Transfer hydrogenation of biomass-derived levulinic acid to γ-valerolactone over supported Ni catalystsElectronic supplementary information (ESI) available: Catalyst characterization (XPS, FTIR, XRD), additional activity (effect of water : IPA and acetone : IPA ratio, catalyst reusability, solvent screening) and metal leaching results are provided. See DOI: 10.1039/c6ra08637c

• Main Authors: Hengne, A. M, Kadu, B. S, Biradar, N. S, Chikate, R. C, Rode, C. V
• Format: Journal Article
• Published: 21.06.2016
• ISSN: 2046-2069
• DOI: 10.1039/c6ra08637c

A sustainable process of catalytic transfer hydrogenation (CTH) of levulinic acid (LA) to γ-valerolactone (GVL) was investigated over Ni on various supports (Al 2 O 3 , ZnO, MMT and SiO 2 ) in the presence of isopropanol (IPA) as the H-donor. Among these, the montmorillonite (MMT) supported Ni catalyst showed almost complete LA conversion (>99%) and selectivity (>99%) to GVL within 1 h. XRD and XPS results showed that the concentration of the metallic species significantly enhanced (two to four times) in the recovered sample as compared to the freshly prepared Ni/MMT. This was due to the in situ reduction of Ni 2+ species present on the catalyst surface, through liberated H 2 under the reaction conditions. The strong acid strength of MMT, evidenced by NH 3 -TPD and py-IR, facilitated the esterification of LA as well as cyclization to GVL. The conversion-selectivity pattern was found to decrease in the IPA-water mixture while, it remained unchanged in the IPA-acetone mixture. Our catalyst could be efficiently recycled up to five times with consistent CTH activity and selectivity to GVL. The plausible mechanism of LA to GVL conversion involves the formation of a levulinate ester with IPA that favours its simultaneous hydrogenation and cyclization in a spontaneous manner to give GVL and regenerating IPA for sustainability. A bifunctional Ni/MMT catalyst for catalytic transfer hydrogenation of levulinic acid to γ-valerolactone with complete conversion and selectivity.