Abstract
Electrochemical surface-enhanced Raman spectroscopy (EC-SERS) is an advanced analytical technique that integrates the molecular specificity and high sensitivity of surface-enhanced Raman scattering with the dynamic control of electrochemistry. This hybrid approach enables real-time investigation of interfacial processes, including adsorption phenomena, charge-transfer interactions, and redox reactions at electrified surfaces. In recent years, significant progress has been achieved through the development of engineered plasmonic substrates, hybrid nanomaterials, and improved spectroelectrochemical configurations, greatly enhancing sensitivity, stability, and analytical performance. This review provides a critical overview of EC-SERS advancements over the last few years, focusing on substrate design strategies, methodological developments, and applications in energy systems, catalysis, and sensing with particular attention to analytical figures of merit, including sensitivity, selectivity, reproducibility, and quantitative reliability. Despite notable progress, several challenges remain, including signal variability, substrate heterogeneity, and limited standardization across studies. Finally, emerging approaches aimed at overcoming these limitations are discussed, highlighting the potential of EC-SERS as a robust and versatile platform for next-generation analytical sensing and in situ characterization of complex electrochemical interfaces.
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