Sonophotocatalytic degradation of sodium diclofenac using low power ultrasound and micro sized TiO2

The nonsteroidal anti-inflammatory drug sodium diclofenac (DC) is an emerging water pollutant which resists conventional wastewater treatments. Here the sonophotocatalytic degradation of DC was carried out using micrometric TiO₂ (both pristine and Ag-decorated), UV-A irradiation and 20 kHz pulsed ultrasound. Sonophotocatalytic tests were compared with photolysis, sonolysis, sonophotolysis, sonocatalysis and photocatalysis data performed in the same conditions. A synergy index of over 2 was determined for tests with pristine TiO₂, while values close to 1.3 were observed for Ag-TiO₂. Reaction intermediates were studied by HPLC–MS, showing degradation mechanisms activated by hydroxyl radicals. Similar pathways were identified for photocatalytic and sonophotocatalytic tests, although the latter led to more oxidized compounds. Different reactor configurations (static and dynamic set ups) were studied. Sequential and simultaneous application of UV light and ultrasound led to similar performance. The role of water matrix was investigated using ultrapure and drinking water, showing marked detrimental effects of electrolytes on the DC degradation. Overall, the combined treatment proved more efficient than photocatalysis alone especially in demanding working conditions, like in drinking water matrices.     

Activation of TiO2 photocatalyst by single-bubble sonoluminescence for water treatment

Single-bubble sonoluminescence (SBSL) continues to attract many researchers because the physics behind it remains uncertain and few applications have appeared. In this study, we propose to apply SBSL to a water-treatment technique. The SBSL flashes contain intense ultraviolet light, which activates a TiO2 photocatalyst to decompose organic compounds in water. This mechanism comes from the similar spectrum patterns between SBSL emission and TiO2 absorption. SBSL in solutions containing small amount of TiO2 powder decomposed phenol and 2,4-dinitrophenol with efficiency several times higher than those by the existing methods.     

Sonophotocatalytic degradation of methyl orange by carbon nanotube/TiO2 in aqueous solutions

In this study, carbon nanotubes (CNTs)/TiO2 composite were prepared and the sonophotocatalytic activity of CNTs/TiO2 nanoparticles was investigated, in which methyl orange (MO) was chosen as an object. The results indicate that the photocatalytic efficiency of CNTs/TiO2 remarkable increases in the presence of ultrasound, and the sonophotocatalysis process followed a first-order kinetics. The kinetic constant of CNTs/TiO2 for the MO degradation is 2.2 times higher than that of P25, which indicated that the sonophotocatalytic ability of CNTs/TiO2 is obviously higher than P25 powder.     

Sonochemical synthesis of TiO(2 nanoparticles on graphene for use as photocatalyst

Using ultrasonication we succeed in a controlled incorporation of TiO(2) nanoparticles on the graphene layers homogeneously in a few hours. The average size of the TiO(2) nanoparticles was controlled at around 4-5 nm on the sheets without using any surfactant, which is attributed to the pyrolysis and condensation of the dissolved TiCl(4) into TiO(2) by ultrasonic waves. The photocatalytic activity of the resultant graphene-TiO(2) composites containing 25 wt.% TiO(2) is better than that of commercial pure TiO(2). This is partly due to the extremely small size of the TiO(2) nanoparticles and partly due to the graphene-TiO(2) composite structure consisting of homogeneous dispersion of crystalline TiO(2) nanoparticles on the graphene sheets. As the graphene in the composites has a very good contact with the TiO(2) nanoparticles it enhances the photo-electron conversion of TiO(2) by reducing the recombination of photo-generated electron-hole pairs.     

TiO2 nanotubes: photocatalyst for cancer cell killing

The present work reports on the use of self‐organized TiO₂ nanotube layers for the photocatalytic killing of cancer cells. TiO₂ nanotube layers with different dimensions (diameter 50 nm and 100 nm, thickness 800 nm and 1.3 μm, respectively) were grown by anodization of Ti. Upon low dose of UV irradiation, the vitality of cancer cells cultured on these nanotube layers was significantly affected – the cells reduced their shape and size and a significant amount of the dead cells was found. These results demonstrate that self‐organized TiO₂ nanotube layers can be used for photo‐induced cancer cell killing. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Sonophotocatalytic degradation of methyl orange by nano-sized Ag/TiO2 particles in aqueous solutions

