Abstract

Protonation of the molecularly rigid polymer of intrinsic microporosity PIM-EA-TB can be coupled to immobilisation of Fe(CN) 6 3−/4− (as well as immobilisation of Prussian blue) into 1–2 nm diameter channels. The resulting films provide redox-active coatings on glassy carbon electrodes. Uptake, transport, and retention of Fe(CN) 6 3−/4− in the microporous polymer are strongly pH dependent requiring protonation of the PIM-EA-TB (pK A ≈ 4). Both Fe(CN) 6 4− and Fe(CN) 6 3− can be immobilised, but Fe(CN) 6 4− appears to bind tighter to the polymer backbone presumably via bridging protons. Loss of Fe(CN) 6 3−/4− by leaching into the aqueous solution phase becomes significant only at pH > 9 and is likely to be associated with hydroxide anions directly entering the microporous structure to combine with protons. This and the interaction of Fe(CN) 6 3−/4− and protons within the molecularly rigid PIM-EA-TB host are suggested to be responsible for retention and relatively slow leaching processes. Electrocatalysis with immobilised Fe(CN) 6 3−/4− is demonstrated for the oxidation of ascorbic acid. [Figure not available: see fulltext.].

Original languageEnglish
Pages (from-to)2797-28067
JournalJournal of Solid State Electrochemistry
Volume24
Early online date26 Apr 2020
DOIs
Publication statusPublished - 30 Nov 2020

Keywords

  • Coordination polymer
  • Electrocatalysis
  • Membrane
  • Porosity
  • Sensor
  • Voltammetry

ASJC Scopus subject areas

  • Materials Science(all)
  • Condensed Matter Physics
  • Electrochemistry
  • Electrical and Electronic Engineering

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