RT info:eu-repo/semantics/article
T1 Unravelling the origin of enhanced CO2 selectivity in amine-PIM-1 during mixed gas permeation
A1 Rizzuto, Carmen
A1 Nardelli, Francesca
A1 Monteleone, Marcello
A1 Calucci, Lucia
A1 Bezzu, Caterina Grazia
A1 Carta, Mariolino
A1 Tocci, Elena
A1 Esposito, Elisa
A1 De Luca, Giorgio
A1 Comesaña Gandara, Bibiana
A1 McKeown, Neil Bruce
A1 Sayginer, Bekir
A1 Budd, Peter M.
A1 Jansen, Johannes Carolus
A1 Fuoco, Alesio
K1 Química física
K1 Ciencia de los materiales
K1 Contaminación atmosférica
K1 Tecnología química
K1 3303 Ingeniería y Tecnología Químicas
K1 3312 Tecnología de Materiales
K1 2304 Química Macromolecular
AB 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.
PB Royal Society of Chemistry
SN 2050-7488
YR 2025
FD 2025
LK https://uvadoc.uva.es/handle/10324/82690
UL https://uvadoc.uva.es/handle/10324/82690
LA eng
NO Journal of Materials Chemistry A, 2022, vol. 13, p. 17865-17876.
NO Producción Científica
DS UVaDOC
RD 05-mar-2026