Catalytic transfer hydrogenation of biomass-derived levulinic acid and its esters to γ-valerolactone over ZrO 2 catalyst supported on SBA-15 silica

A series of ZrO2 catalysts supported on mesoporous SBA-15 silica were synthesized and examined as catalysts in the production of γ-valerolactone (GVL) from biomass-derived levulinic acid and its esters via a catalytic transfer hydrogenation (CTH) using several alcohols as hydrogen donors. Among the catalysts examined, ZrO2 supported on high-surface-area SBA-15 silica bearing highly-dispersed zirconium species exhibited the highest catalytic activity, of which reaction rate was 1.7 times higher than that of the conventional bulk ZrO2 catalyst. Zr K-edge XAFS analysis revealed that Zr4+-oxide species with a low-coordination state anchored on silica surface is the dominant active species. Such a Zr species efficiently converted levulinic acid and its esters to GVL (∼95% yields) under mild reaction conditions (150 °C, 1.0 MPa Ar), and was reusable over multiple catalytic cycles without significant loss of catalytic performances. Comparative experiments, combined with detailed characterizations using NH3/CO2-TPD and in-situ FTIR, proposed a plausible reaction mechanism where basic ZrOH site triggers the CTH reaction involving a six-member ring transition state.