Oxygen Vacancy Engineering on Pt/WOx/Nb2O5 Catalysts toward Efficient 1,3-Propanediol Production from Glycerol Hydrogenolysis

The hydrogenolysis of biomass-derived glycerol to 1,3-propanediol is an important process in biomass valorization, while the selective cleavage of the secondary hydroxyl group (C2–OH) in glycerol remains a key challenge in chemistry and catalysis. We report herein a multistep approach for the construction of Pt/WOx/Nb2O5 featuring abundant oxygen vacancies and strong Ptδ+–O–W interactions thereof, making Pt/WOx/Nb2O5 a robust catalyst for glycerol hydrogenolysis to 1,3-propanediol. Typically, the optimized Pt/WOx/Nb2O5 catalyst achieves remarkable performance in the hydrogenolysis of a high-concentration glycerol solution (50.0 wt %) with a glycerol conversion of 94.9%, a 1,3-propanediol selectivity of 67.3%, and a glycerol space-time yield of 0.490 g gcat–1 h–1, surpassing all known catalyst systems. The presence of abundant oxygen vacancies in Pt/WOx/Nb2O5 is directly visualized by microscopy, and the essential role of Ptδ+–O–W interactions in the reaction is well interpreted by spectroscopic analysis. The Ptδ+–O–W interactions can promote the selective adsorption of the secondary hydroxyl group in glycerol and the hydrogen spillover from Pt to WOx for in situ Brønsted acid site generation, both facilitating the selective hydrogenolysis of glycerol to 1,3-propanediol. Overall, we show here a successful example of catalyst design via oxygen vacancy engineering for an important process, biomass valorization.