Catalytic Conversion of Levulinic Acid over Sn-BTC and Sn-H3-5-SIP Heterogeneous Acid Catalysts

This work presents the synthesis and characterization of materials that contain Sn metal clusters formed by ligands of trimesic acid (Sn-BTC) or 5-sulfobenzene-1,3-dicarboxylic acid (Sn-H3-5-SIP). These catalysts were used to convert levulinic acid with ethanol to produce ethyl levulinate under mild reaction conditions. The characterization results confirmed that Sn is mainly present in the cassiterite crystalline phase with a tetragonal rutile structure in octahedral and tetrahedral coordination in the materials. The assembly of trimesic acid (a hard base) with metal species (Sn) results in the formation of acid and thermally stable metal–organic frameworks. The use of 5-sulfobenzene-1,3-dicarboxylic acid instead of trimesic acid in the synthesis incorporates sulfonic groups in the material, enhancing the total acidity of the Sn-H3-5-SIP catalyst compared to the Sn-BTC material. The Sn-H3-5-SIP catalyst exhibited the highest catalytic activity when converting levulinic acid with ethanol, resulting in a turnover frequency (TOF) of 0.0495 s−1, which is a 50% increase compared to the TOF of the Sn-BTC catalyst (0.0329 s−1). This result can be attributed to its higher concentration of acid sites (2.23 ± 0.05 mmol H+/gcat) and specific area (139 m2/g). Thus, materials containing tin metal clusters and sulfonic groups are promising materials that could be used as catalysts for synthesizing ethyl levulinate under mild reaction conditions.