Effective enhancement of selectivities and capacities for CO₂ over CH₄ and N₂ of polymers of intrinsic microporosity via postsynthesis metalation

Abstract

A series of metalized C‐PIM‐M (M = Na+, Mg2+, Al3+, PIMs = polymers of intrinsic microporosity) materials were prepared from a carboxyl‐functionalized PIM (C‐PIMs). The C‐PIM‐Na exhibited a high CO2 adsorption capacity of 2.44 mmol/g and extreme low CH4 uptake of 0.28 mmol/g at 273 K and 101 kPa among three metallated PIMs. It showed remarkably high CO2/CH4 and CO2/N2 selectivities at both 273 and 293 K due to an advantageous pore‐blocking effect of Na+ cation.

Breakthrough applications of porous organic materials for membrane-based CO2 separation: a review

“…Ling et al fabricated a series of metalized PIMs from a carboxyl-based functionalized PIM (C-PIM). They corroborated that C-PIM-Na demonstrated the greatest CO 2 capture capacity of 2.44 mmol g -1 compared to other metalized PIMs ( Ling et al, 2020 ). Stanovsky et al conducted an experiment with the aim of purifying flue gas applying the ultra-permeable tetramethyl tetrahydronaphthalene - based PIM coupled with bicyclic triptycene.…”

“…Ling et al fabricated a series of metalized PIMs from a carboxyl-based functionalized PIM (C-PIM). They corroborated that C-PIM-Na demonstrated the greatest CO 2 capture capacity of 2.44 mmol g -1 compared to other metalized PIMs (Ling et al, 2020) The development of the membrane separation industry, 1960-2020. Adopted from (Baker, 2004;.…”

Polymers of Intrinsic Microporosity Based on Dibenzodioxin Linkage: Design, Synthesis, Properties, and Applications

“…For example, the PIM-1-carboxylic acid can be metalated with NaOH, which can further be transmetalated with Mg 2 + or Al 3 + . [78] Metalation of the same PIM has been performed with Zn 2 + , Mg 2 + and Ag + by direct treatment of the PIM with corresponding metal nitrates in ethanol medium. [79] PIM-1-carboxylic acid upon reaction with thionyl chloride, triethyl amine and dithiothreitol results in thiolethyl functionalization.…”

“…The functionalities introduced through PSM, for example, carboxylic acid, amine and amidoxime, can be further reacted to introduce new functional groups. For example, the PIM‐1‐carboxylic acid can be metalated with NaOH, which can further be transmetalated with Mg 2+ or Al 3+ [78] . Metalation of the same PIM has been performed with Zn 2+ , Mg 2+ and Ag + by direct treatment of the PIM with corresponding metal nitrates in ethanol medium [79] .…”