An ab initio study of ionic liquid silver complexes as carriers in facilitated olefin transport membranes

Liquid phase isoprene/n-pentane mixtures can be separated through the use of facilitated transport membranes containing complexes of silver ions with an ionic liquid (IL). 1-Butyl-3-methyl imidazolium tetrafluoroborate and zwitterion-type imidazolium compounds containing covalently-bound sulfonate groups form complexes with AgX (X = BF4, NO3, and ClO4). Facilitated isoprene transport has been observed with selectivities that depend on the counteranion of the silver salt. The facilitated transport phenomena of the olefin and IL/silver complexes were investigated theoretically by calculating their complexation energies (i.e., the energy of formation of the silver complexes with the olefin) with the density functional theory method. Among polymer/silver salt systems, the polymer/AgBF4 system has been found to be generally more favorable for facilitated olefin transport than the polymer/AgNO3 system because of the low lattice energy of AgBF4. However, there is a different trend for IL/AgX systems. This difference may arise because the positively charged components of the IL can interact with the anions of the silver salt, which changes the olefin complexation activity. For IL/AgX systems, the selectivity varies inversely with the complexation energy, which implies that the diffusion of the carrier may be the significant factor affecting isoprene/n-pentane separation, once the appropriate complexation has occurred between olefin molecules and the IL⋯silver complexes.