A series of H-ZSM-5 crystallites with different framework Si/Al ratios was studied by analyzing the kinetics and reaction mechanism of the oligomerization of 4-fluorostyrene as molecular probe reaction for Brønsted acidity. The formation of carbocationic species was followed by UV-Vis spectroscopy. Three carbocationic products were observed, namely a cyclic dimer, a conjugated linear dimer and a larger, more conjugated carbocation. Rate constants for the formation of all three products show a maximum at a Si/Al ratio of 25. Oligomerization of 4-fluorostyrene within the larger supercages of zeolite H-Y leads solely to cyclic dimers. The experimental observations were rationalized by DFT calculations, which show that the selectivity of the styrene oligomerization is controlled by the steric properties of the intrazeolite micropore voids. Two reaction pathways were considered for the formation of the conjugated linear carbocation. The conventional mechanism involves a hydride transfer between two dimeric hydrocarbons (HCs) in the zeolite pores. We propose an alternative monomolecular path, in which the hydride transfer takes place between a hydrogen atom of a dimeric HC and a zeolitic proton, yielding a conjugated carbocation and molecular H2. Computed free energies indicate that the preference for a particular reaction mechanism is determined by the local shape of the zeolite micropores.
