Electrochemical quartz crystal impedance study on the overoxidation of polypyrrole–carbon nanotubes composite film for amperometric detection of dopamine

The electrochemical quartz crystal impedance (EQCI) method was used to study the overoxidation of polypyrrole (PPy)–multiwalled carbon nanotubes (MWCNT) nanocomposite film in neutral and alkaline solutions. The values of molar mass per electron transferred (M/n) obtained during the overoxidation of PPy in 0.10 mol L−1 Na2SO4 and 0.20 mol L−1 NaOH aqueous solutions were estimated to be ca. 17 and 22 g mol−1, respectively, suggesting the nucleophilic attack of solution OH− to the pyrrole units during the overoxidation, and the possible partial formation of carboxylic groups after the overoxidation in the NaOH solution. Also, the overoxidized PPy–MWCNT composite film prepared in the NaOH solution showed a notably larger affinity to dopamine (DA) dissolved in a neutral phosphate buffer than that prepared in the Na2SO4 solution. The modification of the overoxidized nanocomposite film improved substantially the sensitivity for DA assay in a neutral phosphate buffer, as compared with the modification of overoxidized PPy or MWCNT alone. At a −6 kHz (201-nm thickness) nanocomposite film prepared in a polymerization bath containing 1.0 mg mL−1 MWCNT and overoxidized in 0.20 mol L−1 aqueous NaOH, the peak current response from differential pulse voltammetric assay of DA was linear with DA concentration from 4.0 × 10−8 to 1.4 × 10−6 mol L−1, with a lower limit of detection of 1.7 nmol L−1, good anti-interferent ability, as well as good stability and reproducibility.