Conversion of biomass to γ-valerolactone by catalytic transfer hydrogenation of ethyl levulinate over metal hydroxides

A series of low-cost readily-assembled eco-friendly metal hydroxides were examined as catalysts in the synthesis of a novel platform molecule, γ-valerolactone (GVL), from biomass-derived ethyl levulinate (EL) via hydrogen transfer reaction. Among these catalysts, ZrO(OH) 2 · x H 2 O was found to be most active. EL conversion of 93.6% and GVL selectivity of 94.5% were achieved when 2-propanol was used as a hydrogen donor at 473   K with a reaction time of only 1   h. The complete reaction pathway and the probable main by-products for the conversion of EL to GVL were clearly deduced for the first time. The ZrO(OH) 2 · x H 2 O catalyst could be reused at least ten times without any significant loss of catalytic activity. Furthermore, characterizations were carried out on the fresh and spent ZrO(OH) 2 · x H 2 O catalysts with XRD, FT-IR, BET, TGA-DTA. Combined with the results of poisoning experiments, a plausible mechanism for catalytic transfer hydrogenation (CTH) of EL to GVL was proposed to be consisted of a catalytic cycle involving a six member ring transition state.