Polymerizable deep eutectic solvents: Convenient reactive dispersion media for the preparation of novel multi-walled carbon nanotubes-based functional materials

Abstract

A new straightforward and green approach for the covalent functionalization of multi-walled carbon nanotubes (MWCNTs) was developed. This carbon nanostructure was efficiently derivatized by polymerizing proper deep eutectic monomers (DEM), a subclass of deep eutectic solvents (DES), based on a series of mono- and bis-vinyl imidazolium salts endowed with different functional groups (–OH, –NH2, –NH3+Br–) in the side chain or in the spacer. Herein, DEM systems played a triple role as convenient dispersion media for MWCNTs, efficient reactive systems, and also as structure-directing agents for the radical-initiated polymerization process onto the surface of MWCNTs. In addition, the new methodology allowed obtaining highly functionalized hybrid materials, as shown by thermogravimetric analyses, in short reaction times (<1h). Transmission electron microscopy (TEM) revealed that the polymeric network orderly develops along the surface of the nanotubes, which act as templating agent for both mono- and bis-vinyl imidazolium salts, despite the random nature of the polymerization process for the latter species. This new functionalization strategy of MWCNTs stands out for its environmentally friendly and time-saving nature leading to the formation of materials with significant potential for applications in a plethora of research fields. As a proof of their possible application, we tested these new hybrid materials as recoverable and recyclable catalysts for the conversion of CO2 into cyclic carbonates under solvent-free conditions, showing good catalytic performances, even in the absence of additional co-catalysts.