ABSTRACT Three different bismuth catalysts (Bi2WO6, BiOI and BiVO4) were synthesized using solvo- and hydrothermal methods. Different reaction times, calcination and the addition of poly (vinyl pyrrolidone) during synthesis were tested to investigate the effect of these variables on the catalysts’ morphology and photocatalytic activity. The photocatalytic activity was evaluated using the degradation of rhodamine B dye under both visible light and natural solar radiation. The Bi2WO6 samples presented good crystallinity and morphological similarities, despite having undergone different treatments. The BiOI and Bi2WO6 catalysts presented a spherical shape, and no morphological difference was observed as a result of the addition of PVP. The BiVO4 sample presented a parallelepiped shape. BiOI containing PVP and ethylene glycol was the catalyst that presented the highest activity, while BiVO4 presented the lowest. In experiments using scavengers, photogenerated holes demonstrated a key role in dye degradation.

A new approach based on multicomponent/domino combined reactions for the synthesis of γ-nitroesters promoted by a mixed aluminium-magnesium oxides derived from hydrotalcite-like material was developed. Different γ-nitroesters were synthesized in 15-95% yield using Meldrum's acid, aromatic aldehydes, nitromethane and different alcohols as reagents and solvents. The γ-aminobutyric acid derivatives, Phenibut and Baclofen, were prepared in 63 and 61% overall yield, respectively, through a two steps synthetic strategy. A mechanistic pathway was proposed based on the gas chromatography mass spectrometry (GC-MS) and electrospray ionization mass spectrometry (ESI-MS) experiments.

A reação de degradação fotocatalítica do estireno foi estudada utilizando-se TiO2 P-25 (Degussa) como catalisador. Os experimentos foram realizados em um reator "slurry" em bateladas, com controle de temperatura, empregando-se uma lâmpada UV. Foram estudados os efeitos do pH, da concentração inicial de estireno, da concentração do catalisador e da adição de H2O2 sobre a velocidade da reação. Os resultados mostraram que, em 90 min, cerca de 95% da quantidade inicial da molécula foi consumida por fotocatálise. Verificou-se também que a reação segue uma cinética de primeira ordem para concentrações iniciais de estireno, entre 15,27 e 57,25 ppm, a 30ºC. A análise cromatográfica das amostras coletadas durante os experimentos de fotodegradação identificou o benzaldeído como um dos intermediários dessa reação. Além disso, a adição de H2O2 aumentou a velocidade de degradação.

The aqueous styrene photocatalytic degradation reaction was evaluated using TiO2 P-25 (Degussa) as a catalyst. These experiments were accomplished in a batch slurry reactor with temperature control and a UV lamp. The effects of the initial styrene concentration, the catalyst concentration, the hydrogen peroxide addition and the initial pH of the solution on the reaction were evaluated. The experimental results showed that in 90 min, 95% of the initial styrene was degraded by photocatalysis. It was verified that the styrene degradation rate fits a pseudo-first-order kinetics for initial styrene concentrations between 15.27 and 57.25 ppm, at 30ºC. The chromatographic analysis of the samples collected during the photocatalytic degradation revealed benzaldehyde as one of the intermediates. The addition of H2O2 accelerated the degradation reaction until the system reached a certain optimum peroxide concentration in the reactor. Further H2O2 additions resulted in a reaction rate reduction.

This review deals with silica based hybrid materials obtained by the sol-gel method. It involves concepts, classifications and important definitions regarding the sol-gel method that allows obtaining materials with organic and inorganic components dispersed in a molecular or nanometric level. We discuss the properties and characteristics of hybrid materials related to experimental synthesis conditions. We devote a special attention to the nanostructured materials, where the self-organization is imposed by the organic component. Finally, we present some important applications of these materials based on their specific properties.

In this work the adsorption features of hydrotalcites (Al, Mg- CO3) and the magnetic properties of iron oxides have been combined in a composite to produce a magnetic adsorbent. These magnetic composites can be used as adsorbents for anionic contaminants in water and subsequently removed from the medium by a simple magnetic process. The magnetic hydrotalcites were characterized by XRD, magnetization measurements, N2 adsorption isotherms and Mössbauer spectroscopy. These magnetic adsorbents show remarkable adsorption capacity for anionic contaminants in water.

Nesse trabalho foi estudada a influência do ácido acético na estrutura de poros e na área superficial de sílicas preparadas pelo método sol-gel. Condições experimentais de síntese, tais como temperatura de policondensação e solventes, também foram estudadas. Isotermas de adsorção de N2 das amostras foram classificadas como do tipo 1, típicas de materiais microporosos, o que explica os altos valores de área superficial obtidos. A adição simultânea dos ácidos acético e clorídrico como catalisadores e de acetona como solvente, bem como o emprego de uma temperatura de policondensação de 20 ºC, possibilitaram a preparação de sílicas amorfas com valores de área superficial de até 850 m² g-1. O alto valor de área superficial dessas amostras pode ser explicado principalmente pela microporosidade e também pelo tamanho nanométrico das partículas.

The influence of acetic acid on the pore structure and surface area of silica prepared by the sol-gel method was investigated. Experimental conditions of synthesis, such as gelation temperature and solvents, were also studied. N2 adsorption isotherms of the samples were type 1, typical of microporous materials, explaining the high surface area values (BET) observed. The simultaneous addition of acetic and hydrochloric acids as catalysts and of acetone as solvent, together with the use of a gelation temperature of 20 ºC, made it possible to prepare amorphous silica materials with surface area values up to 850 m² g-1. The high surface area value of these samples could be explained by the microporosity and the nanometric size of the particles.

Chloride poisoning is known as having an inhibitor effect in the activity of metal catalysis. In this work in situ infrared spectroscopy (FTIR) of adsorbed carbon monoxide and x-ray photoelectron spectroscopy (XPS) were used to investigate the effect of chloride presence in the electronic metal density in the d subshell of palladium dispersed on alumina. The chloride poisoning effect was interpreted as an electronic effect since a weak back-bonded Pd-CO was formed due to the decrease in the electronic density of the d subshell of palladium, which could be also detected by the higher Pd 3d5/2 binding energy in the chloride presence. A similar poisoning effect was also observed for chloride free Pd/Al2O3 reduced at 500 ºC, and it was interpreted based on the interaction of metal with the alumina surface. The use of molybdena/alumina binary system as support, yield a contrary effect due to the metal-support interaction.