POLYCRYSTALLINE METAL-ORGANIC FRAMEWORK MEMBRANES FOR SEPARATION OF MIXTURES
20230001379 · 2023-01-05
Inventors
Cpc classification
B01D67/0079
PERFORMING OPERATIONS; TRANSPORTING
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
B01J20/3085
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28011
PERFORMING OPERATIONS; TRANSPORTING
B01D65/02
PERFORMING OPERATIONS; TRANSPORTING
B01J20/226
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28033
PERFORMING OPERATIONS; TRANSPORTING
C07F7/00
CHEMISTRY; METALLURGY
International classification
B01D17/00
PERFORMING OPERATIONS; TRANSPORTING
B01D61/36
PERFORMING OPERATIONS; TRANSPORTING
B01D65/02
PERFORMING OPERATIONS; TRANSPORTING
B01D67/00
PERFORMING OPERATIONS; TRANSPORTING
B01D69/02
PERFORMING OPERATIONS; TRANSPORTING
B01D69/10
PERFORMING OPERATIONS; TRANSPORTING
B01J20/28
PERFORMING OPERATIONS; TRANSPORTING
B01J20/30
PERFORMING OPERATIONS; TRANSPORTING
Abstract
Disclosed herein is a polycrystalline metal-organic framework membrane comprising a substrate material having a surface and a polycrystalline metal-organic framework attached to the surface of the substrate material, wherein the polycrystalline metal-organic framework is formed from a secondary building unit having the formula Ia or IIb and a ligand as defined in the application.
Claims
1. A polycrystalline metal-organic framework membrane comprising: a substrate material having a surface; and a polycrystalline metal-organic framework attached to the surface of the substrate material, wherein the polycrystalline metal-organic framework is formed from: a secondary building unit having the formula Ia or Ib:
M.sub.6O.sub.4(OH).sub.4 Ia, where M is selected from Zr, Hf, and Ti; or
M′.sub.6(OH).sub.8 Ib where M′ is selected from Sm, Y, Dy, Er, Gd, and Ce; and a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II: ##STR00004## where: R.sub.1 is selected from H, halo, OR.sub.5a, SR.sub.5b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.5cR.sub.5d, SO.sub.3H, CF.sub.3, or CO.sub.2H; R.sub.2 is selected from H, halo, OR.sub.6a, SR.sub.6b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.6cR.sub.6d, SO.sub.3H, CF.sub.3 or CO.sub.2H; R.sub.3 is selected from H, halo, OR.sub.7a, SR.sub.7b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.7cR.sub.7d, SO.sub.3H, CF.sub.3, or CO.sub.2H; R.sub.4 is selected from H, halo, OR.sub.8a, SR.sub.8b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.8cR.sub.8d, SO.sub.3H, CF.sub.3 or CO.sub.2H; R.sub.5a-5d, R.sub.6a-6d, R.sub.7a-7d, R.sub.7a-7d are each independently selected from H or C.sub.1 to C.sub.5 alkyl; or R.sub.1 and R.sub.2 or R.sub.3 and R.sub.4 form, together with the carbon atoms to which they are attached to a C.sub.6 aromatic ring; and n is 0, 1 or 2.
2. The membrane according to claim 1, wherein the substrate material is selected from one or more of a polymer, a ceramic, a carbon cloth, a metal, and a metal oxide.
3. The membrane according to claim 2, wherein, when the substrate material is alumina, then the secondary building unit has formula Ia, where M is Zr, Hf or Ti, or the secondary building unit has formula Ib.
4. The membrane according to claim 1, wherein the polycrystalline metal-organic framework is a UiO-66-type metal-organic framework.
5. The membrane according to claim 1, wherein: R.sub.1 is selected from H, halo, OR.sub.5a, SR.sub.5b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.5cR.sub.5d, SO.sub.3H, CF.sub.3, or CO.sub.2H; R.sub.2 is selected from H, OR.sub.6a, SR.sub.6b, CF.sub.3 or CO.sub.2H; R.sub.3 is selected from H, halo, OR.sub.7a, SR.sub.7b, C.sub.1 to C.sub.5 alkyl, NR.sub.7cR.sub.7d, SO.sub.3H, CF.sub.3, or CO.sub.2H; and R.sub.4 is selected from H, F, OR.sub.8a, SR.sub.8b, CF.sub.3 or CO.sub.2H.
6. The membrane according to claim 1, wherein: when two or more of R.sub.1 to R.sub.4 are not H, then the non-H substituents are identical to each other; and/or n is 0 or 1.
7. The membrane according to claim 1, wherein the ligand is selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, terephthalic acid, 2-fluoroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 2-iodoterephthalic acid, 2-hydroxyterephthalic acid, 2-mercaptoterephthalic acid, 2-methylterephthalic acid, 2-nitroterephthalic acid, 2-aminoterephthalic acid, 2-sulfoterephthalic acid, 2-(trifluoromethyl)terephthalic acid, benzene-1,2,4-tricarboxylic acid, 2,3-dihydroxyterephthalic acid, 2,3-dimercaptoterephthalic acid, 2,5-difluoroterephthalic acid, 2,5-dichloroterephthalic acid, 2,5-dibromoterephthalic acid, 2,5-diiodoterephthalic acid, 2,5-terephthalic acid, 2,5-dihydroxyterephthalic acid, 2,5-dimercaptoterephthalic acid, 2,5-dimethylterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-bis(trifluoromethyl)terephthalic acid, 2,5-diemthoxyterephthalic acid, benzene-1,2,4,5-tetracarboxylic acid, 2,5-disulfoterephthalic acid, 2,5-diethoxyterephthalic acid, 2,5-diisopropylterephthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 2,3,5,6-tetrahydroxyterephthalic acid, 2,3,5,6-tetramethylterephthalic acid, 2,3,5,6-tetrakis(trifluoromethyl)terephthalic acid, benzene-1,2,3,4,5,6-hexacarboxylic acid, [1,1′-biphenyl]-4,4′-dicarboxylic acid, [1,1′:4′,1″-terphenyl]-4,4″-dicarboxylic acid, and naphthalene-1,4-dicarboxylic acid.
8. The membrane according to claim 7, wherein the ligand is selected from or 2-aminoterephthalic acid or 2,5-dihydroxyterephthalic acid.
9. The membrane according to claim 1, wherein the substrate material is provided in the form of a mesh, a sheet or in the form of hollow fibers and other arrangements that are obtainable by the folding of a mesh, a sheet and hollow fibers.
10. The membrane according to claim 1, wherein the polycrystalline metal-organic framework attached to the surface of the substrate material has a thickness of from 20 nm to 20 μm.
11. A method of using a polycrystalline metal-organic framework membrane as described in claim 1 in a process of separating a fluid into a filtrate fluid and a retentate fluid, the process comprising the steps of: (a) providing a fluid in need of separation to the polycrystalline metal-organic framework membrane; (b) allowing or enabling a portion of the fluid to pass through the polycrystalline metal-organic framework membrane to provide a filtrate fluid and thereby providing a filtrate fluid; and (c) collecting the filtrate fluid and retentate fluids.
12. The method according to claim 11, wherein the fluid to be separated is selected from: a mixture of gases; an aqueous solution comprising one or more inorganic materials; an aqueous solution comprising one or more organic materials; an aqueous solution comprising one or more inorganic materials and one or more organic materials; a mixture of organic liquids; a mixture of one or more organic liquids and water; a mixture of one or more organic liquids and one or more organic materials; a mixture of one or more organic liquids and one or more inorganic materials; a mixture of one or more organic liquids, one or more organic materials and one or more inorganic materials; a mixture of water, one or more organic liquids and one or more organic materials; a mixture of water, one or more organic liquids and one or more inorganic materials; and a mixture of water, one or more organic liquids, one or more organic materials and one or more inorganic materials.
13. A method of forming a polycrystalline metal-organic framework membrane as described in claim 1, the method comprising the steps of: providing a seeded substrate having a surface seeded with seed crystals of the metal-organic framework, said seed crystals formed from a secondary building unit having the formula Ia or Ib and the ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or the ligand having formula II; and subjecting the seeded substrate to a first mother liquor comprising a solvent, a metal salt precursor and a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II as described above, for a first period of time under conditions sufficient to form a metal-organic framework membrane, wherein the metal salt precursor and the ligand are selected to form the same metal-organic framework as in the seed crystals.
14. The method of claim 13, wherein the seeded substrate is formed by immersing a substrate having a surface in a second mother liquor that comprises a solvent, a metal salt precursor and the ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or the ligand having formula II for a second period of time to provide a seeded substrate having a surface seeded with seed crystals of the metal organic framework, said seed crystals formed from a secondary building unit having the formula Ia or Ib and the ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or the ligand having formula II.
15. A method of post-synthetic defect healing comprising the steps of: (a) providing a polycrystalline metal-organic framework membrane in need of post-synthetic healing formed by the process of claim 13; (b) subjecting the polycrystalline metal-organic framework membrane in need of post-synthetic healing to a solution comprising a solvent the ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or the ligand having formula II, for a period of time under conditions sufficient to achieve the post-synthetic healing, wherein the ligand are selected to form the same metal-organic framework as in the polycrystalline metal-organic framework membrane.
16. The method according to claim 15, wherein the polycrystalline metal-organic framework membrane is formed from a secondary building unit of formula Ia, where M is Zr and the ligand is 2-aminoterephthalic acid.
