Templated fabrication of hierarchically porous metal–organic frameworks and simulation of crystal growth

Hierarchically porous metal–organic frameworks (MOFs) have recently emerged as a novel crystalline hybrid material with tunable porosity. Many efforts have been made to develop hierarchically porous MOFs, yet their low-energy fabrication remains a challenge and the underlying mechanism is still unknown. In this study, the rapid fabrication of two hierarchically porous MOFs (Cu-BTC and ZIF-8) was carried out at room temperature and ambient pressure for 10 min using a novel surfactant as the template in a (Cu, Zn) hydroxy double salt (HDS) solution, where the (Cu, Zn) HDS accelerated the nucleation of crystals and the anionic surfactants served as templates to fabricate mesopores and macropores. The growth mechanism of hierarchically porous MOFs was analyzed via mesodynamics (MesoDyn) simulation, and then the synthetic mechanism of hierarchically porous MOFs at the molecular level was obtained. The as-synthesized hierarchically porous Cu-BTC showed a high uptake capacity of 646 mg g(−1), which is about 25% higher as compared with microporous Cu-BTC (516 mg g(−1)) for the capture of toluene. This study provides a theoretical basis for the large-scale fabrication of hierarchically porous MOFs and offers a reference for the understanding of their synthetic mechanism.