Facts or Artifacts: Pitfalls in Quantifying Sub-ppm Levels of Ammonia Produced from Electrochemical Nitrogen Reduction.

Synthesis of ammonia through electrochemical nitrogen reduction (ENR) is emerging as one of the attractive research areas in recent years, notwithstanding the enormous challenges it faces in quantification of ammonia at very low concentrations. Several reports claiming high production rate are unwittingly compromised by the accuracy of analyzing a very low concentration (<1 ppm) of ammonia in the electrolyte post-ENR reaction using the indophenol method. Therefore, in this work, we have highlighted the significance of selecting and standardizing a right protocol encompassing admissible levels of oxidants and a complexing agent, citrate (to mitigate the effect of interfering metal ions), through elaborate control experiments. In addition, the importance of setting the lowest limit of ammonia concentration that can be accurately quantified by the indophenol method is also justified. Further, the experimental observations were summarized into a protocol, which was followed to re-evaluate the performance of two well-claimed electrocatalysts for ENR reported recently in the literature.