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Stimuli-responsive Pickering emulsions are recently being progressively utilized as advanced catalyzed systems for green and sustainable chemical conversion. Hierarchically porous metal–organic frameworks (H-MOFs) are regarded as promising candidates for the fabrication of Pickering emulsions because of the features of tunable porosity, high specific surface area and structure diversity. However, CO₂-switchable Pickering emulsions formed by hierarchically porous zirconium-based MOFs have never been seen. In this work, a novel kind of the amine-functionalized hierarchically porous UiO-66-(OH)₂ (H-UiO-66-(OH)₂) has been developed using a post-synthetic modification of H-UiO-66-(OH)₂ by (3-aminopropyl)trimethoxysilane (APTMS), 3-(2-aminoethylamino)propyltrimethoxysilane (AEAPTMS) and 3-[2-(2-aminoethylamino)ethylamino]propyl-trimethoxysilane (AEAEAPTMS), and employed as emulsifiers for the construction of Pickering emulsions. It was found that the functionalized H-UiO-66-(OH)₂ could stabilize a mixture of toluene and water to give an emulsion even at 0.25 wt % content. Interestingly, the formed Pickering emulsions could be reversibly transformed between demulsification and re-emulsification with alternate addition or removal of CO₂. Spectral investigation indicated that the mechanism of the switching is attributed to the reaction of CO₂ with amino silane on the MOF and the generation of hydrophilic salts, leading to a reduction in MOF wettability. Based on this strategy, a highly efficient and controlled Knoevenagel condensation reaction has been gained by using the emulsion as a mini-reactor and the emulsifier as a catalyst, and the coupling of catalysis reaction, product isolation and MOF recyclability has become accessible for a sustainable chemical process.