Physical Chemistry

Towards time resolved characterization of electrochemical reactions: Electrochemically-Induced Raman Spectroscopy

Authors

Abstract

Structural characterization of transient electrochemical species in the sub-millisecond time scale is the holy grail of electrochemistry. Presently, common time resolution of structural spectro-electrochemical methods is about 0.1 seconds. Herein, a transient spectro-electrochemical Raman setup of easy implementation is described which allows sub-ms time resolution. The technique studies electrochemical processes by initiating the reaction with an electric potential (or current) pulse and analyses the product with a synchronized laser pulse of the modified Raman spectrometer. The approach was validated by studying a known redox driven isomerization of a Ru-based molecular switch grafted, as monolayer, on a SERS active Au microelectrode. Density-functional-theory calculations confirmed the spectral assignments to sub-ms transient species. This study paves the way to a new generation of time-resolved spectro-electrochemical techniques which will be of fundamental help in the development of next generation electrolizers, fuel cells and batteries.

Content

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Supplementary material

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Supporting Information to: Towards time resolved characterization of electrochemical reactions: Electrochemically-Induced Raman Spectroscopy
Supporting information regarding further experimental details, control experiments, raw spectra and computational spectra.