Monoacetin was synthesized using a novel green method in which acetonitrile was hydrolyzed and then esterified with glycerol over Cu-Cr phosphates under the CO2 atmosphere. Monoacetin was synthesized with high yield (87.6% glycerol conversion and 86.3% monoacetin selectivity) through this one-pot cascade method. In this process, acetonitrile can react with water to form acetamide and further undergo esterification with glycerol. There are two main reasons for obtaining monoacetin in high yield: (1) the interaction of CO2 with high-temperature liquid water enhances the acid strength of the reaction system and then promotes the activation of acetonitrile; and (2) the introduction of Cr species causes a synergistic effect between Cu and Cr species to adjust the acidity and basicity of the catalyst. The introduction of Cr species converts eight-coordinated Cu2+ into four-coordinated Cu2+ to improve the acidity of the catalyst. The introduction of Cr species also causes the surface oxygen to be transformed into lattice oxygen to enhance the basicity of the catalyst. These bimetallic phosphate materials may provide a new pathway for the application of acid-base bifunctional catalytic reactions.
Keywords: CO2; Cu−Cr phosphates; acetonitrile; glycerol; monoacetin; one-pot process.