17. A method of in situ healing, wherein the method comprises the steps of: (a) providing a damaged polycrystalline metal-organic framework membrane, where the polycrystalline metal-organic framework membrane is as described in claim 1; and (b) subjecting the damaged polycrystalline metal-organic framework membrane to a solution comprising a reaction solution comprising a solvent, a metal salt precursor, the ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or the ligand having formula II, and reactive rare earth-containing secondary building units for a period of time under conditions sufficient to heal the damaged polycrystalline metal-organic framework membrane, wherein the metal salt precursor, the ligand and the rare earth-containing secondary building units are selected to form the same metal-organic framework as in the damaged polycrystalline metal-organic framework membrane.
18. The method according to claim 15, wherein the damaged polycrystalline metal-organic framework membrane is formed from a secondary building unit that has formula Ib, where M′ is Sm and the ligand is 2,5-dihydroxyterephthalic acid.
Description
DRAWINGS
[0046] Certain embodiments of the present disclosure are described more fully hereinafter with reference to the accompanying drawings.
[0047]
[0048]
[0049]
[0050]
[0051]
[0052]
[0053]
[0054]
[0055]
[0056]
[0057]
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
[0066]
[0067]
[0068]
[0069]
[0070]
[0071]
DESCRIPTION
[0072] It has been surprisingly found that the current invention provides superior separation characteristics over a wide range or solvent systems and conditions, while also retaining its chemical stability.
[0073] Thus, there is provided a polycrystalline metal-organic framework membrane comprising: [0074] a substrate material having a surface; and [0075] a polycrystalline metal-organic framework attached to the surface of the substrate material, wherein the polycrystalline metal-organic framework is formed from: [0076] a secondary building unit having the formula Ia or Ib:
M.sub.6O.sub.4(OH).sub.4 Ia, [0077] where M is selected from Zr, Hf, and Ti; or
M′.sub.6(OH).sub.8 Ib [0078] where M′ is selected from Sm, Y, Dy, Er, Gd, and Ce; and [0079] a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II:
##STR00002##
where:
[0080] R.sub.1 is selected from H, halo, OR.sub.5a, SR.sub.5b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.5cR.sub.5d, SO.sub.3H, CF.sub.3, or CO.sub.2H;
[0081] R.sub.2 is selected from H, halo, OR.sub.6a, SR.sub.6b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.6cR.sub.6d, SO.sub.3H, CF.sub.3 or CO.sub.2H;
[0082] R.sub.3 is selected from H, halo, OR.sub.7a, SR.sub.7b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.7cR.sub.7d, SO.sub.3H, CF.sub.3, or CO.sub.2H;
[0083] R.sub.4 is selected from H, halo, OR.sub.8a, SR.sub.8b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.8cR.sub.8d, SO.sub.3H, CF.sub.3 or CO.sub.2H;
[0084] R.sub.5a-5d, R.sub.6a-6d, R.sub.7a-7d, R.sub.7a-7d are each independently selected from H or C.sub.1 to C.sub.5 alkyl; or
[0085] R.sub.1 and R.sub.2 or R.sub.3 and R.sub.4 form, together with the carbon atoms to which they are attached to a C aromatic ring; and n is 0, 1 or 2.
[0086] In embodiments herein, the word “comprising” may be interpreted as requiring the features mentioned, but not limiting the presence of other features. Alternatively, the word “comprising” may also relate to the situation where only the components/features listed are intended to be present (e.g. the word “comprising” may be replaced by the phrases “consists of” or “consists essentially of”). It is explicitly contemplated that both the broader and narrower interpretations can be applied to all aspects and embodiments of the present invention. In other words, the word “comprising” and synonyms thereof may be replaced by the phrase “consisting of” or the phrase “consists essentially of” or synonyms thereof and vice versa.
[0087] When used herein, the term “secondary building unit” (SBU) refers to a molecular complex or a cluster entity in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers. As such an SBU is intended to take its ordinary meaning in the art to which ligands are attached via their carboxylate groups.
[0088] Unless otherwise stated, the term “alkyl” refers to an unbranched or branched, cyclic, saturated or unsaturated (so forming, for example, an alkenyl or alkynyl) hydrocarbyl radical, which may be substituted or unsubstituted (with, for example, one or more halo atoms). Where the term “alkyl” refers to an acyclic group, it is preferably C.sub.1-5 alkyl (such as ethyl, propyl, (e.g. n-propyl or isopropyl), butyl (e.g. branched or unbranched butyl), pentyl or, more preferably, methyl). Where the term “alkyl” is a cyclic group (which may be where the group “cycloalkyl” is specified), it is preferably C.sub.3-5 cycloalkyl and, more preferably, C.sub.5 cycloalkyl.
[0089] The term “halogen”, when used herein, includes fluorine, chlorine, bromine and iodine.
[0090] The substrate material may be formed from any suitable material, which includes, but is not limited to, a polymer, a ceramic (e.g. alumina), a carbon film/cloth, a metal and a metal oxide. The substrate can be in any suitable form, which include, but is not limited to, meshes, sheets and hollow fibers (e.g. porous alumina ceramic hollow fibers), plus other forms that can be obtained by the folding of these primary forms.
[0091] Examples of substrates in the form of sheets include, but are not limited to, polymer film and carbon film/cloth. Meshes may include, but are not limited to, metal meshes and metal oxide meshes. Hollow fiber structures that may be mentioned herein include, but are not limited to ceramics (e.g. alumina) and polymer films.
[0092] It is noted that certain substrates (e.g. carbon films/cloths or stainless steel meshes) can be functionalized by carboxylation or amination, which can facilitate the growth of crystal seeds. In addition, the flexibility of carbon films/cloths as substrates can offer good mechanical properties to the resultant membranes.
[0093] Examples of polymers that may be used as substrates include, but are not limited to, polyethyleneimine (PEI), polyethersulfone (PES), polyvinylidene fluoride (PVDF), polyetherimide (Ultem™ 1000), poly(ether-block-amide) (PEBA), polydimethylsiloxane (PDMS), poly(amic acid), polybenzimidazole (PBI), Pebax, Matrimid™, 6FDA-DAM, 6FDA/BPDA-DAM, poly(amide-imide), polydopamine (PDA), poly tetra fluoroethylene (PTFE), and combinations thereof.
[0094] In certain embodiments that may be mentioned herein, when the substrate material is alumina, then the secondary building unit may have formula Ia, where M is Zr or, more particularly, Hf or Ti or the secondary building unit has formula Ib. For example, when the substrate material is alumina, then the secondary building unit may have formula Ib.
[0095] While the polycrystalline metal-organic frameworks mentioned herein may take any suitable form, in embodiments mentioned herein, the polycrystalline metal-organic framework may be one that is a UiO-66-type metal-organic framework.
[0096] Any suitable ligand (or compatible mixture of ligands) may be used to form the polycrystalline metal-organic frameworks disclosed herein. As noted above, the ligand may be selected from (one or more of) fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, and a ligand having formula II:
##STR00003##
where:
[0097] R.sub.1 is selected from H, halo, OR.sub.5a, SR.sub.5b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.5cR.sub.5d, SO.sub.3H, CF.sub.3, or CO.sub.2H;
[0098] R.sub.2 is selected from H, halo, OR.sub.6a, SR.sub.6b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.6cR.sub.6d, SO.sub.3H, CF.sub.3 or CO.sub.2H;
[0099] R.sub.3 is selected from H, halo, OR.sub.7a, SR.sub.7b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.7cR.sub.7d, SO.sub.3H, CF.sub.3, or CO.sub.2H;
[0100] R.sub.4 is selected from H, halo, OR.sub.8a, SR.sub.8b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.8cR.sub.8d, SO.sub.3H, CF.sub.3 or CO.sub.2H;
[0101] R.sub.5a-5d, R.sub.6a-6d, R.sub.7a-7d, R.sub.7a-7d are each independently selected from H or C.sub.1 to C.sub.5 alkyl
[0102] In embodiments where the ligand has formula II, then,
[0103] R.sub.1 may be selected from H, halo, OR.sub.5a, SR.sub.5b, C.sub.1 to C.sub.5 alkyl, NO.sub.2, NR.sub.5cR.sub.5d, SO.sub.3H, CF.sub.3, or CO.sub.2H;
[0104] R.sub.2 may be selected from H, OR.sub.6a, SR.sub.6b, CF.sub.3 or CO.sub.2H;
[0105] R.sub.3 may be selected from H, halo, OR.sub.7a, SR.sub.7b, C.sub.1 to C.sub.5 alkyl, NR.sub.7cR.sub.7d, SO.sub.3H, CF.sub.3, or CO.sub.2H; and
[0106] R.sub.4 may be selected from H, F, OR.sub.8a, SR.sub.8b, CF.sub.3 or CO.sub.2H.
[0107] In embodiments of formula II where two or more of R.sub.1 to R.sub.4 are not H, then the non-H substituents may be identical to each other. For example, R.sub.1 and R.sub.3 are both OH (with R.sub.2 and R.sub.4 being H), or R.sub.1 and R.sub.2 are both NH.sub.2 (with R.sub.3 and R.sub.4 being H) etcetera.
[0108] In additional or alternative embodiments of the invention, n may be 0 or 1. For example n may be 0. As will be appreciated, when n is 1, the resulting pore size obtained will be larger than obtained when n is 0, but smaller than when n is 2. As such, varying n in the ligands of formula II allows one to vary the size of the pores in the resulting polycrystalline metal-organic framework and overall product. This allows one to tailor the product to the desired porosity to enable it to work for a specific application.
[0109] In addition, when the ligands used in the polycrystalline metal-organic frameworks described herein include reactive groups (e.g. —NH.sub.2 groups), then the polycrystalline metal-organic framework may also be further functionalised to enable it to be used in further applications, such as a gas sensor, oil/water separation, photocatalysis, membrane reactors, and so on. Furthermore, when the ligands used in the polycrystalline metal-organic frameworks described herein include reactive groups, then the membrane can even be used as a reactive layer for the further growth of other membrane layers (J. Membr. Sci. 2019, 573, 97-106).
