Studies of adsorbed species by electrochemically modulated infrared spectroscopy

Abstract

Electrochemically modulated infrared spectroscopy has been used to obtain infrared spectra of adsorbates in different electrochemical systems. This very sensitive technique provides direct information on the indentity and the molecular structure of the adsorbed species present at the electrode surface, as well as their orientation and bonding to the electrode surface.

Systems studied included the adsorption of acrylonitrile on a gold electrode in aqueous sulphuric acid, and the adsorption of cyanide on silver and gold electrodes in aqueous potassium cyanide. The results reported for the gold/acrylonitrile system have shown that the entire molecule is adsorbed over the potential range investigated with a molecular orientation parallel to the electrode surface.

The study of the adsorption of cyanide on a silver electrode has shown that the nature of the adsorbed species is dependent on the concentration of cyanide ions. The nature of the surface complex species, which is thought to be formed on silver and gold electrodes in concentrated solution, is discussed.

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