Mechanistic Insight into the Framework Methylation of H-ZSM-5 for Varying Methanol Loadings and Si/Al Ratios Using First-Principles Molecular Dynamics Simulations

[Image: see text] The methanol-to-hydrocarbon process is known to proceed autocatalytically in H-ZSM-5 after an induction period where framework methoxy species are formed. In this work, we provide mechanistic insight into the framework methylation within H-ZSM-5 at high methanol loadings and varying acid site densities by means of first-principles molecular dynamics simulations. The molecular dynamics simulations show that stable methanol clusters form in the zeolite pores, and these clusters commonly deprotonate the active site; however, the cluster size is dependent on the temperature and acid site density. Enhanced sampling molecular dynamics simulations give evidence that the barrier for methanol conversion is significantly affected by the neighborhood of an additional acid site, suggesting that cooperative effects influence methanol clustering and reactivity. The insights obtained are important steps in optimizing the catalyst and engineering the induction period of the methanol-to-hydrocarbon process.