Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

Christopher Mason; Louise Maynard-Atem; Kane Heard; Bekir Satilmis; Peter M Budd; Karel Friess; Marek Lanc; Paolo Bernardo; Gabriele Clarizia; Johannes C Jansen

doi:10.1021/ma401869p

Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

Christopher Mason, Louise Maynard-Atem, Kane Heard, Bekir Satilmis, Peter M Budd, Karel Friess, Marek Lanc, Paolo Bernardo, Gabriele Clarizia, Johannes C Jansen

Research output: Contribution to journal › Article › peer-review

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 CO2 uptake and higher CO2/ N2 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 timelag 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 CO2, amine−PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.

Original language	English
Pages (from-to)	1021-1029
Number of pages	8
Journal	Macromolecules
Volume	47
DOIs	https://doi.org/10.1021/ma401869p
Publication status	Published - 24 Jan 2014

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@article{51ae9913e1ba438886fb85bc25d027d5,

title = "Enhancement of CO2 Affinity 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 CO2 uptake and higher CO2/ N2 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 timelag 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 CO2, amine−PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.",

author = "Christopher Mason and Louise Maynard-Atem and Kane Heard and Bekir Satilmis and Budd, {Peter M} and Karel Friess and Marek Lanc and Paolo Bernardo and Gabriele Clarizia and Jansen, {Johannes C}",

year = "2014",

month = jan,

day = "24",

doi = "10.1021/ma401869p",

language = "English",

volume = "47",

pages = "1021--1029",

journal = "Macromolecules",

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publisher = "American Chemical Society",

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TY - JOUR

T1 - Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

AU - Mason, Christopher

AU - Maynard-Atem, Louise

AU - Heard, Kane

AU - Satilmis, Bekir

AU - Budd, Peter M

AU - Friess, Karel

AU - Lanc, Marek

AU - Bernardo, Paolo

AU - Clarizia, Gabriele

AU - Jansen, Johannes C

PY - 2014/1/24

Y1 - 2014/1/24

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/ N2 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 timelag 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 CO2, 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/ N2 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 timelag 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 CO2, amine−PIM-1 shows permselectivity toward H2, breaking the Robeson 2008 upper bound.

U2 - 10.1021/ma401869p

DO - 10.1021/ma401869p

M3 - Article

SN - 0024-9297

VL - 47

SP - 1021

EP - 1029

JO - Macromolecules

JF - Macromolecules

ER -

Enhancement of CO2 Affinity in a Polymer of Intrinsic Microporosity by Amine Modification

Abstract

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