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

Abstract

In this work, we have explored the catalytic activity of Keggin-type heteropolyanions PMo_12−nV_nO₄₀⁽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.