Abstract CoMo/MgO catalysts with low loading of cobalt and molybdenum were prepared by incipient wetness impregnation and the sol-gel method for high yield production of carbon nanotubes (CNT). A detailed characterization of the catalysts, as-produced CNT and purified CNT, indicated a relationship between carbon nanotube properties, synthesis and purification steps. Excess of molybdenum in the catalyst caused a decrease in carbon yield and produced CNT with a lower degree of graphitization. Catalysts prepared by the sol-gel method and with higher molybdenum loading showed an improved interaction between cobalt and molybdenum, increasing the formation of CoMoO4, which was not completely removed during the purification step. The purification removed all MgO and part of the cobalt and molybdenum present in samples without significant damage to the CNT structure. An increase in sample purity could be achieved by increasing reaction time.

The support effect on the properties of iridium catalysts for C-C and C-O hydrogenolysis was investigated. Cyclohexane conversion and glycerol hydrogenolysis were used to compare the behavior of iridium catalysts in terms of C-C and C-O cleavage. The nature of the support influenced the catalyst performance in both cyclohexane conversion and glycerol hydrogenolysis. This effect was more evident on the product selectivity. Ir/SiO2 catalyst presented the highest cyclohexane hydrogenolysis activity and the highest selectivity to minor hydrocarbons formed from hexane re-adsorption. For glycerol hydrogenolysis, all catalysts displayed a higher selectivity to products formed by C-O cleavage, mainly 1,2-propanediol (1,2-PDO). Ir/ZrO2 catalyst presented the highest activity in all reaction conditions and the lowest selectivity to minor alcohols produced by C-C cleavage like methanol, ethanol and ethylene glycol. The results were explained in terms of the requirements and the structure of the catalytic sites.

O orçamento energético de animais ectotérmicos antárticos estenotérmicos e/ou estenohalinos é fortemente modulado pelas variações da temperatura e da salinidade. O efeito conjunto desses fatores em animais polares é pouco estudado. Dados sobre esse assunto são necessários para avaliar a demanda energética de organismos antárticos, como os anfípodes, principalmente devido a sua importância ecológica e aos possíveis impactos ocasionados por mudanças globais. Os experimentos foram realizados na Estação Antártica Brasileira "Comandante Ferraz", em condições controladas. Indivíduos de Bovallia gigantea coletados na Baía do Almirantado foram aclimatados às temperaturas de 0ºC, 2,5ºC e 5ºC e às salinidades de 35, 30 e 25. Foram realizadas 30 medições para cada uma das nove combinações possíveis entre os fatores. Foram mensurados o consumo de oxigênio e a excreção de produtos nitrogenados, em câmaras respirométricas seladas. A 0ºC e 2,5ºC, as taxas metabólicas de indivíduos aclimatados às salinidades 30 ou 35 foram muito semelhantes, indicando um possível mecanismo de independência metabólica à temperatura. A 5,0ºC, as taxas metabólicas foram sempre mais elevadas. Os efeitos da temperatura sobre as taxas de consumo de oxigênio e de excreção de produtos nitrogenados foram intensificados pela diminuição da salinidade. Indivíduos de B. gigantea apresentam independência térmica das taxas metabólicas em uma pequena janela de variação, que pode ainda ser modificada pela salinidade.

The energy budget of Antarctic stenothermic and/or stenohaline ectotherms is modulated by variations of temperature and salinity. The joint effects of these latter on polar organisms have been but little studied. Data on this subject are of great importance for an understanding of the energy demand of Antarctic animals such as amphipods, especially when considering their ecological importance and the possible impacts of global changes. Experiments were carried out at the Brazilian Antarctic Station "Comandante Ferraz" under controlled conditions. Specimens of Bovallia gigantea were collected in Admiralty Bay and acclimated to temperatures of 0ºC; 2.5ºC and 5ºC and to salinities of 35, 30 and 25. Thirty measurements were taken for each of the nine possible combinations of the three temperatures and the three salinities. Metabolic rates were assessed based on oxygen consumption and total ammonia nitrogenous excretion in sealed respirometers. At 0ºC and 2.5ºC, the metabolic rates of the animals that were acclimated to salinities of 30 or 35 were similar, indicating a possible mechanism of metabolic independence of temperature. However, the metabolic rates were always higher at 5.0ºC. The effects of temperature on oxygen consumption and on ammonia excretion rates were intensified by lower salinities. Individuals of B gigantea have a temperature-independent metabolic rate within a narrow temperature window that can be modified in accordance with salinity.

