Raman Under Water – Nonlinear and Nearfield Approaches for Electrochemical Surface Science

Electrochemistry is re‐gaining attention among scientists because the complex interplay between electronic and chemical interfacial processes lies at the bottom of a broad range of important research disciplines like alternative energy conversion or green catalysis and synthesis. While rapid progress has been made in recent years regarding novel technological applications, the community increasingly recognizes that the understanding of the molecular processes that govern macroscopic device properties is still rather limited – which hinders a systematic and more complete exploration of novel material and functionality space. Here, we discuss advanced Raman spectroscopies as valuable analysis tools for electrochemists. The chemical nature of a material and its interaction with the environment is contained in the label‐free vibrational fingerprint over a broad energy range so that organic species, solid‐state materials, and hybrids thereof can be investigated alike. For surface studies, the inherently small Raman scattering cross sections can be overcome with advanced nonlinear or nearfield‐based approaches that provide signal enhancements between three and seven orders of magnitude, sufficient to detect few scatterers in nano‐confined spaces or adsorbate (sub)monolayers. Our article highlights how advanced Raman techniques with extreme chemical, spatial and temporal resolution constitute valuable alternative surface analysis tools and provide otherwise inaccessible information about complex interfacial (electro)chemical processes.