Department of Chemical and Biomolecular Engineering, Rice University, Houston, TX, USA.
School for Engineering of Matter, Transport, & Energy, Chemical Engineering Program, Arizona State University, Tempe, AZ, USA.
Nat Nanotechnol. 2022 Jul;17(7):759-767. doi: 10.1038/s41565-022-01121-4. Epub 2022 May 2.
Electrochemically converting nitrate ions, a widely distributed nitrogen source in industrial wastewater and polluted groundwater, into ammonia represents a sustainable route for both wastewater treatment and ammonia generation. However, it is currently hindered by low catalytic activities, especially under low nitrate concentrations. Here we report a high-performance Ru-dispersed Cu nanowire catalyst that delivers an industrial-relevant nitrate reduction current of 1 A cm while maintaining a high NH Faradaic efficiency of 93%. More importantly, this high nitrate-reduction catalytic activity enables over a 99% nitrate conversion into ammonia, from an industrial wastewater level of 2,000 ppm to a drinkable water level <50 ppm, while still maintaining an over 90% Faradaic efficiency. Coupling the nitrate reduction effluent stream with an air stripping process, we successfully obtained high purity solid NHCl and liquid NH solution products, which suggests a practical approach to convert wastewater nitrate into valuable ammonia products. Density functional theory calculations reveal that the highly dispersed Ru atoms provide active nitrate reduction sites and the surrounding Cu sites can suppress the main side reaction, the hydrogen evolution reaction.
将硝酸盐离子(一种在工业废水中广泛存在的氮源和受污染的地下水)电化学转化为氨,代表了一种废水处理和氨生成的可持续途径。然而,目前受到催化活性低的限制,尤其是在硝酸盐浓度低的情况下。在此,我们报告了一种高性能的 Ru 分散 Cu 纳米线催化剂,在保持 93%的高 NH 法拉第效率的同时,实现了 1 A cm 的工业相关硝酸盐还原电流。更重要的是,这种高硝酸盐还原催化活性使得超过 99%的硝酸盐转化为氨,将工业废水中的硝酸盐浓度从 2000 ppm 降低到可饮用的 <50 ppm,同时仍然保持超过 90%的法拉第效率。将硝酸盐还原流出物与空气汽提过程相耦合,我们成功地获得了高纯度的固体 NHCl 和液体 NH 溶液产品,这表明了一种将废水硝酸盐转化为有价值的氨产品的实用方法。密度泛函理论计算表明,高度分散的 Ru 原子提供了活性的硝酸盐还原位点,周围的 Cu 位点可以抑制主要的副反应,即析氢反应。