Unraveling the Mechanism of Ammonia Electrooxidation by Coupled Differential Electrochemical Mass Spectrometry and Surface-Enhanced Infrared Absorption Spectroscopic Studies

Ammonia electrooxidation has received considerable attention in recent times due to its potential application in direct ammonia fuel cells, ammonia sensors, and denitrification of wastewater. In this work, we used differential electrochemical mass spectrometry (DEMS) coupled with attenuated total reflection-surface-enhanced infrared absorption (ATR-SEIRA) spectroscopy to study adsorbed species and solution products during the electrochemical ammonia oxidation reaction (AOR) on Pt in alkaline media, and to correlate the product distribution with the surface ad-species. Hydrazine electrooxidation, hydroxylamine electrooxidation/reduction, and nitrite electroreduction on Pt have also been studied to enhance the understanding of the AOR mechanism. NH₃, NH₂, NH, NO, and NO₂ ad-species were identified on the Pt surface with ATR-SEIRA spectroscopy, while N₂, N₂O, and NO were detected with DEMS as products of the AOR. N₂ is formed through the coupling of two NH ad-species and then subsequent further dehydrogenation, while the dimerization of HNO_ad leads to the formation of N₂O. The NH-NH coupling is the rate-determining step (rds) at high potentials, while the first dehydrogenation step is the rds at low potentials. These new spectroscopic results about the AOR and insights could advance the search and design of more effective AOR catalysts.