Zhou, JingwenJingwenZhouLiu, FuFuLiuXu, ZhihangZhihangXuYin, Jian-AnJian-AnYinGuo, LiangLiangGuoHao, FengkunFengkunHaoWang, YunhaoYunhaoWangXiong, YuechengYuechengXiongZhou, XichenXichenZhouWang, ChengChengWangMa, YangboYangboMaMeng, XiangXiangMengLu, PengyiPengyiLuYin, JinwenJinwenYinZhang, AnAnZhangWang, JieJieWangYe, ChenliangChenliangYeLi, QiangQiangLiLing, ChongyiChongyiLingChen, Hsiao-ChienHsiao-ChienChenChen, Hao MingHao MingChenZhu, YeYeZhuLu, JianJianLuFan, ZhanxiZhanxiFan2025-08-222025-08-222025-06-20https://scholars.lib.ntu.edu.tw/handle/123456789/731572Ammonia (NH3) electrosynthesis from nitrate-polluted wastewater is a challenging but meaningful technique for the future green chemical and sewage disposal industries. The dominant difficulties lie in how to realize a highly selective, low-overpotential, and rapid electrocatalytic nitrate reduction reaction (NO3RR). Herein, we propose a catalyst crystal phase and electrode/electrolyte interface dual engineering strategy to enhance the neutral NO3RR performance of ultrathin alloy nanostructures. The obtained unconventional 2H-RhCu not only shows higher intrinsic NH3 selectivity than its traditional face-centered cubic and amorphous/crystalline counterparts but also delivers superior Faradaic efficiency and yield rate toward NH3 in K+-based electrolyte over those in Li+/Na+-based ones. In situ studies and theoretical calculations reveal that the faster generation/conversion kinetics of key intermediates, weaker N–N recombination, and unique *NObri adsorption configuration at electrode/electrolyte interfaces account for this significant enhancement. In addition, rechargeable Zn-nitrate/methanol flow batteries with 2H-RhCu were constructed as a demonstration of potential applications.en[SDGs]SDG6[SDGs]SDG7journal article10.1021/jacs.5c07490