Sonophotocatalytic behaviour of methyl orange (MeO) in aqueous solution illuminated by light generated by a xenon lamp was investigated. For all three kinds of photocatalysts: Degussa P25 (75% anatase, 25% rutile, with a surface area of 55.07 m(2)/g), Yili TiO(2) (mainly anatase, with a surface area of 10.45 m(2)/g) and Ag/TiO(2) (silver loaded on Yili TiO(2)), the degradation followed pseudo-first order kinetics. The results showed a synergistic effect between sonolysis and photocatalysis. Some parameters affecting the sonophotocatalytic degradation of MeO with nanoparticles Ag/TiO(2) were determined. The results indicated that the degradation ratio of MeO increased with the increase of ultrasonic power. An optimum 60 mg/L of Ag/TiO(2) added to relatively low concentrations of MeO was proved to have the most effective degradation efficiency. The study on the effects of hydroxyl radical (*OH) scavengers (i.e. mannitol and dimethyl sulfoxide) on the MeO degradation indicated that *OH radicals played an important role during MeO degradation, which enhanced MeO to be completely decomposed.     

Sonochemical fabrication of mesoporous TiO2 inside diatom frustules for photocatalyst

Mesoporous titanium dioxide (TiO₂) has been assembled inside the macropores of diatom frustules by sonochemical condensation of titania precursor, and then thermal treated at an elevated temperature. The resulting hierarchical macro/mesoporous-structures of the TiO₂ inside diatom were confirmed by characterizations of X-ray diffraction (XRD) and transmission electron microscopy (TEM). The amount of TiO₂ inside the periodic macropores of diatom was controlled by varying the sonication time. It was found that the resultant composite with only 30 wt% TiO₂ loading delivered a high photocatalytic performance, even better than that of pure P25. This is attributed to its hierarchical macro/mesoporous structure as it provides a large number of accessible active sites for efficient transportations of guest species to framework binding sites. Other macro/mesoporous structures with a nearly endless variety of functional chemistries and shapes are expected to be produced, leading to a range of novel applications in remediation, molecular transportation and environmental field by using this facile strategy.     

Sonophotocatalytic degradation of congo red and methyl orange in the presence of TiO2 as a catalyst

A comparative study between the photocatalytic and sonophotocatalytic oxidation process of congo red was carried out using titanium dioxide as a catalyst. The effect of a number of parameters, such as the initial concentration of dye, the presence of oxygen and ultrasound, the TiO(2) crystalline structure and the amount of TiO(2), was studied using an inexpensive reactor. In the second part of this document, the oxidation and reduction processes of methyl orange was studied using the same reactor, but by changing the chemical environment in order to drive either the oxidation or the reduction reaction. The results showed, for all the cases studied, a sinergistic effect between sonolysis and photocatalysis when an ultrasonic bath of 80W was used as a source of ultrasound. On the other hand, the electrochemical experiments showed that the current densities for the oxidation process of the azodyes were higher when a conducting glass electrode covered with a thin film of TiO(2) was used as a working electrode instead of a platinum electrode, showing that the TiO(2) electrode is not passivated by the oxidation reaction.     

第一性原理研究Eu/N共掺杂锐钛矿TiO2光催化剂的电子和光学性质

基于密度泛函理论的第一性原理平面波赝势方法, 运用Vasp方法计算了Eu, N掺杂及Eu/N共掺杂锐钛矿TiO₂的结构, 并分析了其电子及光学性质. 通过计算发现有一些Eu的4f态电子在Eu掺杂锐钛矿TiO₂的体系的费米能级附近出现杂质能级, 并且N掺杂会使得锐钛矿TiO₂的禁带宽度减小. 对于共掺杂体系而言, Eu/N共掺杂的协同效应能导致锐钛矿TiO₂的晶格畸变及禁带宽度减小. 与此同时, 计算得到的光吸收谱表明Eu/N混合掺杂锐钛矿TiO₂展现出了明显的光谱吸收边缘红移. 这些计算结果表明Eu/N共掺杂锐钛矿TiO₂具有优良的光催化活性. 关键词： 2')" href="#">TiO₂ 共掺杂 可见光催化剂 密度泛函理论     

