Iron Monomers or Trimers on Nitrogen-Doped Carbon: Which Is Better for the Electrocatalytic Nitrogen Reduction Reaction?

The electrocatalytic nitrogen reduction reaction (NRR) presents an alternative method for the Haber-Bosch process, and single-atom catalysts (SACs) to achieve efficient NRR have attracted considerable attention in the past decades. However, whether SACs are more suitable for NRR compared to atomic-cluster catalysts (ACCs) remains to be studied. Herein, we have successfully synthesized both the Fe monomers (Fe 1 ) and trimers (Fe 3 ) on nitrogen-doped carbon catalysts. Both the experiments and DFT calculations indicate that compared to the end-on adsorption of N 2 on Fe 1 catalysts, N 2 activation is enhanced via the side-on adsorption on Fe 3 catalysts, and the reaction follows the enzymatic pathway with a reduced free energy barrier for NRR. As a result, the Fe 3 catalysts achieved better NRR performance (NH 3 yield rate of 27.89 μg h -1 mg -1 cat. and Faradaic efficiency of 45.13%) than Fe 1 catalysts (10.98 μg h -1 mg -1 cat. and 20.98%). Therefore, our research presents guidance to prepare more efficient NRR catalysts.