Enhanced photocatalytic reduction of Hg(II) in aqueous medium by 2-aminothiazole-modified TiO2 particles

This work describes the synthesis and characterization of 2-aminothiazole-modified titania and its application on Hg (II) photoreduction in aqueous medium. Infrared spectroscopy confirmed the chemical modification of the titania matrix. The number of 2-aminothiazole groups attached to the titania was determined by Kjeldahl's method. The photocatalytic experiments were carried out in a cylindrical photoreactor thermostatted at 298 K. The resulting modified photocatalyst 2-aminothiazole titania (TiAT) revealed an enhance in the Hg (II) photoreduction capacity at studied pH values (3, 7 and 9). In addition, sorption studies showed that the photocatalyst TiAT presented a lower equilibrium time and a higher sorption capacity of Hg(II) ion, demonstrating that sorption plays a fundamental role in the photoreduction mechanism. ©2006 Sociedade Brasileira de Química.

Fotocatálise heterogênea em instrumental odontológico recoberto com nanopartículas TiO2 e Ag

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Crescimento de nanotubos de TiO2 na superfície da liga Ti-7,5Mo empregando oxidação anódica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Photocatalytic decomposition of rhodamine-B using scandium and silver-modified TiO2 Powders

Semiconductor-mediated photocatalytic oxidation is an interesting method for water decontamination and a specially modified TiO2 is said to be a promising material. This study verified that the synthesis of 1wt%Ag modified-Sc0.01Ti0.99O1.995 powder samples prepared by Polymeric Precursor Method is capable of forming a mixture of anatase-rutile phase with high photocatalytic performance. This kind of material is found to have a lower bandgap compared to the TiO2-anatase commercial powders, which can be associated to an innovative hybrid modification. The simultaneous insertion of scandium in order to generate a p-type semiconductor and a metallic silver nanophase acting as an electron trapper demonstrated being capable of enhancing the degradation of rhodamine B compared to the commercial TiO2. In spite of the different thermal treatments or phase amounts, the hybrid modified powder samples showed higher photocatalytic activity than the commercial ones.

Understanding growth mechanisms and tribocorrosion behaviour of porous TiO2 anodic films containing calcium, phosphorous and magnesium

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Modificação de eletrodos de carbono vítreo e nanotubos de Ti/TiO2 com aspirinato de cobre (II) para detecção eletroquímica e redução fotoeletrocatalítica de íons nitrito

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Improving the Photoelectrochemical Response of TiO2 Nanotubes upon Decoration with Quantum-Sized Anatase Nanowires

TiO2 nanotubes (NTs) have been widely used for a number of applications including solar cells, photo(electro)chromic devices, and photocatalysis. Their quasi-one-dimensional morphology has the advantage of a fast electron transport although they have a relatively reduced interfacial area compared with nanoparticulate films. In this study, vertically oriented, smooth TiO2 NT arrays fabricated by anodization are decorated with ultrathin anatase nanowires (NWs). This facile modification, performed by chemical bath deposition, allows to create an advantageous self-organized structure that exhibits remarkable properties. On one hand, the huge increase in the electroactive interfacial area induces an improvement by 1 order of magnitude in the charge accumulation capacity. On the other hand, the modified NT arrays display larger photocurrents for water and oxalic acid oxidation than bare NTs. Their particular morphology enables a fast transfer of photogenerated holes but also efficient mass and electron transport. The importance of a proper band energy alignment for electron transfer from the NWs to the NTs is evidenced by comparing the behavior of these electrodes with that of NTs modified with rutile NWs. The NT-NW self-organized architecture allows for a precise design and control of the interfacial surface area, providing a material with particularly attractive properties for the applications mentioned above.

Cobalt promoted TiO2/GO for the photocatalytic degradation of oxytetracycline and Congo Red

A family of titania derived nanocomposites synthesized via sol-gel and hydrothermal routes exhibit excellent performance for the photocatalytic degradation of two important exemplar water pollutants, oxytetracycline and Congo Red. Low loadings of Co3O4 nanoparticles dispersed over the surfaces of anatase TiO2 confer visible light photoactivity for the aqueous phase decomposition of organics through the resulting heterojunction and reduced band gap. Subsequent modification of these Co3O4/TiO2 composites by trace amounts of graphene oxide nanosheets in the presence of a diamine linker further promotes both oxytetracycline and Congo Red photodegradation under simulated solar and visible irradiation, through a combination of enhanced photoresponse and consequent radical generation. Radical quenching and fluorescence experiments implicate holes and hydroxyl radicals as the respective primary and secondary active species responsible for oxidative photodegradation of pollutants.