Non-metal doped TiO2 nanotube arrays for high efficiency photocatalytic decomposition of organic species in water

Titanium dioxide is a well-known photoactive semiconductor with a variety of possible applications. The procedure of pollutant degradation is mainly performed using TiO₂ powder suspension. It can also be exploited an immobilized catalyst on a solid support. Morphology and chemical doping have a great influence on TiO₂ activity under illumination. Here we compare photoactivity of titania nanotube arrays doped with non-metal atoms: nitrogen, iodine and boron applied for photodegradation of organic dye - methylene blue and terephtalic acid. The doped samples act as a much better photocatalyst in the degradation process of methylene blue and lead to the formation of much higher amount of hydroxyl radicals (•OH) than undoped TiO₂ nanotube arrays. The use of a catalyst active under solar light illumination in the form of thin films on a stable substrate can be scaled up for an industrial application.     

Structural properties of TiO2 nanocrystallites condensed in vapor-phase for photocatalyst applications

We have synthesized titanium dioxide (TiO₂) nanocrystallites by pulsed laser ablation (PLA) in oxygen (O₂) background gas for photocatalyst applications. Varying O₂ background gas pressure \( \left( {P_{{{\text{O}}_{ 2} }} } \right) \) or substrate target distance (D _TS), it was possible to change weight fraction of anatase phase in the anatase/rutile mixture from 0.2 to 1.0. Porosity of the deposited TiO₂ films increased with increasing \( \left( {P_{{{\text{O}}_{ 2} }} } \right) \) and D _TS. Relation between the process parameters and the formed crystal phases was explained from the point of cooling process in vapor-phase. Furthermore, rapid thermal annealing (RTA) was performed as post-annealing, suppressing sintering of the nanocrystallites. Photocatalytic activities of the TiO₂ nanocrystallites depended on the RTA temperature and following crystallinity restoring as well as the crystal phase: anatase or rutile.     

Degradation of organic water pollutants through sonophotocatalysis in the presence of TiO(2)

The degradation of 2-chlorophenol and of the two azo dyes acid orange 8 and acid red 1 in aqueous solution was investigated kinetically under sonolysis at 20 kHz and under photocatalysis in the presence of titanium dioxide particles, as well as under simultaneous sonolysis and photocatalysis, i.e. sonophotocatalysis. The influence on the degradation and mineralisation rates of the initial substrate concentration and of the photocatalyst amount was systematically investigated to ascertain the origin of the synergistic effect observed between the two degradation techniques. The evolution of hydrogen peroxide during kinetic runs was also monitored. Small amounts of Fe(III) were found to affect both the adsorption equilibria on the semiconductor and the degradation paths. Ultrasound may modify the rate of photocatalytic degradation by promoting the deaggregation of the photocatalyst, by inducing the desorption of organic substrates and degradation intermediates from the photocatalyst surface and, mainly, by favouring the scission of the photocatalytically and sonolytically produced H(2)O(2), with a consequent increase of oxidising species in the aqueous phase.     

Laser ablation condensation of alpha-PbO(2)-type TiO(2)

A high-pressure phase of TiO(2) with an alpha-PbO(2)-type structure has been synthesized via very energetic Nd-YAG laser pulse irradiation of oxygen-purged Ti target. The nanometer-size alpha-PbO(2)-type particles were (11;0), (010), and (001) faceted but the larger ones were spherical. The combined effects of rapid heating and cooling, the nanophase effect, and dense surfaces account for the formation of coherently strained alpha-PbO(2) particles. The refined cell volume indicated a considerable residual stress to stabilize the dense structure to ambient condition.     

TiO2/carboxylate-rich porous carbon: A highly efficient visible-light-driven photocatalyst based on the ligand-to-metal charge transfer (LMCT) process

