 1000°C. The stabilization of highly dispersed anatase particles facilitated the retention of the developed fine-pore structure of xerogels with a pore diameter of 4 nm up to 900°C.     

Effect of yttrium oxide on the formation of the phase composition and porous structure of titanium dioxide

The formation of the structure of TiO₂ (anatase) doped with 1–5 mol % Y₂O₃ is reported. The dopant changes the anatase structure from regular to nanocrystalline. The nanocruystalline structure consists of incoherently intergrown 5- to 7-nm anatase crystallites (500°C) separated by interblock boundaries accommodating yttrium ions. The formation of the nanocrystalline anatase structure stabilizes small anatase crystallites and raises the anatase-to-rutile phase transition temperature above 900°C. Owing to this structure, the developed specific surface area and fine porous texture of yttrium oxide-doped titanium dioxide survive up to higher temperatures than those of undoped titanium dioxide.     

Photochronocoulometric measurement of the coverage of surface-bound dyes on titanium dioxide crystal surfaces

Atomically flat terraced single-crystal anatase and rutile surfaces can be prepared allowing for the reproducible adsorption of covalently attached sensitizing dyes. Once reproducible surfaces and dye coverages are achieved, a photochronocoulometric technique is developed to measure the surface coverage of the dyes, an important parameter in determining the efficiency of sensitization. The surface-bound dyes are irreversibly oxidized by exposure to a light pulse with the n-type oxide semiconductor electrode held in depletion. A double-exponential decay of the subsequent photocurrent is then measured, where the integration of the faster decay is associated with the adsorbed dye coverage and the second much slower decay is attributed to trace regenerators, including water, in the nonaqueous electrolyte. The ruthenium-based N3 dye shows the expected linear dependence of the rate constant on light intensity whereas a dicarboxylated thiacyanine dye shows a square root dependence of its photooxidation rate on light intensity. The sublinear response of the thiacyanine dye is discussed in terms of the more complex surface chemistry that is known for this family of sensitizing dyes.     

超声波-二氧化钛光催化耦合法降解高效氯氰菊酯

采用超声波-TiO2光催化耦合法降解高效氯氰菊酯,考察了高效氯氰菊酯初始浓度、降解时间、溶液pH、催化剂用量等对高效氯氰菊酯农药残留的降解效果,并利用水果进行了实物模拟.结果表明:利用超声波-TiO2光催化耦合法能够有效地降解高效氯氰菊酯农药残留.在弱酸环境中,当纳米TiO2投放量为1.2g/L时,经2h超声催化降解,不同浓度的高效氯氰菊酯农药稀释液均被有效降解,降解率最高可达98.3%.     

Titanium dioxide photocatalysis of adamantane

TiO₂ photocatalysis of adamantane in oxygen equilibrated MeCN yields 1- and 2-adamantanol and adamantanone with limited degradation and preference for functionalization at the 1 position, particularly in the presence of silver salts. Oxidation in CH₂Cl₂ is less selective. The oxidation of cyclohexane and cyclododecane is slower. In N₂-flushed solutions with Ag⁺ as a sacrificial acceptor, products from the trapping of both 1-adamantyl radical (adamantyl methyl ketone) and cation (N-adamantylacetamide) are obtained. Furthermore, alkylation of an electrophilic alkene (isopropylydenmalononitrile) has been obtained, though in a low yield.     

Preparation of anatase phase titanium dioxide film by non-aqueous electrodeposition

The electrodeposition–annealing route to fabricating thin film of the promising photocatalyst material anatase-titanium dioxide (anatase-TiO₂) has been studied. The sample was deposited with a solution of N,N-dimethylformamide containing titanium compound by controlled-potential technique. SEM image showed the annealed sample at 600 °C for 1 h under air provided a continuous film with a thickness of ca. 350 nm. In this sample, X-ray photoelectron spectrum corresponding to the Ti 2p peak assigned to a chemical bond of TiO₂ and X-ray diffraction peaks assigned to the anatase phase were observed, respectively. Electrochemical oxidation in sodium sulfate solution on this annealed film was enhanced in the presence of UV light radiation. These results confirm the successful synthesis of photocatalytic anatase-TiO₂ film by the electrodeposition and annealing process.     

基于二氧化钛光催化剂生物质转化制备氢气和化学品的研究进展

随着化石能源的枯竭和环境问题的日益严重,发展可再生资源变得越来越重要.太阳能和生物质是自然界中的两大可再生资源.利用太阳能转化生物质制备H2和化学品可以缓解对化石能源的依赖,是解决能源和环境问题的途径之一.本文作者概述了基于TiO2催化剂的光催化生物质制备H2和化学品的研究进展;着重介绍了甲醇、乙醇、甘油和葡萄糖的光催化反应选择性问题和机理研究,分析了存在的问题和可能的解决措施,并就其发展趋势进行了展望.     

