Asymmetric rotations slow down diffusion under confinement

Zhiqiang Liu (), Xun Kan, Mingbin Gao, Yi Ji, Fangxiu Ye, Jingyi Tan, Fengqing Liu, Jiamin Yuan, Xiaomin Tang, Haohan Li, Pan Gao, Jiaao Xue, Qun Cai, Naresh C. Osti, Niina H. Jalarvo, Cheng Li, Yongcun Zou, Yi Li, Shutao Xu, Guangjin Hou (), Mao Ye (), Fujian Liu () and Anmin Zheng ()
Additional contact information
Zhiqiang Liu: Wuhan University of Science and Technology
Xun Kan: Fuzhou University
Mingbin Gao: Xiamen University
Yi Ji: Chinese Academy of Sciences
Fangxiu Ye: Chinese Academy of Sciences
Jingyi Tan: Chinese Academy of Sciences
Fengqing Liu: Chinese Academy of Sciences
Jiamin Yuan: Chinese Academy of Sciences
Xiaomin Tang: Chinese Academy of Sciences
Haohan Li: Chinese Academy of Sciences
Pan Gao: Chinese Academy of Sciences
Jiaao Xue: Wuhan University of Science and Technology
Qun Cai: Wuhan University of Science and Technology
Naresh C. Osti: Oak Ridge National Laboratory
Niina H. Jalarvo: Oak Ridge National Laboratory
Cheng Li: Oak Ridge National Laboratory
Yongcun Zou: Jilin University
Yi Li: Jilin University
Shutao Xu: Chinese Academy of Sciences
Guangjin Hou: Chinese Academy of Sciences
Mao Ye: Chinese Academy of Sciences
Fujian Liu: Fuzhou University
Anmin Zheng: Wuhan University of Science and Technology

Nature Communications, 2025, vol. 16, issue 1, 1-11

Abstract: Abstract 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.

Date: 2025
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DOI: 10.1038/s41467-025-57242-6

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