Electrochemistry and Optical Microscopy

Abstract Electrochemistry exploits local current heterogeneities at various scales ranging from the micrometer to the nanometer. The last decade has witnessed unprecedented progress in the development of a wide range of electroanalytical techniques allowing to reveal and quantify such heterogeneity through multiscale and multifunctional operando probing of electrochemical processes. However, most of these advanced electrochemical imaging techniques, employing scanning probes, suffer from either low imaging throughput or limited imaging size. In parallel, optical microscopies, which can image a widefield of view in a single snapshot, have made considerable progress in terms of sensitivity, resolution, and implementation of detection modes. Optical microscopies are then mature enough to propose, with basic bench equipment, to probe in a nondestructive way a wide range of optical (and therefore structural) properties of a material in situ , in real time: under operating conditions. They offer promising alternative strategies for quantitative high‐resolution imaging of electrochemistry. The first sections recall the optical properties of materials and how they can be probed optically. They discuss fluorescence, Raman, surface plasmon resonance, scattering, or refractive index. Then the different optical microscopes used to image electrochemical processes are examined along with some strategies to extract quantitative electrochemical information from optical images. Finally, the last section reviews some examples of in situ imaging, at micro‐ to nanometer resolution, and quantification of electrochemical processes ranging from solution diffusion to the conversion of molecular interfaces or solids.