Integrated Photosensitive Fragments and Catalytically Active Sites into Zirconium Metal–Organic Frameworks for CO ₂ Photoreduction

The incorporation of multiple functional groups or metal sites into predetermined positions of a metal–organic framework (MOF) cavity would obtain tailored MOF materials, which greatly facilitate their modulated light harvesting, band gap, and consequently photocatalytic activity. Herein, a multicomponent zirconium MOF, JLU-MOF58(Ni)-PDI, was achieved by incorporating PDI (short for perylene diimide) and Ni2+ sites into JLU-MOF58. JLU-MOF58(Ni)-PDI exhibited visible-light-driven reduction of CO2 in the absence of any additives under mild conditions. In addition, the CO production rate of JLU-MOF58(Ni)-PDI was 3.2 to 12.8 times higher than a series of classical materials, which can be assigned to the efficient introduction of the photosensitive fragments and catalytically active sites into the parent MOF. Furthermore, the catalytic mechanism was studied in detail by a series of experiments and density functional theory calculations.