Chemometrics assisted resolving of net faradaic current contribution from total current in potential step and staircase cyclic voltammetry

Total current in the electroanalytical data is assumed to be consisting of three main constituents: faradaic current, step charging current and induced charging current. Both charging currents can cause an interfering effect on precise determination of faradaic currents, and hence insert direct effects on sensitivity and detection limit of the electroanalytical techniques. Despite the widespread techniques introduced until now, the extraction of the net faradaic current from total current still remains a challenge. In this work, by using multivariate curve resolution-alternating least square (MCR-ALS) as a powerful curve resolution-based chemometrics method, a straightforward method has been introduced for resolving faradaic current from the two types of charging currents (step charging current and induced charging current) in single potential step and staircase cyclic voltammetric methods. By simultaneous analyses of the current data matrices for different electrochemical systems, the three sources of current were successfully identified and their contributions in the total signal were easily calculated. Also, in this manner, the cell time constant can be obtained easily. Contrary to the previously reported methods, the present method does not need any pre-determined mathematical method; particularly there is no need to know the cell time constant.

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► A new method for treating of charging current in voltammetry has been proposed.
► Chemometrics analysis of voltammetric data revealed the presence of faradaic, step charging and induced charging currents.
► MCR-ALS analyses could separate the contribution of each current type in the total signal.
► The results were in agreement with previous theoretical models.