Polymer nanosieve membranes for CO2-capture applications

Du, Naiying; Park, Ho Bum; Robertson, Gilles P.; Dal‐Cin, Mauro M.; Visser, Tymen; Scoles, Ludmila; Guiver, Michael D.

doi:10.1038/nmat2989

Cited by 743 publications

(564 citation statements)

References 31 publications

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“…[5] In particular, the latter polymers lie in the region of ultrahigh permeability (order of magnitude of 1000 Barrer for PIM-1 and 10000 Barrer for PTMSP) and low-medium CO 2 /CH 4 selectivity (around 18 for PIM-1 and around 4 for PTMSP). The solubility selectivity values reported range from 3 to 5 [13] for PIM-1, and from 2 to 3 in PTMSP, according to the pure gas solubility measurements. [14] The diffusivity selectivity is estimated to be around 5 for PIM-1 and slightly higher than unity (around 1.5) for PTMSP.…”

Section: Introductionmentioning

confidence: 93%

“…[18] The permselectivity CO 2 /CH 4 of a membrane functionalized with pendant tetrazole groups (TZPIM) decreases with the increasing feed pressure and, at the same time, does not reveal significant difference between the ideal and real permselectivity in those conditions. [13] The aim of the present work is to assess, in a wide range of compositions and pressures, the solubility properties of CO 2 /CH 4 mixtures absorbed in films of PIM-1. In particular, we study and determine the effect of mixture composition, pressure, second component fugacity and concentration on the solubility and solubility selectivity values, as well as on the deviation from the corresponding pure gas properties.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Introductionmentioning

confidence: 93%

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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“…Ethanol-treated PIM-1/CC3 (weight ratio 10:3) exhibits an extremely high CO 2 permeability (37,400 Barrer), an order of magnitude higher than, for example, tetrazole-modified PIM-1, [11] and within the range of values quoted for poly(1-trimethylsilyl-1-propyne) (PTMSP), [12] which was long considered the most permeable polymer. However, amorphous, glassy polymers such as PTMSP lose excess free volume, and hence permeability, rapidly over time.…”

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confidence: 89%

Nanoporous Organic Polymer/Cage Composite Membranes

et al. 2012

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There is an urgent need to develop efficient and economic CO 2 purification technologies to upgrade waste CO 2 to a reusable purity. Membrane-based separation processes are seen as one of the possible solutions to this problem. [1] For large-volume membrane applications, such as CO 2 recovery, high permeability is essential to minimize the membrane area, in combination with good selectivity.For membrane applications, high free-volume polymers [2] exhibit good processability, but they are prone to physical ageing. As transport depends on free volume, physical ageing leads to loss of permeability over time. [3] Porous crystalline solids can give good transport properties, but are less easily fabricated into mechanically stable membranes. Combinations of polymers with inorganic or metal-organic particles in composite or mixed-matrix membranes (MMMs) [4] may give synergistic enhancements in performance, but difficulties are encountered in achieving good dispersion within the membrane. [5] Largely unexplored is the potential of purely organic dispersed phases, comprising only C, H, N, and O atoms, which should show better compatibility with a continuous polymeric matrix and which offer scope for tailoring the physical properties through organic synthesis.Herein we demonstrate a novel route to MMMs in which the dispersed phase is generated by in situ crystallization of porous organic cage molecules from a single homogeneous, molecular solution. The incorporation of porous organic cages significantly enhances permeability, whereas chemically reduced, nonporous cage molecules have an opposite effect.We also compare the gas separation performance of membranes where crystals were generated by in situ crystallization against membranes where pre-formed nanocrystals were dispersed by co-casting with the polymer.The crystallizable precursor is CC3 (Figure 1 a), which has approximately triangular windows of effective diameter 0.6 nm, which is large enough to admit gases and small organic molecules. [6] The imine-linked CC3 was prepared as a powder with a Brunauer-Emmett-Teller (BET) surface area of 620 m 2 g À1 , based on N 2 adsorption at 77 K. A suspension of racemic CC3 nanocrystals (nanoCC3) in dichloromethane was also prepared. The isolated nanocrystalline CC3 had a BET surface area of 770 m 2 g À1 . To examine the importance of rigidity and shape persistence in CC3, its reduced amine form was prepared. Complete reduction with sodium borohydride of all 12 imine linkages in CC3 results in transformation to a much less rigid dodecaamine molecule (redCC3), which does not exhibit permanent porosity in the solid state and which is amorphous in powder form. 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane and 1,4-dicyanotetrafluorobenzene by a step polymerization involving a double aromatic nucleophilic substitution. c) SEM image of a cross-section of a PIM-1/CC3 composite membrane (weight ratio 10:2).

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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%

“…CO 2 discharge into the atmosphere has risen with the increasing consumption of fossil fuels 3 , adversely affecting the fight against global warming 26 . CO 2 scrubbing by ethanolic aqueous amines 27 is yet to be challenged as a practical solution, despite the claims that numerous porous solids have better physicochemical properties and lower energy penalties 2,28 .…”

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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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Polymer nanosieve membranes for CO2-capture applications

Cited by 743 publications

References 31 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)

Nanoporous Organic Polymer/Cage Composite Membranes

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

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