Surface-enhanced Raman spectroscopy (SERS), discovered in the mid-1970s, marked a milestone in the history of surface and interface analysis. Over the past half-century, electrochemical SERS (EC-SERS) has evolved into a powerful spectroelectrochemical technique for studying (sub)monolayer adsorption and interfacial dynamics. In electrochemical systems, in situ/operando probing of solid–liquid interface/interphase remains challenging due to their complex, dynamic nature and the weak signals involved. EC-SERS overcomes these limitations by employing plasmonic nanostructures to generate Raman signal “hot spots” at the electrode–electrolyte interface/interphase.
This review article, co-authored by two teams from Tongji University and Xiamen University, systematically charts the fifty-year development of EC-SERS. It begins with the early proof-of-concept of electrochemical Raman spectroscopy and the discovery of the SERS effect in the mid-1970s. It then highlights major advances driven by nanoscience since the 1990s, including the developments of well-controlled nanostructured substrates, the “borrowing SERS activity” strategy, electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS), and electrochemical tip-enhanced Raman spectroscopy (EC-TERS). More recently, the field has progressed toward operando spectroelectrochemistry, enabling real-time monitoring of the dynamic interphase under real working conditions.
The review elaborates on the critical advances in substrate design, enhancement mechanisms, and instrumentation for EC-SERS, EC-TERS, and EC-SHINERS. It also provides an in-depth discussion of EC-SERS applications in interfacial electrochemistry: revealing the adsorption behavior and hydrogen-bond network dynamics of interfacial water at the molecular level; identifying key intermediates during the hydrogen evolution reaction (HER) and carbon dioxide reduction reaction (CO2RR); and tracking the formation, degradation, and regeneration of the solid electrolyte interphase (SEI) in lithium-ion, lithium–oxygen, and lithium–metal batteries. Additionally, EC-SERS has enabled real-time studies of corrosion inhibition, electroplating, and electrodeposition processes.
Looking forward, the authors discussed the application of “AI–nano-driven” technologies for situ/operando spectroscopy, which heralds a new era for interfacial electrochemistry research.
Method of Research
Literature review