Universal Reversible Hydrogen Potential for Electrocatalytic Ammonia Splitting Reactions in Nonaqueous Solvents from...

In this work, we introduce a new approach of using differential potentiometric measurements in four nonaqueous solvents─MeCN, THF, DMF, and PC─to determine the universal pH_abs^H₂O values aligned to the aqueous pH scale for dilute NH₄⁺/NH₃ solutions. Knowledge of the pH_abs^H₂O values allows simple determination of the reversible hydrogen potential in any given solvent relative to the aqueous standard hydrogen electrode (SHE) and, most importantly, ensures comparability across different solvents. As an independent method, Open Circuit Potenial measurements were carried out in the same solvents titrated with NH₄⁺/NH₃ to obtain alternative values for the reversible hydrogen potential in these solvents. The close agreement of these two methods, as well as calculated potentials from literature values when available, substantiates the new, simpler, and more robust approach to determine the reversible hydrogen potential introduced here. We further use the reversible hydrogen potential values established here to report, for the first time, the overpotential for ammonia oxidation as a function of solvent, with a recently discovered ruthenium catalyst.