Asymmetric rotations slow down diffusion under confinement

作者：Zhiqiang Liu, Xun Kan, Mingbin Gao, Yi Ji, F. Ye, Jingyi Tan, F. Liu, Fengqing Liu, Jiamin Yuan, Xiaomin Tang, Haohan Li, Pan Gao, J XUE, Qun Cai, Naresh C. Osti, Niina Jalarvo, Cheng Li, Yongcun Zou, Yi Li, Shutao Xu, Guangjin Hou, Mao Ye, Fujian Liu, Fujian Liu, Anmin Zheng · 发表于：Nature Communications · 年份：2025 · DOI：10.1038/s41467-025-57242-6 · 被引用次数：16 · 研究领域：Advanced NMR Techniques and Applications、NMR spectroscopy and applications、Zeolite Catalysis and Synthesis

Translation and rotation are the two most fundamental forms of diffusion, yet their coupling mechanism is not clear, especially under confinement. Here, we provided evidence of the coupling between rotation and translation using a substituted benzene molecule as an example. A counterintuitive behavior was observed where the movement of the smaller molecule with an asymmetric shape was unexpectedly slower than the larger one with a symmetric shape in confined channels of zeolite. We showed that this diffusion behavior was caused by the presence of the specific and selective interaction of the asymmetric guest with the pores, which increased the local restricted residence time, thus inhibiting the translation under confinement, as further confirmed by dynamic breakthrough curves, uptake measurements, quasi-elastic neutron scattering, and 2H solid-state NMR techniques. Our work correlated asymmetric rotation and diffusion under a confined environment, which enriched our understanding of the coupling between rotation and translation and could shed light on a fundamental understanding of the diffusion process. Translation and rotation are the two most fundamental forms of diffusion. Here, the authors provide evidence of the coupling between rotation and translation under confinement, and find that asymmetric rotations disrupt the order of molecular diffusion in zeolites, which can be applied to studies of selective separation.