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Various electrochemical TERS approaches were developed to probe electrochemical processes at the nanoscale, in real time and over a wide potential window (around 800 mV). EC-TERS was successfully applied to the investigation of the transformation mechanism of different molecular layer architectures, i.e. self-assembled monolayers (SAMs) on gold electrodes and grafted layers via controlled electro-reduction of aryldiazonium salts. A bimolecular electrochemical reaction path, difficult to evidence from the electrochemical response only, is proposed in light of the EC-TERS analysis. The comparison among the in situ reactivity of different layer structures allowed establishing structure-reactivity relationships.
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Alice Fiocco, Aja Pavlic, Emmanuel Maisonhaute, Jean-Marc Noël, Ivan T. Lucas, "Electrochemical tip-enhanced Raman spectroscopy for the elucidation of complex electrochemical reactions," Proc. SPIE PC12654, Enhanced Spectroscopies and Nanoimaging 2023, PC126540H (5 October 2023); https://doi.org/10.1117/12.2676405