The influence of various deposition techniques on the photoelectrochemical properties of the titanium dioxide thin film

Thin sol–gel TiO₂ layers deposited on the conductive ITO glass by means of three various deposition techniques (dip-coating, inkjet printing and spray-coating) were used as photoanode in the three-compartment electrochemical cell. The thin TiO₂ films were treated at 450 °C and after calcination all samples possessed the crystallographic form of anatase. The relationship between surface structure and photo-induced conductivity of the nanostructured layers was investigated. It was found that the used deposition method significantly influenced the structural properties of prepared layers; mainly, the formation of defects and their quantity in the prepared films. The surface properties of the calcined layers were determined by XRD, Raman spectroscopy, SEM, AFM, UV–Vis analyses and by the optical microscopy. The photo-induced properties of nanoparticulate TiO₂/ITO photoanode were studied by electrochemical measurements combined with UV irradiation.     

The fluorination of titanium dioxide surfaces

Summary Gaseous hydrogen fluoride gave a bulk attack on titanium dioxide but dilute aqueous hydrofluoric acid gave a partial surface fluorination. A specific fluoride for chloride exchange reaction occurs on chloride containing titanium dioxide surfaces. A weak and a strong form of fluoride adsorption may be distinguished, the former being removed by prolonged treatment with water, the latter requiring steam at 1020 K for its complete removal. Some infra-red, electrophoretic and acidity studies on various fluorinated surfaces are reported.

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Zusammenfassung Eine verdünnte wäßrige Fluorwasserstoffsäure fluoriert Titandioxid teilweise an der Oberfläche, während Fluorwasserstoffgas auch das Kristallinnere angreift. Eine spezifische Austauschreaktion Fluorid gegen Chlorid tritt an chloridhaltigen Titandioxidoberflächen auf. Man kann zwischen einer schwachen und einer starken Fluoridadsorption unterscheiden. Die schwächer adsorbierten Fluoridionen werden durch längere Behandlung mit Wasser verdrängt, die stärker adsorbierten dagegen nur durch Dampf bei 1020 K. In der Arbeit wird außerdem über IR-Studien sowie über elektrophoretische Messungen und Aziditätsuntersuchungen an verschiedenen fluorierten Oberflächen berichtet.

     

The adsorption properties of titanium dioxide

The adsorption properties of titanium dioxide were studied by gas chromatography. We used organic compounds from different classes, namely, n-alkanes, n-alkenes (C₆-C₈), and polar compounds (electron donors and acceptors) as test adsorbates. The differential heats of adsorption and the contributions of dispersion and specific intermolecular interaction energies were determined for the systems from the experimental retention data. The electron-donor and electron-acceptor characteristics of the ultimately hydroxylated surface of TiO₂ were evaluated.     

Reduction of NO2 to nitrous acid on illuminated titanium dioxide aerosol surfaces: implications for photocatalysis and atmospheric chemistry

TiO2, a component of atmospheric mineral aerosol, catalyses the reduction of NO2 to nitrous acid (HONO) when present as an aerosol and illuminated with near UV light under conditions pertinent to the troposphere.     

A study of phase transformations in the surface layer of titanium dioxide

The capabilities of the diffuse reflectance spectroscopy in a study of the state of the surface layer of anatase in anatase-rutile phase transformations in successive thermal treatments of anatase in the temperature range 200–900°C and in analysis of titanium dioxide of P25 brand (Degussa) containing anatase and rutile in a 80: 20 ratio, respectively, are demonstrated for the example of dispersed titanium oxide.     

Heterogenous solar photocatalysis of two commercial reactive azo dyes

Two commercial reactive azo dyes--Reactive Black 5 (RB5) and Reactive Orange 16 (RO 16) have been treated by titanium dioxide and Zinc oxide photocatalysts separately under presence of sunlight. It is observed that solar photocatalytic treatment is effective in terms of colour and COD. The photodegradation efficiency of zinc oxide is comparable with TiO2 at pH 5-6 for RO16. The extent of decolourization and degradation of RB5 is greater in presence of zinc oxide photocatalyst than TiO2 at pH 5- 6. Zinc oxide undergoes <1% photodissolution after 6 hours of solar irradiation at working pH.     

Kinetic rules of precipitation of thin films of titanium dioxide from the gas phase containing titanium tetraisopropylate

Precipitation of titanium dioxide layers from the gas phase in the reaction system containing titanium tetraisopropylate and oxygen at the total pressure 1 kPa is studied. It is shown that in the range of 300–500°C the precipitation proceeds in the kinetic regime and is accompanied by the formation of layers of monotonous thickness containing nanocrystalline phases of anatase and rutile. In the temperature range 300–350°C the activation energy value was 92.7 kJ mol^?1, and at higher temperatures (up to 500°C) it decreased to 17.5 kJ mol^?1. The increase in the precipitation temperature caused the increase in relative amount of rutile in the precipitated layers.