Titanium-based metal-organic framework, NH2-MIL-125(Ti), has been widely investigated for photocatalytic applications but has low activity in the hydrogen evolution reaction (HER). In this work, we show a one-step low-cost postmodification of NH2-MIL-125(Ti) via impregnation of Co(NO3)2. The resulting Co@NH2-MIL-125(Ti) with embedded single-site CoII species, confirmed by XPS and XAS measurements, shows enhanced activity under visible light exposure. The increased H2 production is likely triggered by the presence of active CoI transient sites detected upon collection of pump-flow-probe XANES spectra. Furthermore, both photocatalysts demonstrated a drastic increase in HER performance after consecutive reuse while maintaining their structural integrity and consistent H2 production. Via thorough characterization, we revealed two mechanisms for the formation of highly active proton reduction sites: nondestructive linker elimination resulting in coordinatively unsaturated Ti sites and restructuring of single CoII sites. Overall, this straightforward manner of confinement of CoII cocatalysts within NH2-MIL-125(Ti) offers a highly stable visible-light-responsive photocatalyst.

The Ti-containing metal organic framework (MOF) MIL-125 has been used as sacrificial precursor to obtain TiO₂ materials through the MOF-mediated synthesis route. In this study, Fe³⁺ was deposited on the surface of MIL-125 after its hydrothermal synthesis. Targeted Fe-doped titania photocatalysts were prepared through the direct calcination in air of Fe/MIL-125 crystals and/or by using a two-step method, including carbonization in inert atmosphere followed by calcination in air. The relationship between the synthesis conditions and the properties of the Fe-doped titania nanopowders, such as Fe content, porosity, phase composition and particle size was investigated. From elemental mapping, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, UV–Vis absorption spectroscopy and photoluminescence emission spectra, the presence of highly dispersed Fe³⁺ ions incorporated into the TiO₂ crystal lattice was confirmed, which led to a significant red shift of photoresponse towards visible light and reduced the recombination rate of electron-hole pairs at low iron content. By varying the pre-carbonization temperature, both crystal size and phase composition in the final materials were modulated. The performance of Fe-doped titania materials in photocatalytic water-splitting was tested for hydrogen evolution. Optimal photocatalytic performance was found at 0.15 and 0.5 wt% iron concentration and exceeded those of non-doped titania and commercial anatase both under visible and UV light irradiation, respectively, and among the highest reported in literature for these systems.

Metal-organic frameworks (MOFs) containing d⁰ metals such as NH₂-MIL-125(Ti), NH₂-UiO-66(Zr) and NH₂-UiO-66(Hf) are among the most studied MOFs for photocatalytic applications. Despite structural similarities, we demonstrate that the electronic properties of these MOFs are markedly different. As revealed by quantum chemistry, EPR measurements and transient absorption spectroscopy, the highest occupied and lowest unoccupied orbitals of NH₂-MIL-125(Ti) promote a long lived ligandto-metal charge transfer upon photoexcitation, making this material suitable for photocatalytic applications. In contrast, in case of UiO materials, the d-orbitals of Zr and Hf, are too low in binding energy and thus cannot overlap with the π orbital of the ligand, making both frontier orbitals localized at the organic linker. This electronic reconfiguration results in short exciton lifetimes and diminishes photocatalytic performance. These results highlight the importance of orbital contributions at the band edges and delineate future directions in the development of photo-active hybrid solids.