In Situ Attenuated Total Reflection Infrared Spectroscopy on Electrochemical Ammonia Oxidation over Pt Electrode in Alkaline Aqueous Solutions

The electrochemical oxidation of ammonia over Pt electrode in alkaline aqueous solutions was studied by in situ attenuated total reflection infrared (ATR-IR) spectroscopy. In 0.1 M NH3-1 M KOH, the band ascribable to the HNH bending mode of adsorbed NH3 was confirmed at 1662-1674 cm(-1) in the potential range of 0.1-1.1 V. The intensity of this band decreased continuously with a rise in potential, indicating the oxidative consumption of adsorbed ammonia. In response to this behavior, the band at 1269 cm(-1) appeared alternatively above 0.2 V, and its intensity reached the local maximal value at ca. 0.4 V. Note that this potential of ca. 0.4 V agreed well with the onset potential of ammonia oxidation, ca. 0.45 V, in the linear sweep voltammogram. This 1269 cm(-1) band was assigned to the NH2 wagging mode of N2H4, which was one of the active intermediates, N2Hx+y,ad (x = 1 or 2, y = 1 or 2), according to the mechanism proposed by Gerischer and Mauere. To the best of our knowledge, this is the first report for the detection of N2H4 as a reaction intermediate over Pt electrode. Furthermore, the formation of bridged NO was also observed above the onset potential of ammonia oxidation, ca. 0.5 V. Such adsorbed NO species probably inhibit the electrochemical reaction due to the occupation of reaction sites at higher potential.