Tailored carbon dioxide capacity in carboxylate-based ionic liquids.

ABSTRACT

We have used a library of thermally stable tetraalkylphosphonium carboxylate ionic liquids that were easily prepared from available carboxylic acids. Depending on the pKa in water of the precursor acids, the resulting ionic liquids either dissolve or reversibly chemically absorb CO2, with some exhibiting notable gas capacities, reaching a CO2 mole fraction of 0.2 at 1 bar and 343 K. While equilibrium constants and ionic liquid capacities generally correlate with the pKa of the acids, certain exceptions underscore the influence of liquid structure and physical properties of the ionic liquids, elucidated through molecular dynamics simulations and density functional theory calculations. Unlike the trends observed in other CO2-absorbing ILs, phosphonium carboxylates do not experience increased viscosity upon gas absorption; instead, enhanced diffusivities are observed, facilitating efficient gas-liquid transfer.