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WO2022220743A1 - Membranes composites à couches minces, leurs procédés de fabrication et leurs utilisations - Google Patents

Membranes composites à couches minces, leurs procédés de fabrication et leurs utilisations Download PDF

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WO2022220743A1
WO2022220743A1 PCT/SG2022/050202 SG2022050202W WO2022220743A1 WO 2022220743 A1 WO2022220743 A1 WO 2022220743A1 SG 2022050202 W SG2022050202 W SG 2022050202W WO 2022220743 A1 WO2022220743 A1 WO 2022220743A1
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cof
film
thin film
composite membrane
charged
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Dan Zhao
Yunpan YING
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National University of Singapore
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/381—Polyvinylalcohol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • B01D71/383—Polyvinylacetates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/52—Polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B01D71/80—Block polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Definitions

  • the present invention relates, in general terms, to thin film composite membranes and its uses thereof.
  • the thin film composite membrane comprises a covalent organic framework film which can be ultrathin and be used as a membrane gutter layer for high-permeance CO2 capture.
  • CO2 carbon dioxide
  • GPU gas permeation units
  • 1 GPU 10 s cm 3 (STP)'Cm _2 'S 1 'CmHg 1 )
  • CO2/N2 mixture separation selectivity > 20
  • TFCMs Thin film composite membranes
  • a TFCM architecture generally consists of three layers: (i) a bottom porous support to provide the overall mechanical strength, (ii) a top separation layer to separate gases, and (iii) an intermediate gutter layer between them to prevent the penetration of the top separation layer into the bottom porous support and reduce the gas transport resistance.
  • the overall gas transport resistance can be expressed as Rtoi R P + R g + Rs, where Rtoi is the total transport resistance, R P is the resistance of the porous support layer, R g is the resistance of the intermediate gutter layer, and R s is the resistance of the separation layer.
  • decreasing membrane thickness is the most straightforward method to reduce transport resistance and, therefore, increase permeance.
  • the resistance from the support layer is negligible in comparison with that from the gutter layer and selective layer, researchers mainly focused on decreasing the resistance from the last two layers. Historically, thickness reduction of the top separation layer has fueled rapid progress of TFCMs. However, further reduction of the separation layer without sacrificing the membrane integrity remains technically challenging.
  • the present invention provides a thin film composite membrane, comprising: a) a separation layer; and b) a gutter layer adjacent to the separation layer; wherein the gutter layer comprises a covalent organic framework (COF) film; and wherein the COF film has a thickness of about 10 nm to about 300 nm.
  • COF covalent organic framework
  • wholly organic, orientated, two-dimensional covalent organic framework (COF) films are found to have a good pore size, intrinsic porosity, small transport resistance, good compatibility with polymer matrix, good anti-aging capability and high stability.
  • Crosslinked polymer (such as via photo initiation) can be deposited compatiblely on the COF film in the gutter layer with a thickness as thin as 55 nm, an ultrathin thickness that traditional gutter layers are challenging to attain.
  • thin film composite membrane realizes high CO2 capture performance with CO2 permeance of 1843 gas permeation units (GPU) and CO2/N2 separation selectivity of 28.2, which displays unique advantages over other gutter layer- based TFCMs and meets the performance target for CO2 capture (CO2 permeance > 1000 GPU, CO2/N2 selectivity > 20).
  • the thin film composite membrane has a small transport resistance, good compatibility with polymer matrix, good anti-aging capability and high stability. Additionally, it is easy to control the thickness of the COF films and to optimize the transport resistance.
  • the COF film is monocrystalline.
  • the COF film has a c-orientation.
  • the COF film comprises a COF selected from COF-LZU1, TpPa- SOsH, TpTGci, CTF-1, COF-JLU2, COF-5, N3-COF, NUS-2, NUS-3, NUS-14, N-COF, P- COF, T-COF, or a combination thereof.
  • the COF film has a roughness parameter R q of about 0.70 nm to about 0.75 nm.
  • the COF film has a roughness parameter R a of about 0.50 nm to about 0.55 nm.
  • the COF film has a pore size of about 0.7 nm to about 3 nm.
  • the COF film has a resistance of less than about 8% relative to an overall membrane resistance of the thin film composite membrane.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 20% at a relative humidity of less than 85%. In some embodiments, the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 50% at a temperature of about 290K to about 350K.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 20% at a pressure of less than about 5 bar.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 10% for at least one month.
  • the separation layer comprises Pebax 1657, cross linked PEG, Pebax 2533, Pebax 1074, Matrimid 5218, polysulfone, poly(vinyl alcohol), poly(vinyl acetate), or a combination thereof.
  • the separation layer is characterised by a thickness of about 40 nm to about 200 nm.
  • the thin film composite membrane when the separation layer comprises Pebax 1657, has a CO2 permeance of about 23,000 GPU to about 30,000 GPU and a CO2/N2 selectivity of about 1 to about 2.
  • the thin film composite membrane when the separation layer comprises cross linked PEG, has a CO2 permeance of about 1800 GPU to about 2000 GPU and CO2/N2 selectivity of about 27 to about 30.
  • the present invention also provides a thin film composite membrane, wherein the gutter layer comprises a covalent organic framework (COF) film having a thickness of about 10 nm to about 300 nm; and wherein the separation layer comprises at least a first charged COF film and a second charged COF film.
  • COF covalent organic framework
  • the first charged COF film is a negatively charged COF film.
  • the first charged COF film is functionalised with sulfonic acid and/or carboxyl moieties.
  • the second charged COF film is a positively charged COF film.
  • the second charged COF film is functionalised with guanidinium or iminyl and/or ethidium halide moieties.
