Unravelling Channel Structure–Diffusivity Relationships in Zeolite ZSM‐5 at the Single‐Molecule Level

The development of improved zeolite materials for applications in separation and catalysis requires understanding of mass transport. Herein, diffusion of single molecules is tracked in the straight and sinusoidal channels of the industrially relevant ZSM‐5 zeolites using a combination of single‐molecule localization microscopy and uniformly oriented zeolite thin films. Distinct motion behaviors are observed in zeolite channels with the same geometry, suggesting heterogeneous guest–host interactions. Quantification of the diffusion heterogeneities in the sinusoidal and straight channels suggests that the geometry of zeolite channels dictates the mobility and motion behavior of the guest molecules, resulting in diffusion anisotropy. The study of hierarchical zeolites shows that the addition of secondary pore networks primarily enhances the diffusivity of sinusoidal zeolite channels, and thus alleviating the diffusion limitations of microporous zeolites.