Lead oxide-modified TiO2 photocatalyst: tuning light absorption and charge carrier separation by lead oxidation state

Modification of TiO2 with metal oxide nanoclusters such as FeOx, NiOx has been shown to be a promising approach to the design of new photocatalysts with visible light absorption and improved electron–hole separation. To study further the factors that determine the photocatalytic properties of structures of this type, we present in this paper a first principles density functional theory (DFT) investigation of TiO2 rutile(110) and anatase(001) modified with PbO and PbO2 nanoclusters, with Pb2+ and Pb4+ oxidation states. This allows us to unravel the effect of the Pb oxidation state on the photocatalytic properties of PbOx-modified TiO2. The nanoclusters adsorb strongly at all TiO2 surfaces, creating new Pb–O and Ti–O interfacial bonds. Modification with PbO and PbO2 nanoclusters introduces new states in the original band gap of rutile and anatase. However the oxidation state of Pb has a dramatic impact on the nature of the modifications of the band edges of TiO2 and on the electron–hole separation mechanism. PbO nanocluster modification leads to an upwards shift of the valence band which reduces the band gap and upon photoexcitation results in hole localisation on the PbO nanocluster and electron localisation on the surface. By contrast, for PbO2 nanocluster modification the hole will be localised on the TiO2 surface and the electron on the nanocluster, thus giving rise to two different band gap reduction and electron–hole separation mechanisms. We find no crystal structure sensitivity, with both rutile and anatase surfaces showing similar properties upon modification with PbOx. In summary the photocatalytic properties of heterostructures of TiO2 with oxide nanoclusters can be tuned by oxidation state of the modifying metal oxide, with the possibility of a reduced band gap causing visible light activation and a reduction in charge carrier recombination.

Greffage d’un film mince de nano-TiO2 sur les fibres naturelles cellulosiques pour le renforcement de biocomposites polymériques

Abstract : Natural materials have received a full attention in many applications because they are degradable and derived directly from earth. In addition to these benefits, natural materials can be obtained from renewable resources such as plants (i.e. cellulosic fibers like flax, hemp, jute, and etc). Being cheap and light in weight, the cellulosic natural fiber is a good candidate for reinforcing bio-based polymer composites. However, the hydrophilic nature -resulted from the presence of hydroxyl groups in the structure of these fibers- restricts the application of these fibers in the polymeric matrices. This is because of weak interfacial adhesion, and difficulties in mixing due to poor wettability of the fibers within the matrices. Many attempts have been done to modify surface properties of natural fibers including physical, chemical, and physico-chemical treatments but on the one hand, these treatments are unable to cure the intrinsic defects of the surface of the fibers and on the other hand they cannot improve moisture, and alkali resistance of the fibers. However, the creation of a thin film on the fibers would achieve the mentioned objectives. This study aims firstly to functionalize the flax fibers by using selective oxidation of hydroxyl groups existed in cellulose structure to pave the way for better adhesion of subsequent amphiphilic TiO[subscript 2] thin films created by Sol-Gel technique. This method is capable of creating a very thin layer of metallic oxide on a substrate. In the next step, the effect of oxidation on the interfacial adhesion between the TiO[subscript 2] film and the fiber and thus on the physical and mechanical properties of the fiber was characterized. Eventually, the TiO[subscript 2] grafted fibers with and without oxidation were used to reinforce poly lactic acid (PLA). Tensile, impact, and short beam shear tests were performed to characterize the mechanical properties while Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic mechanical analysis (DMA), and moisture absorption were used to show the physical properties of the composites. Results showed a significant increase in physical and mechanical properties of flax fibers when the fibers were oxidized prior to TiO[subscript 2] grafting. Moreover, the TiO[subscript 2] grafted oxidized fiber caused significant changes when they were used as reinforcements in PLA. A higher interfacial strength and less amount of water absorption were obtained in comparison with the reference samples.

