Square-wave voltammetry (SWV), regarded as the most advanced technique within the family of pulse voltammetric methods, still offers substantial room for methodological innovation in terms of SWV itself and for voltammetry more broadly. By comparatively reviewing the novel SWV-derived techniques introduced in the past decade, it becomes evident that methodological advances can emerge along several conceptual directions, including: modification of the current-sampling protocol, alteration of the SW potential modulation, new strategies for processing current–time–potential data, and simplification of the technique toward square-wave chronoamperometry–type methodologies.
Accordingly, we present three novel voltammetric techniques—multi-sampling SWV, double-sampled SWV, and differential SWV, together with three square-wave chronoamperometric methods collectively known as electrochemical Faradaic spectroscopy (EFS). These new approaches aim to enhance the voltammetric and chronoamperometric capabilities of the technique and its analytical application, enabling comprehensive mechanistic and kinetic characterization of electrode processes with a minimal number of experiments, ideally a single one.
Finally, we introduce a completely new type of voltammetry, termed multi-frequency SWV, which integrates the advantages of the a forementioned innovations into a unified methodology, thereby further expanding the conceptual and practical scope of modern voltammetric analysis.
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