Integrating Zeolite and Layered Double Hydroxide for Highly Selective Catalytic Production of γ-Valerolactone

The production of γ-valerolactone (GVL) from biomass derivatives levulinic acid (LA) based on acidbase metallic catalysts offers a sustainable pathway to the synthesis of valuable chemicals and biofuels. However, the development of efficient metallic catalysts with tunable Lewis acid–base and Brønsted acid sites remains a challenge. Herein, for the first time, we integrated zeolite and layered double hydroxide (LDH), in a core–shell structure, wherein zeolite and CoFe-LDH provided the Brønsted acidic sites and Lewis acid sites, respectively. Meanwhile, oxygen vacancies (OV_x) acting as Lewis bases were generated on the surface of LDH via Ga doping. An efficient cascade catalytic reaction from LA to GVL was successfully achieved over the designed Beta@LDH-OV_x catalyst, affording a superior conversion of LA (>99.9%) and an impressive selectivity to GVL (89.18%). Importantly, the “memory effect” of LDH endowed the catalyst with excellent regeneration of metal active sites. Density functional theory calculations revealed that the introduced OV_x facilitated the adsorption of carbonyl oxygen in LA and boosted the production of GVL through the synergistic effect of acid/base sites in the composite catalyst. This work presents a rational design route for the construction of multifunctional catalysts by coupling zeolites and LDHs for highly selective catalytic conversion of biomass.