POM-based MOF materials, which combine the advantages of both POMs and MOFs, have received increasing attention. In this review, we present the recent developments in porous POM-based MOF materials for the first time, including their classification, synthesis strategies and applications, especially in the field of catalysis.

Group 4 metal-based metal–organic frameworks (M^IV-MOFs), including Ti-, Zr-, and Hf-based MOFs, are one of the most attractive classes of MOF materials owing to their superior chemical stability and structural tunability. Despite being a relatively new field, M^IV-MOFs have attracted significant research attention in the past few years, leading to exciting advances in syntheses and applications. In this outlook, we start with a brief overview of the history and current status of M^IV-MOFs, emphasizing the challenges encountered in their syntheses. The unique properties of M^IV-MOFs are discussed, including their high chemical stability and strong tolerance toward defects. Particular emphasis is placed on defect engineering in Zr-MOFs which offers additional routes to tailor their functions. Photocatalysis of M^IV-MOF is introduced as a representative example of their emerging applications. Finally, we conclude with the perspective of new opportunities in synthesis and defect engineering.

A major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.