Surface processes during sorption of aromatic molecules on medium pore zeolites

The elementary steps of sorption and transport of benzene, toluene, and o- and p-xylene from the gas phase to hydroxy groups of zeolite H/ZSM-5 on the outer surface (SiOH groups) and in the pores (SiOHAl groups) were studied using pressure modulations followed by fast time-resolved IR spectroscopy. Sorption on these acid sites occurs via a common physisorbed state on the outer surface. The equilibration of the molecules in this state is fast compared to the sorption rates on SiOH and SiOHAl groups. The relative rates of equilibration of functional groups with the aromatic molecules suggest that the aromatic molecules move freely on the surface of the outer surface before reversibly binding to OH groups, entering the micropores or desorbing. Molecules able to enter into the pores (benzene, toluene, p-xylene) adsorb faster on SiOHAl groups than on SiOH groups. If the access of the molecules into the pores is sterically constrained (o-xylene), the rate of adsorption on the remaining accessible SiOH groups is strongly enhanced.