Role of the ionic environment in enhancing the activity of reacting molecules in zeolite pores.

Abstract

Tailoring the molecular environment around catalytically active sites allows for the enhancement of catalytic reactivity through a hitherto unexplored pathway. In zeolites, the presence of water creates an ionic environment via the formation of hydrated hydronium ions and the negatively charged framework aluminum tetrahedra. The high density of cation-anion pairs determined by the aluminum concentration of a zeolite induces a high local ionic strength that increases the excess chemical potential of sorbed and uncharged organic reactants. Charged transition states (carbocations for example) are stabilized, which reduces the energy barrier and leads to higher reaction rates. Using the intramolecular dehydration of cyclohexanol on H-MFI zeolites in water, we quantitatively show an enhancement of the reaction rate by the presence of high ionic strength as well as show potential limitations of this strategy.