Exploring Hydrogen Evolution Accompanying Nitrogen Reduction on Biomimetic Nitrogenase Analogs: Can Fe-N _xH...

Nitrogen reduction reaction (N₂RR) carried out on biomimetic catalytic systems is considered to be a promising alternative for the traditional Haber-Bosch ammonia synthesis. Unfortunately, the selectivity of the currently known biomimetic catalysts is poor, as they also catalyze the unproductive hydrogen evolution reaction (HER). In the present computational study, we examine the HER activity of early N₂RR intermediates in EP₃ (E = B, Si) ligated single-site biomimetic iron complexes by calculating and comparing the activation Gibbs free energies of HER and N₂RR elementary steps. We find that, in contrast to previous suggestions, early N₂RR intermediates are not likely sources of HER under turnover conditions, as the barriers of the competing N₂RR steps are significantly lower. Consequently, future research should focus on preventing other potential HER mechanisms, e.g., hydride formation, rather than accelerating the consumption of early N₂RR intermediates as proposed earlier to design more efficient biomimetic catalysts.