Single‐Atom Bismuth Catalyst with Sulfur Modulation: Toward Efficient Electrochemical Ammonia Synthesis via NRR‐EGOR Integration

ABSTRACT Exploring a nitrogen reduction reaction (NRR) technology utilizing single‐atom electrocatalysts, our research aims to develop an environmentally benign and highly efficient approach for ammonia (NH 3 ) synthesis. A sulfur‐doped single‐atom bismuth‐based nitride catalyst (S‐BiNSPC) was synthesized via a molecular engineering strategy, and its structure and electrochemical NRR performance were thoroughly characterized. X‐ray photoelectron spectroscopy (XPS) and extended X‐ray absorption fine structure (EXAFS) analyses revealed that sulfur incorporation optimizes the electronic structure and local geometry of bismuth, significantly enhancing NRR activity. Experimental results demonstrated that S‐BiNSPC exhibited excellent NRR performance in 0.1 m KOH electrolyte, achieving an ammonia yield of 77.71 µg.h −1 mgcat −1 and a Faraday efficiency (FE) of 37.03%. Density functional theory (DFT) calculations indicated that sulfur doping lowers the energy barrier for the initial hydrogenation step and optimizes the electronic structure for nitrogen activation. In a system where the NRR is coupled with the ethylene glycol oxidation reaction (EGOR), the reaction potential was reduced and the generation of high‐value‐added products was enabled. This research offers novel perspectives on the advancement of high‐performance NRR catalysts and highlights their potential for practical implementation.