Electronic Coupling Enhanced PtCo/CeO2 Hybrids as Highly Active Catalysts for the Key Dehydrogenation Step in Conversion of Bio-Derived Polyols

Abstract Dehydrogenation, involving C-H bond activation, is one of the key reactions for biomass conversion. We report a unique design principle for electronically coupled metal-ceria hybrids as novel catalysts to demonstrate improved performance of C-H bond cleavage in conversion of polyols. Using PtCo clusters as a model catalyst system, we found that CeO2 with (1 0 0) and (1 1 1) facets display unusual d band modulation for Pt sites. TEM, XPS, Raman and UV–Vis analysis confirmed that, such strong electronic coupling effect contributes to a record high TOF of 10,735 h−1 for C-H cleavage of glycerol at 200 °C, approximately seven-fold higher compared to literature results. Based on kinetic analysis, it was further confirmed that C-H cleavage follows two alternative pathways: metal catalyzed H extraction from oxygenates, and direct OH– insertion promoted by Pt-O-Ce sites. The outcome of this work provides new insights on innovative design of selective dehydrogenation catalysts for other industrial applications.