Optimizing Electrocatalytic Nitrogen Reduction via Interfacial Electric Field Modulation: Elevating d‐Band Center in WS2‐WO3 for Enhanced Intermediate Adsorption

Abstract Electrocatalytic nitrogen reduction reaction (ENRR) has emerged as a promising approach to synthesizing green ammonia under ambient conditions. Tungsten (W) is one of the most effective ENRR catalysts. In this reaction, the protonation of intermediates is the rate‐determining step (RDS). Enhancing the adsorption of intermediates is crucial to increase the protonation of intermediates, which can lead to improved catalytic performance. Herein, we constructed a strong interfacial electric field in WS 2 ‐WO 3 to elevate the d‐band center of W, thereby strengthening the adsorption of intermediates. Experimental results demonstrated that this approach led to a significantly improved ENRR performance. Specifically, WS 2 ‐WO 3 exhibited a high NH 3 yield of 62.38 μg h −1 mg cat −1 and a promoted faraday efficiency (FE) of 24.24 %. Furthermore, in situ characterizations and theoretical calculations showed that the strong interfacial electric field in WS 2 ‐WO 3 upshifted the d‐band center of W towards the Fermi level, leading to enhanced adsorption of −NH 2 and −NH intermediates on the catalyst surface. This resulted in a significantly promoted reaction rate of the RDS. Overall, our study offers new insights into the relationship between interfacial electric field and d‐band center and provides a promising strategy to enhance the intermediates adsorption during the ENRR process.