[0110] Specific ligands that may be used to make the polycrystalline metal-organic frameworks described herein include, but are not limited to fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, terephthalic acid, 2-fluoroterephthalic acid, 2-chloroterephthalic acid, 2-bromoterephthalic acid, 2-iodoterephthalic acid, 2-hydroxyterephthalic acid, 2-mercaptoterephthalic acid, 2-methylterephthalic acid, 2-nitroterephthalic acid, 2-aminoterephthalic acid, 2-sulfoterephthalic acid, 2-(trifluoromethyl)terephthalic acid, benzene-1,2,4-tricarboxylic acid, 2,3-dihydroxyterephthalic acid, 2,3-dimercaptoterephthalic acid, 2,5-difluoroterephthalic acid, 2,5-dichloroterephthalic acid, 2,5-dibromoterephthalic acid, 2,5-diiodoterephthalic acid, 2,5-terephthalic acid, 2,5-dihydroxyterephthalic acid, 2,5-dimercaptoterephthalic acid, 2,5-dimethylterephthalic acid, 2,5-diaminoterephthalic acid, 2,5-bis(trifluoromethyl)terephthalic acid, 2,5-diemthoxyterephthalic acid, benzene-1,2,4,5-tetracarboxylic acid, 2,5-disulfoterephthalic acid, 2,5-diethoxyterephthalic acid, 2,5-diisopropylterephthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 2,3,5,6-tetrahydroxyterephthalic acid, 2,3,5,6-tetramethylterephthalic acid, 2,3,5,6-tetrakis(trifluoromethyl)terephthalic acid, benzene-1,2,3,4,5,6-hexacarboxylic acid, [1,1′-biphenyl]-4,4′-dicarboxylic acid, [1,1′:4,1″-terphenyl]-4,4″-dicarboxylic acid, and naphthalene-1,4-dicarboxylic acid. In particular embodiments that may be mentioned herein, the ligand may be selected from 2-aminoterephthalic acid or 2,5-dihydroxyterephthalic acid. For example, the ligand may be 2-aminoterephthalic acid.
[0111] As will be appreciated, the polycrystalline metal-organic framework attached to the surface of the substrate material will result in a layer on top of the substrate material that will have a thickness. The thickness of this layer may be from 20 nm to 20 μm, such as from 800 nm to 20 μm, such as from 2 μm to 20 μm. In particular embodiments that may be mentioned herein, the thickness may be less than or equal to 500 nm, such as from 20 to 500 nm, such as from 50 to 499 nm, such as from 100 to 400 nm, such as from 200 to 300 nm.
[0112] For the avoidance of doubt, it is explicitly contemplated that where a number of numerical ranges related to the same feature are cited herein, that the end points for each range are intended to be combined in any order to provide further contemplated (and implicitly disclosed) ranges. Thus, in relation to the above related numerical ranges, there is disclosed:
[0113] from 20 nm to 50 nm, from 20 nm to 100 nm, from 20 nm to 200 nm, from 20 nm to 300 nm, from 20 nm to 400 nm, from 20 nm to 499 nm, from 20 nm to 500 nm, from 20 nm to 800 nm, from 20 nm to 2 μm, from 20 nm to 20 μm;
[0114] from 50 nm to 100 nm, from 50 nm to 200 nm, from 50 nm to 300 nm, from 50 nm to 400 nm, from 50 nm to 499 nm, from 50 nm to 500 nm, from 50 nm to 800 nm, from 50 nm to 2 am, from 50 nm to 20 μm;
[0115] from 100 nm to 200 nm, from 100 nm to 300 nm, from 100 nm to 400 nm, from 100 nm to 499 nm, from 100 nm to 500 nm, from 100 nm to 800 nm, from 100 nm to 2 μm, from 100 nm to 20 μm;
[0116] from 200 nm to 300 nm, from 200 nm to 400 nm, from 200 nm to 499 nm, from 200 nm to 500 nm, from 200 nm to 800 nm, from 200 nm to 2 μm, from 200 nm to 20 μm;
[0117] from 300 nm to 400 nm, from 300 nm to 499 nm, from 200 nm to 500 nm, from 300 nm to 800 nm, from 300 nm to 2 μm, from 300 nm to 20 μm;
[0118] from 400 nm to 499 nm, from 400 nm to 500 nm, from 400 nm to 800 nm, from 400 nm to 2 μm, from 400 nm to 20 μm;
[0119] from 499 nm to 500 nm, from 499 nm to 800 nm, from 499 nm to 2 μm, from 499 nm to 20 μm;
[0120] from 500 nm to 800 nm, from 500 nm to 2 μm, from 500 nm to 20 μm; and
[0121] from 800 nm to 2 μm, from 800 nm to 20 μm.
[0122] Any of the ranges mentioned above may be applied to any combination of embodiments listed herein unless otherwise specified.
[0123] In particular examples discussed herein, the thickness of the UiO-66(Zr) membranes fabricated on the carbon cloth and alumina hollow fiber were 800 nm and 3.5 μm, respectively.
[0124] Furthermore, the thickness of a rare earth membrane is about 20 μm.
[0125] When used herein the term “carbon cloth” may also cover carbon films.
[0126] The thickness of MOF membranes with a secondary building unit having the formula Ia fabricated on the carbon cloth and alumina hollow fiber in certain examples herein were 800 nm and 3.5 μm, respectively. Besides, the thickness of the MOF membranes with a secondary building unit having the formula Ib on the alumina hollow fiber was about 20 μm. Therefore, the thicknesses of polycrystalline metal-organic framework membranes mentioned in examples herein are 800 nm to 20 μm.
[0127] These thicknesses mentioned directly above may be reduced through changes in the method of manufacture and it may be desired to achieve a thickness of less than 500 nm, for example, from 200 to 300 nm.
[0128] The membranes described above may have a broad utility in the separation of fluids and materials within said fluids. Thus there is also disclosed a method of using a polycrystalline metal-organic framework membrane as described herein in a process of separating a fluid into a filtrate fluid and a retentate fluid, the process comprising the steps of:
[0129] (a) providing a fluid in need of separation to a polycrystalline metal-organic framework membrane as described herein;
[0130] (b) allowing or enabling a portion of the fluid to pass through the polycrystalline metal-organic framework membrane to provide a filtrate fluid and thereby providing a filtrate fluid; and
[0131] (c) collecting the filtrate fluid and retentate fluids.
[0132] There are multiple possible separations where the current invention may be beneficial. For example, the fluid to be separated may be selected from: a mixture of gases; an aqueous solution comprising one or more inorganic materials; an aqueous solution comprising one or more organic materials; an aqueous solution comprising one or more inorganic materials and one or more organic materials; a mixture of organic liquids; a mixture of one or more organic liquids and water; a mixture of one or more organic liquids and one or more organic materials; a mixture of one or more organic liquids and one or more inorganic materials; a mixture of one or more organic liquids, one or more organic materials and one or more inorganic materials; a mixture of water, one or more organic liquids and one or more organic materials; a mixture of water, one or more organic liquids and one or more inorganic materials; and a mixture of water, one or more organic liquids, one or more organic materials and one or more inorganic materials.
[0133] Without wishing to be bound by theory, metal-organic framework membranes with hydrophilic ligands may have good water-stability and so may be useful in the separation of mixtures involving water, such as desalination, the removal of metals from wastewater, alcohol dehydration, etc.
[0134] Additionally or alternatively, metal-organic framework membranes having ligands endowed with reactive groups (e.g. —NH.sub.2 groups) may also be further functionalised to enable them to be used in further applications, such as a gas sensor, oil/water separation, photocatalysis, membrane reactors, and so on.
[0135] Particular applications that may be mentioned herein for the membranes include, but are not limited to: separation of organic/water mixtures or organic systems; desalination and wastewater purification (i.e. the removal of ions or dyes from wastewater, known as organic solvent nanofiltration); and gas separation. The examples below provide detailed descriptions and results for various membranes of the current invention applied to these technologies. As will be appreciated, application to the other separation methods can be extrapolated from the methods disclosed herein and would be readily achieved by a skilled person based upon the instruction provided in this document and their common knowledge.
[0136] The membranes described herein may be manufactured by any suitable method. A method of forming a polycrystalline metal-organic framework membrane as described herein comprises the steps of: [0137] providing a seeded substrate having a surface seeded with seed crystals of the metal-organic framework, said seed crystals formed from a secondary building unit having the formula Ia or Ib and a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II, where formulae Ia, Ib and II are as described hereinbefore; and [0138] subjecting the seeded substrate to a first mother liquor comprising a solvent, a metal salt precursor and a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II as described above, for a first period of time under conditions sufficient to form a metal-organic framework membrane, wherein the metal salt precursor and the ligand are selected to form the same metal-organic framework as in the seed crystals.
[0139] As will be appreciated, the seeded substrate used in the method outlined above is required for said method to work. The seeded substrate may be formed by immersing a substrate having a surface in a second mother liquor that comprises a solvent, a metal salt precursor and a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II as described hereinbefore for a second period of time to provide a seeded substrate having a surface seeded with seed crystals of the metal organic framework, said seed crystals formed from a secondary building unit having the formula Ia or Ib and a ligand selected from fumaric acid, butynedioic acid, squaric acid, naphthalene-2,6-dicarboxylic acid, [2,2′-bipyridine]-5,5′-dicarboxylic acid, or a ligand having formula II, where formulae Ia, Ib and II are as described hereinbefore.
