Perspectives on the Competition between the Electrochemical Water and N 2 Oxidation on a TiO 2 (110) Electrode.

The electrochemical nitrogen oxidation reaction (NOR) has recently drawn attention due to promising experimental and theoretical results. It provides an alternative, environmentally friendly route to directly synthesize nitrate from N 2 (g). There is to date a limited number of investigations focused on the electrochemical NOR. Herein, we present a detailed computational study on the kinetics of both the NOR and the competing oxygen evolution reaction (OER) on the TiO 2 (110) electrode under ambient conditions. The use of grand canonical density functional theory in combination with the linearized Poisson-Boltzmann equation allows a continuous tuning of the explicitly applied electrical potential. We find that the OER may either promote or suppress the NOR on TiO 2 (110) depending on reaction conditions. The detailed atomistic insights provided on the mechanisms of these competing processes make possible further developments toward a direct electrochemical NOR process.