Generation of Hierarchical Pores in Metal-Organic Frameworks by Introducing Rigid Modulator

The fabrication of hierarchically porous metal-organic frameworks (HP-MOFs) that combine tunable mesopore sizes with high stability is highly desired but remains a technical challenge. Herein, a facile and versatile "rigid modular-assisted defect formation" strategy has been developed to transform microporous MOFs into their corresponding HP-MOFs. By controlling the modulator dose and acid amount, the pore size and mesopore percentage can be finely regulated. Based on the hierarchical pores, the mass transfer of molecules with large sizes is significantly promoted. As a result, the representative HP-UiO-66-NH2-OTf, decorated with a trifluoromethanesulfonate (OTf) group to enhance Lewis acidity, exhibits excellent activity and selectivity in tandem catalysis, far superior to pristine UiO-66-NH2. This work provides a novel strategy to the general synthesis of stable HP-MOFs. [GRAPHICS] .