Cationic and charge segregation in La2/3Ca1/3MnO3 thin films grown on (001) and (110) SrTiO3.

Electron energy-loss spectroscopy is used to map composition and electronic states in epitaxial La2/3Ca1/3MnO3 films grown on SrTiO3 001 and 110 substrates. It is found that in partially relaxed 110 films cationic composition and valence state of Mn3+/4+ ions are preserved across the film thickness. In contrast, in fully strained 001 films, the Ca/La ratio gradually changes across the film, being La rich at film/substrate interface and La depleted at free surface; Mn valence state changes accordingly. These observations suggest that a strongly orientation-dependent adaptative composition mechanism dominates stress accommodation in manganite films and provides microscopic understanding of their dissimilar magnetic properties.

Mecanismo de fotodegradação de compostos orgânicos catalisada por TiO2

Conventional technology used in the treatment of wastewater has been pointed as a major environmental problem for sustainable development, since minimization is not addressed accordingly. Advanced oxidation processes (AOP), based on the formation of hydroxyl radical (•OH), a powerful oxidant agent, have been considered to be a potential technology for the destruction of many toxic compounds. Photocatalysis using solar light, an AOP, has been studied for nearly 20 years and recently attracted great interest as a clean-up technology. However, solar detoxification processes have not yet achieved commercial success. This article presents an overview of reaction mechanisms at the surface of semiconductors used as photocatalysts (specially TiO2), when heterogeneous photocatalysis is used to remove hazardous compounds from contaminated sites.

Study of the optical properties of TeO2-PbO-TiO2 glass system

We describe the preparation and some optical properties of high refractive index TeO2-PbO-TiO2 glass system. Highly homogeneous glasses were obtained by agitating the mixture during the melting process in an alumina crucible. The characterization was done by X-ray diffraction, Raman scattering, light absorption and linear refractive index measurements. The results show a change in the glass structure as the PbO content increases: the TeO4 trigonal bipyramids characteristics of TeO2 glasses transform into TeO3 trigonal pyramids. However, the measured refractive indices are almost independent of the glass composition. We show that third-order nonlinear optical susceptibilities calculated from the measured refractive indices using Lines' theoretical model are also independent of the glass composition.

Estudo por espectroscopia no infravermelho da interação metal-suporte em Pt/TiO2. A influência da adsorção de hidrogênio

The influence of the presence of hydrogen on Pt/TiO2 catalysts submitted to reduction treatment has been studied by FT-IR at room temperature. After submitting to LTR treatment, the hydrogen spillover has been detected and the presence of hydrogen at the bulk is shown to produce a strong absorption in the infrared spectral region. After HTR treatment, the hydrogen is strongly chemissorbed.

Correlação entre a estrutura atômica superficial e o processo de adsorção-dessorção reversível de hidrogênio em eletrodos monocristalinos Pt(111), Pt(100) e Pt(110)

Platinum is widely used as electrode in electrocatalytic processes, however the use of polycrystalline electrodes introduces a series of variables in the electrochemical system due to the aleatory contribution of all the crystallographic orientations with different surface packing of atoms. Single crystal platinum electrodes of low Miller index present surface structure of high regularity and serve as model to establish a correlation among the macroscopic and microscopic properties of the electrochemical interface. Therefore, the main aim of this work is the study of the voltammetric profiles of the reversible adsorption-desorption of hydrogen on Pt(100), Pt(110) and Pt(111), in order to correlate the electrochemical properties of each different orientation with the surface atomic structure.

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.

Imobilização de TiO2 em concreto: fotodegradação de clorofórmio e fenol

TiO2 immobilization on concrete was studied using mixtures with cement, varnish and resin. The UV radiation sources were a germicide UV lamp and solar light. Aqueous solutions of chloroform (CHCl3) and of phenol were prepared and recirculated over the TiO2 immobilized surfaces. The immobilized TiO2 surfaces showed better photocatalytic efficiency for phenol degradation compared to the control. For CHCl3, the presence or absence of the catalyst did not cause any significant difference to its degradation efficiency. The micrographic results showed a more homogeneous surface for TiO2 immobilized in resin and varnish.

Obtenção de filmes finos de TiO2 nanoestruturado pelo método dos precursores poliméricos

This work focuses in optimizing setup for obtaining TiO2 thin films by polymeric precursor route due to its advantages on stoichiometric and morphological control. Precursor stoichiometry, synthesis pH, solids concentration and rotation speed at deposition were optimized evaluating thin films morphology and thickness. Thermogravimetry and RMN were applied for precursor's characterization and AFM, XRD and ellipsometry for thin films evaluation. Results showed successful attainment of homogeneous nanocrystalline anatase TiO2 thin films with outstanding control over morphological characteristics, mean grain size of 17 nm, packing densities between 57 and 75%, estimated surface areas of 90 m²/g and monolayers thickness within 20 and 128 nm.

