Efficient ammonia synthesis from the air using tandem non-thermal plasma and electrocatalysis at ambient conditions

While electrochemical N2 reduction presents a sustainable approach to NH3 synthesis, addressing the emission- and energy-intensive limitations of the Haber-Bosch process, it grapples with challenges in N2 activation and competing with pronounced hydrogen evolution reaction. Here we present a tandem air-NOx-NOx --NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx - reduction. It delivers a high NH3 yield rate of 3 mmol h-1 cm-2 and a corresponding Faradaic efficiency of 92% at -0.25 V versus reversible hydrogen electrode in batch experiments, outperforming previously reported ones. Furthermore, in a flow mode concurrently operating the non-thermal plasma and the NOx - electrolyzer, a stable NH3 yield rate of approximately 1.25 mmol h-1 cm-2 is sustained over 100 h using pure air as the intake. Mechanistic studies indicate that amorphous Ni(OH)x on Cu interacts with hydrated K+ in the double layer through noncovalent interactions and accelerates the activation of water, enriching adsorbed hydrogen species that can readily react with N-containing intermediates. In situ spectroscopies and density functional theory (DFT) results reveal that NOx - adsorption and their hydrogenation process are optimized over the Ni(OH)x/Cu surface. This work provides new insights into electricity-driven distributed NH3 production using natural air at ambient conditions. The conversion of atmospheric N2 into NH3 under ambient pressure is highly interesting but very challenging. In this study, the authors present a tandem air-NOx and NOx-NH3 system that combines non-thermal plasma-enabled N2 oxidation with Ni(OH)x/Cu-catalyzed electrochemical NOx -reduction, resulting in a high NH3 yield from N2 under ambient pressure conditions.