Scanning electrochemical microscopy with conducting polymer probes: Validation and applications

Scanning electrochemical microscopy (SECM) allows spatially and temporally resolved measurements of a broad range of reactive surfaces and specimens, typically using electrochemically active metal probes. While conducting polymers (CPs) present several analytical properties of interest due to their chemical versatility, potentially enabling the measurement of ionic fluxes as well as redox processes, they have not been widely used as probe materials for SECM. CPs can be modified and fine-tuned to improve experimental parameters and they can be easily prepared by electrodeposition. In this paper, we show a new type of CP probe for SECM that retains the spatial resolution of conventional metal probes and introduces the possibility to exploit a wide range of ionic and redox systems. Poly-3,4-ethylenedioxythiophene (PEDOT) was electrochemically deposited on flat and recessed Pt microdisks to generate CP SECM probes. To demonstrate their usefulness, an insulating substrate with conducting features was imaged. Well-defined SECM feedback images were observed for both the CP well-probe and the Pt probe, proving the efficiency of the new electrode to image redox reactions. Additionally, an organosulfur compound was used as mediator taking advantage of the electrocatalytic effect PEDOT has on the molecule's kinetics. Finally, these probes were also used in a mediator-less fashion, taking advantage of the ion flux required to electrochemically oxidize the PEDOT deposit. We investigated the impact of anion size and concentration on current-distance relationships for SECM probe positioning. CP probes pose exciting prospects for the imaging and measurement of combined redox and ionic processes in energy materials.