Water-Induced Micro-Hydrophobic Effect Regulates Benzene Methylation in Zeolite

Water is a ubiquitous component in heterogeneous catalysis over zeolites and can significantly influence the catalyst performance. However, the detailed mechanism insights into zeolite-catalyzed reactions under microscale aqueous environment remain elusive. Here, using multiple dimensional solid-state NMR experiments coupled with ultrahigh magic angle spinning technique and theoretical simulations, we establish a fundamental understanding of the role of water in benzene methylation over ZSM-5 zeolite under water vapor conditions. We show that water competes with benzene for the active sites of zeolite and facilitates the bimolecular reaction mechanism. The growth of water clusters induces a micro-hydrophobic effect in zeolite pores, which reorients benzene molecules and drives their interactions with surface methoxy species (SMS) on zeolite. We identify the formation and evolution of active SMS-Benzene complexes in a microscale aqueous environment and demonstrate that their accumulation in zeolite pores boosts benzene conversion and methylation.