CO2-Switchable Hierarchically Porous Zirconium-Based MOF-Stabilized Pickering Emulsions for Recyclable Efficient Interfacial Catalysis

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.