How Do Deep Eutectic Solvents Form Porous Liquids? The Example of Methyltriphenylphosphonium Bromide: Glycerol and ZIF-8.

Abstract

Porous liquids are new materials that provide permanent porosity in the liquid phase through the dispersion of nanoporous solid particles in a bulky solvent. Herein, we aim at understanding how new sustainable solvents such as deep eutectic solvent (DES) can be used to form porous stable suspensions for the capture of gases of interest for sustainable chemistry. The properties of an ionic DES, methyltriphenylphosphonium bromide/glycerol in a 1:3 molar composition, and its behavior at the interface with a metal-organic framework (MOF), ZIF-8, are here investigated by polarizable molecular dynamics simulations. The structural and dynamic properties of the DES are analyzed in the bulk liquid and in the interfacial regions with the MOF, namely, in the accessible cavities exposed at the surface. The porosity of the suspension is maintained, and it is caused not only by the Coulomb cohesive energy between cations and anions, which prevents the small anions from entering the pores, but also by the glycerol molecules not penetrating the small aperture of the ZIF-8 structure. This was further verified by simulating a system composed of glycerol and ZIF-8. Simulations with CO2 show its partition between the DES and the MOF, with higher concentrations registered in the MOF cavities.