Issue 23, 2025

Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation

Abstract

Previously, it has been reported that amine-PIM-1, a polymer of intrinsic microporosity obtained by reduction of nitrile groups of PIM-1 to primary amine groups, shows enhanced CO2 selectivity during mixed gas permeation studies with respect to single gas measurements for gas pairs involving CO2. This distinct and potentially useful behaviour was ascribed to the affinity of CO2 for the polymer amine groups. Here, we demonstrate that enhanced selectivity originates from both CO2 physisorption and chemisorption. A combination of 13C and 15N solid-state NMR spectroscopic analyses of a CO2-loaded amine-PIM-1 membrane allowed the identification and quantitative determination of both chemisorbed and physisorbed species and the characterization of polymer-CO2 interactions. Experiments with 13C isotopically enriched CO2 unequivocally demonstrated the conversion of 20% of the NH2 groups into carbamic acids at 298 K and a CO2 pressure of 1 bar. Chemisorption was supported by the strong heat of CO2 adsorption for amine-PIM-1 that was estimated as 50 kJ mol−1. Molecular dynamics simulations with models based on the experimentally determined polymer structure gave a detailed description of intra- and interchain hydrogen bond interactions in amine-PIM-1 after chemisorption, as well as of the effect of chemisorption on polymer porosity and physisorption.

Graphical abstract: Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation

Supplementary files

Article information

Article type
Paper
Submitted
12 Dec 2024
Accepted
23 Apr 2025
First published
28 Apr 2025
This article is Open Access
Creative Commons BY license

J. Mater. Chem. A, 2025,13, 17865-17876

Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation

C. Rizzuto, F. Nardelli, M. Monteleone, L. Calucci, C. G. Bezzu, M. Carta, E. Tocci, E. Esposito, G. De Luca, B. Comesaña-Gándara, N. B. McKeown, B. Sayginer, P. M. Budd, J. C. Jansen and A. Fuoco, J. Mater. Chem. A, 2025, 13, 17865 DOI: 10.1039/D4TA08839E

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