TY - JOUR
T1 - Enhancement of CO2 affinity in a polymer of intrinsic microporosity by amine modification
AU - Mason, Christopher R.
AU - Maynard-Atem, Louise
AU - Heard, Kane W.J.
AU - Satilmis, Bekir
AU - Budd, Peter M.
AU - Friess, Karel
AU - Lancì, Marek
AU - Bernardo, Paola
AU - Clarizia, Gabriele
AU - Jansen, Johannes C.
PY - 2014/2/11
Y1 - 2014/2/11
N2 - 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 CO2 uptake and higher CO2/N 2 sorption 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 CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 permeability 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/CO2 gas pair, whereas PIM-1 favors CO 2, amine-PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.
AB - 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 CO2 uptake and higher CO2/N 2 sorption 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 CO2 affinity drastically restricts diffusion at low pressures and lowers CO2 permeability 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/CO2 gas pair, whereas PIM-1 favors CO 2, amine-PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.
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U2 - 10.1021/ma401869p
DO - 10.1021/ma401869p
M3 - Article
AN - SCOPUS:84894188088
SN - 0024-9297
VL - 47
SP - 1021
EP - 1029
JO - Macromolecules
JF - Macromolecules
IS - 3
ER -