Iron-Doped MoO₃ Nanosheets for Boosting Nitrogen Fixation to Ammonia at Ambient Conditions

Nitrogen can be electrochemically reduced to produce ammonia, which supplies an energy-saving and environmental-benign route at room temperature, but high-efficiency catalysts are sought to reduce the reaction barrier. Here, iron-doped α-MoO3 nanosheets are thus designed and proposed as potential catalysts for fixing N2 to NH3. The α-MoO3 band structure is intentionally modulated by the iron doping, which narrows the band gap of α-MoO3 and turns the semiconductor into a metal-like catalyst. Oxygen vacancies, generated by substituting Mo6+ for Fe3+ anions, are beneficial for nitrogen adsorption at the active sites. In 0.1 M Na2SO4, the Fe-doped MoO3 catalyst reached a high faradaic efficiency of 13.3% and an excellent NH3 yield rate of 28.52 μg h–1 mgcat–1 at −0.7 V versus reversible hydrogen electrode, superior to most of the other metal-based catalysts. Theoretical calculations confirmed that the N2 reduction reaction at the Fe–MoO3 surface followed the distal reaction path.