TiO2-Cu photocatalysts: A study on the long- and short-range chemical environment of the dopant

In this study, the short- and long-range chemical environments of Cu dopant in TiO2 photocatalyst have been investigated. The Cu-doped and undoped TiO2 specimens were prepared by the sol-gel approach employing CuSO4·5H2O and Ti(O-iPr)4 precursors and subjecting the dried gels to thermal treatment at 400 and 500 C. The photocatalytic activity, investigated by methylene blue degradation under sunlight irradiation, showed a significantly higher efficiency of Cu-doped samples than that of pure TiO2. The X-ray diffraction results showed the presence of anatase phase for samples prepared at 400 and 500 C. No crystalline CuSO4 phase was detected below 500 C. It was also found that doping decreases the crystallite size in the (004) and (101) directions. Infrared spectroscopy results indicated that the chemical environment of sulfate changes as a function of thermal treatment, and UV-vis spectra showed that the band gap decreases with thermal treatment and Cu doping, showing the lowest value for the 400 C sample. X-ray absorption fine structure measurements and analysis refinements revealed that even after thermal treatment and photocatalytic assays, the Cu2+ local order is similar to that of CuSO4, containing, however, oxygen vacancies. X-ray photoelectron spectroscopy data, limited to the near surface region of the catalyst, evidenced, besides CuSO4, the presence of Cu1+ and CuO phases, indicating the active role of Cu in the TiO2 lattice. © 2013 Springer Science+Business Media New York.

Synthesis of PTSH-modified CeO2 nanoparticles: Effect of the modifier on structure, optical properties, and dispersibility

CeO2 nanoparticles were synthesized by the precipitation method and modified with para-toluene sulfonic acid (PTSH), either in situ or post-synthesis. The presence of PTSH in the samples was confirmed by FTIR. PXRD and FTIR analyses showed that the post-synthesis PTSH modification altered the CeO2 structure, whereas the in situ modification maintained intact the crystalline structure and UV-vis absorbance properties. For both in situ and post-synthesis modifications, TEM images revealed the presence of nanoparticles that were 5nm in size. The dispersibility of the in situ PTSH-modified material in a hydrophilic ureasil-poly(ethylene oxide) matrix was investigated using SAXS measurements, which indicated that CeO2 nanoparticles modified with PTSH in situ were less aggregated within the matrix, compared to unmodified CeO2 nanoparticles. © 2013 Elsevier B.V.

Photoelectrocatalysis based on Ti/TiO2 nanotubes removes toxic properties of the azo dyes Disperse Red 1, Disperse Red 13 and Disperse Orange 1 from aqueous chloride samples

This work describes the efficiency of photoelectrocatalysis based on Ti/TiO2 nanotubes in the degradation of the azo dyes Disperse Red 1, Disperse Red 13 and Disperse Orange 1 and to remove their toxic properties, as an alternative method for the treatment of effluents and water. For this purpose, the discoloration rate, total organic carbon (TOC) removal, and genotoxic, cytotoxic and mutagenic responses were determined, using the comet, micronucleus and cytotoxicity assays in HepG2 cells and the Salmonella mutagenicity assay. In a previous study it was found that the surfactant Emulsogen could contribute to the low mineralization of the dyes (60% after 4h of treatment), which, in turn, seems to account for the mutagenicity of the products generated. Thus this surfactant was not added to the chloride medium in order to avoid this interference. The photoelectrocatalytic method presented rapid discoloration and the TOC reduction was ≥87% after 240min of treatment, showing that photoelectrocatalysis is able to mineralize the dyes tested. The method was also efficient in removing the mutagenic activity and cytotoxic effects of these three dyes. Thus it was concluded that photoelectrocatalysis was a promising method for the treatment of aqueous samples. © 2013 Elsevier Ltd.

Fish exposure to nano-TiO2 under different experimental conditions: Methodological aspects for nanoecotoxicology investigations

The ecotoxicology of nano-TiO2 has been extensively studied in recent years; however, few toxicological investigations have considered the photocatalytic properties of the substance, which can increase its toxicity to aquatic biota. The aim of this work was to evaluate the effects on fish exposed to different nano-TiO2 concentrations and illumination conditions. The interaction of these variables was investigated by observing the survival of the organisms, together with biomarkers of biochemical and genetic alterations. Fish (Piaractus mesopotamicus) were exposed for 96h to 0, 1, 10, and 100mg/L of nano-TiO2, under visible light, and visible light with ultraviolet (UV) light (22.47J/cm2/h). The following biomarkers of oxidative stress were monitored in the liver: concentrations of lipid hydroperoxide and carbonylated protein, and specific activities of superoxide dismutase, catalase, and glutathione S-transferase. Other biomarkers of physiological function were also studied: the specific activities of acid phosphatase and Na,K-ATPase were analyzed in the liver and brain, respectively, and the concentration of metallothionein was measured in the gills. In addition, micronucleus and comet assays were performed with blood as genotoxic biomarkers. Nano-TiO2 caused no mortality under any of the conditions tested, but induced sublethal effects that were influenced by illumination condition. Under both illumination conditions tested, exposure to 100mg/L showed an inhibition of acid phosphatase activity. Under visible light, there was an increase in metallothionein level in fish exposed to 1mg/L of nano-TiO2. Under UV light, protein carbonylation was reduced in groups exposed to 1 and 10mg/L, while nucleus alterations in erythrocytes were higher in fish exposed to 10mg/L. As well as improving the understanding of nano-TiO2 toxicity, the findings demonstrated the importance of considering the experimental conditions in nanoecotoxicological tests. This work provides information for the development of protocols to study substances whose toxicity is affected by illumination conditions. © 2013 Elsevier B.V..

