Electrochemical systems are complex, involving various chemical and physical processes (e.g. electron transfer reactions, diffusive and convective mass transfer, charge transfer processes). In most cases, electrochemical systems are summarised using simple signals (e.g. amperometric or potentiometric signals), which do not, however, adequately capture their complexity. These mostly unidimensional signals are usually insufficient to facilitate the full understanding of the electrochemical system and its underlying, simultaneously occurring processes.Established electroanalytical methods are commonly utilised to characterise specific (electro-) chemical and physical processes of electrochemical systems (e.g. potentiometry, amperometry/voltammetry, electrochemical impedance spectroscopy, etc.). Despite the usefulness of these traditional electroanalysis techniques, they are often restricted to the analysis of a very specific set of system characteristics and parameters. Moreover, the experimental nature of these techniques, usually requiring a specific protocol, sets limits to their employment for on-line measurements of industrial electrochemical systems (e.g. reactors, fuel cells etc.).To avoid these limitations, a new alternative approach to understanding and characterising electrochemical systems is proposed. Computational techniques have the potential to extract various system parameters from periodic chronoamperometry signals of electrochemical systems. Such techniques include methods that are commonly used in chemometric investigations in addition to other modern signal processing tools.Early findings from this ongoing study include the separation of Faradaic and non-Faradaic current contributions from a variety of simulated chronoamperometric signals. Moreover, qualitative sensitivity studies appear promising for the subsequent quantitative recovery of multiple parameters from stagnant and hydrodynamic electrochemical systems (e.g. capacitance, resistance).As a consequence, this novel computer-aided approach can pave the way for real-time analyses of electrochemical applications. Furthermore, this strategy will likely reduce the need for specific electroanalytic experiments to determine certain parameters. Instead, complex electrochemical systems and their underlying chemical and physical processes have the potential to be characterised from simple, continuous chronoamperometric signals by means of computational techniques.
Read full abstract