In Situ Resonance Raman Spectroscopic Characterization of Electrogenerated Methyl Viologen Radical Cation on Carbon Electrode

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Abstract
In situ Raman spectroscopic characterization of solution and surface species on a carbon electrode is reported. An optical flow-through cell has been designed for the characterization of electrode surfaces and electrogenerated solution species during an electrochemical reaction. The electrogeneration of the methyl viologen (1,1′-dimethyl-4,4′-bipyridine) radical cation (MV+) at a carbon electrode in aqueous chloride solution has been studied with the use of laser Raman spectroscopy. In the case of the radical ion, resonance enhancement of the order of 25–30 was observed with 514.5 nm excitation. The effect of concentration, potential, and flow rate on the observed spectrum is discussed. Time-dependent studies with optical multichannel analyzer detection suggest the formation of a multilayer film on the electrode.