Experimental and Theoretical Insights into the Hydrogen-Efficient Direct Hydrodeoxygenation Mechanism of Phenol over Ru/TiO2

Catalytic reduction of pyrolyzed biomass is required to remove oxygen and produce transportation fuels, but limited knowledge of how hydrodeoxygenation (HDO) catalysts work stymies the rational design of more efficient and stable catalysts, which in turn limits deployment of biofuels. This work reports results from a novel study utilizing both isotopically labeled phenol (which models the most recalcitrant components of biofuels) with D2O and DFT calculations to provide insight into the mechanism of the highly efficient HDO catalyst, Ru/TiO2. The data point to the importance of interface sites between Ru nanoparticles and the TiO2 support and suggest that water acts as a cocatalyst favoring a direct deoxygenation pathway in which the phenolic OH is replaced directly with H to form benzene. Rather than its reducibility, we propose that the amphoteric nature of TiO2 facilitates H2 heterolysis to generate an active site water molecule that promotes the catalytic C–O bond scission of phenol. This work has cle...