Theoretical advances in understanding the active site microenvironment toward the electrocatalytic nitrogen reduction reaction in aqueous media

Abstract

The electrocatalytic nitrogen reduction reaction (eNRR) in aqueous media has received substantial attention because it enables the direct conversion of N2 to NH3 under benign conditions. There are, however, many factors limiting the overall eNRR efficiency, including the competing hydrogen evolution reaction (HER) and sluggish reaction kinetics due to a strong N≡N bond. These challenges call for more systematic theoretical insight into the eNRR reaction mechanism to guide the rational optimization of experimental designs. In this review, we present the latest computational advances in eNRR in an aqueous medium, including the key aspects of both catalyst design and proton accessibility. Specifically, we discuss the importance of constant potential and explicit solvent simulations, the role of the electrochemical interface, and the impact of the active center microenvironment on eNRR activity and selectivity. Finally, the current challenges and the future prospects for eNRR are addressed.