Integrating Ozone Pollutant Elimination in N₂ Electrolysis to Produce Nitrate with Reduced Reaction Steps

Abstract The synthesis of nitrate by the electrochemical N₂ oxidation reaction (NOR) is currently one of the most promising routes. However, the traditional generation of nitrate depends on the oxidation reaction between N₂ and H₂O (or ·OH), which involves complex reaction steps and intermediates, showing strong competition from oxygen evolution reaction (OER). Here, an effective NOR method is proposed to directly oxidize N₂ by using O₃ as a reactive oxygen source to reduce the reaction step. Electrochemical tests demonstrate that the nitrate yield of Pd‐Mn₃O₄/CNT electrocatalyst reaches the milligram level, which is the highest yield reported so far for electrocatalytic NOR. Quantitative characterization is employed to establish a comprehensive set of benchmarks to confirm the intrinsic nature of nitrogen activation and test the O₃‐mediated reaction mechanism. Density functional theory (DFT) calculations show that the heterostructure Pd‐Mn₃O₄ leads to a strong adsorption preference for N₂ and O₃, which greatly reduces the activation energy barrier for N₂. This accelerates the synthesis of nitrate based on the direct formation mechanism, which reduces energy barriers and the reaction steps, thus increasing the performance of electrocatalytic nitrate production. The techno‐economic analysis underscores the promising feasibility and sustainable economic value of the presented method.