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

Abstract

The vanadium-doped phosphomolybdic acid (H 4 PMo 11 VO 40 ) was the most active and selective heteropoly catalyst in one-pot oxidative esterification of benzaldehyde 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. , V 5+ 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, N 2 adsorption–desorption isotherms, scanning electronic microscopy, X-ray dispersive spectroscopy, and n -butylamine potentiometric titration. Various catalysts were evaluated; phosphomolybdic acids with general formulae H 3+ n PMo 12− n V n O 40 ( n = 0, 1, 2 and 3), and common Brønsted acids ( i.e. , H 2 SO 4 , H 3 PO 4 , 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.