Hybrid photocatalysts for the degradation of trichloroethylene in air

Hybrid photocatalysts based on an adsorbent SiMgOx and a photocatalyst TiO(2) were developed in a plate shape. The ceramic surface was coated with TiO(2) by the slip-casting technique. The effect of the support in the photocatalytic degradation of trichloroethylene (TCE) was analyzed by modifying TiO(2) loading and the layer thickness. Photocatalysts were characterised by N(2) adsorption-desorption, mercury intrusion porosimetry, SEM, UV-vis spectroscopy and XRD. A direct relationship between the TiO(2) content and the photocatalytic activity was observed up to three layers of TiO(2) (0.66 wt.%). Our results indicate that intermediate species generated on the TiO(2) layer can migrate through relatively long distances to react with the OH(-) surface groups of the support. By increasing the TiO(2) loading of the photocatalyst two effects were observed: trichloroethylene conversion is enhanced, while the efficiency of the oxidation process is decreased at expenses of increasing the selectivity to COCl(2) and dichloroacetylchloride (DCAC). The results are discussed in terms of the layer thickness, TiO(2) amount, TCE conversion and CO(2), and COCl(2) selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Anodic oxidation of wastewater containing the Reactive Orange 16 Dye using heavily boron-doped diamond electrodes

Boron-doped diamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10(21) atoms cm(-3), respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman`s spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 00). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process. (C) 2011 Elsevier B.V. All rights reserved.

Carbon supported electrocatalysts prepared by the sol-gel method and their utilization for the oxidation of methanol in acid media

One of the key objectives in fuel-cell technology is to improve the performance of the anode catalyst for the alcohol oxidation and reduce Pt loading. Here, we show the use of six different electrocatalysts synthesized by the sol -gel method on carbon powder to promote the oxidation of methanol in acid media. The catalysts Pt-PbO(x) and Pt-(RuO(2)-PbO(x)) with 10% of catalyst load exhibited significantly enhanced catalytic activity toward the methanol oxidation reaction as compared to Pt-(RuO(2))/C and Pt/C electrodes. Cyclic voltammetry studies showed that the electrocatalysts Pt-PbO(x)/C and Pt-(RuO(2)-PbO(x))/C started the oxidation process at extremely low potentials and that they represent a good novelty to oxidize methanol. Furthermore, quasi-stationary polarization experiments and cronoamperometry studies showed the good performance of the Pt-PbO(x), Pt-(RuO(2)-PbO(x))/C and Pt-(RuO(2)-IrO(2))/C catalysts during the oxidation process. Thus, the addition of metallic Pt and PbO(x) onto high-area carbon powder, by the sol -gel route, constitutes an interesting way to prepare anodes with high catalytic activity for further applications in direct methanol fuel cell systems.

Degradation of VOCs by phototcatalytic oxidation reactor using TiO2 pellets

Volatile Organic Compounds (VOCs) are air pollutants that come from burning fossil fuels and industrial emissions. They have potentially adverse health effects being carcinogenic and highly persistent in the environment. The use of photocatalytic oxidation to remove VOCs has the potential to be applied in indoor air quality improvement and industrial emission control. A fixed bed photocatalytic reactor was designed and built. UV black light lamps were installed in the reactor to provide a source of UV radiation. A non-film titania media as pellets were placed on the three fixed beds within the reactor. Toluene and acetone were used as indicators of VOCs during the experiment. With a flow rate of 12.75l/min, the oxidation efficiencies were obtained at four different concentrations of acetone laden gas streams ranging from 40ppm to 250ppm. It was found that the lower the acetone concentration of the untreated inlet gas, the higher the oxidation efficiency. The oxidation efficiency was in the range of 40–70% for various concentrations of untreated gases. Two concentrations of toluene laden gas stream were also tested using the same reactor. The oxidation efficiencies were found as 50% for 120ppm toluene gas and 45% for 300ppm toluene gas. It was found that the times required for toluene to reach oxidization equilibrium have been halved than for acetone gas stream. Other parameters such as flow rate and UV intensity were also altered to see their effects on the oxidation efficiency. A full spectrum scan was carried out using a Bio-rad Infrared spectrometer. It was found that the main components of the treated gas stream from the outlet of the reactor were CO2 and water along with small amount of untreated acetone. The suspected intermediates of aliphatic hydrocarbons and CO were found in very minimal amounts or undetectable. The research experiments supported that the TiO2 pellets can work effectively in a fixed bed photocatalytic reactor and achieve significant oxidation efficiencies for degradation of toluene and acetone as indicators of VOCs.

