WO2019135565A1 - Procédé pour la préparation, in situ, d'un réseau métallo-organique à l'aide du réglage de la diffusion au sein d'un polymère ionique - Google Patents

Procédé pour la préparation, in situ, d'un réseau métallo-organique à l'aide du réglage de la diffusion au sein d'un polymère ionique Download PDF

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WO2019135565A1
WO2019135565A1 PCT/KR2018/016894 KR2018016894W WO2019135565A1 WO 2019135565 A1 WO2019135565 A1 WO 2019135565A1 KR 2018016894 W KR2018016894 W KR 2018016894W WO 2019135565 A1 WO2019135565 A1 WO 2019135565A1
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metal
organic structure
matrix
polymer
organic
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정낙천
임정호
이은지
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재단법인대구경북과학기술원
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Priority to US16/954,142 priority Critical patent/US11697104B2/en
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    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/04—Alginic acid; Derivatives thereof

Definitions

  • the present disclosure provides a method for preparing a metal-organic structure (MOF) -containing matrix using anionic polymers; A matrix produced thereby; An adsorbent comprising the matrix; And a method of separating fluid using the matrix.
  • MOF metal-organic structure
  • Metal-Organic Framework is a metal-organic framework in which coordination bonds of inorganic nodes (metal ions or metal oxide clusters) and multitopic organic linkers are linked together to form secondary or tertiary Quot; porous coordination polymers "or" porous organic-inorganic hybrid materials ", as the porous material forming the skeleton.
  • the metal-organic structure has not only well-defined pores but also coordination sites that are vacant in the metal center, and are used to capture guest molecules or to separate molecules, and can be used as an adsorbent, a gas storage material, a chemical separation, a sensor, Thin films, drug delivery materials, redox chemicals, heterogeneous catalysts, catalyst carriers, and the like.
  • MOF-polymer mixed matrices using environmentally friendly polymers are very promising in the fields of molecular adsorption, chemical separation, and chemical sensors, and the worldwide demand for them is rapidly increasing.
  • a post-fabrication method has been proposed in which a MOF is first prepared as a method for manufacturing a MOF-polymer mixed matrix, and then the produced MOF crystal is mixed with a polymer to form a matrix (Michael S Denny, Jr. et al., Angew Chem. Int. Ed., 2015, 54, 9029-9032).
  • the post-manufacturing method has some problems, in which the MOF particles are dispersed unevenly in the polymer matrix, and the bonding and contact between the MOF crystal and the polymer matrix is very poor.
  • the molecules can be adsorbed or passed through voids between the MOF crystal and the polymer matrix, which may cause a problem of reducing the selectivity of the material depending on the size of the window existing in the MOF.
  • the MOF crystal must be grown first, and it takes 10 hours or more to grow the MOF crystal, and the process is inconveniently required, such as heating at 100 DEG C (Zhonghua Zhu et al., ACS Appl. Interfaces 2016, 8, 32041-32049).
  • the MOF crystals grow to have a crystal structure with a certain size window inside.
  • the window size of the MOF crystal in the MOF-polymer mixed matrix grows unevenly, which is a cause of the problem.
  • a MOF-polymer mixed matrix in which the MOF crystal is uniformly dispersed in the matrix, the window between the MOF crystal and the polymer is excellent and the size of the window in the MOF crystal is uniform and the selectivity for the material to be separated is increased .
  • the present inventors have made intensive efforts to solve the above-mentioned problems. As a result, they have found that, instead of forming a MOF crystal first and then mixing it with a polymer, the ionic polymer and the ligand are first mixed with each other, -Multi-polymer mixed matrix, it was confirmed that the MOF crystals are uniformly dispersed in the matrix in a short time without heating, and a mixed matrix having a very excellent bonding property between the polymer and the ligand can also be produced.
  • Non-Patent Document 1 Michael S. Denny, Jr. Etc. Angew. Chem. Int. Ed. 2015, 54, 9029-9032
  • Non-Patent Document 2 Zhonghua Zhu et al., ACS Appl. Mater. Interfaces 2016, 8, 32041-32049
  • a first object of the present disclosure is to provide a method for preparing a mixed solution comprising: 1) mixing an anionic polymer-containing solution and an organic ligand precursor solution to prepare a mixed solution; And 2) adding a metal salt to the mixed solution.
  • the present invention also provides a method for producing a metal-organic structure (MOF) -containing matrix.
  • MOF metal-organic structure
  • Another object of the present disclosure is to provide a matrix comprising the metal-organic structure produced by the above production method.
  • the method comprising passing the fluid mixture through a matrix comprising a metal-organic structure produced according to the method, wherein V1? V2,
  • the metal-organic structure has a window size or adsorption characteristic that does not pass the first fluid but does not pass the first fluid.
