Accelerating Industrial‐Level NO3− Electroreduction to Ammonia on Cu Grain Boundary Sites via Heteroatom Doping Strategy

Although the electrocatalytic nitrate reduction reaction (NO₃ ^- RR) is an attractive NH₃ synthesis route, it suffers from low yield due to the lack of efficient catalysts. Here, this work reports a novel grain boundary (GB)-rich Sn-Cu catalyst, derived from in situ electroreduction of Sn-doped CuO nanoflower, for effectively electrochemical converting NO₃ ^- to NH₃ . The optimized Sn_1% -Cu electrode achieves a high NH₃ yield rate of 1.98 mmol h^-1 cm^-2 with an industrial-level current density of -425 mA cm^-2 at -0.55 V versus a reversible hydrogen electrode (RHE) and a maximum Faradaic efficiency of 98.2% at -0.51 V versus RHE, outperforming the pure Cu electrode. In situ Raman and attenuated total reflection Fourier transform infrared spectroscopies reveal the reaction pathway of NO₃ ^- RR to NH₃ by monitoring the adsorption property of reaction intermediates. Density functional theory calculations clarify that the high-density GB active sites and the competitive hydrogen evolution reaction (HER) suppression induced by Sn doping synergistically promote highly active and selective NH₃ synthesis from NO₃ ^- RR. This work paves an avenue for efficient NH₃ synthesis over Cu catalyst by in situ reconstruction of GB sites with heteroatom doping.