Photocatalytic degradation of dyes in wastewater using TiO2/UV in a flat-plate reactor

The photocatalyst TiO₂ with UV irradiation was used to degrade dyes in textile effluent in a flat-plate photoreactor. A test system was built with the reactor area of 1 x 0.3m2, UV light of six 36W-blacklight. TiO₂ powder P25 with BET surface area 50±15m2/g, average primary particle size 21 nm, purity> 99.5% and content of 83.9% anatase and 16.1 % rutile was used as the photocatalyst. A number of dyes commonly present in dyeing wastewater were tested in this study. The different operating parameters, such as dosage of photocatalyst, the structure of the reactor, flow rates through the flat-plate reactor, UV radiation intensity and tilted angle of the reactor, were investigated. The results showed that the photocatalytic process could efficiently remove most of the colour contained in the dyeing wastewater. It was experimentally observed that first-order kinetics was adequate for characterising the process. The flow rate and the tilted angle had some influence on the film thickness of the fluid in the reactor and the empirical correlation between the film thickness of the fluid and these two parameters was developed. The photoreaction rate was mainly determined by the film thickness of the fluid on the reactor surface and the dosage of the photocatalyst. Optimum operating parameters of the system were found to be at the film thickness of about 1.4mm and a TiO₂ dosage of 1 gIL. The higher the UV intensity, the faster the reaction rate was. The results of these experiments showed that this method has the great potential for colour removal from wastewater at commercial scale.

To overcome the common difficulty of separating the used TiO₂ suspension after treatment precipitation followed with filtration was used in this study to determine the separation efficiencies. On the other hand, TiO₂ in a small pillar shape was also studied for photocatalytic degradation of textile dye effluent. The pillar pellet was made in Oegussa Company, Germany ranging from 2.5 to 5.3mm long and with a diameter of 3.7mm. It was almost pure TiO₂ (83.2% anatase and 16.8% rutile), with a S-content of <20 ppm and a CI content of the order of 0.1 wt. %. No further elements are present in contents above 0.05 wt.%. The TiO₂ pillars were placed on the flat-plate reactor that was divided by the rectangular slots and irradiated under UV light when the treated solution went through the reactor. Four dyes and their mixtures were tested. The results showed that the photocatalytic process under this configuration efficiently remove the colour from textile dyeing effluent, and pillar shape TiO₂ photocatalyst was not dissolved in water and very easy to be separated from solution, enabling it to be reused many times. The first-order kinetics was adequate for characterising the photocatalytic degradation process and the photocatalytic performance was comparable to TiO₂ powder. It is believed that the TiO₂ pellet would be a preferable form of photocatalyst in applications for textile effluent treatment process, and other wastewater treatment processes.

Kinetic modelling for photosynthesis of hydrogen and Methane through catalytic reduction of carbon dioxide with water vapour

In a photocatalytic reduction process when products formed are not effectively desorbed, they could hinder the diffusion of intermediates on the surface of the catalyst, as well as increase the chance of collisions among the products, resulting photo-oxidation in a reserve reaction on the surface. This paper analyses a simple kinetic model incorporating the coupled effect of the adsorptive photocatalytic reduction and oxidation. The development is based on Langmuir–Hinshelwood mechanism to model the formation rates of hydrogen and methane through photocatalytic reduction of carbon dioxide with water vapour. Experimental data obtained from literatures have achieved a very good fit. Such model could aid as a tool for related areas of studies. A comparative study using the model developed, showed that product concentration in term of ppm would be an effective measurement of product yields through photocatalytic reduction of carbon dioxide with water vapour.