[0140] Further aspects and embodiments of the invention are provided in the following non-limiting examples.
[0141] As described in Example 1, the membrane may be a polycrystalline rare-earth MOF membrane (Sm-DOBDC) supported on alumina hollow fiber. When separating 5 wt. % water/ethanol feed solution at 323 K, the Sm-DOBDC membrane exhibits high water stability with a total flux of 786.4±33.7 g.Math.m.sup.−2.Math.h.sup.−1 and a 99.8±0.2 wt. % water concentration in permeate (separation factor: >9481) as shown in Example 2. Because of the reactive RE-containing building units, the Sm-DOBDC membrane can be healed in-situ by treating with reaction solution as shown in Example 3. As such, the membranes disclosed herein may generally have the ability to heal in-situ.
[0142] As described in Example 4, the membrane may be a continuous polycrystalline UiO-66(Zr)—NH.sub.2 membrane supported on flexible carbon cloth substrate. The UiO-66(Zr)—NH.sub.2 membrane possesses sub-micron thicknesses with a certain flexibility and angular bend tolerance up to 10°, as shown in Example 7. In addition, the UiO-66(Zr)—NH.sub.2 membrane exhibits great separation performance in organic solvent nanofiltration (OSN) because of its excellent solvent resistance, with above 99.8% dye rejection and high flux for dichloromethane (ca. 0.17 kg m.sup.−2 h.sup.−1 bar.sup.−1) as shown in Example 6. The UiO-66(Zr)—NH.sub.2 membrane possesses low thickness (ca. 0.8 μm), high chemical stability (stable over a wide pH range from pH 1 to 11 as shown in Example 6), and low defect concentration arising from the optimized fabrication procedure of the membrane afford its excellent separation performance in both aqueous and organic solvent-based liquid separations. In particular, near complete rejection of dyes (MB, OR, and NR) and moderate permeance of organic solvents (0.175 kg m.sup.−2 h.sup.−1 bar.sup.−1 for dichloromethane and 0.24 kg m.sup.−2 h.sup.−1 bar.sup.−1 for methanol) as shown in Example 6 suggest promising applications of the membranes disclosed herein in solvent resistant nanofiltration, both those in the examples mentioned above and more generally.
EXAMPLES
Materials
[0143] Sm(NO.sub.3).sub.3, Y(NO.sub.3).sub.3, Dy(NO.sub.3).sub.3, Er(NO.sub.3).sub.3, and Gd(NO.sub.3).sub.3 were purchased from Sinopharm Group Co. Ltd. 2-Fluorobenzoic acid (2-FBA) and 2,5-dihydroxy-1,4-benzenedicarboxylic acid (DOBDC) were obtained from Energy Chemical and Bepharm Ltd. N,N-dimethylformamide (DMF) and ethanol were supplied by Avantor Performance Materials, Inc. and VWR. Alumina ceramic tubes (O.D.: 1.96 mm, length: 50 mm, porosity: ca. 40%, average pore size: 1.6 μm) were provided by Nanjing Tech University and prepared in accordance with reported procedures (ACS Appl. Mater. Interfaces, 9 (2017) 22268-22277).
Characterization
[0144] The morphology of Sm, Y, Dy, Er, and Gd-DOBDC MOF crystals and Al.sub.2O.sub.3 hollow fiber membranes were observed by field emission scanning electron microscopy (FESEM, JSM-7610F, JEOL). The crystal phases were measured by powder X-ray diffraction (PXRD, MiniFlex 600, Rigaku) equipped with a Cu sealed tube (λ=0.154178 nm) with a scan rate of 0.04 deg.Math.s.sup.−1 in the 2θ range of 5-50°. The original sample (20 mg) with the strongest peak intensity at 7.4° and 8.1° was denoted as 100% crystallinity. The samples were processed by acid/basic solution with different pH value or ethanol aqueous solutions with different ratios of ethanol to water, and the relative crystallinity of samples was obtained by calculating the ratio of the peak intensity. N.sub.2 sorption isotherms were measured using a Micromeritics ASAP 2020 surface area and pore size analyzer. Pore size distribution data were calculated from the N.sub.2 adsorption isotherms at 77 K based on nonlocal density functional theory (NLDFT) model. Thermogravimetric analyses (TGA) were performed at a heating rate of 10° C./min using a Shimadzu DTG-60AH.
Preparation of Rare-Earth MOFs and their Characterisation
[0145] A series of rare-earth fcu MOFs (RE-MOFs, RE=Sm, Y, Dy, Er, Gd) based on 2,5-dihydroxy-1,4-benzenedicarboxylate (DOBDC) as the ligand and 2-fluorobenzoic acid (2-FBA) as the modulator and structure directing agent were prepared via a solvothermal method.
[0146] In a typical experiment, Sm(NO.sub.3).sub.3.6H.sub.2O and DOBDC were firstly dispersed into the DMF/ethanol mixing solution (V.sub.DMF:V.sub.ethanol=2:1) under ultrasonic stirring, followed by adding 2-FBA and cultivating for 3 days at 105° C. A molar composition of 1 Sm(NO.sub.3).sub.3: 1.5 DOBDC: 500 DMF/ethanol: 70 2-FBA was adopted. The resultant products were washed with DMF and ethanol, and then heated at 120° C. under vacuum overnight.
Characterisation Results of RE-MOFs
[0147] The synthesized Sm, Y, Dy, Er, and Gd-MOFs have clear facets with octahedral crystal sizes of about 2-3 μm based on SEM images (
[0148] Their powder X-ray diffraction (PXRD) patterns (
[0149] The activated RE-MOFs exhibit Type I N.sub.2 sorption isotherms at 77 K, with Brunauer-Emmett-Teller (BET) surface areas in the range of 302-653 m.sup.2.Math.g.sup.−1 (
Characterisation Results of Sm-DOBDC MOFs
[0150] Sm-DOBDC was chosen as the target membrane material because of its prominent BET surface area (520 m.sup.2.Math.g.sup.−1) and a mainly microporous structure.
[0151] The pore size distribution of Sm-DOBDC reflects significant microporosity at about 4 Å (
[0152] On the basis of previous studies, the weight loss of MOFs during thermogravimetric analyses (TGA) is inversely correlated with the defects of the MOFs. The theoretical TGA plateau for Sm.sub.6(OH).sub.8(DOBDC).sub.6 after removing all the solvents should be at 212.8% when the weight of the end product, Sm.sub.2O.sub.3, is normalized to 100%. The theoretical ratio between DOBDC and the Sm.sub.6 SBU should be 6 in an ideal framework, therefore the weight contribution per DOBDC linker would be 18.8% [(212.8%-100%)/6]. Based on the experimental TGA plateau of 205% in the obtained Sm-DOBDC after removing all the solvents, the real ratio between DOBDC and the Sm.sub.6 SBU can be determined as 5.6 [(205%-100%)/18.8%] (
Water Stability of Sm-DOBDC MOFs
[0153] The stability of Sm-DOBDC was evaluated by soaking the crystals in water/ethanol solution for 7 days with various ratios of water (i.e., 0, 20, 40, 60, 80, and 100% of water) under different pH values (i.e., 1, 3, 5, 7, 9, 11, and 13), and checking the relative crystallinity based on the PXRD diffraction peak intensity at 26=7.0 and 8.1°.
[0154] The relative crystallinity of Sm-DOBDC is above 80% under a pH value range of 3-11 with various ethanol/water ratios, confirming the excellent chemical stability of Sm-DOBDC that is suitable for alcohol dehydration even under harsh conditions (
Example 1: Preparation and Characterisation of Sm-DOBDC Membranes
[0155] Defect-free Sm-BOBDC membrane was fabricated on alumina hollow fibers by the secondary growth method.
Preparation of Sm-DOBDC Membrane
[0156] The polycrystalline Sm-DOBDC membranes were fabricated on the outer surface of porous alumina ceramic hollow fibers by secondary growth synthesis. The alumina supports with both ends sealed were placed in a polytetrafluoroethylene holder, and immersed into a mother solution with a molar composition of 1 Sm(NO.sub.3).sub.3: 1.5 DOBDC: 500 DMF/ethanol: 70 2-FBA.
[0157] The crystallization was executed at 105° C. for (1+3) days (in-situ growth: 1 day, secondary growth: 3 days) in a Teflon-lined stainless steel autoclave. Specifically, the cultivation was performed at 105° C. for 24 h (1 day) in a Teflon-lined stainless steel autoclave. In this cultivation Sm-DOBDC nanocrystals were seeded on the outer of the support. After cooling to room temperature, the seeded Sm-DOBDC membranes were thoroughly washed with DMF and ethanol for several times, followed by drying at room temperature overnight. The crystal seeds grown on the substrate were further integrated together to form a continuous and well-intergrown polycrystalline Sm-DOBDC membrane by secondary growth in the same mother solution conducted at 105° C. for 72 h (3 days). After cooling to room temperature, the obtained Sm-DOBDC membranes were sequentially washed with DMF and ethanol, then dried at room temperature overnight before further tests.
Characterisation of Seeded Sm-DOBDC Membranes after 1 Day In-Situ Growth
[0158] The seeded Sm-DOBDC membrane mainly comprises an amorphous membrane layer, and some Sm-DOBDC seeds were randomly deposited on the surface of the alumina substrate (
[0159] Due to the large crystal grains (2-3 μm), the thickness of the Sm-DOBDC seeding layer is approximately 4 μm.
