Vanadium-doped phosphomolybdic acids as catalysts for geraniol oxidation with hydrogen peroxide.

In this work, vanadium-doped phosphomolybdic acids were evaluated as catalysts in green oxidation routes of terpene alcohols with hydrogen peroxide. A series of phosphomolybdic acids containing a variable load of vanadium cations (i.e., V5+ ions) were synthesized, and tested as catalysts in geraniol oxidation, the model molecule selected. All the catalysts were characterized by powder X-ray diffraction, attenuated diffuse reflectance infrared spectroscopy, UV-Vis spectroscopy, thermogravimetric analysis, N2 adsorption-desorption isotherms, scanning electronic microscopy, X-ray dispersive spectroscopy, and n-butylamine potentiometric titration. Various catalysts were evaluated; phosphomolybdic acids with general formulae H3+n PMo12-n V n O40 (n = 0, 1, 2 and 3), and common Brønsted acids (i.e., H2SO4, H3PO4, and p-toluene sulfonic acid). Among them, vanadium monosubstituted phosphomolybdic acid was the most active catalyst and selective toward epoxide. The effect of main reaction variables, such as temperature, load catalyst, and reactant stoichiometry was assessed. Evaluating the effect of substrate, it was verified that only allylic alcohols such as geraniol and nerol were successfully epoxidized, demonstrating that this is a hydroxy group-assisted reaction. The effect of vanadium doping on the physicochemical properties of the phosphomolybdic acid catalysts was evaluated and used to explain their catalytic performance.

Novel Hg (II) selective fluorescent green sensor based on carbon dots synthesized from starch and functionalized with methimazole.

We describe a green new method for the synthesis of water-soluble photoluminescent carbon dots (CDs) that were functionalized with methimazole (MTZ) and applied to determine Hg2+ based on the fluorescence extinction. Starch obtained from rice was used as a natural source for the production of CDs by hydrothermal treatment. Also, it was proposed a factorial design to optimize the parameters for CD synthesis and the results showed that the luminescence intensity is a function of temperature and not of the heating time in the hydrothermal process. The synthesized CDs were characterized using fluorescence techniques, Fourier transform infrared spectroscopy (FTIR), and UV-Vis spectroscopy. Through transmission electron microscopy (TEM) and dynamic light scattering (DLS), it was found the formation of CDs on a nanometer scale with an average size of 11 nm. The functionalization with MTZ, eliminated all interferences from other metals, indicating a selective response to Hg2+ ions. The method was applied to Hg2+ determination in waters. Under optimal conditions, was obtained a limit of detection of 1.8 × 10-7 mol L-1 with a linear range from 3.3 × 10-7 to 50.0 × 10-6 mol L-1. Therefore, the proposed method can be considered a simple, selective, and precise alternative that minimizes the number of reagents used for Hg2+ determination in natural waters, and can be applied on a large scale in environmental analyzes.

Na4PMo11VO40-catalyzed one-pot oxidative esterification of benzaldehyde with hydrogen peroxide.

The activity of the sodium salts of vanadium-doped phosphomolybdic acid was assessed in the oxidative esterification reaction of benzaldehyde with hydrogen peroxide in alkyl alcohol solutions. The effect of main reaction parameters, such as temperature, catalyst load, vanadium doping level, and reactant stoichiometry, on the conversion and reaction selectivity was investigated. Among the tested heteropoly salts, Na4PMo11VO40 was the most active and selective catalyst, achieving almost complete conversion of benzaldehyde and high ester selectivity regardless of the alcohol investigated. The efficiency of the catalyst was correlated with its vanadium content. The size of the carbon chain of alcohol and the steric hindrance on the hydroxyl group played a key role in the reaction selectivity. While methyl and ethyl alcohols selectively provided the ester as the main product (ca. 90-95%) and benzoic acid as a subproduct, the other alcohols also afforded acetal, a condensation product, and benzaldehyde peroxide, an oxidation reaction intermediate, as secondary products. The use of an inexpensive, environmentally benign, and atom-efficient oxidant, mild conditions, and short reaction times were the positive aspects of this one-pot process.

Vanadium-doped sodium phosphomolybdate salts as catalysts in the terpene alcohols oxidation with hydrogen peroxide.

In this work, we have explored the catalytic activity of Keggin-type heteropolyanions PMo12-n V n O40 (3+n)- (n = 0, 1, 2, or 3) in the form of sodium salts in green oxidation routes of terpene alcohols with hydrogen peroxide. Nerol was the model molecule selected to assess the impacts of the main reaction parameters, such as temperature, catalyst load, and stoichiometry of reactants. The impacts of the presence of vanadium at different proportions (i.e., V1, V2, and V3 loads/per anion) in the structure of phosphomolybdate catalysts were assessed. All the catalysts were characterized by various techniques such as powder X-ray diffraction, attenuated diffuse reflectance infrared spectroscopy, ultraviolet-visible spectroscopy, thermogravimetric analysis, isotherms of adsorption-desorption of N2 measurements of surface area, scanning electronic microscopy, energy-dispersive X-ray spectroscopy, and n-butylamine potentiometric titration. Among the catalysts assessed, Na4PMo11VO40 was the most active and selective toward epoxides. The efficiency of this catalyst in the epoxidation of different terpene alcohols was investigated. Special attention was dedicated to correlating the composition and properties of the vanadium-doped phosphomolybdic catalysts with their catalytic activity.