title: Enhancement of CO2Affinity in a Polymer of Intrinsic Microporosity by Amine Modification.
abstract: Nitrile groups in the polymer of intrinsic microporosity PIM-1 were reduced to primary amines using borane complexes. In adsorption experiments, the novel amine-PIM-1 showed higher CO2uptake and higher CO2/N2sorption selectivity than the parent polymer, with very evident dual-mode sorption behavior. In gas permeation with six light gases, the individual contributions of solubility and diffusion to the overall permeability was determined via time-lag analysis. The high CO2affinity drastically restricts diffusion at low pressures and lowers CO2permeability compared to the parent PIM-1. Furthermore, the size-sieving properties of the polymer are increased, which can be attributed to a higher stiffness of the system arising from hydrogen bonding of the amine groups. Thus, for the H2/CO2gas pair, whereas PIM-1 favors CO2, amine-PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.
authors.affiliation: School of Chemistry, University of Manchester , Manchester, M13 9PL, U.K.
authors.forename: Christopher R
authors.initials: CR
authors.lastname: Mason
authors.affiliation: School of Chemistry, University of Manchester , Manchester, M13 9PL, U.K.
authors.forename: Louise
authors.initials: L
authors.lastname: Maynard-Atem
authors.affiliation: School of Chemistry, University of Manchester , Manchester, M13 9PL, U.K.
authors.forename: Kane W J
authors.initials: KW
authors.lastname: Heard
authors.affiliation: School of Chemistry, University of Manchester , Manchester, M13 9PL, U.K.
authors.forename: Bekir
authors.initials: B
authors.lastname: Satilmis
authors.affiliation: School of Chemistry, University of Manchester , Manchester, M13 9PL, U.K.
authors.forename: Peter M
authors.initials: PM
authors.lastname: Budd
authors.affiliation: Department of Physical Chemistry, Institute of Chemical Technology , Technická 5, Prague 6, 166 28, Czech Republic.
authors.forename: Karel
authors.initials: K
authors.lastname: Friess
authors.affiliation: Department of Physical Chemistry, Institute of Chemical Technology , Technická 5, Prague 6, 166 28, Czech Republic.
authors.forename: Marek
authors.initials: M
authors.lastname: Lanc̆
authors.affiliation: Institute on Membrane Technology (ITM-CNR), Via P. Bucci, cubo 17/C, 87036 Rende (CS), Italy.
authors.forename: Paola
authors.initials: P
authors.lastname: Bernardo
authors.affiliation: Institute on Membrane Technology (ITM-CNR), Via P. Bucci, cubo 17/C, 87036 Rende (CS), Italy.
authors.forename: Gabriele
authors.initials: G
authors.lastname: Clarizia
authors.affiliation: Institute on Membrane Technology (ITM-CNR), Via P. Bucci, cubo 17/C, 87036 Rende (CS), Italy.
authors.forename: Johannes C
authors.initials: JC
authors.lastname: Jansen