Capacitance measurements for evaluating electrochemical double layer models and potentials of zero charge ‐ A reassessment

Differential capacitances (DCAPs) derived from electrostatic Gouy‐Chapman‐type models for electrochemical double layers (DLs) typically show valley, bell, or camel‐type profiles as a function of the potential, centered around the potential of zero charge (PZC). These DCAP‐profiles are routinely evaluated with measured potential‐dependencies of capacitances. Here, the influences of hydrogen evolution, oxygen reduction, and oxide formation on the potential dependence of the capacitance of a polished gold electrode are experimentally examined. These parasitic reactions are found to cause most of the features that are typically attributed to intrinsic DL properties. With these insights, the historical development of the literature regarding the development of the theoretical framework with capacitance measurements is critically reevaluated and drawbacks of the 100‐year‐old Gouy‐Chapman theory for the double layer are discussed. Moreover, DCAPs as differences of electrostatic states are discussed as unable to portray measured capacitances that result from a capacitive‐resistive dynamic charge displacement in the DL. Hence, the link between theory and experiments is critically assessed, motivating the need for more advanced atomistic models to adequately portray the double layer.