AbstractBrønsted-acid sites are introduced via –OSO3H groups on the coordinatively unsaturated ZrO2 nodes of UiO-66 metal organic frameworks (MOF). Such groups create strong Brønsted acidic sites that are active for cyclohexanol and ethanol dehydration (in liquid organic phase and gas phase, respectively). The intrinsic activity of Brønsted acid sites at nodes increased by increasing the concentration of sulfur, which is attributed to a shift from isolated µ3-OSO3H to two groups [(µ3-OSO3H)2] interacting via hy-drogen bonding. For cyclohexanol dehydration, the relatively low activation enthalpies and negative transition entropies point to an E2 elimination mechanism, similar to dehydration with MFI zeolites in organic solvents. Our results, show that the catalytic activity can be manipulated via the functionalization of zirconia nodes of the MOF framework.
Published: September 20, 2023