[0160] The PXRD spectrum of the crystals collected from the bottom of the reaction container matches well with the simulated one (not included). These results suggest that the Sm-DOBDC crystals prefer homogeneous nucleation rather than membrane formation on alumina substrates because of the limited heterogeneous nucleation sites.
Characterisation of Sm-DOBDC Membranes after 3-Day Secondary Growth
[0161] After solvothermal synthesis at 105° C. for 72 h, well-intergrown polycrystalline Sm-DOBDC membranes without any visible cracks or pinholes were fabricated (
[0162] The thickness of Sm-DOBDC membrane was estimated to be about 20 μm, which is thicker than those of UiO-66 membranes (s 6 μm) while thinner than that of sod-ZMOF membrane (ca. 30 μm).
[0163] The energy-dispersive X-ray (EDX) images (
[0164] To further verify their water stability, Sm-DOBDC membranes were soaked in methanol/water and ethanol/water solutions for several days. After soaking, the crystal grains in the membranes were still closely arranged without any etching, indicating their high stability in alcohol/water solutions (
Example 2: Use of Sm-DOBDC Membrane for Pervaporation-Based Separation of Alcohol/Water Mixtures
[0165] The separation performance of the Sm-DOBDC membrane as prepared according to Example 1 was evaluated by pervaporation-based alcohol dehydration.
[0166] Experimental Set-Up and Calculations
[0167] The performance of the membranes was evaluated via pervaporation for separating water from aqueous organics using a home-built set-up (
[0168] Before collecting samples, 10 min was given to the system for stabilization. The permeate vapour was collected with a cold trap equipped with liquid nitrogen. The alcohol concentration of the permeate side sample was estimated by a refractometer (PAL-RI, ATAGO). This was done by obtaining the relationships between known concentrations of methanol, ethanol, 1-propanol, and 2-propanol versus their refractive indexes, and then comparing the measured refractive index with the obtained relationships to determine the alcohol concentration of the permeate side sample. The permeate sample was collected for three times, and the average value was obtained.
[0169] The total permeation flux (F) was obtained by weighing the condensate of the cold trap (Equation (1)).
F=W/(A×Δt) Eq. (1)
[0170] where W refers to the mass of liquids collected from permeate (g); A is the effective membrane area (m.sup.2); and Δt is the duration of the sample collection (h).
[0171] The separation factor (a) is formulated as (Equation (2))
α=[Y.sub.water/(1−Y.sub.water)]/[X.sub.water/(1−X.sub.water)] Eq. (2)
[0172] where Y.sub.water and X.sub.water represent the mass fraction of water in the permeate and feed sides, respectively.
Effect of Alcohol Kinematic Diameter on Flux and Water Concentration in Permeate
[0173] The measured fluxes appear to decrease with increasing kinetic diameters of the alcohols (
[0174] The water concentration in permeate increases from 85.5±0.35 wt. % (for water/methanol mixture) to above 99 wt. % (for water/2-propanol and water/1-propanol mixtures), and the corresponding separation factors of water/methanol, ethanol, 2-propanol, and 1-propanol feed solutions are 112.0±3.2, 741.0±15, 2514.3±340, and 1881±145, respectively, supporting the molecular sieving separation mechanism.
Effect of Water Content in Feed on Flux and Water Concentration in Permeate
[0175] When the feed concentration increases from 2 wt % water/ethanol to 8% wt % water/ethanol, more water molecules can favorably pass through the MOF layer, and the total flux increases from 265.8±1.4 to 580±28.3 g.Math.m.sup.−2.Math.h.sup.−1 (
[0176] For 2, 5, and 8 wt. % water/ethanol feed solutions, the water concentrations in permeate are 94.29±0.91, 97.5±0.05, and 98.86±0.21 wt. % with the separation factors of 809.1±160, 741.0±15, and 997.2±160, respectively (
Effect of Time on Water Concentration in Permeate
[0177] The long-term stability of the membrane was assessed within 95 h (
[0178] The total flux is about 417.2-460.7 g.Math.m.sup.−2.Math.h.sup.−1 within the time range of 62.6-94.9 h, demonstrating the long-term stability of the membrane in aqueous solutions.
Effect of Feed Temperature on Ethanol Dehydration Performance
[0179] The temperature effect on the ethanol dehydration performance was evaluated using another freshly prepared Sm-DOBDC membrane. Due to the variation in membrane quality, this membrane exhibited even better separation performance for the dehydration of 5 wt. % water/ethanol feed solution, with a total flux of 546.7±18.3 g.Math.m.sup.−2.Math.h.sup.−1 and a 99.8±0.2 wt. % water concentration in permeate being achieved at 298 K, equivalent to a separation factor of above 9481.
[0180] When the testing temperature was raised to 323 K, the total flux increased by 44% to 786.4±33.7 g.Math.m.sup.−2.Math.h.sup.−1 due to accelerated molecular diffusion at higher temperatures; surprisingly, water concentration in the permeate remained unchanged (99.8±0.2 wt. %), suggesting an almost perfect molecular sieving separation mechanism (
Comparing Separation Performance of Sm-DOBDC Membrane Against Other Reported Polycrystalline MOF Membranes
[0181] Compared with other polycrystalline MOF membranes reported previously such as UiO-, ZIF-, and MIL-membranes (
TABLE-US-00001 TABLE 1 Performance summary of membrane-based ethanol dehydration Flux Separation Feed mixture Temp. (gm.sup.−2 .Math. factor (mass ratio) Membrane (K) h.sup.−1) (water/organic) Ref. EtOH/H.sub.2O (95/5) BZSM-5 298 500 8.2 [1] EtOH/H.sub.2O (90/10) UiO-66 303 640 4.3 [2] EtOH/H.sub.2O (90/10) UiO-66 343 3730 ± 120 55.8 ± 1.0 [3] EtOH/H.sub.2O (95/5) ZIF-71 298 322.18 6.07 [4] EtOH/H.sub.2O MIL-96 333 125 6 [5] (94.4/5.6) EtOH/H.sub.2O (95/5) ZIF-71 298 2600 6.88 [6] EtOH/H.sub.2O (90/10) CAU-10-H 313 397 324 [7] EtOH/H.sub.2O (90/10) CAU-10-H 338 493 148 [7] EtOH/H.sub.2O (95/5) ZIF-71/PDMS 323 −900 9.9 [8] EtOH/H.sub.2O MIL-53(AI)- 313 −900 −13 [9] (92.5/7.5) NH2/PVA EtOH/H.sub.2O (95/5) Sm-DOBDC 298 546.7 ± 18.3 >9481 this work EtOH/H.sub.2O (95/5) Sm-DOBDC 323 786.4 ± 33.7 >9481 this work EtOH/H.sub.2O (92/8) Sm-DOBDC 298 580 ± 28.3 997.2 ± 160 this work EtOH/H.sub.2O (98/2) Sm-DOBDC 298 265.8 ± 1.4 809.1 ± 160 this work
TABLE-US-00002 TABLE 2 Performance summary of membrane-based methanol dehydration Flux Separation Feed mixture Temp. (gm.sup.−2 .Math. factor (mass ratio) Membrane (K) h.sup.−1) (water/organic) Ref. MeOH/HO (95/5) B-ZSM-5 333 900 8.4 [10] MeOH/H.sub.2O Pervap 2201 333 280 ≈7.5 [11] (97.1/2.9) MeOH/H.sub.2O (85/15) Polyphenylsulfone 333 33 11 [12] MeOH/H.sub.2O (90/10) UiO-66 323 1580 5.0 [2] MeOH/H.sub.2O (95/5) ZIF-71 298 394.64 21.38 [4] MeOH/H.sub.2O (95/5) ZIF-71/PDMS 323 — 8.0 [8] MeOH/H.sub.2O (95/5) Sm-DOBDC 298 1520.8 ± 69.9 112.0 ± 3.2 this work
TABLE-US-00003 TABLE 3 Performance summary of membrane-based propanol dehydration Flux Separation Feed mixture Temp. (gm.sup.−2 .Math. factor (mass ratio) Membrane (K) h.sup.−1) (water/organic) Ref. IPA/H.sub.2O (95/5) B-ZSM-11 333 310 16 [13] IPA/H.sub.2O (95/5) B-ZSM-5 333 71 42 [10] IPA/H.sub.2O (90/10) UiO-66 343 4620 ± 90 689 ± 55 [3] IPA/H.sub.2O (85/15) ZIF-8/PBI 333 103 1686 [14] IPA/H.sub.2O (95/5) ZIF-71/PDMS 323 — 13.6 [8] IPA/H.sub.2O (85/15) ZIF-90/P84 333 114 385 [15] IPA/H.sub.2O (90/10) ZIF-8/PVA 303 868 132 [16] IPA/H.sub.2O (95/5) Sm-DOBDC 298 305.5 ± 4.95 1881 ± 145 this work Note: EtOH: ethanol; MeOH: methanol; IA: isopropanol; PVA: poly(vinyl alcohol); PDMS: Polydimethylsiloxane; PBI: polybenzimidazole [0182] [1] F. H. Saboor, S. N. Ashrafizadeh, H. Kazemian, Synthesis of BZSM-5 membranes using nano-zeolitic seeds: characterization and separation performance, Chem. Eng. Technol., 35 (2012) 743-753. [0183] [2] M. Miyamoto, K. Hori, T. Goshima, N. Takaya, Y. Oumi, S. Uemiya, An organoselective zirconium-based metal-organic-framework UiO-66 membrane for pervaporation, Eur. J. Inorg. Chem., 2017 (2017) 2094-2099. [0184] [3] X. Liu, C. Wang, B. Wang, K. Li, Novel organic-dehydration membranes prepared from zirconium metal-organic frameworks, Adv. Funct. Mater., 27 (2017) 1604311. [0185] [4] X. Dong, Y. S. Lin, Synthesis of an organophilic ZIF-71 membrane for pervaporation solvent separation, Chem. Commun., 49 (2013) 1196-1198. [0186] [5] Y. Hu, X. Dong, J. Nan, W. Jin, X. Ren, N. Xu, Y. M. Lee, Metal-organic framework membranes fabricated via reactive seeding, Chem. Commun., 47 (2011) 737-739. [0187] [6] K. Huang, Q. Li, G. Liu, J. Shen, K. Guan, W. Jin, A