Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials

Budd, Peter M.; Ghanem, Bader S.; Makhseed, Saad; McKeown, Neil B.; Msayib, Kadhum J.; Tattershall, Carin E.

doi:10.1039/b311764b

Cited by 1,181 publications

(964 citation statements)

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“…[16][17] For example, a permselectivity of ca. 12-25 was reported for the equimolar carbon dioxide/methane mixture being separated on a PIM-1 membrane at 25 ºC up to the pressure of ca.…”

Section: Introductionmentioning

confidence: 99%

Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Vopička

Angelis

et al. 2014

Journal of Membrane Science

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The individual solubility of CH 4 and CO 2 from binary gas mixtures was measured at 35 °C and up to 35 bar in a polymer of intrinsic microporosity (PIM-1), at different compositions of the gas phase (from 0 to 50 mol% of CO 2 ). The experiments were conducted on a pressure-decay apparatus equipped with a gas chromatograph, allowing a highly flexible measuring procedure. The gas solubility was plotted versus gas phase composition, total pressure, gas fugacity and second gas concentration. The mixed gas solubility of both species, CH 4 and CO 2 , is lower than the pure gas value at the same fugacity, but the reduction of methane solubility due to the presence of CO 2 is generally more significant. Such behavior is due to the fact that CO 2 has normally higher solubility than methane: indeed the depression of the solubility coefficient with respect to the pure gas value is similar for both gases, when reported at the same concentration of the second gas.The real, mixed gas solubility selectivity is in general higher than the ideal value calculated from pure gas behavior. The ratio between real and ideal solubility selectivity increases with CO 2 concentration in the membrane, according to a single mastercurve, reaching a maximum value of 4, and increases also with the ratio between CO 2 and CH 4 concentration in the membrane. In particular, as in the case of other glassy polymers, the real solubility selectivity of CO 2 over CH 4 is higher than the ideal value if c(CO 2 )>c(CH 4 ), and it is lower than the ideal value if the opposite condition holds true. Such behavior occurs because the competition for sorption is normally less effective on the more abundant penetrant in the polymer. A selectivity-solubility performance plot can be drawn for this system.

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“…[16][17] For example, a permselectivity of ca. 12-25 was reported for the equimolar carbon dioxide/methane mixture being separated on a PIM-1 membrane at 25 ºC up to the pressure of ca.…”

Section: Introductionmentioning

confidence: 99%

Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Vopička

Angelis

et al. 2014

Journal of Membrane Science

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“…N anoporous polymers [1][2][3][4][5][6] (pore width 1-100 nm) show considerable promise in gas capture 7 , storage 8 and separation technologies 9 , and as nano-filtration membranes 3 , catalysts 10 , drug delivery vehicles 11 and charge carriers 12,13 . These mostly organic polymers can easily be designed and constructed via facile synthetic protocols.…”

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confidence: 99%

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

et al. 2013

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Post-combustion CO 2 capture and air separation are integral parts of the energy industry, although the available technologies remain inefficient, resulting in costly energy penalties. Here we report azo-bridged, nitrogen-rich, aromatic, water stable, nanoporous covalent organic polymers, which can be synthesized by catalyst-free direct coupling of aromatic nitro and amine moieties under basic conditions. Unlike other porous materials, azo-covalent organic polymers exhibit an unprecedented increase in CO 2 /N 2 selectivity with increasing temperature, reaching the highest value (288 at 323 K) reported to date. Here we observe that azo groups reject N 2 , thus making the framework N 2 -phobic. Monte Carlo simulations suggest that the origin of the N 2 phobicity of the azo-group is the entropic loss of N 2 gas molecules upon binding, although the adsorption is enthalpically favourable. Any gas separations that require the efficient exclusion of N 2 gas would do well to employ azo units in the sorbent chemistry.

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“…4,7,8 In general, higher membrane gas permeability can be obtained by significantly increasing free volume by the introduction of intrinsic microporosity and enhancing the rigidity of polymer chains. 9−12 The rigid and contorted macromolecular chain architecture of polymers of intrinsic microporosity (PIMs), 9,13−25 (e.g., the notable PIM-1 14 is the archetype of this class of materials) provides a desirable combination of poor chain packing and high chain rigidity, giving excellent gas permeability and moderate selectivity, with some PIMs exceeding the Robeson's upper bound for some commercially important gas pairs. 9,24,25 In conventional PIMs, the rigidity of polymer chains is endowed by the fused-ring dibenzodioxane moieties and high free volume is imparted by the sites of contortion, such as spiro-centers (spirobisindane unit or spirobifluorene unit).…”

Section: ■ Introductionmentioning

confidence: 99%

Intrinsically Microporous Soluble Polyimides Incorporating Tröger’s Base for Membrane Gas Separation

et al. 2014

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Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials

Abstract: Microporous materials can be derived directly from soluble polymers whose randomly contorted shapes prevent an efficient packing of the macromolecules in the solid state.

Cited by 1,181 publications

References 9 publications

Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Mixed gas sorption in glassy polymeric membranes: II. CO2/CH4 mixtures in a polymer of intrinsic microporosity (PIM-1)

Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous covalent organic polymers

Intrinsically Microporous Soluble Polyimides Incorporating Tröger’s Base for Membrane Gas Separation

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