We report on the limiting conditions for ion-transfer voltammetry between an ion-exchanger doped and plasticized poly(vinyl chloride) (PVC) membrane and an electrolyte solution that was triggered via the oxidation of a poly(3-octylthiophene) (POT) solid-contact (SC), which was unexpectedly related to the thickness of the POT SC. An electropolymerized 60 nm thick film of POT coated with a plasticized PVC membrane exhibited a significant sodium transfer voltammetric signal whereas a thicker film (180 nm) did not display a measurable level of ion transfer due to a lack of oxidation of thick POT beneath the membrane film. In contrast, this peculiar phenomenon was not observed when the POT film was in direct contact with an organic solvent-based electrolyte. This evidence is indicative of three key points: (i) the coated membrane imposes a degree of rigidity to the system, which restricts the swelling of the POT film and its concomitant p-doping; (ii) this phenomenon is exacerbated with thicker POT films due to an initial morphology (rougher comprising a network of large POT nanoparticles), which gives rise to a diminished surface area and electrochemical reactivity in the POT SC; (iii) the rate of sodium transfer is higher with a thin POT film due to a smoother surface morphology made up of a network of smaller POT nanoparticles with an increased surface area and electrochemical reactivity. A variety of techniques including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), ellipsometry, scanning electron microscopy (SEM), atomic force microscopy (AFM), and synchrotron radiation-X-ray photoelectron spectroscopy (SR-XPS) were used to elucidate the mechanism of the POT thickness/POT surface roughness dependency on the electrochemical reactivity of the PVC/POT SC system.
This research output has an Altmetric Attention Score of 2. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 28 June 2016.
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