Origins of non-ideal behaviour in voltammetric analysis of redox-active monolayers

Disorder in redox-active monolayers convolutes electrochemical characterization. This disorder can come from pinhole defects, loose packing, heterogeneous distribution of redox-active headgroups, and lateral interactions between immobilized redox-active molecules. Identifying the source of non-ideal behaviour in cyclic voltammograms can be challenging as different types of disorder often cause similar non-ideal cyclic voltammetry behaviour such as peak broadening, large peak-to-peak separation, peak asymmetry and multiple peaks for single redox processes. This Review provides an overview of ideal voltammetric behaviour for redox-active monolayers, common manifestations of disorder on voltammetric responses, common experimental parameters that can be varied to interrogate sources of disorder, and finally, examples of different types of disorder and how they impact electrochemical responses. Disorder in redox-active monolayers arising from pinhole defects, loose packing, heterogeneous distribution of redox-active headgroups, and lateral interactions between immobilized redox-active molecules can cause non-ideal cyclic voltammetry behaviour.