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

Abstract Electrochemical N 2 fixation is considered to be a promising alternative to Haber–Bosch technology. Inspired by the composition and structure of natural nitrogenase, Fe‐doped VS 2 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‐VS 2 nanosheets and the electrode in electrocatalytic N 2 reduction reaction (NRR). The obtained 1‐AAQ‐PA−Fe‐VS 2 electrode converted N 2 to NH 3 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 N 2 adsorption and activation, while the Li−S bond between Fe‐VS 2 and Li 2 SO 4 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 N 2 was preferentially adsorbed on Fe and reduced to NH 3 via both distal and alternating mechanism.