This tutorial review first describes the early history of SERS as the first SERS spectra were obtained from an electrochemical cell, which led to the discovery of the SERS effect in mid-1970s. Up to date, over 500 papers have been published on various aspects of SERS from electrochemical systems. We then highlight important features of electrochemical SERS (EC-SERS). There are two distinctively different properties of electric fields, the electromagnetic field and static electrochemical field, co-existing in electrochemical systems with various nanostructures. Both chemical and physical enhancements can be influenced to some extent by applying an electrode potential, which makes EC-SERS one of the most complicated systems in SERS. Great efforts have been made to comprehensively understand SERS and analyze EC-SERS spectra on the basis of the chemical and physical enhancement mechanisms in order to provide meaningful information for revealing the mechanisms of electrochemical adsorption and reaction. The EC-SERS experiments and applications are then discussed from preparation of nanostructured electrodes to investigation of SERS mechanisms and from characterization of adsorption configuration to elucidation of electrochemical reaction mechanisms. Finally, prospective developments of EC-SERS in substrates, methods and theory are discussed.
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