Construction of Three-Dimensional Dendritic Hierarchically Porous Metal–Organic Framework Nanoarchitectures via Noncentrosymmetric Pore–Induced Anisotropic Assembly

As a unique class of modular nanomaterials, metal–organic framework (MOF) nanoparticles have attracted widespread interest for use in various fields because of their diverse chemical functionalities, intrinsic microporosity, and three-dimensional (3D) nanoarchitectures. However, endowing MOF nanomaterials with precisely controlled structural symmetries and hierarchical macro/mesoporosities remains a formidable challenge for the researchers. Herein, we report a facile noncentrosymmetric pore-induced anisotropic assembly strategy to prepare a series of 3D dendritic MOF (UiO-66) nanomaterials with highly controllable structural symmetries and hierarchical macro/meso/microporosities. The synthetic route of these nanomaterials depends on the anisotropic nucleation of MOF spherical nanocones with noncentrosymmetric center-radial channels and their oriented growth to isotropic nanospheres through a continuous increase in radius and solid angle. This strategy enables the controllable fabrication of asymmetric MOF nanostructures with abundant geometries and porous structures by regulating the concentration of amphiphilic triblock copolymer templates. Furthermore, the average pore diameter of the resultant MOF nanospheres can be systematically manipulated in a wide range from 35 to 130 nm by finely tuning the reaction temperature. Meanwhile, the strategy can also be extended to synthesize other MOF nanoparticles with similar architectures. Compared with microporous UiO-66 nanocrystals, the MOF nanoparticles with controllable structural symmetries and macro/meso/microporosities show enhanced catalytic activity in the CO₂ cycloaddition reaction. The methodology provides new insights into the rational construction of sophisticated asymmetric open nanostructures of hierarchically porous MOFs for many potential applications.