Improved visible light photocatalytic nitrogen fixation activity using a FeII-rich MIL-101(Fe): breaking the scaling relationship by photoinduced FeII/FeIII cycling

Abstract

The scaling relations between nitrogen adsorption and NH_x destabilization are key challenges to the widespread adoption of the photocatalytic synthesis of ammonia. In this work, a Fe^II-rich MIL-101(Fe) (MIL-101(Fe^II/Fe^III)) was synthesized using a one-step solvent thermal method with ethylene glycol (EG) as a reducing agent, which can break the scaling relationship by photoinduced Fe^II (high nitrogen adsorption ability) and Fe^III (high NH_z destabilization ability) cycling. XPS was used to detect the change in iron valence state in the MIL-101(Fe^II/Fe^III) material. The photocatalytic nitrogen fixation efficiency of MIL-101(Fe^II/Fe^III) under visible light without any sacrificial agent was 466.8 μmol h⁻¹ g⁻¹, five times that of MIL-101(Fe). After photocatalytic experiments, MIL-101(Fe^II/Fe^III) retained an unchanged Fe^II/Fe^III rate, indicating that this Fe^II/Fe^III cycling can be maintained. DFT modeling of the Fe^II-rich MOF material showed that a Fe^II₁ Fe^III₂ system has a higher N₂ activation capacity than a Fe^III₃ system. The catalytic mechanism was further proved by in situ infrared spectra and N¹⁵ isotopic tracers. Therefore, the improvement of photocatalytic activity was mainly attributed to the change in the nitrogen adsorption capacity during the photoinduced Fe^II/Fe^III cycling.