Hierarchical porous materials based on nanoscale metal-organic frameworks dominated with permanent interparticle porosity

• We develop a general strategy for construction of mesoporous MOFs (mesoMOFs).
• The mesoMOFs show hierarchical porosity with the interparticle mesopores.
• The permanent interparticle mesopores are based on the sufficiently small NMOFs.
• The mesopores are size-tunable and cover almost the all mesoscopic regime.
• The large mesopores can be used for immobilization of the biological molecules.

In order to extensively synthesize mesoporous metal-organic frameworks (mesoMOFs), we developed a strategy to construct permanent interparticle porosity based on nanoscale metal-organic frameworks (NMOFs). Using the strategy, we have attained a series of interparticle porosity dominated mesoMOFs (IPD-mesoMOFs) from six MOF-types with MIl-100, MIL-53, HKUST-1, DUT-5, DUT-4 and MIL-101(Cr) (termed as IPD-mesoMOF-1, -2, -3, -4, -5 and -6) structure, respectively. All members of this series are not only comparable to inorganic mesoporous materials to have the tunable mesopore apertures varying from a few nanometers to over a dozen nanometers, but also superior to the inorganic counterparts to remain hierarchical porosity with higher surface area (up to 2130 m2 g−1), larger mesopore volume (the highest to 2.59 cm3 g−1) and optional micro-porosity of diverse crystalline structures. The large mesopore apertures and rich carboxyl residues on the mesopore-walls also allow the IPD-mesoMOF series to accommodate large organic and inorganic molecules, especially to immobilize the bulky natural protein, such as, hemoglobin.

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