Electrocatalytic reduction of N2 on FeRu dual-atom catalyst anchored in N-doped phosphorene

Abstract

The highly efficient electrochemical synthesis of ammonia is regarded as a promising alternative compared to the traditional Haber-Bosch (H-B) process. However, the high-activity, low-cost, and long-term stability of electrocatalysts are still barriers to their rapid development. Herein, utilizing density functional theory (DFT), FeRu dual-atom catalyst anchored in N-doped phosphorene (FeRu@N4-P) is developed as a potential candidate for reducing inert N2 through electrocatalysis. Our results reveal that the distal and alternating pathways occur on the FeRu@N4-P with the lowest overpotential (0.29 V and 0.36 V). Moreover, we notice that there is a transformation from the alternating pathway to the enzymatic pathway for the step *NH2NH2 + H+ + e−→*NH2+*NH3. Considering the influence of the electrolyte solution in the actual experiment, we compared the sensitivity of electrocatalytic N2 reduction reaction (e-NRR) catalyst to the adsorption of H, demonstrating the efficient selectivity of FeRu@N4-P. The catalysts still maintain good stability and performance at room temperature. Finally, combining the physical properties of the metal atom, Φ is chosen to as the descriptor linearly correlating to the ΔG*N2 on the catalyst. This study deepens our understanding on the e-NRR mechanism on the dual-atoms doped phosphorene and opens a new way for the design of catalyst of the N2 fixation.