Electrocatalytic nitrogen reduction in continuous-flow cell via water oxidation at ambient conditions: Promising for ammonia or diazene?

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Electrochemical nitrogen reduction reaction (eNRR) is recognized as an alternative green approach to the traditional energy-demanding and fossil-based catalytic processes (e.g. Haber Bosch). In this study, we implement eNRR in a proton exchange membrane (PEM) water electrolyzer in which nitrogen (N2) is fed in the cathode. This operation mode has been suggested as a way to overcome mass transfer limitations, however, there is a lack of developed evaluation protocols for appropriate product identification. Herein, we exemplify the spirit of the evaluation protocols for gas phase operation at the device level with a combination of online product analysis and isotopic labeling. Our protocol involves control experiments by replacing the cathodic N2 feed with (i) inert gas (i.e. Ar) and (ii) isotopic labeled 15N2 and by replacing the anodic water feed with isotopic labeled D2O. Taking advantage of the gas phase operation in the cathode product analysis is realized with online techniques i.e. quadrupole mass-spectrometer (QMS) and Fourier transform infrared (FTIR) spectrometer. This allows us to verify the production of diazene (N2H2) resulted from genuine N2 reduction, rather than from nitrogen-containing contaminants. Our methodology provides a pathway for how the false positive results can be eliminated in the gas phase study and a platform for follow-up studies using promising or exotic catalysts in the cathode, especially to validate the eNRR products or discover more products.