Voltammetric and in situ infrared spectroscopy studies of hydroxyurea electrooxidation at Au(111) electrodes in HClO4 solutions

Abstract

The oxidation of hydroxyurea (H2NCONHOH, HU) at Au(111) single crystal and Au(111)-25 nm thin film electrodes is studied spectroelectrochemically in HClO4 solutions using external reflection infrared and Surface Enhanced Infrared Reflection Absorption Spectroscopy under Attenuated Total Reflection conditions (ATR-SEIRAS). The in situ external reflection spectra prove the formation of dissolved carbon dioxide and adsorbed cyanate during the electrooxidation of HU. The enhanced surface sensitivity of the ATR-SEIRAS experiments facilitates the detection of adsorbed cyanate and allows the observation of other adsorbate bands tentatively ascribed to reaction intermediates involving partial oxidation of the HU molecules, some of them corresponding to nitrosyl groups.