A catalyst comprised of SnO2 impregnated on ZnO nanowires, which presented remarkable ability to catalyze fatty acid esterification/transesterification reactions, is reported. For optimization of reaction conditions, artificially acidified soybean oil with 10 wt.% oleic acid was used as a model feed. The optimized conditions were: 150 °C, 6 h, 5 g of oil, catalyst concentration of 5%, and methanol:oil molar ratio of 15:1. The catalyst achieved 92% of total fatty acid methyl esters (FAME) content and was used five times without the necessity of catalyst washing from one reaction to the other. Then, such conditions were applied to produce biodiesel from the oil extracted from Scenedesmus sp. microalgae; the system reached 72% of FAME content, without any previous refining or degumming process of the oil. Rietveld refinement, X-ray diffraction, elemental mapping in scanning transmission electron microscopy, X-ray photoelectron spectroscopy, and pyridine-desorption Fourier-transform infrared spectroscopy were used to characterize the material.

AuPd nanoparticles have gained substantial attention due to their application in selective oxidation of alcohols. However, due to the radical nature of the oxidation of benzyl alcohol, under specific conditions, even without a catalyst, the reaction occurs and affects the selectivity of the system. Therefore, we aimed to develop a catalyst that enables the control of the oxidation leading to higher reaction selectivity. To accomplish this, we have prepared a catalytic support comprised of CoFe2O4 nanoparticles impregnated with Sr(OH)2 that presented a significant control of the reaction selectivity without any metal or external base addition. After the impregnation of AuPd nanoparticles in a specific ratio, the reaction reached a selectivity of > 99% for benzaldehyde, in 3.5 h, with a recycle regime of five runs without loss of activity and selectivity. Our results show that the judicious choice of the ratio of the metals prevents the necessity of manipulating the reaction conditions to improve the performance of the system. Additionally, studies under N2 and O2 environments, with or without water, confirmed the role of the O2 in the system. Holding all this information, we propose a possible mechanism for the prepared system.

We have prepared, by a sol-immobilization method, bimetallic catalysts with different Au:Pt atomic ratios supported on commercial SrCO3. The catalytic performance for the oxidation reaction of benzyl alcohol of such materials was compared to the monometallic counterparts, aiming at the obtaining of the best composition of the material. It was found that the Au:Pt atomic ratio presents a remarkable effect on the system performance, i.e., Pt-rich systems are more selective; however, less active. Thus, an equilibrium related to the activity and selectivity of the system was obtained by considering the yield of the system. Also, some density functional theory (DFT) insights were obtained by using a cluster of 14 atoms of Au and 1 or 2 atoms of Pt. X-ray photoelectron spectroscopy, elemental mapping in scanning transmission electron microscopy before and after catalyst usage, flame atomic absorption spectroscopy, Rietveld refinement, among other techniques, were used and associated to the experimental data, which allowed us to propose a catalytic mechanism for the system, which was important since SrCO3 has not been considered before as catalyst support for alcohol oxidation reactions.

The synthesis of efficient and reusable gold-based catalysts for the selective oxidation of alcohols is a strategy for the development of green processes. Pre-formed nanoparticles syntheses are an easy way to produce controlled-nanosized gold materials; however, the selection of a support is not trivial. Herein, we proposed a CoFe2O4 support enriched with Sr(OH)2, which holds remarkable properties and is suitable for the synthesis of a stable gold-based catalyst for the oxidation of benzyl alcohol. We suggested that the interaction between the CoFe2O4 and the Sr(OH)2 is highly important for the performance of the catalyst. Under the base-free condition of 2.5 h, 100 ºC and 2 bar of O2, the catalyst reached 58% of conversion with 76% of selectivity to benzaldehyde. With K2CO3 addition, the conversion and selectivity to benzaldehyde increased to 87% and 88%, respectively. Any gold leaching was detected in 5 successive runs, attesting the noticeable stability that the catalyst presents. This work provides great potential for the selective oxidation of alcohols with high activity since the magnetic properties of the catalyst provide an easy route and allows the separation of the medium reaction. In addition, we are here proposing an important interaction between the Sr(OH)2 and the magnetic nanoparticles.

Microalgae lipid-derived biofuels is considered promising candidates for substitution of petroleum-based energy sources. However, the lipid extraction from the algal biomass stands as a challenge due to its low yields and cost-intensive cell disruption procedures. In this study a multivariate optimization of the extraction conditions was suggested, aiming a maximization of the lipid extraction from Scenedesmus sp. microalgae grown using wastewater as a nutrient medium. The extraction method, extraction time, solvent mixture and pretreatment were considered between upper and lower levels in order to access their significance, including their interactions, on the experimental response, while using a reduced number of experiments. The studies were performed using low-cost extraction methods (magnetic stirring and ultrasonication). The optimal extraction condition was obtained using CHCl3:MeOH (2:1) solvent mixture, in a 2-hour extraction period using ultrasonication. Fatty acid profiles of extracted lipids were also evaluated.

Quantification of metal loading in supported catalysts is imperative; however, the analytical methods are usually time-consuming, expensive, and require sophisticated equipment and sample extraction with hazardous and corrosive strong acids. Herein, we report a new method for quantification of metal in supported catalysts using slurry sampling flame atomic absorption spectrometry. The slurry sampling method was used for determination of gold and the results were similar to those obtained with the traditional extraction method using aqua regia; however, it overcomes the main drawbacks associated with sample digestion by avoiding the use of concentrated toxic reagents, minimizing sample manipulation, and consequently, reducing the risks of contamination and the sample preparation time. Ultrasound radiation optimization associated with the solvent, mass of sample, concentration, and matrix effect in the slurry analysis allowed direct analysis by using the calibration in aqueous medium. The slurry sampling procedure could be applied to other catalysts with different supports and in bimetallic systems.

O objetivo deste Account é fornecer uma visão geral de nossas atividades atuais de pesquisa, as quais envolvem a síntese e modificação de nanomateriais superparamagnéticos para aplicação na área de separação magnética e catálise. Primeiramente, uma introdução ao magnetismo e à separação magnética é feita. Em seguida, estratégias sintéticas que têm sido desenvolvidas para gerar nanopartículas superparamagnéticas revestidas esfericamente por sílica e outros óxidos, com destaque a sistemas bem caracterizados e preparados por metodologias que geram amostras de elevada qualidade e que, a princípio, podem ser produzidas em maior escala, são discutidas. Uma série de catalisadores magneticamente recuperáveis preparados em nosso grupo de pesquisa pela combinação única de suportes superparamagnéticos e nanopartículas metálicas é destacada. Este Account é concluído com observações pessoais e perspectivas neste campo de pesquisa.

The aim of this Account is to provide an overview of our current research activities on the design and modification of superparamagnetic nanomaterials for application in the field of magnetic separation and catalysis. First, an introduction of magnetism and magnetic separation is done. Then, the synthetic strategies that have been developed for generating superparamagnetic nanoparticles spherically coated by silica and other oxides, with a focus on well characterized systems prepared by methods that generate samples of high quality and easy to scale-up, are discussed. A set of magnetically recoverable catalysts prepared in our research group by the unique combination of superparamagnetic supports and metal nanoparticles is highlighted. This Account is concluded with personal remarks and perspectives on this research field.