Fabrication of Hierarchical Quaternary Architectures of Metal-Organic Frameworks through Programmed Transformation

A new method to construct hierarchical architectures has been developed by programmed transformation of metal-organic frameworks (MOFs). A MOF precursor was fabricated by reaction of Cu(OAC)₂ and 2,5-dihydroxyterephthalic acid (H₄DOBDC), which could perform transformation in pure methanol solvent and the sodium dodecyl benzene sulfonate (SDBS) solution of methanol, respectively. Interestingly, two kinds of immersion solutions could induce the transformation of the MOF precursor into MOF-74, which resulted in different morphologies: nanoneedles for the methanol and nanosheets for the SDBS. Herein, nanosheets-mesorods-microcuboid hierarchical quaternary architectures of MOF have been successfully achieved by sequential immersion of the precursor in two kinds of transformation solutions, which demonstrates well-defined hierarchy from the nanoscale to mesoscale to microscale. A unique hierarchical architecture could be recognized as quaternary structures, taking the MOF unit cell as the primary structure, the nanosheets as the secondary structure, the mesorods as the tertiary structure, and the microcuboid as the quaternary structure. Our study indicated the potential of programmed transformation between MOFs in the construction of hierarchical architectures, offering a new approach to sophisticated materials.