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Molecular insights into the nanoconfinement effect on the structure and dynamics of ionic liquids in carbon nanotubes
Sun Yat Sen Univ, Peoples R China.
Linköping University, National Supercomputer Centre (NSC).
Sun Yat Sen Univ, Peoples R China.
2024 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 26, no 20, p. 14691-14704Article in journal (Refereed) Published
Abstract [en]

The properties and applications of ionic liquids (ILs) have been widely investigated when they are confined within nanochannels such as carbon nanotubes (CNTs). The confined ILs exhibit very different properties from their bulk state due to a nanoconfinement effect, which plays an important role in the performances of devices with ILs. In this work, we studied the effect of the charge carried by CNTs on confined ILs inside CNTs using molecular dynamics simulations. In charged CNTs, cations and anions are distributed separately along the radial directions, and the transition of orientations of the cations between parallel and vertical to CNTs occurs by changing the charge state of CNTs. The number of hydrogen bonds (HBs) formed by the confined ILs can be reduced by switching the surface charge of CNTs from positive to negative due to the contact modes between cations and anions as well as the distributions of cations in CNTs. The diffusivities along and vertical to the axial direction of CNTs were found to be non-monotonic owing to the "trade-off" effect from both ion pair interlocking and anchoring ILs on the CNT walls. Additionally, the region-dependent dynamics of ILs were also related to the intermolecular interactions in different regions of CNTs. Furthermore, the vibrational modes of ILs were obviously influenced in highly charged CNTs as determined by calculating the density of vibrational states, which demonstrated the transitions in the structure and interactions. The density distributions changed from single layer to double layers when increasing the pore size of neutral CNTs while the hydrogen bonds exhibited a non-monotonic tendency versus the pore sizes. Our results might help to understand the structure and dynamics of confined ILs as well as aid optimizing the performance of devices with ILs. Exploration of the impact of charge states of carbon nanotubes on region-dependent properties of confined ionic liquids and the relation between ionic dynamics and interactions.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY , 2024. Vol. 26, no 20, p. 14691-14704
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:liu:diva-203583DOI: 10.1039/d4cp00695jISI: 001215421200001PubMedID: 38716569Scopus ID: 2-s2.0-85192959153OAI: oai:DiVA.org:liu-203583DiVA, id: diva2:1859302
Note

Funding Agencies|Basic and Applied Basic Research Foundation of Guangdong Province [2022A1515010873, 2023A1515012535]; Guangdong Basic and Applied Basic Research Foundation [22003080]; National Natural Science Foundation of China

Available from: 2024-05-21 Created: 2024-05-21 Last updated: 2025-02-04Bibliographically approved

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