Improvement of the biomedical properties of titanium using SMAT and thermal oxidation

Titanium and its alloys are excellent candidates for biomedical implant. However, they exhibit relatively poor tribological properties. In this study, a two-step treatment including surface mechanical attrition treatment (SMAT) combined with thermal oxidation process has been developed to improve the tribological properties and biocompatibility of Ti. Ti after two-step treatment shows excellent wear-resistance and biocompatibility among all Ti samples, which can be ascribed to the highest surface energy, well crystallinity of rutile layer on its surface. Overall, the two-step treatment is a prospective method to produce excellent biomedical Ti materials.

Conditions favoring the formation of monomeric Pt(III) derivatives in the electrochemical oxidation of trans-[Pt(II){(p-BrC6F4)NCH2CH2NEt2}Cl(py)]

Characterization of the anticancer active compound trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] is described along with identification of electrochemical conditions that favor formation of a monomeric one-electron-oxidized Pt^III derivative. The square-planar organoamidoplatinum(II) compound was synthesized through a carbon dioxide elimination reaction. Structural characterization by using single-crystal X-Ray diffraction reveals a trans configuration with respect to donor atoms of like charges. As Pt^III intermediates have been implicated in the reactions of platinum anticancer agents, electrochemical conditions favoring the formation of one-electron-oxidized species were sought. Transient cyclic voltammetry at fast scan rates or steady-state rotating disc and microelectrode techniques in a range of molecular solvents and an ionic liquid confirm the existence of a well-defined, chemically and electrochemically reversible one-electron oxidation process that, under suitable conditions, generates a Pt^III complex, which is proposed to be monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Electron paramagnetic resonance spectra obtained from highly non-coordinating dichloromethane/([Bu4N][B(C6F5)4]) solutions, frozen to liquid nitrogen temperature immediately after bulk electrolysis in a glove box, support the Pt^III assignment rather than formation of a Pt^II cation radical. However, the voltammetric behavior is highly dependent on the timescale of the experiments, temperature, concentration of trans-[Pt^II{(p-BrC6F4)NCH2CH2NEt2}- Cl(py)], and the solvent/electrolyte. In the low-polarity solvent CH2Cl2 containing the very weakly coordinating electrolyte [Bu4N][B(C6F5)4], a well-defined reversible one-electron oxidation process is observed on relatively long timescales, which is consistent with the stabilization of the cationic platinum(III) complex in non-coordinating media. Bulk electrolysis of low concentrations of [Pt{(p-BrC6F4)NCH2CH2NEt2}Cl(py)] favors the formation of monomeric [Pt^III{(p-BrC6F4)NCH2CH2NEt2}Cl(py)]⁺. Simulations allow the reversible potential of the Pt^II/Pt^III process and the diffusion coefficient of [Pt^III{(p-BrC6F4)- NCH2CH2NEt2}Cl(py)]⁺ to be calculated. Reversible electrochemical behavior, giving rise to monomeric platinum(III) derivatives, is rare in the field of platinum chemistry.

Photodegradation of the pharmaceuticals amoxicillin, bezafibrate and paracetamol by the photo-Fenton process - Application to sewage treatment plant effluent

Photodegradation of the pharmaceuticals amoxicillin (AMX), bezafibrate (BZF) and paracetamol (PCT) in aqueous solutions via the photo-Fenton process was investigated under black-light and solar irradiation. The influences of iron source, initial H2O2 concentration and matrix (distilled water and sewage treatment plant effluent) on degradation efficiency were discussed in detail. The results showed that (i) the degradation of the drugs was favored in the presence of potassium ferrioxalate (FeOx) in comparison to Fe(NO3)(3): (ii) the increase of the H2O2 concentration improved the efficiency of AMX and BZF oxidation; however, the same was not observed for PCT: (iii) the influence of the matrix was observed for the degradation of BZF and PCT: (iv) under solar irradiation, the oxidation of the BZF and PCT is faster than under black-light irradiation. All these pharmaceuticals can be efficiently degraded employing the process evaluated. (C) 2008 Elsevier B.V. All rights reserved.

