121st General Meeting of the KCS

Type Symposium
Area Functional Nanocomposite Materials
Room No. Samda Hall A
Time FRI 14:50-:
Code MAT3-2
Subject Conversion of ethyl levulinate to γ-valerolactone via catalytic transfer hydrogenation over zirconium based metal-organic frameworks
Authors Do-Young Hong*, u-hwang lee1, Jong-San Chang1, Young Kyu Hwang*
Carbon Resources Institute, Korea Research Institute of Chemical Technology, Korea
1Center for Convergent Chemical Process, Korea Research Institute of Chemical Technology, Korea
Abstract A series of highly crystalline, porous, zirconium-based metal-organic frameworks (Zr-MOFs) with different ligand functionality and porosity were applied for conversion of ethyl levulinate (EL) to form γ–valerolactone (GVL) via catalytic transfer hydrogenation using using isopropanol as a hydrogen donor. The role of ligand functionality and the metal center of the Zr-MOFs were characterized by a number of complementary techniques. Reaction parameters were optimized for selective production of GVL. Maximum yield of GVL (up to 92.7%) was achieved in 2 h at 200oC with UiO-66(Zr). Interestingly, zirconium trimesate (MOF-808) emerged as the most suitable candidate, with the highest GVL formation rate (94.4 μmol/g/min) among the catalysts tested at 130oC. It was also found effective in conversion of EL to GVL in an open system using the solvent refluxing method. Both the catalysts (UiO-66(Zr) and MOF-808) were recycled at least five times under their specified reaction conditions without notable change in catalytic activity and product selectivity. Fresh and recycled catalysts were characterized by using X-ray diffraction (XRD), N2 adsorption-desorption, thermal gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) to generate understanding of the catalyst structure changes and stability, allowing correlation of the catalytic behavior. Finally, a plausible reaction mechanism was presented on the basis of active sites present in catalysts confirmed by characterization results.
E-mail dyhong@krict.re.kr