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.

氧化还原活性单层的无序使电化学表征变得复杂。这种紊乱可能来自针孔缺陷、松散堆积、氧化还原活性头基的不均匀分布以及固定氧化还原活性分子之间的横向相互作用。识别循环伏安图中非理想行为的来源可能具有挑战性，因为不同类型的紊乱通常会导致类似的非理想循环伏安行为，例如峰展宽、峰间分离大、峰不对称和单个氧化还原过程的多个峰。本综述概述了氧化还原活性单分子层的理想伏安行为、伏安响应无序的常见表现、可以改变以询问无序来源的常见实验参数，最后，不同类型无序的示例以及它们如何影响电化学回应。