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Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol

Zhongkai Li, Philip J. Fletcher, Mariolino Carta Orcid Logo, Neil B. McKeown, Frank Marken

Journal of Electroanalytical Chemistry, Volume: 922, Start page: 116751

Swansea University Author: Mariolino Carta Orcid Logo

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DOI (Published version): 10.1016/j.jelechem.2022.116751

Abstract

Intrinsically microporous polyamines (PIM-EA-TB) provide tertiary amine binding sites for protons and in this way allow switching/gating from a low ionic conductivity state to semipermeable anion conductivity through micropores. In ethanolic NaClO4 media ionic conductivity in PIM-EA-TB films (approx...

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Published in: Journal of Electroanalytical Chemistry
ISSN: 1572-6657
Published: Elsevier BV 2022
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URI: https://cronfa.swan.ac.uk/Record/cronfa61000
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spelling 2023-01-05T13:04:58.8194176 v2 61000 2022-09-01 Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol 56aebf2bba457f395149bbecbfa6d3eb 0000-0003-0718-6971 Mariolino Carta Mariolino Carta true false 2022-09-01 CHEM Intrinsically microporous polyamines (PIM-EA-TB) provide tertiary amine binding sites for protons and in this way allow switching/gating from a low ionic conductivity state to semipermeable anion conductivity through micropores. In ethanolic NaClO4 media ionic conductivity in PIM-EA-TB films (approx. 10 μm thick; deposited asymmetrically onto a 10 μm diameter microhole in 5 μm thick Teflon) is lowered by ion exclusion compared to conductivity observed in aqueous environments. However, in the presence of protons in ethanol PIM-EA-TB films are shown to switch from essentially insulating to anionic diode behaviour. Similar observations are reported for Cu2+ but not for other types of cations such as Na+, K+, Mg2+ (all as perchlorate salts). Binding constants are evaluated, and protonation is identified to cause gating for both H+ and Cu2+. Both chemical and electrochemical gating/switching is demonstrated by placing a platinum electrode close to the PIM-EA-TB film and applying positive or negative bias to locally generate acid/base. Journal Article Journal of Electroanalytical Chemistry 922 116751 Elsevier BV 1572-6657 Ionics, Membrane, Solvent, Ion transport, Rectification, Electro osmosis 1 10 2022 2022-10-01 10.1016/j.jelechem.2022.116751 COLLEGE NANME Chemistry COLLEGE CODE CHEM Swansea University Another institution paid the OA fee EPSRC (EP/K004956/1). 2023-01-05T13:04:58.8194176 2022-09-01T09:57:05.9237367 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Zhongkai Li 1 Philip J. Fletcher 2 Mariolino Carta 0000-0003-0718-6971 3 Neil B. McKeown 4 Frank Marken 5 61000__25261__d0b156e4c496445fb63b11d4e21e9a1c.pdf VOR.61000.pdf 2022-09-29T14:22:34.4529298 Output 3386497 application/pdf Version of Record true Distributed under the terms of a Creative Commons Attribution 40 Licence. true eng https://creativecommons.org/licenses/by/4.0/
title Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
spellingShingle Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
Mariolino Carta
title_short Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
title_full Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
title_fullStr Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
title_full_unstemmed Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
title_sort Switching ionic diode states with proton binding into intrinsically microporous polyamine films (PIM-EA-TB) immersed in ethanol
author_id_str_mv 56aebf2bba457f395149bbecbfa6d3eb
author_id_fullname_str_mv 56aebf2bba457f395149bbecbfa6d3eb_***_Mariolino Carta
author Mariolino Carta
author2 Zhongkai Li
Philip J. Fletcher
Mariolino Carta
Neil B. McKeown
Frank Marken
format Journal article
container_title Journal of Electroanalytical Chemistry
container_volume 922
container_start_page 116751
publishDate 2022
institution Swansea University
issn 1572-6657
doi_str_mv 10.1016/j.jelechem.2022.116751
publisher Elsevier BV
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description Intrinsically microporous polyamines (PIM-EA-TB) provide tertiary amine binding sites for protons and in this way allow switching/gating from a low ionic conductivity state to semipermeable anion conductivity through micropores. In ethanolic NaClO4 media ionic conductivity in PIM-EA-TB films (approx. 10 μm thick; deposited asymmetrically onto a 10 μm diameter microhole in 5 μm thick Teflon) is lowered by ion exclusion compared to conductivity observed in aqueous environments. However, in the presence of protons in ethanol PIM-EA-TB films are shown to switch from essentially insulating to anionic diode behaviour. Similar observations are reported for Cu2+ but not for other types of cations such as Na+, K+, Mg2+ (all as perchlorate salts). Binding constants are evaluated, and protonation is identified to cause gating for both H+ and Cu2+. Both chemical and electrochemical gating/switching is demonstrated by placing a platinum electrode close to the PIM-EA-TB film and applying positive or negative bias to locally generate acid/base.
published_date 2022-10-01T04:19:34Z
_version_ 1763754298193215488
score 11.037056

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