Deep-Eutectic Solvents as MWCNT Delivery Vehicles in the Synthesis of Functional Poly(HIPE) Nanocomposites for Applications as Selective Sorbents

We report an alternative green strategy based on deep-eutectic solvents (DES) to deliver multiwalled carbon nanotubes (MWCNTs) for a bottom-up approach that allows for the selective interfacial functionalization of nonaqueous poly(high internal phase emulsions), poly(HIPEs). The formation and polymerization of methacrylic and styrenic HIPEs were possible through stabilization with nitrogen doped carbon nanotube (CN_X) and surfactant mixtures using a urea-choline chloride DES as a delivering phase. Subtle changes in CN_X concentration (less than 0.2 wt % to the internal phase) produced important changes in the macroporous monolith functionalization, which in turn led to increased monolith hydrophobicity and pore openness. These materials displayed great oleophilicity with water contact angles as high as 140° making them apt for biodiesel, diesel, and gasoline fuel sorption applications. Overall, styrene divinylbenzene (StDvB) based poly(HIPEs) showed hydrophobicity and fuel sorption capacities as high as 4.8 (g/g). Pore hierarchy, namely pore openness, regulated sorption capacity, and sorption times where greater openness resulted in faster sorption and increased sorption capacity. Monoliths were subject to 20 sorption-desorption cycles demonstrating recyclability and stable sorption capacity. Finally, CN_X/surfactant hybrids made it possible to reduce surfactant requirements for successful HIPE formation and stabilization during polymerization. All poly(HIPEs) retained acceptable conversion as a function of CN_X loading nearing 90% or better with thermal stability as high as 283 °C.