'Ti''O IND.2'/'Sn''O IND. 2 modificado com 'Ag IND. 2''O', para obtenção de fotocatalisadores

Pós-graduação em Química - IQ

Síntese e caracterização de nanopartículas e filmes finos de óxidos semicondutores

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Clareamento dental com perôxido de hidrogênio contendo nano partículas de óxido de titânio como semicondutor: efeito de concentrações, tempos e formas de ativação

Pós-graduação em Ciências Odontológicas - FOAR

Desenvolvimento de sistemas líquido-cristalinos multifuncionais contendo nanopartículas de TiO2 para proteção solar e liberação controlada de terpinem-4-ol

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

Degradação fotocatalítica de efluente simulado de refinaria de petróleo e monitoramento de sua toxicidade com microrganismos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Avaliação da atividade fotocatalítica sobre a inativação de Escherichia coli, Staphylococcus aureus e Saccharomyces cerevisiae utilizando dióxido de titânio, para aplicação em desinfecção de águas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Indicadores na estimativa do fluxo de nutrientes no duodeno, produção fecal, consumo de concentrado e volumoso por bovinos

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

Estudo e desenvolvimento de cerâmicas porosas de dióxido de titânio aditivadas com proteínas de soja

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Caracterização térmica e mecânica de cerâmicas porosas com camadas de TiO2 e Al2O3

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Influência da presença de um filme fino de platina na resistência de união titânio-cerâmica

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Obtenção de fotocatalisadores magnéticos a partir de resíduos industriais e TiO2 para a degradação de contaminantes orgânicos

In this work, magnetic photocatalysts were synthesized containing differents levels of TiO2 (40, 60 e 80%) supported at the supporter of C/LV, forming the photocatalysts 40, 60, 80Ti/C/LV, using tar pitch as carbon (C) source and red mud (LV) as iron source. The prepared magnetic photocatalysts and TiO2 were used to degrade the Remazol Black textile dye (PR5) and the organic material present in samples of a textile dye effluent. The characterization of photocatalysts by Raman, X-Ray Diffraction, Transmission Electron Micoscope and Scanning, Energy Dispersive X-ray Spectrometry, Termogravimetry and Elemental Analysis, confirms the presence of carbon and magnetite in support C/LV and the presence of TiO2 in prepared photocatalysts. The photocatalytic reactions with TiO2 were analyzed by different experimental conditions, such as: mass of TiO2 (30-240 mg), solution pH (2-10), light intensity (0.871 and 1.20 mWcm-2), type of radiation (UV and sunlight-1.420 mWcm-2), radiation incidence area (44.2 to 143.1 cm2) and dissolved oxygen (OD, 1.9 and 7.6 mg L- 1). Results showed that reactions with the following conditions: 220 mg of TiO2, pH 10, solar radiation, 7.6 mg L-1 of OD and an incidence area of radiation of 143.1 cm2 showed the best results for degradation of PR5 dye. Photocatalytic reactions with magnetic photocatalysts for degrading PR5 shows that efficiency increases with TiO2 content in the C/LV support, where, above 60% of TiO2, there was not significant increase in reaction velocity. In addition, solar radiation has proved to be advantageous for photocatalytic reactions. In order to verify the presence of a non-magnetic fraction in the photocatalyst 60Ti/C/LV0, magnetic separation was proceeded. The characterizations of the magnetic (FM) and nonmagnetic (NMF) fraction confirmed that about 25% of TiO2 did not fixed in 60Ti/C/LV photocatalyst. Results of photocatalytic reactions with FM and FNM showed that both phases have photocatalytic activity for degradation of PR5. The reactions executed for the degradation of organic matter present in the actual sample of textile effluent showed that TiO2 and magnetic photocatalyst 60Ti/C/ LV have better results for color removal (85 to 35%), soluble solids ( 11 and 3%), DQO (90 and 86%) and turbidity (94 and 11%) than the treatment done by the textile industry. Sedimentation kinetics tests in presence of a magnet showed that photocatalysts are separated faster from aqueous environment than pure TiO2. Obtained results showed that magnetic photocatalysts have excellent photocatalytic activity and can be separated from the reaction environment on a simple and quick way when a magnetic field is applied.