FeIr Alloy Optimizes the Trade‐Off Between Nitrate Reduction and Active Hydrogen Generation for Efficient Electro‐Synthesis of Ammonia in Neutral Media

Abstract Electrochemically promoted nitrate reduction reaction (NITRR) holds great potential for the “green” synthesis of ammonia (NH 3 ). However, NITRR in neutral media, though close to the practical scenario, is often limited by an insufficient supply of active hydrogen (*H) due to sluggish water cleavage. In this work, it is demonstrated that a bimetallic alloy FeIr can optimize the trade‐off between nitrate reduction and *H formation in neutral media. As a result, FeIr exhibits excellent catalytic performance toward neutral NITRR with a Faradaic efficiency of NH 3 up to 97.3% and a high yield rate up to 11.67 mg h −1 cm −2 at a low working potential of −0.6 V (versus reversible hydrogen electrode (RHE)), surpassing the monometallic catalysts as well as the majority of Fe‐based state‐of‐the‐art. It is also found that the FeIr displays remarkable electron rearrangement between hetero‐atoms due to their significant orbital hybridization, which benefits not only the *H formation but also the NITRR process. Moreover, coupling FeIr‐based NITRR with methanol oxidation reaction (MOR) results in sustainable productions of NH 3 and formate with a combined FE of nearly 200% at a cell‐voltage of 2 V. This work thus demonstrates a promising strategy for designing efficient catalysts toward neutral NITRR.