Degradação fotoeletroquímica de corantes dispersos em efluente têxtil utilizando fotoanodos de Ti/TiO2

The degradation of disperses dyes in aqueous solution and in effluents from textile industry has been investigated by photoelectrocatalytic oxidation using nanoporous thin films electrodes of Ti/TiO2. Samples of dispersil black dye and dispersil blue dye after 300 min of photoelectrolyzed at applied potential of +1.0 V and UV irradiation exhibited 100% of discoloration and 90% and 64% reduction total organic carbon, respectively. The proposed method was applied with success in a textile industry effluent containing residues of these dyes, which after 300 min of treatment leads to reduction of 60% of COD and 64% removal of TOC.

Fotocatálise heterogênea com TiO2 para oxidação de arsênio e sua remoção de águas por coprecipitação com sulfato férrico

The oxidation of arsenic (As(III) to As(V)) in water samples was performed by heterogeneous photocatalysis using a TiO2 film immobilized inside a photochemical reactor. After oxidation, As(V) was removed from the water samples by coprecipitation with ferric sulfate. The final conditions of oxidation and arsenic removal (TiO2 film prepared with a suspension: 10% (w/v); pH: 7.0; oxidation time: 30 min and Fe3+ concentration: 50 mg L-1) were applied in natural water samples which were supplemented with 1.0 mg L-1 of As(III) to verify the influence of the matrix. After treatment, more than 99% of arsenic was removed from the water.

Estudo da fotocatálise heterogênea sobre Ti/TiO2 na descoloração de corantes sintéticos

The main goal of this paper was to study the degradation of synthetic dyes using photoelectrocatalytic properties of particulate films of TiO2 supported on plates of titanium and stimulated by UV-Vis radiation. The dyes decolorizations were measured using spectrophotometric methods to verify which the conditions on Ti/TiO2 electrode was the best for the photoelectrodegradation of them. The results showed that decolorization rates were higher than 90% during a period of 270 min. FT-IR spectroscopy showed that intermediate substances were formed after the decolorization and N=N group/aromatic structures were preserved independently of the specific structure of the dyes.

Selective hydrogenation of furfural on Ir/TiO2 catalysts

Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

TiO2 photocatalytic inactivation under simulated solar light of bacterial consortia in domestic wastewaters previously treated by UASB, duckweed and facultative ponds

In this work, TiO2 photocatalysis was used to disinfect domestic wastewaters previously treated by different biological treatment systems: Upward-flow Anaerobic Sludge Blanket (UASB), facultative pond, and duckweed pond. The microorganisms monitored were E. coli, total coliforms, Shigella species, and Salmonella species. Photocatalytic experiments were carried out using two light sources: a solar simulator (UV intensity: 68-70 W m-2) and black-light lamps (BLL UV intensity: 17-20 W m-2). Samples were taken after each treatment stage. Results indicate that bacterial photocatalytic inactivation is affected by characteristics of the effluent, including turbidity, concentration of organic matter, and bacterial concentration, which depend of the type of biological pretreatment previously used.

Estudo da reação de oxidação preferencial do co sobre o sistema CuO/CeO2-TiO2

Cu catalysts supported on CeO2, TiO2 and CeO2/TiO2 were prepared by precipitation method and used for preferential oxidation of carbon monoxide contained in a hydrogen flow generated by methane steam reforming. The samples were characterized by XRD, BET and TPR techniques. The catalytic properties were studied in the 50-330ºC range by using a quartz micro-reactor vertically positioned on an electrical furnace. The results showed that the small copper particles generated with the lower metal content are the most easily reducible and give the best catalytic performance. In respect of support effect, the strong metal-support interaction and the redox characteristics of the CuOx-CeO2 series resulted in the best catalytic results, especially with the sample with 1% copper content.

Generación de estados superficiales durante la formación electroforética catódica de películas de TiO2 sobre ito

In the present work TiO2 films were formed over Indium Tin Oxide (ITO) employing cathodic electrophoretic deposition (Cathodic-EPD) and Dr. Blade Technique. The films were characterized by electrochemical techniques in order to compare their electronic properties; as well as, their photoelectrochemical behavior. The electrochemical performance showed by the films, allowed to relate the modification occurring during the Cathodic-EPD, with the partial reduction of TiO2 nanoparticles, generating Ti3+ defects. These trapping states are modifying the electronic properties of the film, and diminishing the transport of the photoelectrogenerated electrons toward ITO.