| Abstract
| - The reduction of nitrate ions on platinum, rhodium, and platinum−rhodium alloy electrodes has beeninvestigated using differential electrochemical mass spectrometry and in situ FTIR measurements. For3 M HNO3 concentration it has been found that nitrate starts the reduction with partial N−O bonddissociation and N−N bond formation generating NO and N2O. At potentials lower than 0.2 V the reactionproceeds forming dissolved NH4+. For potentials lower than 0 V the reduction continues via a multiplepathway reaction leading to the nonselective production of N2, NH2OH, and N2H2. On the alloyed electrodes,the production of NO and N2O has been observed in both cathodic and anodic scans, while on pure platinumand rhodium electrodes the reaction has been observed only during the cathodic scan. Contrasting withthe pure platinum and rhodium alloys, where the N−O bond break starts forming NO and N2O, on thealloys HNO2 has been observed as the first reaction step. For alloys with higher rhodium composition, likePt75Rh25, no N2 has been detected for potentials lower than 0 V.
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