Methanol diffusion and dynamics in zeolite H-ZSM-5 probed by quasi-elastic neutron scattering and classical molecular dynamics simulations

作者：Matam SK, Silverwood IP, Boudjema L, O'Malley AJ, Catlow CRA · 发表于：Philosophical transactions. Series A, Mathematical, physical, and engineering sciences · 年份：2023 · DOI：10.1098/rsta.2022.0335

Zeolite ZSM-5 is a key catalyst in commercially relevant processes including the widely studied methanol to hydrocarbon reaction, and molecular diffusion in zeolite pores is known to be a crucial factor in controlling catalytic reactions. Here, we present critical analyses of recent quasi-elastic neutron scattering (QENS) data and complementary molecular dynamics (MD) simulations. The QENS experiments show that the nature of methanol diffusion dynamics in ZSM-5 pores is dependent both on the Si/Al ratio (11, 25, 36, 40 and 140), which determines the Brønsted acid site density of the zeolite, and that the nature of the type of motion observed may vary qualitatively over a relatively small temperature range. At 373 K, on increasing the ratio from 11 to 140, the observed mobile methanol fraction increases and the nature of methanol dynamics changes from rotational (in ZSM-5 with Si/Al of 11) to translational diffusion. The latter is either confined localized diffusion within a pore in zeolites with ratios up to 40 or non-localized, longer-range diffusion in zeolite samples with the ratio of 140. The complementary MD simulations conducted over long time scales (1 ns), which are longer than those measured in the present study by QENS (≈1-440 ps), at 373 K predict the occurrence of long-range translational diffusion of methanol in ZSM-5, independent of the Si/Al ratios (15, 47, 95, 191 and siliceous MFI). The rate of diffusion increases slightly by increasing the ratio from 15 to 9...