Bimetallic Fe, Co-Modified TiO₂ Derived from NH₂-MIL-125(Ti) as an Efficient Photocatalyst for N₂ Fixation

The conversion of nitrogen (N₂) and water (H₂O) into NH₃ by photocatalysis under ambient conditions has been considered an environmentally friendly strategy. However, developing effective catalysts for N₂ fixation is still challenging. Herein, we report a bimetallic JH Fe, Co/TiO₂ derived from NH₂-MIL-125(Ti) by the fast Joule heating (FJH) method for visible–light–driven catalytic N₂ fixation. It was found that the photocatalytic N₂ reduction efficiency of bimetallic FC@TiO₂-JH was improved, enabling an NH₃ yield rate of 110.14 µmol g⁻¹ h⁻¹ without any sacrificial agents. Furthermore, the rate was higher than those of Fe@TiO₂-JH and Co@TiO₂-JH, suggesting that the synergistic effect between Fe and Co broke the electronic equilibrium and increased the center of its d-band, enhancing electronic feedback to the antibonding π* orbitals of N₂ while weakening the bonding energy of N≡N. Meanwhile, the rate was about 2.75 times higher than that of FC@TiO₂-TF, which was calcined in a tube furnace. It is assumed that FJH might lead to the formation of lattice defects, leading to localized charge deficiency, enhanced carrier separation, and transport. Thus, doping of Fe and Co synergistically interacted with the defects produced from FJH, facilitating the photocatalytic reduction process. As detected, it had a greater ability to separate hole–electron pairs and transferred electrons to adsorbed N₂ at faster rates. Our work demonstrates a prospective strategy for designing bimetallic catalysts derived from NH₂-MIL-125(Ti) for N₂ fixation.