A novel visible-light-driven photocatalyst based on TiO₂/carboxylate-rich porous carbon composite (TiO₂/CRPC) was successfully synthesized by low temperature carbonization process in air. Sodium gluconate plays a crucial role in the formation of TiO₂/CRPC. Different functional groups of sodium gluconate play synergetic roles in the formation of TiO₂/CRPC. XRD and Raman spectra studies indicated that there are two different TiO₂ crystalline phases existing in TiO₂/CRPC, which are anatase and brookite, and the CRPC is amorphous. Via FT-IR and XPS spectra investigations, it was demonstrated that carboxylate group, the ligand-to-metal charge transfer (LMCT) forming functional group, was solidified into the CRPC and form the LMCT complex on TiO₂ surface through the fabrication of TiO₂/CRPC. Compared with the pure TiO₂, TiO₂/CRPC exhibit enhanced absorption in the UV and visible light region around 260–600 nm. The strong absorption in the visible light region gives TiO₂/CRPC advantages over pure TiO₂ for the degradation of organic pollutants. TiO₂/CRPC can activate O₂ in air under mild conditions and exhibit excellent visible-light-driven photocatalytic activities. However, TiO₂/C composite obtained by using glucose instead of sodium gluconate exhibits poor photocatalytic activity, which demonstrated that carboxylate–TiO₂ complexes are responsible for the prominent photocatalytic properties of TiO₂/CRPC under visible light irradiation.     

Nanostructured carbon nanotube/TiO2 composite coatings using electrophoretic deposition (EPD)

Electrophoretic deposition (EPD) has been used to combine multi-walled carbon nanotubes of diameter in the range 20–30 nm and commercially available TiO₂ nanoparticles (23 nm particle size) in composite films. Laminate coatings with up to four layers were produced by sequential EPD, while composite coatings were obtained by electrophoretic co-deposition of carbon nanotubes and TiO₂ nanoparticles, respectively. Scanning electron microscopy was used to characterize the resultant microstructures. The mechanism of EPD of carbon nanotube/TiO₂ nanoparticle composites is discussed.     

Surface structure of TiO2(011)-(2x1)

A combined experimental and first principles study of the (2x1)-reconstructed rutile TiO2(011) surface is presented. Our results provide evidence that the surface structure is described by a model that includes onefold coordinated (titanyl) oxygen atoms giving rise to double bonded Ti=O species. These species should play a special role in the enhanced photocatalytic activity of the TiO2(011) surface.     

Development of photocatalyst coated fluoropolymer based microreactor using ultrasound for water remediation

Formation of thin layers of photocatalyst in photo-microreactor is a challenging work considering the properties of both catalyst and the microchannel material. The deposition of semiconductor materials on fluoropolymer based microcapillary requires the use of economical methods which are also less energy dependent. The current work introduces a new method for depositing nanoparticles of TiO₂ on the inner walls of a hexafluoropropylene tetrafluoroethylene microtube under mild conditions using ultrasound technique. During the ultrasonication process, changes in the polymer surface were observed and characterized using Attenuated Total Reflectance spectroscopy, Scanning Electron Microscopy and Confocal Microscopy. The rough patches form sites for catalyst deposition resulting in the formation of thin layer of TiO₂ nanoparticles in the inner walls of the microtube. The photocatalytic activity of the TiO₂ coated fluoropolymer based microcapillary was evaluated for removal of phenol present in water.     

Titanium overlayers on TiO2(110)

Non-stoichiometric, Ti-rich TiO₂(110) surfaces were prepared by evaporation of Ti on stoichiometric TiO₂(110). Changes in the spectra of core levels, valence bands, Auger emissions, electron energy losses, conductivities and work functions were investigated during overlayer formation in the monolayer range and during subsequent annealing of non-stoichiometric surfaces at high temperatures and high oxygen partial pressures. These annealing procedures make it possible to restore the ideal stoichiometry of TiO₂(110). The results are discussed quantitatively by calculating concentrations of (sub)surface intrinsic defects in a space-charge layer model.     

A periodic DFT study of water and ammonia adsorption on anatase TiO2 (001) slab

Water and ammonia adsorption mechanisms on anatase TiO₂ (001) slab surface are investigated by means of periodic DFT approach. Molecular and dissociative adsorption energies for water are calculated to be ? 15 kcal/mol and ? 32 kcal/mol, respectively. Similarly, molecular and dissociative adsorption energies of ammonia on the same surface are found as ? 25 kcal/mol and ? 20 kcal/mol. A reverse result in this order is reached for the previous case of ONIOM cluster study (? 23 kcal/mol and ? 37 kcal/mol, respectively). The vibration frequency values are computed for the optimized geometries of adsorbed water and ammonia molecules on anatase TiO₂ (001) slab surface and compared with the values reported in the literature.