ZIF-71 hollow fiber membrane fabricated by contra-diffusion, ACS Appl. Mater. Interfaces, 7 (2015) 16157-16160. [0188] [7] H. Jin, K. Mo, F. Wen, Y. Li, Preparation and pervaporation performance of CAU-10-H MOF membranes, J. Membr. Sci., 577 (2019) 129-136. [0189] [8] Y. Li, L. H. Wee, J. A. Martens, I. F. J. Vankelecom, ZIF-71 as a potential filler to prepare pervaporation membranes for bio-alcohol recovery, J. Mater. Chem. A, 2 (2014) 10034-10040. [0190] [9] G. Wu, M. Jiang, T. Zhang, Z. Jia, Tunable pervaporation performance of modified MIL-53(Al)—NH.sub.2/poly(vinyl alcohol) mixed matrix membranes, J. Membr. Sci., 507 (2016) 72-80. [0191] [10] T. C. Bowen, H. Kalipcilar, J. L. Falconer, R. D. Noble, Pervaporation of organic/water mixtures through B-ZSM-5 zeolite membranes on monolith supports, J. Membr. Sci., 215 (2003) 235-247. [0192] [11] D. Van Baelen, B. Van der Bruggen, K. Van den Dungen, J. Degreve, C. Vandecasteele, Pervaporation of water-alcohol mixtures and acetic acid-water mixtures, Chem. Eng. Sci., 60 (2005) 1583-1590. [0193] [12] Y. Tang, N. Widjojo, G. M. Shi, T. S. Chung, M. Weber, C. Maletzko, Development of flat-sheet membranes for C1-C4 alcohols dehydration via pervaporation from sulfonated polyphenylsulfone (sPPSU), J. Membr. Sci., 415-416 (2012) 686-695. [0194] [13] S. Li, V. A. Tuan, R. D. Noble, J. L. Falconer, ZSM-11 membranes: characterization and pervaporation performance, AlChE J., 48 (2002) 269-278. [0195] [14] G. M. Shi, T. Yang, T. S. Chung, Polybenzimidazole (PBI)/zeolitic imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation dehydration of alcohols, J. Membr. Sci., 415-416 (2012) 577-586. [0196] [15] D. Hua, Y. K. Ong, Y. Wang, T. Yang, T. S. Chung, ZIF-90/P84 mixed matrix membranes for pervaporation dehydration of isopropanol, J. Membr. Sci., 453 (2014) 155-167. [0197] [16] M. Amirilargani, B. Sadatnia, Poly(vinyl alcohol)/zeolitic imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation dehydration of isopropanol, J. Membr. Sci., 469 (2014) 1-10.
[0198] To further interpret the mechanism governing the excellent alcohol dehydration performance of the membrane, vapor sorption tests of water, methanol, and ethanol were performed at 293 K using a commercial instrument Quantachrome iQ3 (
Example 3: In-Situ Healing of Sm-DOBDC Membranes
[0199] The possibility of in-situ healing in Sm-DOBDC membranes was demonstrated to address defect formation during the operation of polycrystalline membranes.
Procedure
[0200] A partially degraded Sm-DOBDC membrane was prepared by immersing a freshly prepared membrane into a 80 wt. % water/ethanol solution (pH=2) for a certain period of time (up to 35 h, please refer to the experimental details in the next paragraph) to mimic the possible membrane degradation during long-term operation under corrosive environments. In-situ healing was conducted by treating the partially degraded membrane at 105° C. with the supernatant generated during the Sm-DOBDC membrane preparation process (
[0201] To elaborate on the healing procedure, the degraded Sm-DOBDC membrane was placed into a 20 mL scintillation vial filled with the supernatant which can be repeatedly gathered in the membrane preparation or healing procedure. Then, the membrane was cultivated at 105° C. for 2100 min (35 h). Finally, the healed membrane was washed with DMF and ethanol for three times, respectively, followed by activation in the fume hood overnight.
[0202] To identify the appropriate healing time, pure Al.sub.2O.sub.3 hollow fiber was treated with the supernatant under different periods (21.7, 25, or 35 h). A continuous Sm-DOBDC layer could be formed at 35 h. Therefore, the in-situ healing process of defective Sm-DOBDC membranes was proceeded at 35 h (
Effect of Healing on Membrane Morphology
[0203] After the healing process, the apparent intercrystal gaps in the partially degraded Sm-DOBDC membrane were completely covered with newly grown small Sm-DOBDC crystals (
Effect of Healing on Separation Performance
[0204] The membrane performance was evaluated using 5 wt. % water/ethanol feed solution at 298 K based on the set-up described in Example 2. For the deteriorated Sm-DOBDC membrane, the total flux increased to 948.8±4.1 g.Math.m.sup.−2.Math.h.sup.−1, and the permeation water concentration decreased to 60.0±1.3 wt. %. In contrast, the total flux of the healed membrane could reach 563.4±7.0 g.Math.m.sup.−2.Math.h.sup.−1, and the permeate water concentration reverted to 94.6±0.2 wt. % even after 18 h of test, confirming that the healing treatment can effectively restore the separation performance (
[0205] Without wishing to be bound by theory, the healing mechanism can be explained as follows. Since there are many small nuclei in the solution adopted for the healing process, the Sm-DOBDC nanocrystals were gradually shaped and deposited on the surface of the defective Sm-DOBDC membranes after incubation at 105° C. for a period of time. Notably, the new Sm-DOBDC grains preferentially grew on the gaps and deficiencies of the membranes, without altering the thickness of the membranes in the chosen reaction time. Therefore, excellent separation performance was obtained in the healed Sm-DOBDC membrane.
Comparative Example: Healing of Zr-DOBDC Membranes
[0206] In order to further illustrate the unique in-situ healing property of Sm-DOBDC membrane, a similar healing procedure was applied to Zr-MOF membranes. Briefly, pure Al.sub.2O.sub.3 substrate was treated with the supernatant generated during the preparation of Zr-DOBDC membrane (aka UiO-66-(OH).sub.2 membrane, ACS Appl. Mater. Interfaces 2017, 9, 37848-37855).
[0207] At 21.7, 25, and 35 h, the substrate surface was all deposited with amorphous solid particles, and no continuous Zr-DOBDC polycrystalline membrane layers could be found (
Example 4: Preparation and Characterization of Polycrystalline UiO-66-NH.SUB.2 .Membrane
[0208] A continuous polycrystalline UiO-66(Zr)—NH.sub.2 membrane supported on flexible carbon cloth substrate was fabricated by a secondary growth method as summarised by
Materials and Characterization
[0209] Zirconium (IV) chloride (ZrCl.sub.4) and formic acid were purchased from Alfa Aesar. Benzoic acid and calcium chloride were purchased from Sinopharm Chemical Reagent Co, Ltd. 2-Aminoterephthalic acid (ATC) was purchased from Tee Hai Chem Pte Ltd. Carbon cloth was purchased from Hengqiu Technology, China. N,N-Dimethylformamide (DMF) was purchased from Avantor Performance Materials, Inc. Aluminum chloride (AlCl.sub.3), methylene blue, and Nile red were purchased from TCI. Sodium chloride was purchased from VWR. 1,4-Dicarboxybenzene (BDC), oil red and anhydrous magnesium chloride were purchased from Sigma. All the chemicals were used without further purification.
[0210] Scanning electron microscope (SEM) images of the pure carbon cloth, seeded carbon cloth, and the prepared polycrystalline UiO-66(Zr)—NH.sub.2 membranes were observed via a field-emission scanning electron microscope (FESEM, JSM-7610F, JEOL). The elements present in the prepared membranes were determined by EDS (Oxford Instruments, 80 mm.sup.2 detector). Crystal phase was characterized by X-ray diffraction (XRD) on an X-ray powder diffractometer (Rigaku MiniFlex 600) at a scan rate of 1° min.sup.−1. Water contact angles (WCAs) were measured using a contact angle meter (DSA30, US). Fourier transform infrared spectroscopy (FTIR) spectra were obtained with a Nicolet 6700 FTIR spectrometer.
Carboxylation
[0211] Carbon cloth was initially carboxylated by placing the carbon cloth in a mixed solution containing nitric acid (65-68%) and hydrochloric acid (36-38%) (v/v=1/10) for one day, and then thoroughly rinsed with water and dried under vacuum for one day.
[0212] Carboxyl groups on the surface serve as anchoring sites for the growth of MOF layers. Therefore, carboxyl groups were introduced onto the surface of the carbon cloth by acid treatment. Fourier-transform infrared spectroscopy and water contact angle tests verified the successful introduction of carboxyl groups on the surface of the carbon cloth. It can be seen from the FTIR spectra that the carboxylated carbon cloth has peaks in the ranges of 2500-3300 and 1250-1428 cm.sup.−1, representing the O—H bond in the carboxyl groups. In addition, a strong absorption peak at around 1700 cm.sup.−1 can be found in the carboxylated carbon cloth, representing the expansion and contraction of C═O double bonds in the carboxyl groups.
