No abstract

Photocatalysis is one of the most important chemical methods to mitigate the energy and environmental crisis via converting inexhaustible solar energy into clean chemical potential. The general history of the development of photocatalysis based on porous metal−organic frameworks (MOFs) is simply divided into three branches with a focus placed on the distinct structural role of the photocatalytic center: the inorganic cluster nodes, the organic linkers, and the guests in the pores of MOFs. In each branch, these photocatalytic centers are considered to be monodispersed within the crystal lattices with the other two structure roles regularly distributed to isolate the active centers and sometimes to provide more functions other than photoactivity. This distinctive nature has rendered MOFs as promising candidates for photocatalysis not only because they combine the benefits of heterogeneous catalysis and homogeneous catalysis but also because they facilitate the possibility of merging multifunctional catalytic sites for concerted or cascade photocatalysis. The design strategy and improvement approaches for MOF-based photocatalysts are also introduced with an emphasis on structure. Our intention is for this comprehensive view of MOFs-involved photocatalysts to inspire new ideas for designing heterogeneous photocatalysts toward the better utilization of solar energy.

The consecutive photo-induced electron-transfer (conPET) process found with perylene diimide (PDI) overcomes the limitation of visible-light photocatalysis and sheds light on effective solar energy conversion. By the incorporation of PDI into a metal-organic polymer Zn-PDI, a heterogeneous approach was achieved to tackle the poor solubility and strong tendency to aggregate of PDIs that restricted the exploitation of this outstanding homogeneous process. The interplay between metal-PDI coordination and π···π stacking of the organized PDI arrays in Zn-PDI facilitates the conPET process for the visible light-driven reduction of aryl halides by stabilizing the radical-anion intermediate and catalyst-substrate interacted moiety. These synergistic effects between the PDI arrays and Zn sites further render Zn-PDI photoactivity for fundamental oxidation of benzyl alcohols and amines. The tunable and modular nature of the two-dimensional metal-organic polymers makes the catalyst-embedding strategy promising for the development of ideal photocatalysts toward the better utilization of solar energy.