  • the present invention also provides a method of fabricating a thin film composite membrane comprising a separation layer and a gutter layer adjacent to the separation layer, wherein the gutter layer comprises a covalent organic framework (COF) film, the method comprising: interfacially reacting a mixture of a first subunit and a second subunit in order to form a covalent organic framework (COF) film; wherein the COF film has a thickness of about 10 nm to about 300 nm.
  • COF covalent organic framework
  • the first subunit has at least two amine moieties.
  • the first subunit is selected from p-phenylenediamine (PDA), 2,5-diaminobenzenesulfonic acid, hydrazine hydrate, benzene-1, 3, 5-triamine or a combination thereof.
  • PDA p-phenylenediamine
  • 2,5-diaminobenzenesulfonic acid 2,5-diaminobenzenesulfonic acid
  • hydrazine hydrate benzene-1, 3, 5-triamine or a combination thereof.
  • the second subunit has at least two acyl moieties.
  • the second subunit is selected from 1,3,5-triformylbenzene (TFB), 2,4,6-trihydroxybenzene-l,3,5-tricarbaldehyde, 1,4-benzenedicarboxaldehyde or a combination thereof.
  • TFB 1,3,5-triformylbenzene
  • 2,4,6-trihydroxybenzene-l,3,5-tricarbaldehyde 1,4-benzenedicarboxaldehyde or a combination thereof.
  • a molar ratio of the first subunit to the second subunit is about 10:1 to about 1:10.
  • the interfacial reaction is performed for up to 5 days.
  • the interfacial reaction is performed at room temperature and pressure.
  • the present invention also provides a method of fabricating a thin film composite membrane, wherein the gutter layer comprises a covalent organic framework (COF) film having a thickness of about 10 nm to about 300 nm, and wherein the separation layer comprises at least a first charged COF film and a second charged COF film, the method comprising: a) interfacially reacting a mixture of a first subunit and a second subunit in order to form the COF film; b) interfacially reacting a mixture of a third subunit and fourth charged subunit in order to form the first charged COF film adjacent to the COF film; and c) interfacially reacting a mixture of a fifth subunit and sixth charged subunit in order to form the second charged COF film adjacent to the first charged COF film; and d) optionally repeating step a) and/or step b) at least one more time.
  • COF covalent organic framework
  • FIG. 1 is a schematic of preparation of thin film composite membranes (TFCMs) with COF film as the gutter layer for CO2 capture;
  • FIG. 2 illustrates atomic force microscopy (AFM) results of interfacially crystalized COF-LZU1 films of certain embodiments
  • Figure 3 shows structure and crystallinity of interfacially crystalized COF-LZU1 films of certain embodiments
  • Figure 4 shows morphologies of the thin film composite membranes based on COF-LZU1 gutter layer of certain embodiments
  • Figure 5 shows attenuated total reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR) and X-ray Photoelectron Spectroscopy (XPS) results of the thin film composite membranes based on COF-LZU1 gutter layer of certain embodiments;
  • Figure 6 illustrates the effect of the COF gutter layer thickness on the overall C02/N2 separation performance of Pebax/COF-LZUl/PAN membranes of certain embodiments
  • Figure 7 illustrates the effect of the Pebax concentration on the overall C02/N2 separation performance of Pebax/COF-LZUl/PAN membranes of certain embodiments
  • Figure 8 shows a comparison of CO2/N2 separation performance of embodiments of the present invention with other TFCMs;
  • Figure 9 shows long-term operational stability of XLPEG/COF-LZU1/PAN membrane for CO2 capture under various conditions of certain embodiments; and Figure 10 plots the long-term stability of XLPEG/COF-LZU1/PAN membrane.
  • the operational stability was studied by exposing the membrane to lab conditions (room temperature, in the air) for four weeks and tracking its gas separation performance every week;
  • Figure 11 plots the effect of pressure difference on CO2/N2 separation performance of XLPEG/COF-LZU1/PAN membrane
  • Figure 12 plots the effects of COF gutter layer incorporation on the performance of the TFCMs
  • Figure 13 is a schematic of the fabrication and gas separation application of the ultrathin COF membranes with narrowed apertures using a multi-interfacial engineering strategy.
  • TFCMs Thin film composite membranes
  • Traditional and recently developed gutter layer materials face some issues such as physical aging, thickness-dependent permeability, instability, or poor compatibility.
  • gutter layer properties can be critical for developing TFCMs with attractive CO2 capture performance.
  • Ideal gutter layers should have low transport resistance, ideal compatibility, and high stability.
  • Traditional gutter layer materials like poly(l-(trimethylsilyl)-l-propyne) (PTMSP) and polydimethylsiloxane (PDMS) face some issues such as serve aging phenomenon (above 80% of its original CO2 permeability is lost within two weeks) or undesired thickness-dependent permeability property that negates the effectiveness of thickness reduction.
  • PTMSP poly(l-(trimethylsilyl)-l-propyne)
  • PDMS polydimethylsiloxane
  • face some issues such as serve aging phenomenon (above 80% of its original CO2 permeability is lost within two weeks) or undesired thickness-dependent permeability property that negates the effectiveness of thickness reduction.
  • MOFs metal-organic frameworks
  • COFs covalent organic frameworks
  • covalent organic frameworks are crystalline porous polymers with ordered and extended structures, in which organic building blocks are connected through strong covalent linkages. Two- or three- dimensional structures through reactions between organic units or precursors can result in porous, stable, and crystalline materials.
  • COF can be formed using linkage reactions such as boron condensation, triazine based trimerisation, and imine condensation. Pore sizes can range from 7-23 A and feature a diverse range of shapes and dimensionalities that remain stable during the evacuation of solvent.
  • the rigid scaffold of the COF structure enables the material to be evacuated of solvent and retain its structure, resulting in high surface areas as seen by the Brunauer-Emmett-Teller analysis.
  • COF can also be, but not necessarily, crystalline.
  • COFs are made entirely from light elements (H, B, C, N, and 0) with extended structures.