Seeding
[0213] The carboxylated carbon cloth substrate was seeded with UiO-66(Zr)—NH.sub.2 crystals via in situ solvothermal method in a seeding solution with a molar ratio of 1 ZrCl.sub.4/1 ATC/1 H.sub.2O/500 DMF/100 benzoic acid. The seeding process was conducted in a Teflon-lined stainless steel autoclave at 120° C. for 1 day. After cooling to room temperature, the seeded carbon cloth was thoroughly washed with DMF and ethanol, and then dried at room temperature for further usage.
[0214] As shown by
Secondary Growth and Activation
[0215] A continuous and well-intergrown polycrystalline UiO-66(Zr)—NH.sub.2 membrane can be obtained by a secondary growth method, in which the seeded substrate was treated in the growth solution with a molar ratio of 1 ZrCl.sub.4/1 ATC/500 DMF/100 benzoic acid. The membrane growth was conducted at 120° C. for 3 days.
[0216] The prepared membranes were activated by soaking in fresh DMF for 12 h and repeating several times to ensure that the membrane surface does not have extra crystals deposited or residual reaction precursors. After that, the residual ligands and DMF were completely exchanged with hot ethanol before membrane performance tests.
[0217] UiO-66(Zr)—NH.sub.2 powders were collected from the membrane growth solution after membrane preparation, and thoroughly washed with DMF and ethanol before further usage.
Post-Synthetic Defect Healing
[0218] Post-synthetic defect healing was conducted by soaking the as-prepared polycrystalline MOF membranes or recovered MOF powders in healing solutions with a molar ratio of 2 ATC/500 DMF at 120° C. for 24 h.
Characterization of Healed MOF Crystals
[0219] The healed crystals exhibit a reduced Brunauer-Emmett-Teller (BET) surface area (from 893 to 786 m.sup.2 g.sup.−1,
[0220] The thermogravimetric analysis also indicates reduction in the proportion of missing linkers following the healing process (from 12.1% to 5.7%). The thermogravimetric analyses (TGA) were performed using a Shimadzu DTG-60AH instrument. Each TGA run was made in two different heating stages under a simultaneous feed of air (20 mL min.sup.−1). In the first step, the samples were heated in the temperature range of 20-100° C. and kept for 30 min at a rate of ° C. min.sup.−1; in the second step, the samples were continually heated to 950° C. at a rate of 5° C. min.sup.−1.
Characterization of as-Prepared Membrane
[0221] As shown by the SEM images in
[0222] Elemental mapping based on energy dispersive spectroscopy (EDS) was conducted to analyze the chemical composition of the membrane (
[0223] The water contact angle of the final UiO-66-NH.sub.2 membrane was tested. The water contact angle of the membrane became 0° after 6 minutes, indicating that the final membrane is hydrophilic. In contrast, the water contact angle of the initial pristine carbon cloth could reach 130°, suggesting its high hydrophobicity.
[0224] The prepared UiO-66-NH.sub.2 membrane displays negative surface zeta potentials of −22.1, −33.1, and −41.7 mV at pH=4, 7, and 10, respectively.
Effect of Carboxylation of Carbon Substrate and Two-Step Process on Membrane Growth
[0225] Polycrystalline UiO-66(Zr)—NH.sub.2 membranes were grown in accordance with the procedures above except that a pristine carbon cloth was used with two-step growth (instead of a carboxylated carbon cloth). In another experiment, polycrystalline UiO-66(Zr)—NH.sub.2 membranes were grown on a carboxylated cloth with direct growth. Both experiments did not yield high quality continuous membranes (
Effect of Ligand on Membrane Growth
[0226] Polycrystalline UiO-66(Zr)—NH.sub.2 membranes were grown in accordance with the procedures above except terephthalic acid (BDC) was selected as the ligand instead of aminoterephthalic acid (ATC). High quality continuous membranes were not obtained in spite of the use of a carboxylated carbon cloth with a two-step membrane growth procedure (
[0227] The above results underline the importance of carboxylation in carbon cloth and two-step procedure in growing high quality polycrystalline Zr-MOF membranes on carbon cloth substrate, in which the selection of ligand also plays an important role.
Example 5: Use of Healed Polycrystalline UiO-66-NH.SUB.2 .Membrane for Gas Separation and Separation Under Aqueous Conditions
[0228] The membranes as prepared according to Example 4 was evaluated for gas separation and separation under aqueous conditions.
Use of Healed Membrane for Single Gas Permeation
[0229] The integrity of the healed membranes was evaluated by single-gas permeation under a transmembrane pressure of 1.0 bar using H.sub.2 (2.89 Å), CO.sub.2 (3.3 Å), N.sub.2 (3.64 Å), CH.sub.4 (3.8 Å), and SF.sub.6 (5.13 Å,
[0230] The single gas permeation performance of the membrane was tested at room temperature under a transmembrane pressure difference of 1.0 bar using a home-made Wicke-Kallenbach gas permeation apparatus reported in ACS Appl. Mater. Interfaces 9 (2017) 37848-37855. The volumetric gas flow rates were controlled by mass flow controllers (MFC, D07-26C, SevenStar, China). Argon with a volumetric flow rate of 50 mL min.sup.−1 was used as the sweep gas. The molar concentrations of permeate side gas were analysed by a gas chromatograph (GC-2014, Shimadzu) 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. Every data point was tested at least three times to verify their reproducibility. The gas permeance (P.sub.i, GPU) and ideal selectivity (IS) of one gas over other gases were calculated by the following equations.
[0231] where J.sub.i is the flux through membrane, mol m.sup.−2 s.sup.−1; ΔP.sub.i is the transmembrane pressure difference of gases i, Pa.
[0232] where P.sub.i and P.sub.j are the permeance of gas i and gas j, respectively.
[0233] As shown by the results in
[0234] The ideal permselectivities (IS) were calculated to be 3.036 for H.sub.2/CO.sub.2, 10.47 for H.sub.2/N.sub.2, 7.764 for H.sub.2/CH.sub.4, and 41.44 for H.sub.2/SF.sub.6.
Liquid Separation Performance of Healed Membranes
[0235] Brackish water (0.2 wt. % NaCl, CaCl.sub.2, MgCl.sub.2, or AlCl.sub.3) were used as feed solutions under a transmembrane pressure of 3.0 bar to evaluate the liquid separation performance and membrane stability.
[0236] Specifically, the tests were carried out in a dead-end system at room temperature under a transmembrane pressure of 3.0 bar. Before each test, the separation system was stabilized for 12 h to eliminate the adsorption effect. The filtrate was collected every 12 h, and each data point was tested for 3 times. The raw salt solution and filtrate concentrations were determined via a conductivity meter (D-82362 Wellheim). The ion rejections (R, %) were calculated as follows:
[0237] where C.sub.f and C.sub.p are the ion concentrations in the feed and permeate solutions, respectively.
[0238] For the feed of NaCl aqueous solution, the liquid permeance of the healed membrane is around 0.31 kg m.sup.−2 h.sup.−1 bar.sup.−1 with a rejection of around 50% (
[0239] The tests with other feeds containing multivalent cations indicate similar permeance but much higher rejection rates (86.2±0.4% for Ca.sup.2+, 98.2±0.1% for Mg.sup.2+, and 99.1±0.1% for Al.sup.3+,
Example 6: Use of Polycrystalline UiO-66-NH.SUB.2 .Membrane for Separations Involving Organic Solvents
[0240] Having confirmed the excellent membrane quality for the applications in aqueous conditions, the membranes prepared in accordance with Example 4 (that were subjected to post-synthetic defect healing) were tested for separations involving organic solvents or organic solvent nanofiltration. A series of filtration experiments were conducted on the prepared UiO-66(Zr)—NH.sub.2 membrane using organic solutions containing dyes with various molecular weight, size, and charge, including methylene blue (MB, M.sub.w=319.85 g mol.sup.−1, 14.21×5.63 Å, cationic), oil red O (OR, M.sub.W=408.495 g mol.sup.−1, 19.39×10.34 Å, neutral), and Nile red (NR, M.sub.W=318.37 g mol.sup.−1, 14.12×6.51 Å, neutral).
Experimental Set-Up
[0241] The dyes (methylene blue, MB; oil red 0, OR; and Nile red, NR) were dissolved in dichloromethane (CH.sub.2Cl.sub.2) or methanol with a concentration of 100 ppm to prepare the feeds.
[0242] The OSN experiment was carried out in a dead-end system at room temperature under a transmembrane pressure of 6.0 bar (
[0243] In order to study the dye adsorption properties of the original and post-repaired UiO-66-NH.sub.2 crystals, 20 mg of crystals were placed in 100 ppm Nile red methanol solution. After three days to reach adsorption equilibrium, the solution was tested by UV-Vis to determine the content of residual Nile red. Only about 1.0% of Nile red has been adsorbed by original and post-repaired UiO-66-NH.sub.2 crystals, which is expected because the size of Nile red (14.12×6.51 Å) is larger than the aperture size of UiO-66-NH.sub.2 (ca. 6.0 Å), and suggesting that the membrane separation performance should be due to diffusion and size exclusion mechanism.
[0244] The dye rejections (R, %) were calculated as Equation 5, with C, and C, representing the dye concentrations in the feed and permeate solutions, respectively. The permeance of organic solvent (P, kg m.sup.−2 h.sup.−1 bar.sup.−1) was calculated as follows:
[0245] where w is the weight of collected organic solvent from the permeate side (kg); A is the effective membrane area (m.sup.2); Δt is the time (h); ΔP is the transmembrane pressure (bar).
