Fe‐VS2 Electrocatalyst with Organic Matrix‐Mediated Electron Transfer for Highly Efficient Nitrogen Fixation

Abstract Electrochemical N2 fixation is considered to be a promising alternative to Haber–Bosch technology. Inspired by the composition and structure of natural nitrogenase, Fe‐doped VS2 nanosheets were prepared via one‐step solvothermal method. The electron transfer system mediated by organic conductive polymer (1‐AAQ‐PA) was constructed to promote the electron transfer between Fe‐VS2 nanosheets and the electrode in electrocatalytic N2 reduction reaction (NRR). The obtained 1‐AAQ‐PA−Fe‐VS2 electrode converted N2 to NH3 with a yield of 31.6 μg h−1 mg−1 at −0.35 V vs. reversible hydrogen electrode and high faradaic efficiency of 23.5 %. The introduction of Fe dopants favored N2 adsorption and activation, while the Li−S bond between Fe‐VS2 and Li2SO4 effectively inhibited hydrogen evolution. The highly efficient electron utilization in the electrocatalytic NRR process was realized using the 1‐AAQ‐PA as the electron transfer medium. Density functional theory calculations showed that N2 was preferentially adsorbed on Fe and reduced to NH3 via both distal and alternating mechanism.