Cu/TiO₂ Derived from Cu-Doped MIL-125 for Enhanced Photocatalytic CO₂-to-CH₄ Conversion

Photocatalytic CO₂ reduction into CH₄ is a promising route for solar fuel production, but its efficiency is still limited by poor charge separation, insufficient CO₂ activation, and sluggish multi-electron transfer kinetics. Herein, Cu-modified TiO₂ (Cu/TiO₂) was prepared by calcining a Cu-modified defective MIL-125(Ti) precursor, denoted as Cu-MIL-125, through a temperature-controlled calcination strategy. The effects of calcination temperature on the structural evolution, surface chemical states, interfacial charge transport, and CO₂ photoreduction performance were examined. These results indicated that the Cu/TiO₂ was successfully prepared, while the crystallinity, porous structure, and interfacial electronic properties of Cu/TiO₂ were strongly dependent on the calcination temperature. Among the obtained samples, the Cu/TiO₂ sample obtained by calcining Cu-MIL-125 at 450 °C (450 Cu/TiO₂) exhibited the highest CH₄ formation rate, reaching 15.90 μmol g^-1 h^-1, corresponding to an approximately 9.8-fold enhancement over TiO₂ calcined from defective MIL-125(Ti) at 450 °C, together with a high CH₄ selectivity of 93.05%. Control experiments and ¹³CO₂ isotope-labeling tests confirmed that the detected carbon-containing products were generated from CO₂ under photocatalytic conditions. In situ diffuse reflectance infrared Fourier transform spectroscopy measurements further revealed the formation of carbonate, bicarbonate and hydrogenated carbon-containing intermediates during the reaction. This work offers a practical route for constructing metal-organic framework-derived Cu/TiO₂ photocatalysts for selective CH₄ production from CO₂.