Water born Zirconium-based Metal Organic Frameworks as Green and Effective Catalysts for Catalytic Transfer Hydrogenation of Levulinic Acid to γ-Valerolactone: Critical Roles of Modulators

• Main Authors: Wan-Chu Yun, 雲莞筑
• Other Authors: Kun-Yi Lin
• Format: Others
• Language: en_US
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/cgi-bin/gs32/gsweb.cgi/login?o=dnclcdr&s=id=%22107NCHU5087027%22.&searchmode=basic

碩士 === 國立中興大學 === 環境工程學系所 === 107 === While the conversion of levulinic acid (LA) to γ-valerolactone (GVL) through catalytic transform hydrogenation (CTH) by using zirconium (Zr)-based metal organic frameworks (MOFs) are promising, it is reported that Zr MOFs catalyzed LA conversion must be synthesized by using toxic dimethylformamide (DMF) as solvents. However, it is preferable to avoid the usage of DMF-based solvents to prepare these Zr-MOFs from the viewpoint of sustainability. Thus, the aim of this study is to investigate the preparation of Zr MOFs for LA conversion to GVL under green solvents. Specifically, monocarboxylic acids (e.g., formic acid, acetic acid and propanoic acid) are employed as modulators during the preparation of water-born ZrF. The role of modulators is extremely important for the well-developed formation of water-born ZrF. In addition, different monocarboxylic acid modulators also significantly influence the morphology of water-born ZrF; Nevertheless, their crystalline structures and acidities are equivalent. As for LA conversion, these water-born modulated ZrF MOFs are validated to successfully convert LA to GVL. In particularly, the formic acid-modulated ZrF can exhibit LA conversion = 96%, selectivity for GVL = 98% and yield of GVL = 98%. These water-born modulated ZrF also exhibit even higher catalytic activities than the typical DMF-based ZrF and reported Zr-based MOFs in LA conversion to GVL. These results and findings prove that the water-born ZrF is not only environmentally benign but also more effective for LA conversion to GVL.