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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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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
Online Access: Check full text

URI: https://cronfa.swan.ac.uk/Record/cronfa61000
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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. 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.
Keywords: Ionics, Membrane, Solvent, Ion transport, Rectification, Electro osmosis
College: College of Science
Funders: EPSRC (EP/K004956/1).
Start Page: 116751