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Acquiring stable photocatalysts in possession of efficacious CO 2 adsorption capacity and high charge-separation efficiency is crucial for carbon dioxide (CO 2 ) photoreduction into fossil resources. Hereby, via a direct integration of copper(II)-porphyrin zirconium metal−organic framework (PCN-224(Cu)) and TiO 2 nanoparticles, we establish an efficacious photocatalytic system capable of greatly enhancing the catalytic activity of TiO 2 in CO 2 photoreduction. In the absence of either cocatalyst or sacrifice reagent, CO evolution rate can reach up to 37.21 μmol g −1 h −1 , ca. 10 and 45.4 times that of mere PCN-224(Cu) (3.72 μmol g −1 h −1 ) and pure TiO 2 (0.82 μmol g −1 h −1 ), respectively. There are two contributors making devotion to the melioration of the catalytic activity. One is the augmented ability of light-harvesting given by the integrated metalloporphyrin-based MOF. The other is due to the conjunction between the MOF and TiO 2 , which constructs a Z-Scheme mechanism favoring beneficial promotion on the separation of photoexcited charges. This study provides theoretical support for meliorating photocatalytic performance through the combination of metalloporphyrin-based MOF and other inorganic semiconductors.

FeIII–TCPPCl-incorporated UiO-66 MOF could reliably achieve both photocatalysis and a Fenton-like reaction under visible light, with effective degradation against organic pollutants.