Asymmetric rotations slow down diffusion under confinement

Liu, Zhiqiang [Wuhan University of Science and Technology (China)] (ORCID:0000000328720125); Kan, Xun [Fuzhou University (China)]; Gao, Mingbin [Xiamen University (China)] (ORCID:0000000271432658); Ji, Yi [Chinese Academy of Sciences (CAS), Dalian (China)]; Ye, Fangxiu [Chinese Academy of Sciences (CAS), Dalian (China)]; Tan, Jingyi [Chinese Academy of Sciences (CAS), Wuhan (China); University of Chinese Academy of Sciences, Beijing (China)]; Liu, Fengqing [Chinese Academy of Sciences (CAS), Wuhan (China); University of Chinese Academy of Sciences, Beijing (China)] (ORCID:0009000658974141); Yuan, Jiamin [Chinese Academy of Sciences (CAS), Wuhan (China)]; Tang, Xiaomin [Chinese Academy of Sciences (CAS), Wuhan (China)] (ORCID:0000000256514444); Li, Haohan [Chinese Academy of Sciences (CAS), Dalian (China)]; Gao, Pan [Chinese Academy of Sciences (CAS), Dalian (China)]; Xue, Jiaao [Wuhan University of Science and Technology (China)]; Cai, Qun [Wuhan University of Science and Technology (China)]; Osti, Naresh C. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000202132299); Jalarvo, Niina H. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000306446866); Li, Cheng [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000265466413); Zou, Yongcun [Jilin University, Changchun (China)]; Li, Yi [Jilin University, Changchun (China)] (ORCID:0000000252223674); Xu, Shutao [Chinese Academy of Sciences (CAS), Dalian (China)] (ORCID:0000000347228371); Hou, Guangjin [Chinese Academy of Sciences (CAS), Dalian (China)] (ORCID:000000018216863X); Ye, Mao [Chinese Academy of Sciences (CAS), Dalian (China)] (ORCID:0000000270782402); Liu, Fujian [Fuzhou University (China)]; Zheng, Anmin [Wuhan University of Science and Technology (China); Chinese Academy of Sciences (CAS), Wuhan (China)] (ORCID:0000000171156510)

doi:10.1038/s41467-025-57242-6

DOE OSTI · 2538040

Asymmetric rotations slow down diffusion under confinement

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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 2 H 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.

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Liu, Zhiqiang [Wuhan University of Science and Technology (China)] (ORCID:0000000328720125), Kan, Xun [Fuzhou University (China)], Gao, Mingbin [Xiamen University (China)] (ORCID:0000000271432658), Ji, Yi [Chinese Academy of Sciences (CAS), Dalian (China)], Ye, Fangxiu [Chinese Academy of Sciences (CAS), Dalian (China)], Tan, Jingyi [Chinese Academy of Sciences (CAS), Wuhan (China); University of Chinese Academy of Sciences, Beijing (China)], Liu, Fengqing [Chinese Academy of Sciences (CAS), Wuhan (China); University of Chinese Academy of Sciences, Beijing (China)] (ORCID:0009000658974141), Yuan, Jiamin [Chinese Academy of Sciences (CAS), Wuhan (China)], Tang, Xiaomin [Chinese Academy of Sciences (CAS), Wuhan (China)] (ORCID:0000000256514444), Li, Haohan [Chinese Academy of Sciences (CAS), Dalian (China)], Gao, Pan [Chinese Academy of Sciences (CAS), Dalian (China)], Xue, Jiaao [Wuhan University of Science and Technology (China)], Cai, Qun [Wuhan University of Science and Technology (China)], Osti, Naresh C. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000202132299), Jalarvo, Niina H. [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000306446866), Li, Cheng [Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)] (ORCID:0000000265466413), Zou, Yongcun [Jilin University, Changchun (China)], Li, Yi [Jilin University, Changchun (China)] (ORCID:0000000252223674), Xu, Shutao [Chinese Academy of Sciences (CAS), Dalian (China)] (ORCID:0000000347228371), Hou, Guangjin [Chinese Academy of Sciences (CAS), Dalian (China)] (ORCID:000000018216863X), Ye, Mao [Chinese Academy of Sciences (CAS), Dalian (China)] (ORCID:0000000270782402), Liu, Fujian [Fuzhou University (China)], Zheng, Anmin [Wuhan University of Science and Technology (China); Chinese Academy of Sciences (CAS), Wuhan (China)] (ORCID:0000000171156510). 2025-02-27. Asymmetric rotations slow down diffusion under confinement. https://doi.org/10.1038/s41467-025-57242-6

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