Phase Engineering of High‐Entropy Alloy for Enhanced Electrocatalytic Nitrate Reduction to Ammonia

Abstract Directly electrochemical conversion of nitrate (NO 3 − ) is an efficient and environmentally friendly technology for ammonia (NH 3 ) production but is challenged by highly selective electrocatalysts. High‐entropy alloys (HEAs) with unique properties are attractive materials in catalysis, particularly for multi‐step reactions. Herein, we first reported the application of HEA (FeCoNiAlTi) for electrocatalytic NO 3 − reduction to NH 3 (NRA). The bulk HEA is active for NRA but limited by the unsatisfied NH 3 yield of 0.36 mg h −1 cm −2 and Faradaic efficiency (FE) of 82.66 %. Through an effective phase engineering strategy, uniform intermetallic nanoparticles are introduced on the bulk HEA to increase electrochemical active surface area and charge transfer efficiency. The resulting nanostructured HEA (n‐HEA) delivers enhanced electrochemical NRA performance in terms of NH 3 yield (0.52 mg h −1 cm −2 ) and FE (95.23 %). Further experimental and theoretical investigations reveal that the multi‐active sites (Fe, Co, and Ni) dominated electrocatalysis for NRA over the n‐HEA. Notably, the typical Co sites exhibit the lowest energy barrier for NRA with *NH 2 to *NH 3 as the rate‐determining step.