Remediation Of 17-α-ethinylestradiol Aqueous Solution By Photocatalysis And Electrochemically-assisted Photocatalysis Using Tio2 And Tio2/wo3 Electrodes Irradiated By A Solar Simulator.

TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 μmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 μm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

Azul de metileno imobilizado na celulose/TiO2 e SiO2/TiO2: propriedades eletroquímicas e planejamento fatorial

The electrochemical properties of methylene blue immobilized on cellulose/TiO2 and mixed oxide SiO2/TiO2 matrices were investigated by means of cyclic voltammetry. The electron mediator property of the methylene blue was optimized using a factorial design, consisting of four factors in two levels. The experimental observations and data analyses on the system indicate that the lowest peak separation occurs for Sil/TiOAM, 1.0 mol L-1 KCl solution and 20 mV s-1 scan rate, while values of current ratio closest to unity were found for Cel/TiOAM independent of electrolyte concentration, 0.2 or 1.0 mol L-1, and scan rate, 20 mV s-1 or 60 mV s-1.

TiO2-Photocatalyzed degradation of phenol in saline media in an annular reactor: hydrodynamics, lumped kinetics, intermediates, and acute toxicity

The photocatalytic degradation of phenol in aqueous suspensions of TiO2 under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen-Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

Modification of composition of a nanoemulsion with different cholesteryl ester molecular species: Effects on stability, peroxidation, and cell uptake

Purpose: Use of lipid nanoemulsions as carriers of drugs for therapeutic or diagnostic purposes has been increasingly studied. Here, it was tested whether modifications of core particle constitution could affect the characteristics and biologic properties of lipid nanoemulsions. Methods: Three nanoemulsions were prepared using cholesteryl oleate, cholesteryl stearate, or cholesteryl linoleate as main core constituents. Particle size, stability, pH, peroxidation of the nanoemulsions, and cell survival and uptake by different cell lines were evaluated. Results: It was shown that cholesteryl stearate nanoemulsions had the greatest particle size and all three nanoemulsions were stable during the 237-day observation period. The pH of the three nanoemulsion preparations tended to decrease over time, but the decrease in pH of cholesteryl stearate was smaller than that of cholesteryl oleate and cholesteryl linoleate. Lipoperoxidation was greater in cholesteryl linoleate than in cholesteryl oleate and cholesteryl stearate. After four hours' incubation of human umbilical vein endothelial cells (HUVEC) with nanoemulsions, peroxidation was minimal in the presence of cholesteryl oleate and more pronounced with cholesteryl linoleate and cholesteryl stearate. In contrast, macrophage incubates showed the highest peroxidation rates with cholesteryl oleate. Cholesteryl linoleate induced the highest cell peroxidation rates, except in macrophages. Uptake of cholesteryl oleate nanoemulsion by HUVEC and fibroblasts was greater than that of cholesteryl linoleate and cholesteryl stearate. Uptake of the three nanoemulsions by monocytes was equal. Uptake of cholesteryl oleate and cholesteryl linoleate by macrophages was negligible, but macrophage uptake of cholesteryl stearate was higher. In H292 tumor cells, cholesteryl oleate showed the highest uptakes. HUVEC showed higher survival rates when incubated with cholesteryl stearate and smaller survival with cholesteryl linoleate. H292 survival was greater with cholesteryl stearate. Conclusion: Although all three nanoemulsion types were stable for a long period, considerable differences were observed in size, oxidation status, and cell survival and nanoemulsion uptake in all tested cell lines. Those differences may be helpful in protocol planning and interpretation of data from experiments with lipid nanoemulsions.

A NOTES Modification of the Transanal Pull-Through

Transanal endorectal pull-through (TAEPT) surgery is primarily performed for rectosigmoid aganglionosis, generally with excellent results. There is evidence that overstretching the anus and tension traction in the sigmoid during the procedure could impair the final continence of the patient. Many researchers suggest the use of small umbilical or laparoscopic access to aid in colon mobilization, thus preventing excessive handling within the anal canal. We assumed that transabdominal mobilization of the sigmoid could be prevented by utilizing the NOTES (natural orifices transluminal endoscopic surgery) technique. We performed a TAEPT with NOTES access of the sigmoid vascular pedicle, keeping the surgery exclusively transanal, which prevented scars in the abdomen and minimized the stretching of perineal structures.