Emerging Pristine MOF‐Based Heterostructured Nanoarchitectures: Advances in Structure Evolution, Controlled Synthesis, and Future Perspectives

Abstract Metal–organic frameworks (MOFs) can be customized through modular assembly to achieve a wide range of potential applications, based on their desired functionality. However, most of the initially reported MOFs are limited to microporous systems and are not sufficiently stable, which restricts their popularization. Heterogeneity is introduced into a simple MOF framework to create MOF‐based heterostructures with fascinating properties and interesting functions. Heterogeneity can be introduced into the MOFs via postsynthetic/ligand exchange. Although the ligand exchange has shown potential, it is difficult to precisely control the degree of exchange or position. Among the various synthesis strategies, hierarchical assembly is particularly attractive for constructing MOF‐based heterostructures, as it can achieve precise regulation of MOF‐based heterostructured nanostructures. The hierarchical assembly significantly expands the compositional diversity of MOF‐based heterostructures, which has high elasticity for lattice matching during the epitaxial growth of MOFs. This review focuses on the synthetic evolution mechanism of hierarchical assemblies of MOF‐based nanoarchitectures. Subsequently, the precise control of pore structure, pore size, and morphology of MOF‐based nanoarchitectures by hierarchical assembly is emphasized. Finally, possible solutions to address the challenges associated with heterogeneous interfaces are presented, and potential opportunities for innovative applications are proposed.