Electrochemical ion transfer with thin films of poly(3-octylthiophene)

Cuartero, Maria, Acres, Robert G., De Marco, Roland, Bakker, Eric and Crespo, Gastón A. (2016) Electrochemical ion transfer with thin films of poly(3-octylthiophene). Analytical Chemistry, 88 3: 6939-6946. doi:10.1021/acs.analchem.6b01800


Author Cuartero, Maria
Acres, Robert G.
De Marco, Roland
Bakker, Eric
Crespo, Gastón A.
Title Electrochemical ion transfer with thin films of poly(3-octylthiophene)
Journal name Analytical Chemistry   Check publisher's open access policy
ISSN 1520-6882
0003-2700
Publication date 2016-06-08
Sub-type Article (original research)
DOI 10.1021/acs.analchem.6b01800
Open Access Status Not Open Access
Volume 88
Issue 3
Start page 6939
End page 6946
Total pages 8
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2017
Language eng
Abstract 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.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: HERDC Pre-Audit
School of Chemistry and Molecular Biosciences
 
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Created: Fri, 22 Jul 2016, 08:30:03 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences