Microelectrode Combinations of Gold and Polypyrrole Enable Highly Stable Two‐electrode Electrochemical Impedance Spectroscopy Measurements under Turbulent Flow Conditions.

An electrochemical impedance spectroscopy (EIS) sensor design is proposed based on a standard interdigitated electrode layout in which the smaller working electrode consists of gold (Au) whereas the larger combined counter and reference electrode is coated with a porous layer of polypyrrole (PPy) doped with polystyrene sulfonate (PSS) (PPy : PSS). Each electrode material was first characterized by EIS in a standard 3‐electrode setup with subsequent spectra fitting by a modified Randles equivalent circuit. The differences in the spectra obtained by the PPy : PSS coated electrodes can be explained by an increased electroactive surface area due to the porous polymer film. The changes in morphology of the film are discussed with respect to the evolution of the elements of the electric equivalent circuit. When applying the Au/PPy : PSS electrode combination to a standard 2‐electrode arrangement, the enlarged highly electroactive surface area of the PPy : PSS coating lowers the interfacial impedance in a way that mainly the gold working electrode contributes to the overall system impedance. Therefore, obtaining reproducible EIS signals depends only on the electrode's open‐circuit potential (OCP) and on additional adsorption events at the gold electrode/electrolyte interface. We present a protocol for microelectrode coating with PPy : PSS, which enables highly stable 2‐electrode EIS experiments without the need of a reference electrode. This combination is believed to be very useful if an integration of sensing electrodes inside Micro Total Analysis Systems is aspired. [ABSTRACT FROM AUTHOR]