  • MOFs metal- organic frameworks
  • MOFs are a class of compounds consisting of metal ions or clusters coordinated to organic ligands to form one-, two-, or three-dimensional structures.
  • MOFs are coordination networks with organic ligands containing potential voids.
  • MOFs are composed of two major components: a metal ion or cluster of metal ions and an organic molecule called a linker. The choice of metal and linker dictates the structure and hence properties of the MOF.
  • the metal's coordination preference influences the size and shape of pores by dictating how many ligands can bind to the metal and in which orientation.
  • MOFs are prone to structural defects which leave metal- containing nodes incompletely coordinated, and hence at most partially crystalline. While high defects in MOFs is beneficial for catalytic reactions because defects can possibly exhibit acid and/or basic properties, this is not so in the present application where consistency in pore size is desirable.
  • MOFs Zn2DOT 2,5-dihydroxyterephthalate
  • BTB 1,3,5-benzenetribenzoate
  • BDC 1,4- benzenedicarboxylate
  • BPYDC 2,2'-bipyridine-5,5'-dicarboxylate
  • MIM 2- methylimidazolate
  • the present invention provides a thin film composite membrane, comprising: a) a separation layer; and b) a gutter layer adjacent to the separation layer; wherein the gutter layer comprises a covalent organic framework (COF) film; and wherein the COF film has a thickness of about 10 nm to about 300 nm.
  • COF covalent organic framework
  • wholly organic, orientated, two-dimensional covalent organic framework (COF) films are found to have a good pore size, intrinsic porosity, small transport resistance, good compatibility with polymer matrix, good anti-aging capability and high stability.
  • Commercial or photo-initiated crosslinked polymer can be deposited compatiblely on the COF film in the gutter layer with a thickness as thin as 55 nm, an ultrathin thickness that traditional gutter layers are challenging to attain.
  • one optimized TFCM realizes high CO2 capture performance with CO2 permeance of 1843 gas permeation units (GPU) and CO2/N2 separation selectivity of 28.2, which displays unique advantages over other gutter layer-based TFCMs and meets the performance target for CO2 capture (CO2 permeance > 1000 GPU, CO2/N2 selectivity > 20).
  • the thin film composite membrane has a small transport resistance, good compatibility with polymer matrix, good anti-aging capability and high stability. Additionally, it is easy to control the thickness of the COF films and to optimize the transport resistance.
  • the COF film has a thickness of about 10 nm to about 250 nm, about 10 nm to about 200 nm, about 15 nm to about 200 nm, about 15 nm to about 150 nm, about 15 nm to about 100 nm, about 30 nm to about 100 nm, or about 55 nm to about 100 nm. In other embodiments, the COF film has a thickness of less than about 250 nm, about 200 nm, about 150 nm, about 100 nm, about 90 nm, about 80 nm, about 70 nm, about 60 nm, about 50 nm, or about 40 nm.
  • the COF film has a thickness of about 55 nm. In some embodiments, the COF film is monocrystalline. In this regard, the COF film is formed as a single crystal, in which the crystal lattice of the entire sample is continuous and unbroken to the edges of the sample, with no grain boundaries.
  • the COF film has a c-orientation.
  • the crystallographic c axis of the COF is vertical to the film surface.
  • the COF film is beneficial for allowing the separation layer to form due to its low roughness or smoothness.
  • the COF film has a roughness parameter R q of about 0.70 nm to about 0.75 nm. This can be obtained, for example, using three-dimensional (3D) AFM techniques.
  • the roughness parameter R q is about 0.70 nm to about 0.74 nm, about 0.71 nm to about 0.74 nm, or about 0.71 nm to about 0.73 nm. In other embodiments, the roughness parameter R q is about 0.70 nm, about 0.71 nm, about 0.72 nm, about 0.73 nm, about 0.74 nm, or about 0.75 nm.
  • the COF film has a roughness parameter R a of about 0.50 nm to about 0.55 nm. This can be obtained, for example, using three-dimensional (3D) AFM techniques.
  • the roughness parameter R a is about 0.51 nm to about 0.55 nm, about 0.51 nm to about 0.54 nm, or about 0.51 nm to about 0.53 nm.
  • the roughness parameter R a is about 0.50 nm, about 0.51 nm, about 0.52 nm, about 0.53 nm, about 0.54 nm, or about 0.55 nm.
  • the COF film is characterised by an acid stability at about pH 1 to less than pH 7.
  • the acid stability is about pH 2 to less than pH 7, about pH 3 to less than pH 7, or about pH 4 to less than pH 7.
  • the COF film is characterised by a thermal stability of less than about 700 K. In other embodiments, the thermal stability is less than about 680 K, about 660 K, about 640 K, about 620 K, or about 600 K.
  • the pore size of the COF can be varied by altering the size and/or morphology of the subunits.
  • aryl subunits can be used to increase the spanning width.
  • the positioning of the linkers on the subunits and/or the number of linkers can also be altered to vary the pore size.
  • the type of linkers used can alter the physical property of the COF, such as its stiffness and hydrophilicity.
  • the COF film comprises iminylene linkages.
  • the COF film comprises b -ketoenamine, boronate, hydrazone, or azine linkages.
  • the COF film is a COF-LZU1 film.
  • Imine-linked COF-LZU1 possesses a two-dimensional eclipsed layered-sheet structure and was first produced in Lanzhou University in 2011.
  • COF-LZU1 is formed from p-phenylenediamine and 1,3,5- triformylbenzene.
  • Other COFs such as TpPa-SOsFI, TpTGci, CTF-1, COF-JLU2, COF-5, I b- COF, NUS-2, NUS-3, NUS-14, N-COF, P-COF, T-COF, or a combination thereof can also be used.
  • TpPa-S03hl is a COF formed from 1,3,5-triformylphloroglucinol (Tp) and 1,4- phenylenediamine-2-sulfonic acid (Pa-S03FI).
