A Review of Transition Metal Nitride-Based Catalysts for Electrochemical Nitrogen Reduction to Ammonia

Electrochemical nitrogen reduction (NRR) has attracted much attention as a promising technique to produce ammonia at ambient conditions in an environmentally benign and less energy-consuming manner compared to the current Haber-Bosch process. However, even though much research on the NRR catalysts has been conducted, their low selectivity and reaction rate still hinder the practical application of the NRR process. Among various catalysts, transition metal nitride (TMN)-based catalysts are expected to be promising catalysts for NRR. This is because the NRR process can proceed via the unique Mars-Van Krevelen (MvK) mechanism with a compressed competing hydrogen evolution reaction. However, a controversial issue exists regarding the origin of ammonia produced on TMN-based catalysts. The instability of the TMN-based catalysts can lead to ammonia generation from lattice nitrogen instead of supplied N-2 gas. Thus, this review summarizes the recent progress of TMN-based catalysts for NRR, encompassing the NRR mechanism, synthetic routes, characterizations, and controversial opinions. Furthermore, future perspectives on producing ammonia electrochemically using TMN-based catalysts are provided.