Ambient CO₂/N₂ Switchable Pickering Emulsion Emulsified by TETA-Functionalized Metal-Organic Frameworks

In recent years, metal-organic frameworks (MOFs) have been explored as emulsifiers for the fabrication of Pickering emulsions and then used for hybrid material synthesis and interface catalysis. Nevertheless, stimuli-responsive Pickering emulsions stabilized by MOFs have been rarely reported so far, although they are of great importance for fundamental research studies and practical applications. Herein, for the first time, triethylenetetramine (TETA)-functionalized MOFs (ZIF-90/TETA) have been designed, synthesized, and used for fabricating CO₂-/N₂-response Pickering emulsions. It is shown that even at the ZIF-90/TETA content of 0.25 wt %, the functional MOF can still efficiently emulsify n-hexane and water to form a high internal phase Pickering emulsion. Importantly, the Pickering emulsion can be easily and reversibly switched between emulsification and demulsification by bubbling of CO₂ and N₂ alternatively at atmospheric pressure. The possible mechanism of the CO₂/N₂ switchable emulsion is investigated by zeta potential, water contact angle, interfacial tension, ¹³C NMR spectroscopy, and an optical microscope. It is found that the acid-base reaction of CO₂ with TETA anchored on the surface of ZIF-90 leads to the production of hydrophilic ammonium bicarbonate and carbamate, which results in the emulsification of the Pickering emulsion. However, when N₂ is bubbled to remove CO₂, the reverse reaction takes place to cause the demulsification of the Pickering emulsion. Moreover, the CO₂/N₂ switchable Pickering emulsion has been successfully used as a microreactor for Knoevenagel reactions to demonstrate a highly efficient integration of chemical reaction, product separation, and ZIF-90/TETA recycling for a sustainable chemical process.