Surface-enhanced infrared absorption spectroscopy (SEIRAS) in conjunction with cyclic voltammetry has been applied to in situ and real-time monitoring of the electrochemical redox reactions of heptylviologen at a silver electrode surface. The high sensitivity of SEIRAS enables the real-time spectral monitoring of the irreversible reaction processes on the millisecond time scale with rapid-scan interferometry. With the combination of the molecular information obtained from the spectra and the kinetic data obtained by cyclic voltammetry, the complex voltammetric behavior of the molecule can be discussed in detail at the molecular scale. The results demonstrate the utility of the real-time infrared monitoring in analyzing electrochemical reactions.

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