Enhanced adsorption-catalysis combination for the removal of sulphur from fuels using polyoxometalates supported on amphipathic hybrid mesoporous silica nanoparticles.

Polyoxometalate (POM) mesoporous silica-based materials with a low POM loading have been designed with hydrophilic and hydrophobic properties. These materials act as powerful heterogeneous catalysts in oxidative desulfurization (ODS), owing to their ability to adsorb both HO and sulphur-containing compounds from the model oil simultaneously. The formation of charge transfer salts through ion pair interaction with a choline functionality, available on the hybrid silica support, affords robust and recyclable heterogeneous catalysts for the ODS process under mild conditions (45 min and 40 °C). Besides, the nature of the polyoxometalate anions is highly dependent on the characteristics of the silica surface. The masking of silanol groups present on the silica surface using silylating agents, with diverse reactivity and steric hindrance, influences the silica surface-heteropolyanion interactions, as well as heteropolyanion-heteropolyanion interactions. In addition, it modifies the hydrophobic properties of the surface, which is a determining factor in the adsorption properties of non-polar dibenzothiophene (DBT) by the catalysts. Adsorption, an anterior step to the oxidation reaction, has been demonstrated to be key to the superior activity of POM-SiMe-Chol-MSN, where the silanol groups have been capped by trimethylsilyl groups. For the first time, and to better understand POM-surface and POM-POM anion interactions, an extensive characterization of the materials has been performed using C, P, and Mo MAS NMR spectroscopy and solid-state electrochemical techniques, among others.