The electrocatalytic N2 oxidation reaction
(NOR) using
renewable electricity is a promising alternative to the industrial
synthesis of nitrate from NH3 oxidation. However, breaking
the triple bond in the nitrogen molecule is one of the most essential
challenges in chemistry. In this work, we use density functional theory
simulations to investigate the plausible reaction mechanisms of electrocatalytic
NOR and its competition with oxygen evolution reaction (OER) at the
atomic scale. We focus on the electrochemical conversion of inert
N2 to active *NO during NOR. We propose formation of *N2O from *N2 and *O as the rate-determining step
(RDS). Following the RDS, a microkinetic model is utilized to study
the rate of NOR on metal oxides. Our results demonstrate that a lower
activation energy is obtained when a catalyst binds *O weakly. We
show that the reaction is extremely challenging but also that design
strategies have been suggested to promote electrochemical NOR