Catalytic Transfer Hydrogenation of Biomass-Derived Levulinic Acid and Its Esters to γ-Valerolactone over Sulfonic Acid-Functionalized UiO-66

Production of γ-valerolactone (GVL) from biomass-derived levulinic acid and its esters via a catalytic transfer hydrogenation (CTH) process over sulfonic acid-functionalized UiO-66, a microporous zirconium-based metal–organic framework (Zr-MOF), is reported herein. On the basis of comprehensive structural analyses by means of XRD, N2 physisorption, IR, TG, and Zr K-edge XAFS, we show that free sulfonic acid (−SO3H) groups can uniformly be tethered on a UiO-66 framework without affecting the coordination state of Zr atoms, while crystallinity and surface area decrease along with the functionalization. As a consequence, UiO-66 bearing a 60 mol % fraction of sulfonic acid-containing benzene dicarboxylate (BDC) linker and retaining a high surface area exhibits the highest catalytic activity in the CTH reaction of levulinic acid and its esters to give GVL with the maximum GVL yield of up to 85% at 140 °C. Comparative experiments, together with characterization results, reveal that the high catalytic activity i...

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