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

[Display omitted] •HClO4 leads to protonation of PIM-EA-TB and to chemical gating as confirmed by EDX and binding constant measurements.•Electrochemical gating is achieved by localised acid/base generation close to the PIM-EA-TB membrane.•Ethanol lower polarity (compared to water) causes ion exclusion from PIM-EA-TB and thereby a stronger transition from insulating to ionically conducting.•Ionic diodes in ethanol exhibit switching time constants and rectification ratios as those in aqueous solution. 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.