Monitoring pharmaceuticals photo-Fenton degradation process by using Solid Phase Extraction and liquid chromatography

The recovery of the pharmaceuticals bezafibrate and tetracycline from water was evaluated, using Solid Phase Extraction (SPE) with the aim of applying this technique to interrupt the pharmaceuticals' photodegradation by photo-Fenton process for further analysis. Sep-Pack C-18, Strata X, and Oasis HLB cartridges were evaluated. Oasis HLB showed the most satisfactory recovery and repeatability results: 98% (CV - 1%) for bezafibrate (20.0 mg L-1) and 76% (CV = 1%) for tetracycline (25.0 mg L-1). There was not a significant decrease in recovery at lower concentrations of the pharmaceuticals, and neither when present in Sewage Treatment Plant (STP) effluent matrix.

Diclofenac Abatement using Modified Solar Photo-Fenton Process with Ammonium Iron(III) Citrate

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Degradation of tetracycline by photo-Fenton process - Solar irradiation and matrix effects

The degradation of the antibiotic tetracycline (TC) by the photo-Fenton process was evaluated under black-light and solar irradiation. The influences of iron source (Fe(NO3)(3) or ferrioxalate), hydrogen peroxide and matrix (pure water, surface water and a sewage treatment plant effluent-STP) were evaluated. Under black-light irradiation, TC degradation was favored in the presence of Fe(NO3)(3), achieving total degradation after 1 min irradiation, while under solar light the use of ferrioxalate favors the degradation. Nevertheless, no significant difference in total organic carbon removal was observed between these two iron sources, achieving a residual concentration of around 5 mg L-1 under black-light and 2 mg L-1 under solar light irradiation. No decrease of the degradation efficiency relative to pure water was observed when TC was irradiated in a sample of surface water, under either black-light or solar irradiation. However, lower efficiency was obtained under black-light when TC was present in a sample of STP effluent, indicating the interference of the constituents of this sample on the overall efficiency of the process. on the other hand, under solar irradiation in the presence of ferrioxalate, no influence of the matrix was observed, even in the sample of STP effluent, achieving total degradation of TC in 1.5 min. (c) 2006 Elsevier B.V. All rights reserved.

The application of a surface response methodology in the solar/UV-induced degradation of dairy wastewater using immobilized ZnO as a semiconductor

An Advanced Oxidation Process (AOPs) was carried out in this study with the use of immobilized ZnO and solar/UV as an energy source to degrade dairy wastewater. The semibatch reactor system consisted of metal plate of 800 × 250 mm and a glass tank. The reaction time was of 3 h for 3 L of dairy wastewater. Experiments were performed based on a surface response methodology in order to optimize the photocatalytic process. Degradation was measured in percentage terms by total organic carbon (TOC). The entry variables were ZnO coating thickness and pH, using three levels of each variable. The optimized results showed a TOC degradation of 31.7%. Optimal parameters were metal-plate coating of 100 m of ZnO and pH of 8.0. Since solar/UV is a constant and free energy source in most tropical countries, this process tends to suggest an interesting contribution in dairy wastewater treatment, especially as a pretreatment and the optimal conditions to guarantee a better efficiency of the process. © 2013 Gisella R. Lamas Samanamud et al.

Tratamento fotocatalítico de corante ácido usando filmes finos de vidro/Ti 'O IND. 2' e degradação fotoeletrocatalítica de corante vat sobre eletrodos de filmes finos de Ti/Ti 'O IND. 2'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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.