The Mechanism of Glucose Isomerization to Fructose over Sn‐BEA Zeolite: A Periodic Density Functional Theory Study

Abstract The isomerization of glucose to fructose in the presence of Sn‐containing zeolite BEA (beta polymorph A) was studied by periodic DFT calculations. Focus was placed on the nature of the active site and the reaction mechanism. The reactivities of the perfect lattice Sn IV site and the hydroxylated SnOH species are predicted to be similar. The isomerization activity of the latter can be enhanced by creating an extended silanol nest in its vicinity. Besides the increased Lewis acidity and coordination flexibility of the Sn center, the enhanced reactivity in this case is ascribed to the reaction environment that promotes activation of the confined sugar intermediates through hydrogen bonding. The resulting multidentate activation of the substrate favors the rate‐determining hydrogen‐shift reaction. These findings suggest the important role of defect lattice sites in Sn‐BEA for catalytic glucose isomerization.