Abstract
A major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.
Highlights
A major goal of metal–organic framework (MOF) research is the expansion of pore size and volume
The pore sizes of most reported MOFs are limited to micropore range, which is suitable for the adsorption and separation of small guest molecules, such as gas, small organic molecules and coordination complexes
This method only proves to be effective for certain MOF systems, whereas in most cases, elongated linkers often result in interpenetrated structures[10] or undesired topologies[11], which restricts the pore size and porosity
Summary
A major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. The robust AZDC linkers can support the framework, whereas the CBAB can be removed by acid treatment to increase the MOF porosity. The exchange ratio, defined as moles of CBAB divided by the moles of organic linkers (CBAB þ AZDC) in PCN-160, was calculated based on the AZDC concentration in the solution and the weight of the MOF material, which matches well with the 1H-NMR result of digested samples.
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