Overcoming Energy‐Scaling Barriers: Efficient Ammonia Electrosynthesis on High‐Entropy Alloy Catalysts

Abstract Electrochemically converting nitrate (NO ₃ ⁻ ) to value‐added ammonia (NH ₃ ) is a complex process involving an eight‐electron transfer and numerous intermediates, presenting a significant challenge for optimization. A multi‐elemental synergy strategy to regulate the local electronic structure at the atomic level is proposed, creating a broad adsorption energy landscape in high‐entropy alloy (HEA) catalysts. This approach enables optimal adsorption and desorption of various intermediates, effectively overcoming energy‐scaling limitations for efficient NH ₃ electrosynthesis. The HEA catalyst achieved a high Faradaic efficiency of 94.5 ± 4.3% and a yield rate of 10.2 ± 0.5 mg h ⁻¹ mg _cat ⁻¹ . It also demonstrated remarkable stability over 250 h in an integrated three‐chamber device, coupling electrocatalysis with an ammonia recovery unit for continuous NH ₃ collection. This work elucidates the catalytic mechanisms of multi‐functional HEA systems and offers new perspectives for optimizing multi‐step reactions by circumventing adsorption‐energy scaling limitations.