  • a method of preparing a mixed solution comprising: 1) mixing an anionic polymer-containing solution and an organic ligand precursor solution to prepare a mixed solution; And
  • a second aspect of the present disclosure provides a matrix comprising a metal-organic structure produced according to the above process.
  • a third aspect of the present disclosure provides an adsorbent comprising the metal-organic structure containing matrix.
  • a fourth aspect of the present disclosure is a method of separating a first fluid or a second fluid from a fluid mixture comprising a first fluid having a first monomolecular size (V1) and a second fluid having a second monomolecular size (V2) (In this case, V1? V2)
  • the method comprising passing the fluid mixture through a matrix comprising a metal-organic structure produced according to the method of the first aspect, wherein the metal-organic structure passes the first fluid and the second fluid passes
  • the adsorbent has a window size or adsorption property that does not allow adsorption.
  • the term " metal-organic structure (MOF) " used in the present invention is a succession or repetition of a structural unit consisting of a metal segment and an organic linker, through a multiple link of the structural unit Means a formed network structure.
  • the metal node is a bond between metal ions or a bond between metal and oxygen
  • the organic linker is usually a ligand coordinated to the coordination site of the metal node.
  • the structural unit refers to cages having nano-sized pores, and these cages are interconnectionally interchanged to share a window.
  • the metal-organic structure may have a two-dimensional or three-dimensional conformation including one or more types of cages and one or more windows.
  • metal-organic structure-containing matrix used in the present invention means a polymer and a metal-organic structure dispersed therein, and the polymer is in the form of a continuous polymer matrix.
  • a conventional metal-organic structure containing matrix is prepared by a post-manufacturing method in which a crystal of a metal-organic structure is first prepared and then dispersed in a polymer solution to prepare a matrix.
  • this method it is difficult for the crystal of the metal-organic structure to disperse evenly in the matrix, and the bonding property is deteriorated due to the low interaction between the metal-organic structure crystal and the polymer, The molecules could pass through and the selectivity of adsorption of the fluid through the metal-organic structure was reduced.
  • the post-production process requires a heating process and takes a long time to produce the metal-organic structure crystal, which is inconvenient in the process.
  • the present inventors have found that by dispersing an organic ligand in a polymer by using an ionic polymer, the metal-organic structure crystals are uniformly dispersed as compared with the post-manufacturing method, and the metal-organic structure having increased bonding between the polymer and the metal- Containing matrix can be prepared.
  • the disclosure herein is based on this finding.
  • ionic polymer refers to a polymer having a functional group or moiety that exhibits a positive or negative charge.
  • the ionic polymer is an anionic polymer.
  • anionic polymers include, but are not limited to, alginate, carboxymethylcellulose, hyaluronic acid, or a combination thereof, and may include polyacrylic acid (PA) and derivatives thereof, polymethacrylic acid (PMA) poly (methyl acrylate) and derivatives thereof, poly (thiophene acetic acid) and derivatives thereof, poly (sulfonate styrene) (PSS) and derivatives thereof, or combinations thereof .
  • Alternative polymers having properties similar to anionic polymers can also be used, for example, anionic cellulose microfibers such as TEMPO-oxidized cellulose nanofibers (TOCN) are also available.
  • the anionic functional group in the anionic polymer may be a carboxyl group (-COO-), a sulfonic acid group (-SO3-), or an acetoxy group (-CH2COO-).
  • the anionic polymer may be provided in the form of a salt.
  • the anionic polymer may be provided in the form of a metal salt combined with a metal ion, for example, a sodium ion.
  • the organic ligand precursor referred to herein may be a two or more-valent organic ligand compound capable of binding to the metal ion of the metal salt.
  • the organic ligand precursor may be an organic ligand compound having two or more sites capable of coordinating with a metal ion in one molecule.
  • the organic ligand precursor may be 1,4-benzenedicarboxylic acid (BDCA), isophthalic acid, 1,3,5-benzenetricarboxylic acid (1,3,5- benzenetricarboxylic acid (BTCA), 2,5-dihydroxyterephthalic acid, 2-aminoterephthalic acid, 2-nitroterephthalic acid, 2-methylterephthalic acid 2-methylterephthalic acid, 2-haloterephthalic acid, azobenzene tetracarboxylic acid, 1,3,5-tri (4-carboxyphenyl) ) benzene, 2,6-naphthalene dicarboxylic acid (NDCA), benzene-1,3,5-tribenzoic acid (BTB) Fumaric acid, glutaric acid, 2,5-furanedicarboxylic acid (FDCA), 1,4-pyridinedicarboxylic acid ), 2-methylimidazole e, alkyl-substituted imidazole, aromatic ringsubstitute
  • the organic ligand precursor may be a bulky ligand comprising one or more, preferably two or three, benzene rings.
