Rigorous Assessment of Cl(−)‐Based Anolytes on Electrochemical Ammonia Synthesis

Many challenges in the electrochemical synthesis of ammonia have been recognized with most effort focused on delineating false positives resulting from unidentified sources of nitrogen. However, the influence of oxidizing anolytes on the crossover and oxidization of ammonium during the electrolysis reaction remains unexplored. Here it is reported that the use of analytes containing halide ions (Cl(−) and Br(−)) can rapidly convert the ammonium into N(2), which further intensifies the crossover of ammonium. Moreover, the extent of migration and oxidation of ammonium is found to be closely associated with external factors, such as applied potentials and the concentration of Cl(−). These findings demonstrate the profound impact of oxidizing anolytes on the electrochemical synthesis of ammonia. Based on these results, many prior reported ammonia yield rates are calibrated. This work emphasizes the significance of avoiding selection of anolytes that can oxidize ammonium, which is believed to promote further progress in electrochemical nitrogen fixation.