Controllable Microporous Framework Isomerism within Continuous Mesoporous Channels: Hierarchically Porous Structure for Capture of Bulky Molecules

To date, some attempts have been made to synthesize hierarchically porous metal–organic frameworks (HPMOFs), and in most cases, mesopores are formed in microporous frameworks. However, mass transfer and diffusion are still limited in such HPMOFs since micropores connect mesopores and mesopores are noncontinuous. Here, we fabricate a new hierarchical structure through the formation of microporous MOFs within continuous mesoporous channels. Confined space in the as-prepared mesoporous silica-containing template was used to prepare well-dispersed metal precursor of ZnO. The strategy of ligand vapor-induced crystallization was then designed to construct MOFs inside mesoporous channels, in which vapored ligand at elevated temperature diffuses and reacts with metal precursor. Our results indicate that framework isomerism is controllable by adjusting the crystallization conditions. In comparison to their microporous and mesoporous counterparts, the hierarchically porous materials show obviously enhanced adsorption performance on a series of bulky molecules including dye, enzyme, and metal–organic polyhedron.