Multi‐Site CuZn Alloy Boosts Nitrate Reduction to Ammonia via Optimized Intermediate Adsorption

Abstract Electrocatalytic nitrate reduction reaction (NO 3 RR) is an effective way to solve nitrate pollution and a promising strategy for ammonia (NH 3 ) synthesis under ambient temperature and pressure. However, NO 3 RR is still hindered by the lack of efficient catalysts and an understanding of mechanisms that enhance the catalytic performance. In this study, we propose intermetallic alloying as a promising strategy to optimize the NO 3 RR reaction pathway by tuning the adsorption energies and configurations of intermediates, as demonstrated by density functional theory (DFT) calculations comparing NO 3 RR performance of Cu (111) and CuZn (110) surfaces. In CuZn alloy, the electron‐donating property of Cu weakens the adsorption of NO x ( x = 1, 2, and 3) intermediates, whereas the electron‐accepting property of Zn strengthens the binding of NO x H intermediates, thus lowering the protonation reaction energy. Zn sites preferentially promote the removal of O species, whereas Cu sites dominate the protonation of N species. This synergistic effect enables CuZn (110) surface to successfully break the undesirable scaling relationship in traditional metal catalysts, resulting in excellent catalytic activity for NO 3 RR, with an ultra‐low limiting potential of −0.28 V. This work provides valuable insights and theoretical guidance for NO 3 RR.