Electrochemical (EC) reactions are crucial in many applications, yet most EC analytical tools lack the sensitivity to access molecular-level information of reactants and products. By combining sum-frequency vibrational spectroscopy (SFVS) and surface plasmon resonance (SPR) at EC interfaces, we demonstrated the feasibility of measuring in situ and real-time vibrational spectra during EC reactions at noble metal electrodes. Application of the technique to EC reactions at a gold surface helped understand how the surface in a basic solution was oxidized and reduced during a cyclic voltammetry cycle. Study of desorption of a thiol self-assembled monolayer from gold through EC reactions in a basic solution showed that contrary to intuition, the desorbed thiols by reductive reaction remained as an ordered layer near the gold interface, but did diffuse away if they are desorbed oxidatively from gold.11 Wei-Tao Liu and Y. Ron Shen, PNAS 111 (4), 1293-1297 (2014).

In situ sum-frequency vibrational spectroscopy of electrochemical interfaces with surface plasmon resonance

248th National Meeting (2014)

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