Ordered macroporous MOF-based materials for catalysis

Metal–organic frameworks (MOFs) possess various excellent properties. However, most MOFs exhibit microporosity, which restricts their applications in diffusion-related processes. Recently, single-crystal ordered macroporous MOFs (SOM-MOFs) have been successfully fabricated via monolith templates combined with heterogeneous nucleation approaches. SOM-MOFs exhibit improved mass transfer efficiency and catalytic activity compared with their microporous counterparts. SOM-MOFs can be integrated with other functional materials, including metal nanoparticles, polyoxometalates, and biomacromolecules, to enhance the characteristics of SOM-MOFs. Moreover, SOM-MOFs can act as ideal precursors and/or templates for the fabrication of ordered macroporous functional materials with well exposed active sites, good stability, and high conductivity. This review intends to offer an overview of recent advances in the synthesis of SOM-MOF-based nanomaterials and their applications in thermo-, photo-, and electrocatalysis, with particular emphasis on the discussion of the synthesis, properties, and structure–activity relationships. Furthermore, we propose the current challenges and future prospects of SOM-MOF-based materials.