Varias técnicas, como fisissorção, espectroscopia de fotoelétrons excitados por raios X (XPS), difração de raios X (XRD), redução à temperatura programada (TPR) e quimissorção foram usadas para a caracterização de catalisadores de Co/γAl2O3 para a produção de nanotubos de carbono por deposição de metano. Os catalisadores apresentaram três principais espécies de cobalto: CoAl2O4, CoO e Co3O4. As espécies de CoAl2O4 estavam bem dispersas nos catalisadores e apresentaram elevada temperatura de redução, fazendo com que estas espécies sejam inativas para a produção de nanotubos. Para o catalisador 1%Co/Al2O3, a principal espécie encontrada foi o CoAl2O4. Contudo, com o aumento do teor de cobalto nos catalisadores, ocorreu um aumento na formação das espécies Co3O4 em relação às espécies CoO e CoAl2O4. Os catalisadores 2 e 3%Co/Al2O3 apresentaram aglomeração das partículas de cobalto após a etapa de redução e baixa seletividade para produção de nanotubos. Entretanto, o catalisador 4%Co/Al2O3 não apresentou aglomeração, resultando em uma melhor seletividade para formação de nanotubos, 71%, principalmente do tipo nanotubos de carbono de paredes múltiplas (MWNT).

Several analytical techniques, such as N2 physisorption, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), temperature programmed reduction (TPR) and chemisorption were employed to characterize the structure of Co/γAl2O3 catalysts used for the production of carbon nanotubes by methane vapor deposition. The catalysts were studied after the calcination step and presented three main cobalt species, CoAl2O4, CoO and Co3O4. The CoAl2O4 species were well dispersed and were reduced only at high temperatures, rendering them inactive for the carbon nanotube production. In the case of the 1%Co/Al2O3 catalyst, the main cobalt species found was CoAl2O4. However, increasing the cobalt content in the catalysts led to a higher formation of Co3O4 as compared to CoO and CoAl2O4 species. The 2 and 3%Co/Al2O3 catalysts showed particle agglomeration during the pretreatment step that decreased selectivity towards nanotube production. The 4%Co/Al2O3 catalyst did not show particle agglomeration and presented a higher selectivity to carbon nanotube production, 71%, mainly multi-walled carbon nanotubes (MWNT).

A oxidação parcial do metano sobre catalisadores de ródio suportados em γ-Al2O3, CeO2, ZrO2 e Ce-ZrO2 foi investigada. Medidas de DRIFTS (espectroscopia no infravermelho com reflectância difusa) de CO adsorvido mostraram que houve a formação de diferentes espécies de ródio nos diferentes suportes, o que por sua vez influenciou na dispersão do metal. Os efeitos da dispersão metálica e da capacidade de armazenamento de oxigênio sobre a atividade dos catalisadores na oxidação parcial foram discutidos.

The partial oxidation of methane with γ-Al2O3-, CeO2-, ZrO2- and Ce-ZrO2-supported rhodium catalysts was investigated. DRIFTS (diffuse reflectance infrared spectroscopy) measurements of adsorbed CO showed the formation of different rhodium species on different supports, which influenced the dispersion of the metal. The effects of the metal dispersion, oxygen storage capacity on the activity of these catalysts for the partial oxidation of methane are discussed.

