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.

Development of water-stable metal–organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear a wide range of pH environment in aqueous solution. Both experimental and theoretical results indicate a feasible electron transfer from the H4TBAPy ligand (light-harvesting center) to the Ni–O cluster node (catalytic center), on which water splitting to produce hydrogen can be efficiently driven free of cocatalyst. Compared to the single crystal, the exfoliated two-dimensional (2D) nanobelts show more efficient charge separation due to its shortened charge transfer distance and remarkably enhanced active surface areas, resulting in 164 times of promoted water reduction activity. The optimal H2 evolution rate on the nanobelt reaches 98 μmol h–1 (ca. 5 mmol h–1 g–1) showing benchmarked apparent quantum efficiency (AQE) of 8.0% at 420 nm among water-stable MOFs photocatalysts.