Fabrication of Hierarchical Macroporous ZIF-8 Monoliths Using High Internal Phase Pickering Emulsion Templates

The shaping of metal-organic frameworks (MOFs), referring to the integration of small sub-millimeter MOF crystals into bulk samples of desired size and shape, is an important step in the practical use of this class of porous material in many applications. Herein, we demonstrate for the first time the fabrication of hierarchical 3D MOF monoliths in situ within an MOF particle-stabilized high internal phase emulsion (HIPE). In this approach, a subfamily MOF (ZIF-8) is selected as the sole Pickering emulsion stabilizer for an oil-in-water (O/W) HIPE. With 2-methylimidazole and zinc nitrate in the continuous phase, ZIF-8 is formed in the emulsion to "bond" the ZIF-8 particles fabricating a ZIF-8 monolith without the addition of a polymer or polymerization of monomers. Freeze-drying of the HIPE produces a 3D ZIF-8 monolith. The monolith is packed into a chromatography column to test its catalytic performance as a flow-through catalyst in the Knoevenagel reaction. The monolith catalyst exhibits very high catalytic efficiency. Almost all the reaction mixture transforms to product within 2 min. Besides, the 3D ZIF-8 monolith showed excellent performance as an oil absorbent in oil-water separation. It achieved an absorption equilibrium of oil in less than 5 s, much faster than traditional high oil absorption materials.