A influência do suporte na produção de nanotubos de carbono por deposição química a vapor (CVD) de metano sobre catalisadores de cobalto foi investigada. As técnicas de fisissorção de N2, difratometria de raios X (XRD), redução à temperatura programada (TPR) e quimissorções de H2 e CO foram usadas na caracterização dos catalisadores de cobalto suportados em diferentes óxidos (Al2O3, SiO2, Nb2O5 e TiO2). As técnicas de espectroscopia Raman, oxidação a temperatura programada (TPO) e microscopia eletrônica de varredura (SEM) foram utilizadas na caracterização e quantificação de espécies de carbono produzidas. No crescimento dos nanotubos, o catalisador produziu três espécies principais de carbono: carbono amorfo, nanotubos de carbono de parede única (SWNT) e nanotubos de carbono de parede múltiplas (MWNT). Técnicas de caracterização mostraram que a seletividade catalítica a cada tipo de nanotubo depende da distribuição do tamanho de partículas de cobalto, a qual depende das propriedades texturais do suporte. O catalisador Co/TiO2 apresentou alta seletividade para a produção de nanotubos de parede única. Esta alta seletividade se deve a uma distribuição estreita do tamanho de partículas de cobalto sobre TiO2.

The influence of the support on carbon nanotube production by methane chemical vapor deposition (CVD) on cobalt catalysts was investigated. N2 physisorption, X-ray diffractometry (XRD), temperature programmed reduction (TPR) and H2 and CO chemisorption techniques were used to characterize the structure of cobalt catalysts supported on different metal oxides (Al2O3, SiO2, Nb2O5 and TiO2). Raman spectroscopy, temperature programmed oxidation (TPO) and scanning electron microscopy (SEM) were used for the characterization and quantification of produced carbon species. On carbon nanotube growth, the catalyst produced three main carbon species: amorphous carbon, single walled carbon nanotubes (SWNT) and multi walled carbon nanotubes (MWNT). The characterization techniques showed that the catalyst selectivity to each kind of nanotube depended on the cobalt particle size distribution, which was influenced by the textural properties of the support. Co/TiO2 showed the highest selectivity towards single wall nanotube formation. This high selectivity results from the narrow size distribution of cobalt particles on TiO2.

Heterogeneous catalysts are of fundamental importance in several modern chemical processes. The characterization of catalysts is an issue of very present interest as it can provide a better understanding of the fundamental aspects of the catalytic phenomena, thus helping in the development of more efficient catalysts. In order to extend and improve the characterization of catalysts, new and less conventional methods are being applied, such as nuclear spectroscopies. In this paper we focus on the application of angular correlation, with can be used to resolve different local environments of probe atoms in solids and can be applied, as shown here, in the characterization of heterogeneous catalysts. A brief theoretical introduction is given and experimental results related to catalytic systems of alumina and niobia-supported Pt-In and Pd-In catalysts are presented.

Foram preparados catalisadores de prata suportados em a-alumina e caracterizados por técnicas de BET, SEM, XRD e AFM. Resultados mostraram que são técnicas poderosas para a determinação da textura, morfologia e propriedades superficiais. Mostrou-se que a adição de Cs ao catalisador de Ag/Al2O3 aumentou a dispersão de prata com a formação de pequenas partículas de prata sobre um filme fino formado sobre o suporte alumina. É importante salientar que as medidas feitas por AFM foram significativas para observar o filme e a dispersão da Ag e, ao contrário, XPS não detectou, contudo isto permite concluir que a prata está presente indistintamente no estado metálico ou óxido sobre a superfície. Resultados de XRD confirmam a presença dominante de prata metálica.

Silver supported catalysts on alpha-alumina were prepared and characterized by Brunauer-Emmet-Teller equations, scanning electronic microscopy, X-ray diffraction and atomic force microscopy techniques. Results show that these are powerful techniques for the determination of texture, morphology and surface properties. It has been shown that the addition of Cs in the Ag/Al2O3 catalyst increased the dispersion of silver with the formation of small silver particles over a thin silver film already formed over the alumina support. It is important to stress that atomic force microscopy measurements are significant to observe the film and the dispersion of Ag and, on the contrary, X-ray photoelectronic spectroscopy did not, however, it allows to the conclusion that undistinguishable silver, either as metallic or oxidation state, are present at the surface. X-ray diffraction results confirm predominantly metallic silver.