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

Electrocatalytic nitrate reduction reaction (NO₃RR) is an effective way to solve nitrate pollution and a promising strategy for ammonia (NH₃) synthesis under ambient temperature and pressure. However, NO₃RR 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 NO₃RR reaction pathway by tuning the adsorption energies and configurations of intermediates, as demonstrated by density functional theory (DFT) calculations comparing NO₃RR 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_xH 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 NO₃RR, with an ultra-low limiting potential of -0.28 V. This work provides valuable insights and theoretical guidance for NO₃RR.