Electrochemical Ion Transfer with Thin Films of Poly(3-octylthiophene).
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.
Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
Maria
M
Cuartero
Australian Synchrotron , 800 Blackburn Road, Clayton, Victoria 3168, Australia.
Robert G
RG
Acres
Faculty of Science, Health, Education and Engineering, University of the Sunshine Coast , 90 Sippy Downs Drive, Sippy Downs, Queensland 4556, Australia.|School of Chemistry and Molecular Biosciences, The University of Queensland , Brisbane, Queensland 4072, Australia.|Department of Chemistry, Curtin University , GPO Box U1987, Perth, Western Australia 6109, Australia.
Roland
R
De Marco
Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
Eric
E
Bakker
Department of Inorganic and Analytical Chemistry, University of Geneva , Quai Ernest-Ansermet 30, CH-1211 Geneva, Switzerland.
Gastón A
GA
Crespo