Yiyong Wang, Yingying Cheng, Mingxin Gao, Shiqiang Liu, Huisheng Qin, Wenling Zhao, Xing Tong, Xueqing Xing, Lihong Jing, Pei Zhang, Qinggong Zhu, Xiaofu Sun, Jianling Zhang, Zhimin Liu, Yi Xu, Xinchen Kang, Buxing Han
ABSTRACT The electrochemical nitrate reduction reaction (NO 3 RR) represents a promising strategy for sustainable NH 3 synthesis and environmental remediation. However, developing an NH 3 production process that achieves both high current density and Faradaic efficiency (FE) is challenging owing to the strong electrostatic repulsion of NO 3 − from the electrode surface and the competing hydrogen evolution reaction at high current densities. Here, Cu/C electrode, modified using 1‐dodecanol (C 12 OH), achieves an exceptional NH 3 yield rate of 4.50 mmol cm −2 h −1 and FE NH3 of 98.9% at 1.0 A cm −2 . This performance significantly surpasses that of the pristine Cu/C catalyst and most reported state‐of‐the‐art catalysts. C 12 OH modification, which induces the reconstruction of the hydrogen‐bonded network on the electrode surface, not only enhances NO 3 − enrichment but also promotes H • radical generation. This new pathway, mediated by H • radicals, is both thermodynamically and kinetically favorable and underlies the promoted NH 3 production.