Iontronic microscopy of a tungsten microelectrode: “seeing” ionic currents under an optical microscope†

Optical methods for monitoring electrochemical reactions at an interface are advantageous because of their table-top setup and ease of integration into reactors. Here we apply EDL-modulation microscopy to one of the main components of amperometric measurement devices: a microelectrode. We present experimental measurements of the EDL-modulation contrast from the tip of a tungsten microelectrode at various electrochemical potentials inside a ferrocene-dimethanol Fe(MeOH)₂ solution. Using the combination of the dark-field scattering microscope and the lock-in detection technique, we measure the phase and amplitude of local ion-concentration oscillations in response to an AC potential as the electrode potential is scanned through the redox-activity window of the dissolved species. We present the amplitude and phase map of this response, as such this method can be used to study the spatial and temporal variations of the ion-flux due to an electrochemical reaction close to metallic and semiconducting objects of general geometry. We discuss the advantages and possible extensions of using this microscopy method for wide-field imaging of ionic currents.