Mechanochemical route to fabricate an efficient nitrate reduction electrocatalyst

The electrochemical nitrate reduction reaction (NO3RR) to ammonia under ambient conditions is a promising approach for addressing elevated nitrate levels in water bodies, but the progress of this reaction is impeded by the complex series of chemical reactions involving electron and proton transfer and competing hydrogen evolution reaction. Therefore, it becomes imperative to develop an electro-catalyst that exhibits exceptional efficiency and remarkable selectivity for ammonia synthesis while maintaining long-term stability. Herein the magnetic biochar (Fe-C) has been synthesized by a two-step mechanochemical route after a pyrolysis treatment (450, 700, and 1000 degrees C), which not only significantly decreases the particle size, but also exposes more oxygen-rich functional groups on the surface, promoting the adsorption of nitrate and water and accelerating electron transfer to convert it into ammonia. Results showed that the catalyst (Fe-C-700) has an impressive NH3 production rate of 3.5 mol center dot h-1 center dot gcat-1, high Faradaic efficiency of 88%, and current density of 0.37 A center dot cm-2 at 0.8 V vs. reversible hydrogen electrode (RHE). In-situ Fourier transform infrared spectroscopy (FTIR) is used to investigate the reaction intermediate and to monitor the reaction. The oxygen functionalities on the catalyst surface activate nitrate ions to form various intermediates (NO2, NO, NH2OH, and NH2) and reduce the rate determining step energy barrier (*NO3 -> *NO2). This study presents a novel approach for the use of magnetic biochar as an electro-catalyst in NO3RR and opens the road for solving environmental and energy challenges.