Ag ₃ Sn Alloy for Nitrogen Electroreduction: False Positives and Theoretical Basis of Inactivity

Abstract The electrochemical nitrogen reduction reaction (NRR) has emerged as a promising route for the production of green ammonia (NH 3 ). In many studies, alloying strategies have been employed to enhance the performance of electrocatalysts in this process. This study assesses the NRR activity of a silver–tin (Ag–Sn) alloy, a mixture of metals, each of which has been previously reported for its high selectivity toward the NRR. Extended control experiments revealed that the detected NH 3 stemmed from contamination rather than catalytic activity. Complementary density functional theory (DFT) calculations revealed that, although Ag 3 Sn exhibits a theoretically lower onset potential than pure Ag or Sn, the associated overpotentials remain excessively high. These findings highlight the critical need for stringent, long‐duration control experiments to prevent erroneous attribution of NH 3 formation to nitrogen (N 2 ) reduction.