  • Schiff-base-type COF TpTGCI can be formed from 1,3,5-triformylphloroglucinol (Tp) and triaminoguanidinium chloride (TGCI).
  • CTF-1 can be formed from terephthalonitrile and ZnCh.
  • COF-JLU2 can be formed from hydrazine hydrate and 1,3,5-triformylphloroglucinol.
  • COF-5 can be formed from 1,4-benzene diboronic acid and 2,3,6,7,10,11-hexahydroxytriphenylene.
  • N3-COF can be formed from 4,4',4"-(l,3,5-Triazine-2,4,6-triyl)tris[benzaldehyde] and hydrazine hydrate.
  • NUS-2 is a COF synthesized from 1, 3, 5-triformylphloroglucinol and hydrazine hydrate.
  • NUS-3 is a COF synthesized from triformylphloroglucinol (TFP) and 2, 5- diethoxyterephthalo-hydrazide (DETFI).
  • the monomers for NUS-14 are l,3,5-tris(4- formyl-phenyl)triazine (TFPT) and p-phenylenediamine (PDA);
  • the monomers for N-COF are 1,3,5- benzenetricarbaldehyde (BTCA) and tri(4-aminotriphenyl)amine (TAPA);
  • the monomers for P-COF are 1,3,5- benzenetricarbaldehyde (BTCA) and l,3,5-trisIJ4- aminophenyl)benzene (TAPB);
  • the monomers for T-COF are 1,3,5- benzenetricarbaldehyde (BTCA) and 2,4,6-trisIJ4-aminophenyl)-s-triazine (TAPT).
  • the COF film has a pore size of about 0.7 nm to about 3 nm. In other embodiments, the pore size is about 1 nm to about 3 nm, about 1 nm to about 2.5 nm, about 1 nm to about 2 nm, or about 1.5 nm to about 2 nm.
  • the COF film can be chosen to be of a low cost material, have the pore size larger than the size of permeated gas molecules and reduce the penetration of top polymer separation layer into the COF film layer.
  • the COF film has a resistance of less than about 8% relative to an overall membrane resistance of the thin film composite membrane. In other embodiments, the resistance is less than about 7.5%, about 7%, about 6.5%, or about 6%.
  • the composite membrane is characterised by a thickness of about 100 nm to about 500 nm. In other embodiments, the thickness is about 100 nm to about 450 nm, about 100 nm to about 400 nm, about 100 nm to about 350 nm, about 100 nm to about 300 nm, about 100 nm to about 250 nm, about 100 nm to about 200 nm, or about 150 nm to about 200 nm.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 20% at a relative humidity of less than 85%.
  • the thin film composite membrane is stable at a relative humidity of less than about 85%.
  • the change in CO2 permeance and/or CO2/N2 selectivity is less than about 18%, about 16%, about 14%, about 12%, or about 10%.
  • the relative humidity is less than about 80%, about 75%, about 70%, about 65%, about 60%, about 55%, about 50%, about 45%, or about 40%.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 50% at a temperature of about 290K to about 350K.
  • the thin film composite membrane is stable at a temperature of about 290K to about 350K.
  • the change in CO2 permeance and/or CO2/N2 selectivity of less than about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, or about 10%.
  • the temperature is about about 300K to about 350K, about 310K to about 350K, about 320K to about 350K, or about 330K to about 350K.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 20% at a pressure of less than about 5 bar.
  • the thin film composite membrane is stable in a pressure of less than about 5 bar.
  • the change in CO2 permeance and/or CO2/N2 selectivity is less than about 18%, about 16%, about 14%, about 12%, or about 10%.
  • the pressure is less than about 4.5 bar, about 4 bar, about 3.5 bar, about 3 bar, about 2.5 bar or about 2 bar.
  • the thin film composite membrane has a change in CO2 permeance and/or CO2/N2 selectivity of less than about 10% for at least one month.
  • the thin film composite membrane is stable for at least one month when exposed to atmospheric conditions.
  • the change in CO2 permeance and/or CO2/N2 selectivity is less than about 8%, about 6%, about 4%, about 2%, or about 1%.
  • the thin film composite membrane is stable for at least 30 days, 25 days, 20 days, 15 days, 10 days or 5 days.
  • the change in CO2 permeance and/or CO2/N2 selectivity is less than about 18%, about 16%, about 14%, about 12%, or about 10%.
  • the pressure is less than about 4.5 bar, about 4 bar, about 3.5 bar, about 3 bar, about 2.5 bar or about 2 bar.
  • the separation layer can comprise Pebax 1657, cross linked PEG, Pebax 2533, Pebax 1074, Matrimid 5218, polysulfone, poly(vinyl alcohol), poly(vinyl acetate), or a combination thereof.
  • the separation layer comprises Pebax 1657.
  • Pebax ® MH 1657 by Arkema is an anti-static polyether block amide grade with increased electrical conductivity. It is made of flexible polyether and rigid polyamide.
  • the thin film composite membrane when the separation layer comprises Pebax 1657, has a CO2 permeance of about 23,000 GPU to about 30,000 GPU and/or a CO2/N2 selectivity of about 1 to about 2. In other embodiments, the CO2 permeance is about 25,000 GPU. In other embodiments, the CO2/N2 selectivity is about 1.3. In other embodiments, the CO2 permeance is about 1700 GPU and CO2/N2 selectivity is about 25.
  • the separation layer comprises cross linked PEG.
  • Polyethylene glycol can, for example, be cross linked through reacting acrylate moieties and ether moieties.
  • the cross linked PEG is made up of PEG monomeric units comprising about 5 to about 30 ethylene oxide repeating units. In other embodiments, there are about 10 to about 30 repeating units, about 10 to about 25 repeating units, about 10 to about 20 repeating units, or about 10 to about 15 repeating units.
