Ammonia Detection Methods in Photocatalytic and Electrocatalytic Experiments: How to Improve the Reliability of NH₃ Production Rates?

The enzyme nitrogenase inspires the development of novel photocatalytic and electrocatalytic systems that can drive nitrogen reduction with water under similar low-temperature and low-pressure conditions. While photocatalytic and electrocatalytic N₂ fixation are emerging as hot new areas of fundamental and applied research, serious concerns exist regarding the accuracy of current methods used for ammonia detection and quantification. In most studies, the ammonia yields are low and little consideration is given to the effect of interferants on NH₃ quantification. As a result, NH₃ yields reported in many works may be exaggerated and erroneous. Herein, the advantages and limitations of the various methods commonly used for NH₃ quantification in solution (Nessler's reagent method, indophenol blue method, and ion chromatography method) are systematically explored, placing particular emphasis on the effect of interferants on each quantification method. Based on the data presented, guidelines are suggested for responsible quantification of ammonia in photocatalysis and electrocatalysis.