Insight into Carbocation Induced Non-covalent Interactions in Methanol-to-olefins Reaction over ZSM-5 Zeolite from Solid-State NMR Spectroscopy

Carbocations such as cyclic carbenium ions are important intermediates in the zeolite-catalyzed methanol-to-olefins (MTO) reaction. The MTO reaction propagates through a complex hydrocarbon pool process. Understanding the carbocation-involved hydrocarbon pool reaction on a molecular level still remains challenging. Here we show that electron-deficient cyclopentenyl cations stabilized in ZSM-5 zeolite are able to capture the alkanes, methanol, and olefins produced during MTO reaction via noncovalent interactions. Intermolecular spatial proximities/interactions are identified by using two-dimensional 13 C-13 C correlation solid-state NMR spectroscopy. Combined NMR experiments and theoretical analysis suggests that in addition to the dispersion and CH/π interactions, the multiple functional groups in the cyclopentenyl cations produce strong attractive force via cation-induced dipole, cation-dipole and cation-π interactions. These carbocation-induced noncovalent interactions modulate the product selectivity of hydrocarbon pool reaction.