Electrochemical Nitrogen Reduction Reaction on Transition Metal Nitride Nanoparticles in Proton Exchange Membrane Electrolyzers


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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 × 10−10 mol s−1 cm−2 (6.6 × 10−10 mol s−1 mg−1) and 5.95% at −0.1 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 −0.1 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.