(705e) Understanding Trends in Electrochemical Dinitrogen Oxidation

The electrochemical oxidation of nitrogen (N2OR) presents a sustainable method for producing nitrate and offers a promising way for sustainable synthesis of ammonia (NH3). N2OR involves the direct oxidation of N₂ to NO_x, leading to the formation of NO₃^- under ambient conditions. However, the kinetics of this reaction are slow, resulting in poor selectivity and reported low reaction rates for nitrate formation in the previous literature. Significant attention has been directed towards the necessity of mitigating the competing Oxygen Evolution Reaction (OER), similar to the inhibition of the Hydrogen Evolution Reaction (HER) during Nitrogen Reduction Reaction (N2RR). In this work, we investigate the competition among Oxygen Evolution Reaction (OER) intermediates on rutile oxide surfaces and aim to an advanced molecular-level comprehension of potential mechanisms underlying Nitrogen Oxidation Reaction (N2OR): direct N2 adsorption on a metal site, dissociative adsorption of N2, and a Mars-Van-Krevelen (MvK) type mechanism. Our results indicate that employing dynamic potential control can substantially enhance overall selectivity towards the desired process while minimizing interference from the competing Oxygen Evolution Reaction (OER). The insights from our research will anticipated to discover the novel catalysts for this critical reaction, towards the ultimate objective of achieving sustainable NO₃^- and NH₃ synthesis.