| Summary: | Carbon paste electrodes <i>ex-situ</i> modified with different surfactants were studied using cyclic voltammetry with two model redox couples, namely hexaammineruthenium (II)/(III) and hexacyanoferrate (II)/(III), in 0.1 mol L<sup>−1</sup> acetate buffer (pH 4), 0.1 mol L<sup>−1</sup> phosphate buffer (pH 7), and 0.1 mol L<sup>−1</sup> ammonia buffer (pH 9) at a scan rate ranging from 50 to 500 mV s<sup>−1</sup>. Distinct effects of pH, ionic strength, and the composition of supporting media, as well as of the amount of surfactant and its accumulation at the electrode surface, could be observed and found reflected in changes of double-layer capacitance and electrode kinetics. It has been proved that, at the two-phase interface, the presence of surfactants results in elctrostatic interactions that dominate in the transfer of model substances, possibly accompanied also by the effect of erosion at the carbon paste surface. The individual findings depend on the configurations investigated, which are also illustrated on numerous schemes of the actual microstructure at the respective electrode surface. Finally, principal observations and results are highlighted and discussed with respect to the future development and possible applications of sensors based on surfactant-modified composited electrodes.
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