Robust synergistic effect between Zn1Mo1bifunctional TiO2for efficient ethyl levulinate production from furfural alcohol

Bifunctional ZnxMoy-TiO2were prepared through sol-gel methodology for efficient furfuryl alcohol (FAL) alcoholysis to ethyl levulinate (EL). From the comprehensive analysis, the abundant Brønsted and Lewis acidity distribution, enhanced reducibility ability, and the synergistic effect between Zn and Mo were found in Zn1Mo1–TiO2. Specially, Zn played an important role in enhancing acidity strength and reducibility from NH3-TPD and H2-TPR profiles, whereas Mo exhibited the highest FAL adsorption capacity. The simulative structure with the adjacent Zn–Mo and non-adjacent Zn–Mo with O vacancies in TiO2showed no difference in FAL adsorption energy and bader charge transfer capacity. After optimization, Zn1Mo1–TiO2exhibited the highest FAL conversion (98 %) and EL yield (80 %) with negligible 2-(ethoxymethyl)furan (EMF) and 5-ethoxy-5-(ethyl-oxidaneylidene) pentan-2-one (intermediate 4) yield under optimum condition (50 mg Zn1Mo1–TiO2, 170 °C, 7 h). Most importantly, the catalyst recyclability was performed in continuous flow until 700 min without obvious EL yield decrease. The rational design of the cost-effective bimetallic based TiO2will drive the green and efficient EL production in industrial scale.