Rational Positioning of Metal Ions to Stabilize Open Tin Sites in Beta Zeolite for Catalytic Conversion of Sugars

Via hydrothermal synthesis of Sn-Al gels, mild dealumination and ion exchange, a bimetallic Sn-Ni-Beta catalyst was prepared which can convert glucose to methyl lactate (MLA) and methyl vinyl glycolate (MVG) in methanol at yields of 71.2 % and 10.2 %, respectively. Results from solid-state magic-angle spinning nuclear magnetic resonance, X-ray photoelectron spectroscopy, transmission electron microscopy, spectroscopic analysis, probe-temperature-programmed desorption, and density functional theory calculations conclusively reveal that the openness of the Sn sites, such as by the formation of [(SiO)3 -Sn-OH] entities, is governed by an adjacent metal cation such as Ni2+ , Co2+ , and Mn2+ . This relies on the low structure-defective pore channel, provided by the current synthesis scheme, and the specific silica hydroxyl anchor point is associated with the incorporation of Sn for additional and precise metal ion localization. The presence of metal cations significantly improved the catalytic performance of Sn-Ni-Beta for glucose isomerization and conversion to MLA of sugar compared with Sn-Beta.