Fundamental Insights on the Electrochemical Nitrogen Oxidation over Metal Oxides

Electrocatalytic nitrogen oxidation reaction (eN 2 OR) has emerged as a sustainable strategy for nitrogen fixation. In this work, density functional theory calculations were performed to rationalize the reaction mechanisms, activity, and selectivity of eN 2 OR on metal dioxides. The anatase (101), anatase (100), and rutile (110) surfaces were investigated to obtain more generalized insights. Based on the reaction phase diagram analysis, the thermochemical mechanisms were identified as most energetically favorable for N 2 and *N 2 O oxidation, and a theoretical activity map was constructed for eN 2 OR, explaining well the experimental activity trend. Anatase PtO 2 (100) was screened as the most active catalyst for nitrate production, which could be covered by a monolayer of *OH under the reaction conditions according to the Pourbaix diagram. A method of electric field controlling constant potential was used to calculate the electrochemical barriers on anatase PtO 2 (100). It was found that the electrochemical barriers of the oxygen evolution reaction will increase with the decrease of potential, while the thermochemical limiting step of the eN 2 OR is insensitive to potential. Thus, the eN 2 OR selectivity can be improved by lowering the applied potential. This work unveils fundamental insights into eN 2 OR and provides a unified understanding to experiments.