In this communication, we will present the concept of Electrochemical Tip Surface-Enhanced Raman Spectroscopy (EC-Tip-SERS) on a redox- and Raman- active model molecule, the Nile blue, in which a temporal resolution in the order of millisecond can be attained. Then, we will consider the use of Tip-SERS in the characterization of complex rotaxane-based giant assemblies containing porphyrins, and in probing their molecular motion on gold surfaces . Finally, we will demonstrate the use of EC-Tip-SERS in scrutinizing electrocatalytic transient mechanisms, such as those associated to the oxygen reduction reaction using methyl viologen SAMs as electrocatalyts.
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