Identification of M‐NH2‐NH2 Intermediate and Rate Determining Step for Nitrogen Reduction with Bioinspired Sulfur‐Bonded FeW Catalyst

The multimetallic sulfur‐framework catalytic site of biological nitrogenases allows the efficient conversion of dinitrogen (N2) to ammonia (NH3) under ambient conditions. Inspired by biological nitrogenases, a bimetallic sulfide material (FeWSx@FeWO4) was synthesized as a highly efficient N2 reduction (NRR) catalyst by sulfur substitution of the surface of FeWO4 nanoparticles. Thus prepared FeWSx@FeWO4 catalysts exhibit a relatively high NH3 production rate of 30.2 ug h−1 mg−1cat and a Faraday efficiency of 16.4 % at −0.45 V versus a reversible hydrogen electrode in a flow cell; these results have been confirmed via purified 15N2‐isotopic labeling experiments. In situ Raman spectra and hydrazine reduction kinetics analysis revealed that the reduction of undissociated hydrazine intermediates (M‐NH2‐NH2) on the surface of the bimetallic sulfide catalyst is the rate‐determing step for the NRR process. Therefore, this work can provide guidance for elucidating the structure–activity relationship of NRR catalysts. Inspired by biological nitrogenases, a bimetallic sulfide material (FeWSx@FeWO4) was synthesized for a highly efficient N2 reduction (NRR) catalyst. In situ Raman spectra and hydrazine reduction kinetics analysis revealed that the reduction of undissociated hydrazine intermediates (M‐NH2‐NH2) on the surface of the catalyst is the rate‐determing step for the NRR process.