  • the thin film composite membrane when the separation layer comprises cross linked PEG, has a CO2 permeance of about 1800 GPU to about 2000 GPU and CO2/N2 selectivity of about 27 to about 30. In other embodiments, the CO2 permeance is about 1800 GPU. In other embodiments, the CO2/N2 selectivity is about 28.
  • the separation layer is characterised by a thickness of about 40 nm to about 200 nm.
  • the thickness is about 40 nm to about 180 nm, about 40 nm to about 160 nm, about 40 nm to about 140 nm, about 40 nm to about 120 nm, about 60 nm to about 120 nm, about 80 nm to about 120 nm, or about 90 nm to about 120 nm.
  • the thickness is about 100 nm.
  • the present invention also provides a thin film composite membrane, wherein the gutter layer comprises a covalent organic framework (COF) film having a thickness of about 10 nm to about 300 nm; and wherein the separation layer comprises a multilayered COF film.
  • COF covalent organic framework
  • the present invention also provides a thin film composite membrane, wherein the gutter layer comprises a covalent organic framework (COF) film having a thickness of about 10 nm to about 300 nm; and wherein the separation layer comprises at least a first charged COF film and a second charged COF film.
  • COF covalent organic framework
  • the first charged COF film is a negatively charged COF film. In some embodiments, the first charged COF film is functionalised with sulfonic acid and/or carboxyl moieties.
  • the second charged COF film is a positively charged COF film.
  • the second charged COF film is functionalised with guanidinium and/or iminyl and/or ethidium halide moieties. Through the attraction of oppositely charged moieites, the second charged COF films can be formed on the first charged COF film.
  • the separation layer comprises at least 2, 3, 4, 5 or 6 first charged COF films and at least 2, 3, 4, 5 or 6 second charged COF films, the first and second charged COF films alternatingly layered on each other.
  • the first and second charged COF films forms a bilayered COF film.
  • the separation layer comprises at least a bilayer of oppositely charged COF films. In other embodiments, the separation layer comprises at least 2, 3, 4, 5 or 6 bilayers of oppositely charged COF films. In other embodiments, the separation layer comprises 2 bilayers.
  • the present invention also provides a method of fabricating a thin film composite membrane comprising a separation layer and a gutter layer adjacent to the separation layer, wherein the gutter layer comprises a covalent organic framework (COF) film, the method comprising: interfacially reacting a mixture of a first subunit and a second subunit in order to form a covalent organic framework (COF) film; wherein the COF film has a thickness of about 10 nm to about 300 nm.
  • Interfacial reaction or polymerization is a type of step-growth polymerization in which polymerization occurs at the interface between two immiscible phases (generally two liquids), resulting in an entity that is constrained to the interface.
  • the first subunit has at least two, three or four linker moieties. In other embodiments, the first subunit has at least two amine, cyano and/or hydroxyl moieties. In other embodiments, the first subunit has at least two amine moieties. In other embodiments, the first subunit has at least three amine moieties.
  • the first subunit is selected from p-Phenylenediamine (PDA), 2,5-diaminobenzenesulfonic acid (l,4-phenylenediamine-2-sulfonic acid), hydrazine hydrate, benzene-1, 3, 5-triamine, triaminoguanidinium chloride, 2, 5- diethoxyterephthalo-hydrazide, terephthalonitrile, 2,3,6,7,10,11- hexahydroxytriphenylene or a combination thereof.
  • the first subunit has a concentration of about 1 to about 10 mM.
  • the concentration is about 1 to about 9 mM, about 1 to about 8 mM, about 1 to about 7 mM, about 1 to about 6 mM, about 1 to about 5 mM, about 1 to about 4 mM, about 1 to about 3 mM, or about 1 to about 2 mM.
  • the second subunit has at least two, three or four linker moieties. In other embodiments, the second subunit has at least two acyl and/or boronic moieties. In other embodiments, the second subunit has at least two acyl moieties. In other embodiments, the second subunit has at least three acyl moieties.
  • the second subunit is selected from 1,3,5-triformylbenzene (TFB), 1,3,5-triformylphloroglucinol, 2,4,6-trihydroxybenzene-l,3,5-tricarbaldehyde (1,3,5-triformylphloroglucinol), 1,4-benzenedicarboxaldehyde, 4,4',4"-(l,3,5-Triazine- 2,4,6-triyl)tris[benzaldehyde], 1,4-benzene diboronic acid or a combination thereof.
  • the second subunit has a concentration of about 1 to about 20 mM.
  • the concentration is about 1 to about 19 mM, about 1 to about 18 mM, about 1 to about 17 mM, about 1 to about 16 mM, about 1 to about 15 mM, about 1 to about 14 mM, about 1 to about 13 mM, about 1 to about 12 mM, about 1 to about 10 mM, about 1 to about 9 mM, about 1 to about 8 mM, or about 1 to about 6 mM.
  • a molar ratio of the first subunit to the second subunit is about 10: 1 to about 1: 10, about 9: 1 to about 1 :10, about 8: 1 to about 1 : 10, about 7: 1 to about 1 : 10, about 6: 1 to about 1 : 10, about 5: 1 to about 1: 10, about 4: 1 to about 1 : 10, about 3: 1 to about 1: 10, about 2: 1 to about 1: 10, or about 1 : 1 to about 1: 10.
  • a molar ratio of the first subunit to the second subunit is about 10: 1 to about 1:9, about 10: 1 to about 1:8, about 10: 1 to about 1:7, about 10: 1 to about 1:6, about 10: 1 to about 1:5, about 10: 1 to about 1:4, about 10: 1 to about 1:3, about 10: 1 to about 1 :2, or about 10: 1 to about 1: 1.
  • the COF is COF-LUZ1
  • the first subunit is PDA and the second subunit is 1,3,5-triformylbenzene
  • the molar ratio can be about 3:2. Using this molar ratio can provide a COF thickness of about 55 nm.
