The discovery of surface enhanced Raman scattering (SERS) from an electrochemical (EC)-SERS experiment is known as a historic breakthrough. Five decades have passed and Raman spectroelectrochemistry (SEC) has developed into a common characterization tool that provides information about the electrode-electrolyte interface. Recently, this technique has been successfully explored for analytical purposes. EC was found to highly improve the performances of SERS sensors, providing, among others, controlled adsorption of analytes and increased reproducibility. In this review, we highlight the potential of EC-SERS sensors to be implemented for point-of-need (PON) analyses as miniaturized devices, and their ability to revolutionize fields like quality control, diagnosis or environmental and food safety. Important developments have been achieved in Raman spectroelectrochemistry, which now represents a promising alternative to conventional analytical methods and interests more and more researchers. The studies included in this review open endless possibilities for real-life EC-SERS analytical applications.

The increasing pollution of surface and groundwater bodies by pharmaceuticals is a general environmental problem requiring routine monitoring. Conventional analytical techniques used to quantify traces of pharmaceuticals are relatively expensive and generally demand long analysis times, associated with difficulties in performing field analyses. Propranolol, a widely used β-blocker, is representative of an emerging class of pharmaceutical pollutants with a noticeable presence in the aquatic environment. In this context, we focused on developing an innovative, highly accessible analytical platform based on self-assembled metal colloidal nanoparticle films for the fast and sensitive detection of propranolol based on Surface Enhanced Raman Spectroscopy (SERS). The ideal nature of the metal used as the active SERS substrate was investigated by comparing silver and gold self-assembled colloidal nanoparticle films, and the improved enhancement observed on the gold substrate was discussed and supported by Density Functional Theory calculations, optical spectra analyses, and Finite-Difference Time-Domain simulations. Next, direct detection of propranolol at low concentrations was demonstrated, reaching the ppb regime. Finally, we showed that the self-assembled gold nanoparticle films could be successfully used as working electrodes in electrochemical-SERS analyses, opening the possibility of implementing them in a wide array of analytical applications and fundamental studies. This study reports for the first time a direct comparison between gold and silver nanoparticle films and, thus, contributes to a more rational design of nanoparticle-based SERS substrates for sensing applications.