A BRIEF OVERVIEW ON SINGLE-ATOM CATALYSIS: CONCEPTS AND APPLICATIONS. Catalytic processes became extremely important for the development of our society, especially after the second industrial revolution. Thus, the research for more efficient catalysts is an obstacle to overcome to achieve cheaper processes, higher yields, and selectivity of desired products. In this context, single-atom catalysis emerges as a promising alternative to unite the advantages of traditional homogeneous and heterogeneous catalysis. Catalysis by single-atoms is a bridge that unites in a single catalyst the ease of recovery and reuse (from heterogeneous catalysis) with the high exposure and uniformity of sites (from homogeneous catalysis). Thus, single-atom catalysts (SACs) and single-atom alloys (SAAs) have already found several applications in the literature, such as in hydrogenation, oxidation, conversion of biomass derivatives, electrocatalysis, and photocatalysis. However, it is essential to emphasize that it is still a field that is expanding and relatively new, with several opportunities and many barriers to surpass. In this review, concepts of homogeneous, enzymatic, and heterogeneous catalysis will be addressed, as well as fundamental aspects of single-atom catalysis, preparation methods, characterization, and current challenges.

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.

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).

Nowadays algal biofuels are considered one of the most promising solutions of global energy crisis and climate change for the years to come. By manipulation of the culture conditions, many algal species can be induced to accumulate high concentrations of particular biomolecules and can be directed to the desired output for each fuel. In this context, the present study involved the assessment of the effects of CO2 availability and nitrogen starvation on growth and chemical composition of the cyanobacterium Synechococcus subsalsus, testing a fast-growing native strain. The control experiments were performed with Conway culture medium in 12-day batch cultures, in 6-liter flasks and 12 h photoperiod, with addition of 2 L min-1 filtered air to each flask. Other two experimental conditions were also tested: (i) the placement into the cultures of additional dissolved nutrients except nitrogen, one week after the start of growth (N-), and (ii) the input of pure CO2 into the flasks from the 5th day of growth (C+). In all cultures, daily cell counts were done throughout the cultivation, as well as measurements of pH and cell biovolumes. Maximum cell yield were found in N-experiments, while cell yields of C+ and control were similar. Dissolved nitrogen was exhausted before the end of the experiments, but dissolved phosphorus was not totally consumed. Protein and chlorophyll-a concentrations decreased from the exponential to the stationary growth phase of all experiments, except for protein in the control. In all experiments, carbohydrate, lipid and total carotenoid increased from the exponential to the stationary growth phase, as an effect of nitrogen limitation. Increments in carbohydrate concentrations were remarkable, achieving more than 42% of the dry weight (dw), but concentrations of lipid were always lower than 13% dw. The addition of pure CO2 did not cause a significant increase in biomass of S. subsalsus nor generated more lipid and carbohydrate than the other treatments. Nitrogen starvation caused an intense accumulation of carbohydrate, but the increments of lipid were small. Despite the fast growth, the cyanobacterium S. subsalsus has a virtually null potential for biodiesel production, given its low lipid concentrations. The high concentrations of carbohydrate combined with fast growth point to the potential use of this species as raw material for other possible biotechnological processes, after a demonstration of technical and economic viability.

Actualmente los biocombustibles elaborados con algas se consideran una de las soluciones más prometedoras de la crisis energética mundial y el cambio climático para los años venideros. Mediante la manipulación de las condiciones de cultivo, muchas especies de algas pueden ser inducidas para acumular altas concentraciones de biomoléculas particulares que se pueden dirigir a la producción de diferentes combustibles. En este contexto, el presente estudio consistió en la evaluación de los efectos de la disponibilidad de CO2 y falta de nitrógeno sobre el crecimiento y la composición química de la cianobacteria Synechococcus subsalsus, probando una cepa nativa de rápido crecimiento. Los experimentos de control se realizaron con medio de cultivo Conway en cultivos durante 12 días, en matraces de 6 L y 12 h de fotoperíodo, con la adición de 2 L min-1 de aire filtrado a cada matraz. También se ensayaron otras dos condiciones experimentales: (i) la colocación en los cultivos de nutrientes disueltos adicionales excepto de nitrógeno, una semana después del inicio del crecimiento (N-), y (ii) la adición de CO2 puro en los matraces desde el quinto día de crecimiento (C+). En todos los cultivos, los recuentos de células se realizaron a diario durante todo el cultivo, así como mediciones de pH y biovolumes de células. El rendimiento celular máximo se encontró en los experimentos N-, mientras que los rendimientos celulares de C+ y del control fueron similares. El nitrógeno disuelto se agotó antes del final de los experimentos, pero el fósforo disuelto no se consumió totalmente. Las concentraciones de proteínas y clorofila-a disminuyeron de la fase exponencial a la fase estacionaria de crecimiento en todos los experimentos, excepto para la proteína en el control. En todos los experimentos, los hidratos de carbono, lípidos y carotenoides totales se incrementaron de la fase exponencial a la fase de crecimiento estacionario, como un efecto de limitación de nitrógeno. Incrementos en las concentraciones de hidratos de carbono fueron notables, alcanzando más del 42% del peso en seco (ps), pero las concentraciones de lípidos fueron siempre inferiores a 13% peso seco. La adición de CO2 puro no causó un aumento significativo en la biomasa de S. subsalsus ni generó más lípidos e hidratos de carbono que los otros tratamientos. La falta de nitrógeno causó una intensa acumulación de hidratos de carbono, pero los incrementos de lípidos fueron pequeños. A pesar del rápido crecimiento, la cianobacteria S. subsalsus tiene un potencial prácticamente nulo para la producción de biodiesel, debido a sus bajas concentraciones de lípidos. Las altas concentraciones de hidratos de carbono combinadas con crecimiento rápido apuntan para el uso potencial de esta especie como materia prima para otros procesos biotecnológicos posibles, después de una demostración de la viabilidad técnica y económica

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.