Identification of M?NH ₂ ?NH ₂ 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 dinitrogen (N2) to ammonia (NH3) under ambient conditions. Inspired by nitrogenases, a bimetallic sulfide material (FeWSx@FeWO4) was synthesized as highly N2 reduction (NRR) catalyst sulfur substitution surface FeWO4 nanoparticles. Thus prepared FeWSx@FeWO4 catalysts exhibit relatively high NH3 production rate 30.2 ug h?1 mg?1cat and Faraday efficiency 16.4 % at ?0.45 V versus reversible hydrogen electrode in flow cell; these results have been confirmed via purified 15N2-isotopic labeling experiments. In situ Raman spectra hydrazine kinetics analysis revealed that undissociated intermediates (M-NH2-NH2) on is rate-determing step for NRR process. Therefore, this work can provide guidance elucidating structure–activity relationship catalysts.