Voltammetry Beyond the Peaks: Experimental Pitfalls, Mechanistic Ambiguities and Theoretical Challenges

Voltammetric techniques are widely applied for mechanistic investigations and analytical determinations because the recorded current–potential responses often provide valuable information about the kinetics and thermodynamics of redox processes. However, interpretation of voltammetric data frequently extends far beyond the simple analysis of peak shapes and positions. In practical experiments, the electrode material itself can introduce additional signals and artifacts that complicate the mechanistic interpretation of the voltammograms. For instance, gold electrodes typically exhibit two prominent peaks originating from the intrinsic redox activity of surface gold oxides, which may overlap with signals of the investigated redox systems. Platinum electrodes, on the other hand, commonly display characteristic features associated with the proton reduction and hydrogen evolution reaction (H⁺/H₂), often appearing as additional peaks in the voltammetric response. Carbon-based electrodes, including various graphite materials, are prone to adsorption phenomena involving organic compounds, which can significantly distort peak currents and shapes unless the electrode surface is regularly cleaned and regenerated. Furthermore, screen-printed electrodes, although highly convenient for portable and disposable sensing applications, are generally optimized for single-use measurements, limiting their reproducibility in mechanistic electrochemical studies. These practical limitations highlight the experimental pitfalls and mechanistic ambiguities inherent to voltammetric measurements and illustrate the ongoing theoretical and methodological challenges in identifying a truly universal electrode material for voltammetric investigations. We give in this short draft some practical examples of the undesired redox activities going on when working voltammetry with these electrodes.