Supported Bifunctional Molybdenum Oxide-Palladium Catalysts for Selective Hydrodeoxygenation of Biomass-Derived Polyols and 1,4-Anhydroerythritol

Selective removal of oxygen from biomass-derivedpolyols is critical toward bridging the gap between biomassfeedstocks and the production of commodity chemicals. In thiswork, we show that earth-abundant molybdenum oxide basedheterogeneous catalysts are active, selective, and stable for thecleavage of vicinal C-O bonds in biomass-derived polyols.Catalyst characterization (Raman spectroscopy, X-ray photo-electron spectroscopy (XPS), diffuse reflectance infrared Fouriertransform spectroscopy (DRIFTS)) shows that partially reducedMoOxcenters are responsible for C-O bond cleavage and aregeneratedin situby hydrogen dissociated atoms over palladium(Pd) nanoparticles. Wefind that the support, TiO2, facilitatescommunication between the hydrogen dissociating metal and dispersed MoOxsites through hydrogen spillover. Reactivity studiesusing a biomass-derived model substrate (1,4-anhydroerythritol) show the effective removal of vicinal hydroxyls over MoOx-Pd/TiO2producing tetrahydrofuran with >98% selectivity at 29% conversion. Catalyst stability is demonstrated upon cycling. Thesestudies are critical toward the development of low-cost heterogeneous catalysts for sustainable hydrodeoxygenation of biobased polyols to platform chemicals