Electrochemical Reflective Absorption Microscopy for Probing the Local Diffusion Behavior in the Electrochemical Interface.

Electrochemical interfaces determine the performance of electrochemical devices, including energy-related systems. An in-depth understanding of the heterogeneous interfaces requires in situ techniques with high sensitivity and high temporal and spatial resolution. We develop here an electrochemical reflective absorption microscope (EC-RAM) by using the absorption signals of reacting species with a reasonably good spatial resolution and high sensitivity. We systematically study the response of absorbance ( A) and its derivative, i.e. d A/d t, at different positions of the electrode surface and at electrodes with different sizes (50 µm, 500 µm, and 2 mm) both experimentally and theoretically. We find that the derivative cyclic voltabsorptometry (DCVA) frequently used to obtain the local current response in conventional electrochemical optical microscopy techniques is only applicable to reactions of surface species or solution species under linear diffusion control. For processes when the radial diffusion cannot be ignored, as in the case of a microelectrode or the edge of a large electrode, the DCVA curves show distinct diffusion behaviors for the electroactive species in different regions of the electrode, which cannot be directly related to the CV curves. When the radial diffusion dominates the reaction, CVA curves follow the same shape as the CV curves. The developed EC-RAM technique can be applied to extract in situ the local response of an electrochemical system during the dynamic reaction processes.