Interfacial Engineering of MoxSy via Boron‐Doping for Electrochemical N2‐to‐NH3 Conversion

Abstract The electrocatalytic synthesis of ammonia (NH 3 ) through the nitrogen reduction reaction (NRR) under ambient temperature and pressure is emerging as an alternative approach to the conventional Haber–Bosch process. However, it remains a significant challenge due to poor kinetics, low nitrogen (N 2 ) solubility in aqueous electrolytes, and the competing hydrogen evolution reaction (HER), which can significantly impact NH 3 production rates and Faradaic efficiency (FE). Herein, a rationally designed boron‐doped molybdenum sulfide (B‐Mo‐Mo x S y ) electrocatalyst is reported that effectively enhances N 2 reduction to NH 3 with an onset potential of −0.15 V versus RHE, achieving a FE of 78% and an NH 3 yield of 5.83 µg h⁻¹ cm⁻ 2 in a 0.05 m H 2 SO 4 (aq). Theoretical studies suggest that the effectiveness of NRR originates from electron density redistribution due to boron (B) doping, which provides an ideal pathway for nitrogenous species to bind with electron‐deficient B sites. This work demonstrates a significant exploration, showing that Mo‐based electrocatalysts are capable of facilitating artificial N 2 fixation.