Revisiting Thin-Layer Electrochemistry in a Chip-Type Cell for the Study of Electroorganic Reactions

It is important but challenging to elucidate the electrochemical reaction mechanisms of organic compounds using electroanalytical methods. Particularly, a rapid and straightforward method may be helpful if it can provide information on reaction intermediates or other key electrochemical parameters. In this work, we exploited the advantages of classic thin-layer electrochemistry to develop a thin-layer electroanalysis microchip (TEAM). TEAM provided better resolved voltammetric peaks than under semi-infinite diffusion condition owing to the small height. Importantly, rapid and accurate determination of the number of electrons transferred, n, was enabled by mechanically confining the microliter-scale volume analyte at the electrode, while securing ionic conduction using polyelectrolyte gels. The performance of the TEAM was validated using voltammetry and coulometry of standard redox couples. Utilizing TEAM, a (spectro)electrochemical analysis of FM 1-43, an organic dye widely used in neuroscience, was successfully performed. It was also applied to study the electrochemical oxidation mechanism of pivanilides and alkyltrifluoroborate salts with different substituents and solvents. This work suggests the TEAM as a promising tool to provide invaluable mechanistic information and promote the rational design of electrosynthetic strategies.