  • the amine moiety reacts with the acyl moiety to form an iminylene linkage.
  • the method comprises interfacially reacting a mixture of a first aryl subunit comprising at least two amine moieties with a second aryl subunit comprising at least two acyl moieties in order to form a covalent organic framework (COF) film.
  • COF covalent organic framework
  • the interfacial reaction is performed for up to 5 days. In other embodiments, the reaction is performed for up to 4 days, 3 days, 2 days or 1 day.
  • the interfacial reaction is performed at room temperature and pressure. In other embodiments, the reaction is performed at about 15 °C to about 35 °C. In other embodiments, the reaction is performed at about 1 atm.
  • the separation layer is formed by spin coating a polymer solution on the gutter layer and allowing it to dry.
  • the polymer solution is provided at a concentration of about 0.1 wt% to about 5 wt%, about 0.1 wt% to about 4 wt%, about 0.1 wt% to about 3 wt%, or about 0.5 wt% to about 3 wt%.
  • the polymer solution is provided at a concentration of about 1 wt%.
  • the thin film composite membrane can further be transferred onto a support such that the gutter layer is sanwiched between the support layer and separation layer.
  • the present invention also provides a method of fabricating a thin film composite membrane, wherein the gutter layer comprises a covalent organic framework (COF) film having a thickness of about 10 nm to about 300 nm, wherein the separation layer comprises at least a first charged COF film and a second charged COF film, the method comprising: a) interfacially reacting a mixture of a third subunit and fourth charged subunit in order to form the first charged COF film adjacent to the COF film; and b) interfacially reacting a mixture of a fifth subunit and sixth charged subunit in order to form the second charged COF film adjacent to the first charged COF film; and c) optionally repeating step a) and/or step b) at least one more time.
  • COF covalent organic framework
  • the COF film is formed by interfacially reacting a mixture of a first subunit and a second subunit.
  • the third subunit has at least two, three or four linker moieties. In other embodiments, the third subunit has at least two acyl moieties. In other embodiments, the third subunit has at least three acyl moieties.
  • the third subunit is selected from 2,4,6-triformylphloroglucinol, 1,3,5-Benzenetricarboxaldehyde, 1,4-Benzenedicarboxaldehyde or a combination thereof.
  • the fourth charged subunit has at least two, three or four linker moieties. In other embodiments, the fourth charged subunit has at least two amine moieties. In other embodiments, the fourth charged subunit has at least three amine moieties.
  • the fourth charged subunit is negatively charged.
  • the fourth charged subunit is selected from 2,5- diaminobenzenesulfonic acid, p-Phenylenediamine, Flydrazine hydrate or a combination thereof.
  • the fifth subunit has at least two, three or four linker moieties. In other embodiments, the fifth subunit has at least two acyl moieties. In other embodiments, the fifth subunit has at least three acyl moieties.
  • the fifth subunit is selected from 2,4,6-triformylphloroglucinol, 1,3,5-Benzenetricarboxaldehyde, 1,4-Benzenedicarboxaldehyde or a combination thereof.
  • the sixth charged subunit has at least two, three or four linker moieties. In other embodiments, the sixth charged subunit has at least two amine moieties. In other embodiments, the sixth charged subunit has at least three amine moieties.
  • the sixth charged subunit is positively charged.
  • the sixth charged subunit is selected from triaminoguanidinium halide, ethidium halide, guanidine hydrohalide or a combination thereof.
  • the fourth charged subunit and the sixth charged subunit are oppositely charged relative to each other. Towards this end, the first charged COF film and the second charged COF film can be electrically attracted to each other to form a bilayer.
  • the optional step c) is repeated at least 1, 2, 3, 4, 5, 6 or 7 times. Accordingly, there can be at least 1, 2, 3, 4, 5, 6, 7 or 8 layers of the first and/or second charged COF films.
  • step a) and/or step b) further comprises a catalyst.
  • the catalyst can be p-toluenesulfonic acid, acetate acid, trifluoroacetic acid or a combination thereof.
  • the method comprises: a) interfacially reacting a mixture of a third aryl subunits comprising at least two acyl moieties with a fourth charged aryl subunits comprising at least two amine moieties in order to form the first charged COF film; and b) interfacially reacting a mixture of a fifth aryl subunits comprising at least two acyl moieties with a sixth charged alkyl subunits comprising at least two amine moieties in order to form a second COF film adjacent to the first charged COF film; and c) optionally repeating step a) and/or step b) at least one more time.
  • the inventors fabricated a series of ultrathin and oriented two-dimensional (2D) COF films with controllable thickness to optimize the overall CO2 capture performance in TFCMs ( Figure 1).
  • COF-LZU1 was used as an example, but is not limited to as such.
  • Figure 1 shows a commercially available polymer (Pebax 1657) or a photo-initiated crosslinked polyethylene glycol (XLPEG) separation layer prepared on the COF- LZU1/PAN gutter layer/support, respectively.
  • the used 2D COF-LZU1 has a relatively large pore size of 1.8 nm.
  • PAN polyacrylonitrile support.
  • the gutter layer can be used as a platform to fabricate a thin photo-initiated crosslinked polyethylene glycol (XLPEG) separation layer.
  • XLPEG crosslinked polyethylene glycol
  • the separation layer is a XLPEG layer with a thickness of about 120 nm.
  • the gutter layer is a COF-LZU1 film and the separation layer is a XLPEG layer
  • a CO2 permeance of 1843 GPU and a CO2/N2 mixture selectivity of 28.2 is obtainable, meeting the practical requirements for CO2 capture.
  • the stability of the TFCMs enables the retention of industrially relevant performance against humid flue gas at 333 K (typical flue gas temperature).
  • COFs possess smaller and controllable transport resistance, which is believed to inspire the design of next-generation gas separation membranes.
