Mechanistic Insight into Photocatalytic Pathways of MIL-100(Fe)/TiO₂ Composites

The integration of metal-organic frameworks (MOFs) with semiconductors has attracted mounting attention for photocatalytic applications. However, more efforts are needed to unravel the interface structure in MOF/semiconductor composites and its role in charge transfer. Herein, a MIL-100(Fe)/TiO₂ composite was synthesized as a prototypical photocatalyst and studied systematically to explore the interface structure and unravel the charge transfer pathways during the photocatalytic processes. The composite was fabricated by growing MIL-100(Fe) crystals on TiO₂ using surface-coated FeOOH as the precursor. The as-prepared MIL-100(Fe)/TiO₂ exhibited significantly improved photocatalytic performance over pristine TiO₂, which was mainly because of the enhanced charge separation as confirmed by transient absorption spectroscopy analysis. This enhancement partially arose from the special chemical structure at the interface, where the Fe-O-Ti bond was formed. As verified by the density functional theory calculation, this distinct structure would create defect energy levels adjacent to the valence band maximum of TiO₂. During the photocatalytic processes, the defect energy levels serve as sinks to capture excited charge carriers and retard the recombination, which subsequently leads to the increased charge density and promoted photocatalytic efficiency. Meanwhile, the intimate interactions between MIL-100(Fe) and TiO₂ would also help to improve the charge separation by transferring photo-induced holes through the ligands to Fe-O clusters. These findings would advance the fundamental understanding of the interface structure and the charge transfer pathways in MOF/semiconductor composite photocatalysts.