Plasma-Electrocatalysis Cascade Synthesis of Deuterated Ammonia

Deuterated ammonia (ND₃) exhibits growing market demand in the fields of chemical analysis, pharmaceutical industry and semiconductor manufacturing. Currently, industrial production of ND₃ relies on harsh conditions and complex processes, leading to high production cost and security risk. Herein, we propose a sustainable relay strategy to produce ND₃ by using air and deuterium oxide (D₂O) as raw materials, including plasma-driven air-to-NO_x conversion and electrocatalytic NO_x ^--to-ND₃ conversion. The insufficient supply of reactive deuterium (*D) leads to sluggish kinetics of electrocatalytic deuterium reaction. The well-designed F modified cobalt (F-Co) catalyst exhibits a remarkable yield of 0.75 mmol h^-1 cm^-2 and a Faradaic efficiency of 80.43% for ND₃ at 200 mA cm^-2. The combined results of characterizations reveal that fluorine (F) atom can boost D₂O dissociation and suppress competing deuterium evolution reaction, thereby providing abundant *D for deuteration reaction. Notably, a pilot-scale demonstration system, consisting of non-thermal plasma, flow electrolyzer, air stripping and ammonia absorber, is constructed to produce practicable ND₃ solution (2.8 wt%) with ∼21.45 mmol h^-1 ND₃ production capability by using air and D₂O as sources.