Transition metal nitride nanoparticles are synthesized and utilized as catalysts for electrochemical nitrogen reduction reaction (ENRR) to produce ammonia in a proton exchange membrane electrolyzer (PEMEL). The catalysts show an average ENRR rate and Faradaic efficiency (FE) of 3.3 Ã 10â10 mol sâ1 cmâ2 (6.6 Ã 10â10 mol sâ1 mgâ1) and 5.95% at â0.1 V within 1 h, respectively. Both the ENRR rate and FE are approximately two orders of magnitude higher than those of noble metal catalysts. Time-dependent results suggest that the catalytic activity of transition metal nitride nanoparticles is stable at â0.1 V, with the catalytic activity decreasing by only 28% during 4 h test. Ex situ X-ray photoelectron spectroscopy (XPS) and operando electrochemical and synchrotron-based X-ray absorption spectroscopic (XAS) analysis reveal that transition metal oxynitride is the active phase for nitrogen reduction.