Separation of Methylene Blue/Oil Red/Nile Red from Dichloromethane Solution
[0246] The dye solutions turned clear after passing through the UiO-66(Zr)—NH.sub.2 membrane, indicating near-complete dye rejections. This was experimentally confirmed by the disappearance of the characteristic peaks corresponding to the dye molecules from the UV-Vis spectra of the filtrates. Using the Beer-Lambert law, the rejections of MB, OR, and NR in dichloromethane solutions were calculated to be 99.90, 99.95, and 99.85%, respectively (
Separation of Nile Red from Methanol Solution
[0247] The NR separation in methanol solution were also tested (
Separation of Mixture of Oil Red and Methylene Blue from Methanol Solution
[0248] The membrane separation performance using a methanol solution containing both OR and MB (100 ppm each) were tested. The rejections of OR and MB were both higher than 99.9%, and the methanol permeance was 0.235 kg m.sup.−2 h.sup.−1 bar.sup.−1, confirming good membrane separation performance.
Membrane Stability Over Time and pH
[0249] The liquid flux and rejection remained almost unchanged over an operation period of >48 h during the filtration experiments in both aqueous and organic solvents (
[0250] X-ray diffraction (
[0251] The original carbon cloth and the carbon cloth after solvothermal reaction were observed for three days by SEM (not provided). No morphological changes can be found between these two samples, indicating that the solvothermal reaction has no effect on the structure of the carbon cloth.
5-Day Continuous Separation Test
[0252] Dichloromethane solution containing 100 ppm OR was used as the separation liquid for a five-day continuous separation test, and no significant change in separation performance was observed (rejection rate>99.9%), indicating excellent solvent resistance. The high stability in water and organic solvents, as well as the excellent separation performance make the UiO-66(Zr)—NH.sub.2 membrane an outstanding candidate for water treatment and OSN.
Separation Performance of Membrane Variants
[0253] The separation performance of membranes variants prepared under the section “Effect of carboxylation of carbon substrate and two-step process on membrane growth” and “Effect of ligand on membrane growth” under Example 4 were evaluated and presented in Table 4. The tests were conducted using a similar set-up described in the current example at room temperature under a transmembrane pressure of 3 bar using methanol solutions containing 100 ppm of OR.
[0254] It is evident that the membrane variants exhibited poorer separation performance, which may be attributed to at least the absence of a continuous well-intergrown polycrystalline UiO-66(Zr)—NH.sub.2 layer.
TABLE-US-00004 TABLE 4 Separation performance of UiO-66-NH.sub.2 membranes prepared under different conditions Preparation Conditions Permeance (kg/m.sup.2 h bar) Rejection (%) Non-Acidized Direct Growth 30.8 33.2 Non-Acidized Secondary 5.97 96.3 Growth Acidized Direct Growth 46.9 29.5 UiO-66(BDC) Secondary 12.6 89.6 Growth
Comparison of Membrane Performance with Reported Results
[0255] By way of background, various strategies have been developed to modify the established membrane configurations for OSN, such as integrally skinned asymmetric (ISA) membranes, thin film composite (TFC) membranes, and ceramic membranes. The performance of some reported OSN/SRNF membranes, along with the results of the as-prepared UiO-66(Zr)—NH.sub.2 membranes (as discussed above) are summarized in Table 5. With few exceptions, the rejection of low molecular weight organics (M.sub.W of ca. 300-400 g mol.sup.−1) is difficult without substantially compromising the permeance in reported membranes.
TABLE-US-00005 TABLE 5 The separation performance of some state-of-the-art membranes Membrane Membrane Permeance M.sub.w Type Material Solvent [kg/(m.sup.2 .Math. h .Math. bar)] Marker (g/mol) Rejection Ref Polymeric PA/PP Methanol 0.0948 Safranin O 351 45 [17] TFC PA/PSf Methanol 1.58 Bromothymol blue 624 >90 [18] Membranes PS-b PEO/PAA Methanol 0.079 Polyethylene glycols 370 80 [19] Mixed Matrix Polyimide Acetone 11.82 Styrene oligomers 1800 90 [20] Membranes P84/HKUST-1 PDMS/(gold Isopropanol 0.0314 Bromothymol blue 624 97 [21] nanoparticles)/PI Polyamide/MOFs Methanol 3.081 Styrene oligomers 236 >90 [22] Ceramic TiO.sub.2/alumina n-Hexane 0.248 Linoleic acid 280.5 50 [23] Membranes Grignard grafted Acetone 7.88 Styrene oligomers 580 85 [24] TiO.sub.2/alumina Inopor Methanol 0.316 Victoria blue 506 99 [25] TiO.sub.2/alumina Polycrystalline ZIF-8 Ethanol 1.1 Rose bengal 1018 83.9 [26] Membranes IPA 0.3 Rose bengal 1018 93.5 Water 5.6-37.5 Rose bengal 1018 98 [27] UiO-66(Zr)—NH.sub.2 Dichloromethane 0.17 Methylene blue 319 99.90 This 0.18 Oil red O 408 99.95 work 0.18 Nile red 318 99.85 Methanol 0.24 Nile red 318 99.88 [0256] 17. P. B. Kosaraju, K. K. Sirkar, Interfacially polymerized thin film composite membranes on microporous polypropylene supports for solvent-resistant nanofiltration, J. Membr. Sci. 321 (2008) 155-161. [0257] 18. M. Peyravi, A. Rahimpour, M. Jahanshahi, Thin film composite membranes with modified polysulfone supports for organic solvent nanofiltration, J. Membr. Sci. 423 (2012) 225-237. [0258] 19. X. F. Li, W. Egger, I. F. J. Vankelecom, Ordered nanoporous membranes based on diblock copolymers with high chemical stability and tunable separation properties, J. Mater. Chem. 20 (2010) 4333-4339. [0259] 20. J. Campbell, G. Székely, A. G. Livingston, Fabrication of hybrid polymer/metal organic framework membranes: mixed matrix membranes versus in situ growth, J. Mater. Chem. A 2 (2014) 9260-9271. [0260] 21. Y. B. Li, T. Verbiest, I. Vankelecom, Improving the flux of PDMS membranes via localized heating through incorporation of gold nanoparticles, J. Membr. Sci. 428 (2013) 63-69. [0261] 22. S. Sorribas, P. Gorgojo, J. Coronas, A. G. Livingston, High flux thin film nanocomposite membranes based on metal-organic frameworks for organic solvent nanofiltration, J. Am. Chem. Soc. 135 (2013)15201-15208. [0262] 23. T. Tsuru, M. Narita, R. Shinagawa, T. Yoshioka, Nanoporous titania membranes for permeation and filtration of organic solutions, Desalination 233 (2008) 1-9. [0263] 24. S. R. Hosseinabadi, K. Wyns, R. Carleer, P. Adriaensens, A. Buekenhoudt, B. V. Bruggen, Organic solvent nanofiltration with Grignard functionalised ceramic nanofiltration membranes, J. Membr. Sci. 454 (2014) 496-504. [0264] 25. J. Geens, K. Boussu, C. Vandecasteele, B. V. Bruggen, Modelling of solute transport in non-aqueous nanofiltration, J. Membr. Sci. 281 (2006) 139-148. [0265] 26. Y. B. Li, L. H. Wee, A. Volodin, J. A. Martens, I. F. J. Vankelecom, Polymer supported ZIF-8 membranes prepared via an interfacial synthesis method, Chem. Commun. 51 (2015) 918-920. [0266] 27. Y. B. Li, L. H. Wee, A. Volodin, J. A. Martens, I. F. J. Vankelecom, Interfacial synthesis of ZIF-8 membranes with improved nanofiltration performance, J. Membr. Sci. 523 (2017) 561-566.
Example 7: Bending Performance Test of Polycrystalline UiO-66-NH.SUB.2 .Membrane
[0267] The bending tolerance of the polycrystalline UiO-66-NH.sub.2 membrane was examined because this factor is important in designing membrane modules and increasing membrane packing density. The membrane separation performance was re-examined after varying degrees of bending, which is defined as the angular displacement of the ends of the membrane relative to the center (
Bending Tolerance Test
[0268] In order to test the extent of bending the prepared UiO-66(Zr)—NH.sub.2 membrane could withstand without damaging its separation performance, the bending tolerance test was performed by fixing the middle of the membrane as prepared according to Example 4 and then slowly bending the two sides to obtain a specific bending-angle. Each bending test was completed by bending the membrane three times under a specific bending-angle. After bending test, the separation performance of the membrane was evaluated using the experimental set-up described in Example 6, and each data point was tested for three times.
Effect of Bending on Membrane Separation Performance
[0269] In the separation tests of brackish water (2 wt. % NaCl feed solution), the rejection and permeance remain almost unchanged when the bend angle is within 10°, indicating a good preservation of the membrane integrity within this bend angle range (
[0270] The bend tolerance of membrane using NR in dichloromethane as the feed solution was also tested, and the membrane performance can be preserved within a bend angle of 150 (
Effect of Bending on Morphological Properties
[0271] The UiO-66(Zr)—NH.sub.2 membrane after the 100 bending test was subject to morphological characterization, in which visible cracks could not be found from the large area SEM image (
CONCLUSION
[0272] Overall, these results suggest that the polycrystalline UiO-66(Zr)—NH.sub.2 membrane grown on carbon cloth substrate exhibits a certain flexibility (with bending-angle<10°) without affecting its separation performance, which should come from the flexible substrate and the framework dynamics of UiO-66-type MOFs. However, it should be noted that this level of flexibility is still not up to the degree required by spiral wound membranes. A short-term solution would be to apply these membranes in plate and frame configurations for OSN applications once the membrane sealing issues can be fully addressed.