Sustainable removal of nitrite waste to value-added ammonia on Cu@Cu2O core-shell nanostructures by pulsed laser technique

Abstract

The biochemical reduction of nitrite (NO2-) ions to ammonia (NH3) requires six electrons and is catalyzed by the cytochrome c NO2-reductase enzyme. This biological reaction inspired scientists to explore the reduction of nitrogen oxyanions, such as nitrate (NO3-) and NO2-in wastewater, to produce the more valuable NH3 product. It is widely known that copper (Cu)-based nanoparticles (NPs) are selective for the NO3-reduction reaction (NO3-RR), but the NO2-RR has not been well explored. Therefore, we attempted to address the electrocatalytic conversion of NO2-to NH3 using Cu@Cu2O core-shell NPs to simultaneously treat wastewater by removing NO2-and producing valuable NH3. The Cu@Cu2O core-shell NPs were constructed using the pulsed laser ablation of Cu sheet metal in water. The core-shell nanostructure of these particles was confirmed by various character-ization techniques. Subsequently, the removal of NO2-and the ammonium (NH4+)-N yield rate were estimated using the Griess and indophenol blue methods, respectively. Impressively, the Cu@Cu2O core-shell NPs exhibited outstanding NO2-RR activity, demonstrating a maximum NO2-removal efficiency of approximately 94% and a high NH4+-N yield rate of approximately 0.03 mmol h-1.cm-2 at-1.6 V vs. a silver/silver chloride reference electrode under optimal conditions. The proposed NO2-RR mechanism revealed that the (111) facet of Cu favors the selective conversion of NO2-to NH3 via a six-electron transfer. This investigation may offer a new insight for the rational design and detailed mechanistic understanding of electrocatalyst architecture for the effective conversion of NO2-to NH4+.