Electrocatalytic conversion of nitrate to ammonia on the oxygen vacancy engineering of zinc oxide for nitrogen recovery from nitrate-polluted surface water.

Nitrate pollution in surface water poses a significant threat to drinking water safety. The integration of electrocatalytic reduction reaction of nitrate (NO3RR) to ammonia with ammonia collection processes offers a sustainable approach to nitrogen recovery from nitrate-polluted surface water. However, the low catalytic activity of existing catalysts has resulted in excessive energy consumption for NO3RR. Herein, we developed a facile approach of electrochemical reduction to generate oxygen vacancy (Ov) on zinc oxide nanoparticles (ZnO1-x NPs) to enhance catalytic activity. The ZnO1-x NPs achieved a high NH3-N selectivity of 92.4% and NH3-N production rate of 1007.9 [Formula: see text] h-1 m-2 at -0.65 V vs. RHE in 22.5 mg L-1NO3--N, surpassing both pristine ZnO and the majority of catalysts reported in the literature. DFT calculations with in-situ Raman spectroscopy and ESR analysis revealed that the presence of Ov significantly increased the affinity for the NO3- (nitrate) and key intermediate of NO2- (nitrite). The strong adsorption of NO3- on Ov decreased the energy barrier of potential determining step (NO3- →∗NO3) from 0.49 to 0.1 eV, boosting the reaction rate. Furthermore, the strong adsorption of NO2- on Ov prevented its escape from the active sites, thereby minimizing NO2- by-product formation and enhancing ammonia selectivity. Moreover, the NO3RR, when coupled with a membrane separation process, achieved a 100% nitrogen recycling efficiency with low energy consumption of 0.55 kWh molN-1 at a flow rate below 112 mL min-1 for the treatment of nitrate-polluted lake water. These results demonstrate that ZnO1-x NPs are a reliable catalytic material for NO₃RR, enabling the development of a sustainable technology for nitrogen recovery from nitrate-polluted surface water.