Electrochemical Oxidation of Hydroxylamine on Gold in Aqueous Acidic Electrolytes: An in Situ SERS Investigation

Abstract

The electrooxidation of hydroxylamine (HAM) on roughened Au electrodes has been examined in aqueous buffered electrolytes (pH 3) using in situ surface-enhanced Raman scattering (SERS). Two distinct spectral features were observed at potentials, E, within the range in which HAM oxidation was found to ensue, centered at 803 cm(-1) for 0.55 < E < 0.8 V and at 826 cm(-1) for 1.0 < E < 1.40 V versus SCE, attributed, respectively, to adsorbed nitrite and adsorbed NO(2). Similar experiments performed in solutions containing nitrite instead of HAM under otherwise identical conditions displayed only the peak ascribed to adsorbed nitrite over the range of 0.1 < E < 0.8 V versus SCE with no additional features at higher potentials. These observations strongly suggest that under the conditions selected for these studies the oxidation of HAM on Au proceeds at least in part through a pathway that does not involve nitrite as a solution-phase intermediate.