  • FIG. 2a-e shows AFM images of the COF-LZU1 films with different thicknesses using different concentrations of TFB-toluene solution: (a) 1 mM, (b) 2 mM, (c) 3 mM, (d) 5 mM, and (e) 10 mM. (f) 3D AFM image of the interfacia I ly crystalized COF-LZU1 film with roughness parameters.
  • SAED Selected area electron diffraction
  • FIRTEM transmission electron microscopy
  • Figure 3 shows structure and crystallinity of interfacia lly crystalized COF-LZU1 films
  • SAED pattern of the COF-LZU1 film b
  • HRTEM image of the COF-LZU1 film c
  • 2D GISAXS/GIWAXS image of the COF-LZU1 film transferred on S i O 2/ S i wafer d
  • ID GISAXS/GIWAXS pattern of the COF-LZU1 film extracted from out-of-plane (top), inplane (middle) in (c), and the synthesized COF-LZU1 powder bottom
  • XRD pattern of the collected large amount of as-synthesized COF-LZU1 films and the one after being immersed in hydrochloric acid (pH 1) for 7 days
  • FTIR Fourier transform infrared
  • the as-crystallized COF-LZU1 film on the water surface could be freely transferred onto either a commercial porous polymer support (polyacrylonitrile (PAN), MWCO ⁇ 100 k) or Si wafer for the TFCMs preparation and characterizations.
  • the smooth COF film gutter layer provides a suitable surface for the coating of the polymer separation layer ( Figure 4a).
  • Figure 4 shows top (a-c) and cross-sectional (d-f) SEM images of (a, d) COF-LZU1/PAN, (b, e) Pebax/COF-LZU 1/PAN, and (c, f) XLPEG/COF-LZU1/PAN.
  • Attenuated total reflection-FTIR (ATR-FTIR; Figure 5a) and X-ray photoelectron spectroscopy (XPS; Figure 5c) results demonstrated the successful coating of the Pebax separation layer.
  • Figure 5 shows (a) ATR-FTIR of Pebax/COF-LZUl/PAN. (b) ATR-FTIR of XLPEG/COF- LZU1/PAN. (c) XPS C Is spectrum of Pebax/COF-LZUl/PAN. (d) XPS C Is spectrum of XLPEG/COF-LZU1/PAN.
  • the XLPEG/COF-LZU1/PAN membrane was prepared by spin-coating the PEG precursor onto COF-LZU1/PAN, followed by an ultraviolet (UV) photo-initiated crosslinking process.
  • the separation layer thickness could be controlled by adjusting the precursor concentration and spin coating speed.
  • the stated conditions yielded a membrane with a thickness of about 175 nm, including the COF gutter layer and the top separation layer ( Figure 4c, 4f).
  • CO2/N2 separation performance of TFCMs was evaluated using mixed feed gases (CO2/N2 is 15/85 by volume) on a home-built constant pressure, variable volume (CPVV) equipment.
  • COF film thickness ranging from 31 to 200 nm in the Pebax-based TFCM system using a lwt.% of Pebax solution was used.
  • CPVV constant pressure, variable volume
  • Figure 6 shows the effect of the COF gutter layer thickness on the overall CO2/N2 separation performance of Pebax/COF-LZUl/PAN membranes.
  • Such an ultrathin COF film gutter layer unlike the conventional polymer competitor such as PDMS, is more than eight times more permeable, showing significantly lower gas transport resistance, which is an important discovery for the design of future TFCMs.
  • the high permeance can be maintained for at least one month, indicating that the 'aging' phenomenon commonly encountered in traditional polymer gutter layers can be mitigated in the COF film gutter layer.
  • the good anti-aging capability can be attributed to the relatively rigid property of COFs.
  • the thickness of the separation layer has a great effect on the overall separation performance of the TFCMs.
  • Figure 7 shows the effect of the Pebax concentration on the overall CO2/N2 separation performance of Pebax/COF-LZUl/PAN membranes.
  • the resultant XLPEG/COF-LZU1/PAN TFCM exhibited higher separation performance of CO2 permeance of 1843 GPU and CO2/N2 selectivity of 28.2 when using a COF gutter layer of 55 nm. This excellent performance highlighted the potential of the COF-based gutter layer to further enhance the separation performance in leading TFCMs.
  • Figure 8 is a comparison of CO2/N2 separation performance with other TFCMs. a represents ideal selectivity. Membrane performance was evaluated using singlecomponent gas. Table 1. Comparison of the state-of-art thin film composite membranes for CO2/N2 separation.
  • GPU Selective layer Gutter layer thickness
  • Figure 9 shows long-term operational stability of XLPEG/COF-LZU1/PAN membrane for CO2 capture under various conditions, including humid feed gas (relative humidity is 85%) and (or) high temperature (typically 333 K).
  • the COF gutter layer can be used as a platform to fabricate multilayer COF membranes for FI2/CO2 separation (H2 permeance of 2163 GPU and FI2/CO2 selectivity of 26), holding the potential to scale up the production of neat COF membranes and avoid the defects formation.
  • Figure 13 is a scheme of the fabrication and gas separation application of the ultrathin COF membranes with narrowed apertures using a multi-interfacial engineering strategy.
  • the oriented COF-LZU1 film was prepared at the water-toluene interface and then transferred onto anodic aluminum oxide (AAO) support as a gutter layer.
  • AAO anodic aluminum oxide
  • Ultrathin, compact, and multilayer COF separation layer was prepared by the interfacial crystallization of two COFs (TpPa-SOsFI and TpTGci) with different pore sizes in a layer- by-layer (LBL) manner.
  • the narrowed apertures are formed at the COF-COF interfaces.
  • the resulted multilayer COF-COF membranes displayed excellent separation performance for small gases.
