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

Abstract

While zirconium (Zr)-based metal organic frameworks (MOFs) are promising for conversion of levulinic acid (LA) to γ-valerolactone (GVL) through catalytic transform hydrogenation (CTH), these reported Zr MOFs for LA conversion must be synthesized in toxic dimethylformamide (DMF). From the viewpoint of sustainability, it is preferable to avoid usage of DMF-based solvents to prepare these Zr MOFs. As water is a green solvent, the aim of this study is to develop and investigate Zr MOFs, which are prepared in water, for LA conversion to GVL. 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. Especially, 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 water-born ZrF could be also reused even without regeneration for multiple cyclic LA conversion. These results and findings prove that the water-born ZrF is not only environmentally benign but also more effective for LA conversion to GVL.

Keywords: Levulinic acid; MOF-801; Modulators; Zr fumarate; γ-valerolactone.