Hydrogenation of levulinic acid into gamma-valerolactone over in situ reduced CuAg bimetallic catalyst: Strategy and mechanism of preventing Cu leaching

Metal leaching is a major issue in efficient production of γ-valerolactone (GVL) from levulinic acid (LA) under mild reaction conditions. In this study, Ag was added to Cu-supported γ-Al₂O₃ catalyst to suppress Cu leaching in the hydrogenation of LA into GVL. The CuAg/Al₂O₃ catalyst was reduced in situ during the reaction, and Cu leaching in the solution was significantly suppressed. The bimetallic catalyst without reduction pretreatment achieved approximately 100% yield to GVL and exhibited good reusability in nine consecutive cycles under mild reaction conditions of 180 °C and 1.4 MPa H₂ pressure in tetrahydrofuran (THF). The strong interplay in the geometric and electronic effects between Cu and Ag was verified through XPS, H₂-TPR, TEM, STEM/EDS, and XRD analyses. This paper extensively discussed the mechanism of Ag on preventing Cu leaching and the superiority of in situ reduction in solution over external reduction in gas.