Copper‐Catalyzed Electrosynthesis of Nitrite and Nitrate from Ammonia: Tuning the Selectivity via an Interplay Between Homogeneous and Heterogeneous Catalysis

Abstract Electrocatalytic oxidation of ammonia is an appealing, low‐temperature process for the sustainable production of nitrites and nitrates that avoids the formation of pernicious N 2 O and can be fully powered by renewable electricity. Currently, however, the number of known efficient catalysts for such a reaction is limited. The present work demonstrates that copper‐based electrodes exhibit high electrocatalytic activity and selectivity for the NH 3 oxidation to NO 2 − and NO 3 − in alkaline solutions. Systematic investigation of the effects of pH and potential on the kinetics of the reaction using voltammetric analysis andin situ Raman spectroscopy suggest that ammonia electrooxidation on copper occurrs via two primary catalytic mechanisms. In the first pathway, NH 3 is converted to NO 2 − via a homogeneous electrocatalytic process mediated by redox transformations of aqueous [Cu(OH) 4 ] −/2− species, which dissolve from the electrode. The second pathway is the heterogeneous catalytic oxidation of NH 3 on the electrode surface favoring the formation of NO 3 − . By virtue of its nature, the homogeneous‐mediated pathway enables higher selectivity and was less affected by electrode poisoning with the strongly adsorbed “N” intermediates that have plagued the electrocatalytic ammonia oxidation field. Thus, the selectivity of the Cu‐catalyzed NH 3 oxidation towards either nitrite or nitrate can be achieved through balancing the kinetics of the two mechanisms by adjusting the pH of the electrolyte medium and potential.