Chemical and Structural Parameter Connecting Cavity Architecture, Confined Hydrocarbon Pool Species, and MTO Product Selectivity in Small-Pore Cage-Based Zeolites

The catalysts used in the methanol-to-olefins (MTO) reaction are considered dual systems comprising an inorganic zeolite framework and organic compounds hosted inside that act as cocatalysts. The influence of zeolite cavity architecture on the preferential stabilization of cationic intermediates involved in the paring and side-chain routes of the hydrocarbon pool mechanism is analyzed by means of density functional theory (DFT) calculations, catalyst testing, and 13 C NMR spectroscopy for some small-pore cage-based zeolites. A correlation between the degree of methylation of the entrapped methylbenzenium (MB + ) cations and the selectivity to ethene and propene is found experimentally and explained in terms of the electronic distribution of the first intermediate of the paring route. A deep understanding of the reaction mechanism and of the specific host–guest interactions taking place inside zeolite catalysts allows establishing a quantitative parameter that is indicative for the contribution of the paring route and therefore the C 3 = /C 2 = ratio in the MTO reaction.