Hydrogenation Catalysis by Hydrogen Spillover on Platinum‐Functionalized Heterogeneous Boronic Acid‐Polyoxometalates

Abstract

The activation of molecular hydrogen is a key process in catalysis. Here, we demonstrate how polyoxometalate (POM)-based heterogeneous compounds functionalized with Platinum particles activate H₂ by synergism between a hydrogen spillover mechanism and electron-proton transfer by the POM. This interplay facilitates the selective catalytic reduction of olefins and nitroarenes with high functional group tolerance. A family of polyoxotungstates covalently functionalized with boronic acids is reported. In the solid-state, the compounds are held together by non-covalent interactions (π-π stacking and hydrogen bonding). The resulting heterogeneous nanoscale particles form stable colloidal dispersions in acetonitrile and can be surface-functionalized with platinum nanoparticles by in situ photoreduction. The resulting materials show excellent catalytic activity in hydrogenation of olefins and nitrobenzene derivatives under mild conditions (1 bar H₂ and room temperature).