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 mg_cat^-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.