(437e) Electrochemical Reduction of Nitrates to Ammonia on Oxide Derived Cobalt
AIChE Annual Meeting
Wednesday, November 10, 2021 - 8:00am to 8:20am
NH3 is manufactured in an industrial scale by Haber-Bosch process which is highly energy intensive as it requires high temperatures (500 to 600 Â°C) and high pressures (150 to 200 atm), and it leaves a massive carbon footprint. Electrochemical route is an alternate process to synthesize NH3 by using renewable electricity at ambient conditions. Direct electrochemical reduction of dinitrogen would be ideal, but the NH3 Faradaic efficiency and yield is low in this case due to high mass transfer resistances and the competing hydrogen evolution reaction (HER). Electrochemical reduction of NO3- to NH3 is less challenging when compared to direct N2 reduction to NH3 due to lower dissociation energy of N = O bond (204 kJ/mol) than N â¡ N (941 kJ/mol). A catalyst that can selectively reduce nitrates to ammonia is required. DFT calculations were performed on late transition metals to identify the most active metal for the electrochemical nitrate reduction to NH3. Ni and Co were found to be most active among the late transition metals. Experimental investigations corroborated with the theoretical findings and Co was found to give the highest NH3 Faradaic efficiency. Oxide-derived Cobalt was used for the electrochemical nitrate reduction as it had low onset potential compared to other forms of Co. We obtained a maximum NH3 Faradaic efficiency of 68.13 % at -0.6 V vs RHE (pH = 14), and a high NH3 current density of 245.34 mA/cm2 at -0.8 V vs RHE (pH = 14). The oxide derived Co was found to be stable during the test period of 24 h. NMR Control studies were performed using N-15 nitrates to confirm that the source of NH3 is nitrates.