  • the formed film can be transferred onto various supports such as PAN ultrafiltration membrane, Cu grid, or SiC /Si wafer for the following membrane preparation and characterizations. After drying under vacuum overnight, the COF-LZU1 films on support were washed with tetrahydrofuran, ethanol, and hexane for one day, respectively. Then, the films were dried under a vacuum overnight.
  • supports such as PAN ultrafiltration membrane, Cu grid, or SiC /Si wafer for the following membrane preparation and characterizations.
  • Pebax/COF-LZUl/PAN membranes Preparation of Pebax/COF-LZUl/PAN membranes.
  • Equal weights of poly(ethylene glycol) diacrylate (PEGDA) and poly(ethylene glycol) dimethyl ether (PEGDME) were dissolved in isopropanol to form a 20 wt.% solution, and then 1-hydroxycyclohexyl phenyl ketone (FICPK; 0.2% of PEGDA weight) was added and mixed homogenously.
  • the precursor solution (0.2 mL) was spin-coated on the COF-LZU1/PAN at 3000 rpm for 60 s.
  • An ultraviolet (UV) photo-initiated crosslinking (90 s) occurred 5 cm above the coated precursor. After that, another process of spin coating and photo-initiated crosslinking was repeated.
  • the resultant XLPEG/COF-LZU1/PAN membranes were dried in a vacuum oven one day before CO2/N2 separation test.
  • COF-LZU1 powder was prepared at room temperature. Briefly, TFB (96 mg) and PDA (96 mg) were dissolved in 6 mL of dioxane. Sonication was used to dissolve the monomers. Then, 1.2 mL of acetic acid (3 M) aqueous solution was added dropwise into the dissolved monomers. The reaction system was kept for 3 days statically. The product was washed with dioxane, tetrahydrofuran, acetone, and hexane for 2 days, respectively.
  • TpTGci@TpPa-S03H/C0F-LZUl/AA0 multilayer membranes is similar to the preparation of commercially successful polyamide thin film composites (TFCs) for nanofiltration or reverse osmosis, which is an interfacial polymerization method and holds the great potential to scale up.
  • TFCs polyamide thin film composites
  • the COF-LZU1/AAO film was clamped between two frames with a hole diameter of 15 mm.
  • Half one milliliter of 2,4,6- triformylphloroglucinol (Tp)-hexane saturated solution was dropped onto the clamped COF-LZU1 film and the film surface was wetted for 10 min.
  • an aqueous solution 0.5 mL containing monomer 2,5- diaminobenzenesulfonic acid (Pa-SCHH, 0.2 mM) and catalyst p-toluenesulfonic acid (PTSA, 0.3 mM) was poured onto the Tp containing COF-LZU1/AAO film for interfacial reaction at room temperature for 12 h.
  • a TpPa-SOsH/COF-LZUl/AAO membrane was formed.
  • half one milliliter of Tp-hexane saturated solution was dropped onto the clamped TpPa-S03H@COF-LZUl/AAO membranes for reaction lasting for 1 h.
  • CO2/N2 (15/85 of mol/mol) or H2/CO2 (50/50 of mol/mol) separation performance of the prepared TFCMs was evaluated on our home-made constant pressure-variable volume (CPVV) apparatus (Wicke-Kallenbach method) described previously.
  • the membrane was fixed and sealed in the permeation cell.
  • the permeation cell containing membrane was placed in a furnace to control the test temperature.
  • Mass flow controllers MFC, D07- 26C, SevenStar, China
  • the membranes were measured either under dry or humidified conditions. In the separation tests with humid feed gases (relative humidity is 85%), the feed gases with saturated water vapour were produced by flowing through a pure water tank prior to the membrane permeation cell.
  • Argon was used as the sweep gas to carry the permeate components, and the volumetric flow rate was controlled by MFC (D07-19C).
  • MFC volumetric flow rate
  • the molar concentrations of permeate side gases were analysed by gas chromatograph (Agilent 7890B) with two TCD detectors. The permeation data were recorded at steady state when the composition concentrations of permeate side gas analysed by GC were constant.
  • Equation SI The gas permeance ⁇ Pi, GPU) of component gas / was calculated using Equation SI, Equation (SI) where /V, is the molar flow rate of gas / at standard temperature and pressure (STP) (mol s 1 ), A is the membrane effective area (m 2 ), and D Pi is the partial pressure difference of component / (Pa).
  • the separation selectivity (a) of gas pair i/j was calculated using Equation S2, Equation (S2) where Pi and Pj are the permeance of gas / and gas j, respectively.
  • COF films as gutter layers was explored and shown to have low transport resistance, good compatibility, good anti-aging capability, and high stability for highly permeable CO2 capture or H2 permeation in TFCMs or multilayer COF membranes.
  • the composite membrane can have remarkable separation performance for post-combustion CO2 capture (CO2 permeance of 1843 GPU and CO2/N2 selectivity of 28.2) and pre-combustion CO2 capture (FI2 permeance of 2163 GPU and FI2/CO2 selectivity of 26), which can be substantially retained even under elevated temperature and humid conditions.
  • the generality of this approach and suitability of COF films for efficient large-scale processing methods are expected to inspire next-generation gas separation membranes.

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Abstract

La présente divulgation concerne, d'une manière générale, des membranes composites à couches minces, leurs procédés de fabrication et leurs utilisations. La membrane composite à couches minces comprend une couche de séparation et une couche gouttière adjacente à la couche de séparation. La couche gouttière comprend un film à structure organique covalente (COF) d'une épaisseur d'environ 10 nm à environ 300 nm. La membrane composite à couches minces peut être utilisée pour la capture de CO2 avec une perméance élevée.
PCT/SG2022/050202 2021-04-14 2022-04-07 Membranes composites à couches minces, leurs procédés de fabrication et leurs utilisations Ceased WO2022220743A1 (fr)

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