Synchronizing Deoxygenation and Hydrogenation to Effect Glycerol Hydrogenolysis over Pt/Nb₂W₁₅O₅₀ at Low H₂ Pressure

The selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) necessitates the precise tandem reactions of deoxygenation at a specific location and the ensuing hydrogenation steps. Herein, a solid solution-supported catalyst Pt/Nb₂W₁₅O₅₀ was reported for the hydrogenolysis of glycerol to 1,3-PDO. We engineered the exceptional interaction between active Pt and oxygen vacancies to efficiently integrate the deoxygenation and hydrogenation steps in tandem. The strong interaction between active Pt and oxygen vacancies was established via hydrogen (H₂) spillover and induced the generation of 1,3-PDO in situ. This synergistic effect confers Pt/Nb₂W₁₅O₅₀ with high catalytic performance, combining a 75.6% conversion of glycerol and 66.5% selectivity to 1,3-PDO at a low H₂ pressure of 1.0 MPa (noting that most catalysts require H₂ pressures of ≥4 MPa). Moreover, the structure-performance relationship validated that there is a linear correlation between active Pt, oxygen vacancies, and 1,3-PDO yield. This study provides mechanistic insights into further catalyst developments for the valorization of other biomass-derived oxygenates.