Biodiesel fuel (fatty acid esters) has become more and more attractive due to its environmental benefits. Transesterification is the most common and important method for making biodiesel from vegetable oils or animal fats. Several studies have focused on the development and improvement of analytical methods for monitoring biodiesel production and determining the fuel quality. Analytical procedures reported in the literature include chromatographic methods (e.g., gas chromatography, high-performance liquid chromatography, gel permeation chromatography, etc.) and spectroscopic methods [e.g., 1H and 13C NMR, near infrared, Fourier transform infrared spectroscopy, and recently, Fourier transform (FT)-Raman]. The study presented in this paper expands our previous research, in which FT-Raman spectroscopy combined with partial least squares (PLS) multivariate analysis was successfully applied to the quantification of soybean oil/ethyl ester mixtures. The FT-Raman/PLS methods developed by our group were used to monitor and quantify a transesterification reaction process involving soybean oil and ethanol to produce fatty acid ethyl esters (biodiesel) over 22 h catalyzed by a heterogeneous Lewis acid catalyst. The results were successfully correlated with two 1H NMR spectroscopic methods reported in the literature and a new 1H NMR method proposed in this work that can be easily extended to other vegetable oils. The correlation coefficients (R 2) obtained from the linear fit between FT-Raman measurements and the above 1H NMR methods were 0.9974, 0.9847, and 0.9972, respectively.

No abstract

Bronsted and Lewis acid catalysts with ionic tags under homogeneous and heterogeneous conditions have been tested to perform the Biginelli synthesis of 3,4-dihydropyrimidin-2­(1H)-one (DHPMs). Metal-containing ionic liquids were evaluated as the catalysts with reasonable results (homogeneous systems). Heterogeneous catalysts (zeolite β and H3PW12O40 supported on zeolite β) have been tested, as well, with good to excellent results. The use of a functionalized acid ionic liquid with a heteropolyacid in the anion moiety (homogeneous system) gave the best results using no excess of the three reagents. The preferred mechanistic pathway was investigated by electrospray ionization (tandem) mass spectrometry in both positive and negative ion modes with very elucidative results. The ionic liquid effect and its origin were also investigated using mass spectrometry and DFT calculations.

No abstract

Supported niobium pentoxide materials have been effective catalysts for a variety of acid and redox reactions (e.g., dehydration of alcohols, esterifications, etc.). To the best of our knowledge, there are no reports about Nb 2 O 5 supported on silica-alumina. Catalysts of Nb 2 O 5 /SiO 2 -Al 2 O 3 were prepared with 2, 5, 10, 15, 20, and 25 wt % of Nb 2 O 5 by aqueous solution impregnation using ammonium niobium oxalate on silica-alumina. The materials, after being dried at 100 °C, were calcined at 800 °C and characterized by several methods. Investigation through X-ray diffraction showed the typical patterns of crystalline Nb 2 O 5 , which were composed of mixtures of orthorhombic and monoclinic phases (T, M, and H, respectively) present in the materials with content higher than 10 wt %. DTA curves displayed an exothermic peak at 1356 °C (average) without mass loss (confirmed by TG), which may be ascribed to a phase transition (H phase formation) of Nb 2 O 5 supported on silica-alumina. Pure Nb 2 O 5 ‚nH 2 O showed a transition from amorphous to hexagonal or orthorhombic phase (TT or T, respectively) at 567 °C. FTIR and DRIFTS results confirmed the reaction of the niobium oxide with the hydroxyl functionality of silica-alumina. The formation of surface niobium pentoxide species over the support through selective and progressive consumption of hydroxyl groups from the support and the appearance of characteristic niobium hydroxylated species on the surface were demonstrated. Raman spectra attested a two-dimensional overlayer of niobium pentoxide on silica-alumina at contents below 10 wt %. At higher concentrations, the absorptions characterize the formation of phases T and H of bulk Nb 2 O 5 .