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Effect of Aromaticity in Anion on the Cation–Anion Interactions and Ionic Mobility in Fluorine-Free Ionic Liquids
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering.ORCID iD: 0000-0002-7940-7297
Institute of Physics, Kazan Federal University, 420008 Kazan, Russia.
Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, SE-106 91 Stockholm, Sweden.
Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Chemical Engineering. Medical and Biological Physics, Kazan Medical University, 420012, Kazan, Russia.ORCID iD: 0000-0002-6810-1882
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2020 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 124, no 52, p. 11962-11973Article in journal (Refereed) Published
Abstract [en]

Ionic liquids (ILs) composed of tetra(n-butyl)phosphonium [P4444]+ and tetra(n-butyl)ammonium [N4444]+ cations paired with 2-furoate [FuA], tetrahydo-2-furoate [HFuA], and thiophene-2-carboxylate [TpA] anions are prepared to investigate the effects of electron delocalization in anion and the mutual interactions between cations and anions on their physical and electrochemical properties. The [P4444]+ cations-based ILs are found to be liquids, while the [N4444]+ cations-based ILs are semi-solids at room temperature. Thermogravimetric analysis revealed higher decomposition temperatures and differential scanning calorimetry analysis showed lower glass transition temperatures for phosphonium-based ILs than the ammonium-based counterparts. The ILs are arranged in the decreasing order of their ionic conductivities as [P4444][HFuA] (0.069 mS cm–1) > [P4444][FuA] (0.032 mS cm–1) > [P4444][TpA] (0.028 mS cm–1) at 20 °C. The oxidative limit of the ILs followed the sequence of [FuA]> [TpA]> [HFuA], as measured by linear sweep voltammetry. This order can be attributed to the electrons’ delocalization in [FuA] and in [TpA] aromatic anions, which has enhanced the oxidative limit potentials and the overall electrochemical stabilities.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2020. Vol. 124, no 52, p. 11962-11973
National Category
Physical Chemistry
Research subject
Chemistry of Interfaces
Identifiers
URN: urn:nbn:se:ltu:diva-82139DOI: 10.1021/acs.jpcb.0c08421ISI: 000605372100019PubMedID: 33347763Scopus ID: 2-s2.0-85099084649OAI: oai:DiVA.org:ltu-82139DiVA, id: diva2:1513751
Funder
The Kempe Foundations, SMK-1838Swedish Research Council, 2018-04133Knut and Alice Wallenberg Foundation, KAW 2018.0380
Note

Validerad;2021;Nivå 2;2021-01-05 (alebob);

Finansiär: Kazan Federal University (0671-2020-0051)

Available from: 2020-12-31 Created: 2020-12-31 Last updated: 2021-12-13Bibliographically approved

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Khan, Inayat AliFilippov, AndreiShah, Faiz Ullah

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