ZIF‐Induced d‐Band Modification in a Bimetallic Nanocatalyst: Achieving Over 44 % Efficiency in the Ambient Nitrogen Reduction Reaction

The electrochemical nitrogen reduction reaction (NRR) offers a sustainable solution towards ammonia production but suffers poor reaction performance owing to preferential catalyst–H formation and the consequential hydrogen evolution reaction (HER). Now, the Pt/Au electrocatalyst d‐band structure is electronically modified using zeolitic imidazole framework (ZIF) to achieve a Faradaic efficiency (FE) of >44 % with high ammonia yield rate of >161 μg mgcat−1 h−1 under ambient conditions. The strategy lowers electrocatalyst d‐band position to weaken H adsorption and concurrently creates electron‐deficient sites to kinetically drive NRR by promoting catalyst–N2 interaction. The ZIF coating on the electrocatalyst doubles as a hydrophobic layer to suppress HER, further improving FE by >44‐fold compared to without ZIF (ca. 1 %). The Pt/Au‐NZIF interaction is key to enable strong N2 adsorption over H atom. A kinetically driven ambient nitrogen reduction reaction has a Faradaic efficiency of over 44 % and an ammonia yield rate of over 161 μg mgcat−1 h−1. It employs a zeolitic imidazole framework to induce electron‐deficient sites on the catalyst and a lower d‐band to weaken catalyst–H interactions whilst promoting the catalyst–N2 interaction.