Mechanistic Insights into Electrochemical Nitrogen Reduction Reaction on Vanadium Nitride Nanoparticles

Renewable production of ammonia, a building block for most fertilizers, via the electrochemical nitrogen reduction reaction (ENRR) is desirable; however, a selective electrocatalyst is lacking. Here we show that vanadium nitride (VN) nanoparticles are active, selective, and stable ENRR catalysts with an ENRR rate and a Faradaic efficiency (FE) of 3.3 X 10(-10) mol s(-1) cm(-2) and 6.0% at -0.1 V within 1 h, respectively. ENRR with N-15(2) as the feed produces both (NH3)-N-14, and (NH3)-N-15, which indicates that the reaction follows a Mars-van Krevelen mechanism. Ex situ X-ray photoelectron spectroscopy characterization of fresh and spent catalysts reveals that multiple vanadium oxide, oxynitride, and nitride species are present on the surface and identified VN0.7O0.45 as the active phase in the ENRR. Operando X-ray absorption spectroscopy and catalyst durability test results corroborate this hypothesis and indicate that the conversion of VN0.7O0.45 to the VN phase leads to catalyst deactivation. We hypothesize that only the surface N sites adjacent to a surface O are active in the ENRR. An ammonia production rate of 1.1 X 10(-10) mol s(-1) cm(-2) can be maintained for 116 h, with a steady-state turnover number of 431.