  • benzene rings For example, there can be mentioned 1,4-benzene dicarboxylic acid, 1,3,5-benzenetricarboxylic acid, 2,5-dihydroxyterephthalic acid, 2,6-naphthalene dicarboxylic acid, azobenzene tetracarboxylic acid Or derivatives thereof may be used, but the present invention is not limited thereto.
  • the organic ligand precursor By adjusting the organic ligand precursor, the pore size, shape, and chemical environment of the finally formed metal-organic structure can be changed.
  • the step 1) may further include a step 1-1) of adding a crosslinkable metal salt to the mixed solution.
  • the crosslinkable metal salt may function to crosslink the ionic polymer by binding with the ionic polymer.
  • the crosslinkable metal salt may crosslink the anionic polymer through electrostatic bonding.
  • the crosslinkable metal salt may be one which provides a divalent or trivalent metal cation and may be selected from the group consisting of Ca 2+ , Fe 2+ , Zn 2+ , Mn 2+ , Cu 2+ , Mg 2+ , Sr 2+ , Co 2+ , Ni 2+ , Sc 2+ , Ti 4+ , V 2+ Cr 2+ , Fe 3+ , Y 3+ , Zr 4+ , Nb 3+ , Mo 2+ , Tc 2+ , Ru 2+ , Rh 3 + , Pd 2+, Cd 2+ , and the like. Additional divalent or trivalent transition metals are also available.
  • Anionic polymers can undergo electrostatic repulsion with negatively charged ligands, but stable matrix forms can be formed through crosslinked metal salts.
  • Ca (NO 3 ) 2 was used as a crosslinkable metal salt, and immediately upon addition, a white spherical solid was formed. The addition step may be carried out for from 5 minutes to 60 minutes so that sufficient ion exchange takes place.
  • alginate was used as an anionic polymer.
  • Alginic acid (H + ALG) is (1-4) -linked -D-mannuronate (M) and its C-5 epimer -L-gluconate (G) is a linear copolymer covalently linked in random order (MG-block) or in block form (M-block and G-block).
  • H + ALG contains a carboxylic acid, which may be substituted with an alkali metal, an alkaline earth metal, or a transition metal through exchange with a proton of the carboxylic acid.
  • H + ALG can easily be replaced with sodium alginate (Na + ALG), and when exchanged with divalent metal ions such as Ca 2+ , Mg 2+ , Cu 2+ and Zn 2+ , Na + ALG Can be cross-linked. Therefore, alginate can be easily crosslinked through reaction with the crosslinkable metal salt of the present invention, and thus can be used as an anionic polymer in this embodiment.
  • Alginate (ALG) which is an anion form of H + ALG, is an environmentally friendly polymer and can be used in a wide variety of fields such as food, medicine, medicine, and chemical industry. Alginate not only has biocompatibility but also can be easily decomposed at the time of disposal, which is attracting attention as an environmentally friendly material. Thus, in one embodiment of the present invention, alginate was used as an anionic polymer, and it was confirmed that the characteristics of the metal-organic structure-containing matrix prepared from the matrix were excellent.
  • the organic ligand precursor solution may comprise a basic material.
  • the basic substance may be a weak basic substance having a pK b value of 3 to 6, for example, an organic amine, specifically, triethylamine (TEA), trimethylamine, tripropylamine, or 1,4-diazabicyclo [ Diazabicyclo [2.2.2] octane (DABCO).
  • the basic substance may be an amide, imidazolium series, or the like.
  • triethylamine (TEA) was used. It is necessary to deprotonate the organic ligand material at the time of formation of the metal-organic structure crystal.
  • a heating process at a high temperature of 100 ° C or more is required for the deprotonation, .
  • a weakly basic substance can be used to deprotonate an organic ligand material to easily form a metal-organic structure crystal without heating.
  • the above step 1) may be carried out at a room temperature of 20 to 25 ° C. As described above, since the heating process is not required, the reaction can be performed at room temperature, and the process convenience can be increased.
  • the solvent of each solution in the step 1) and the step 1-1) may be any solvent capable of dissolving the anionic polymer, the organic ligand precursor, the flexible polymer and the crosslinkable metal salt, Mixed use is also possible.
  • the solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), acetonitrile, chloroform, n-Hexane ), Benzene, toluene, xylene, diethyl ether, acetone, and water. More specifically, it may be ethanol, acetonitrile, water or a combination thereof.
  • the method may further comprise immersing the matrix formed in step 1) or step 1-1) in the organic ligand solution to sufficiently disperse the organic ligand of step 1) in the matrix.
  • the step of immersing in the organic ligand solution may be repeated an appropriate number of times, for example, three times.
  • Step 2) is a step of forming a metal-organic structure by adding a metal salt to the mixed solution of step 1).
  • the metal salt may be a conventionally used metal ion-containing metal ion compound such as metal nitrate, metal sulfate, metal phosphate, metal hydrochloride, or a hydrate thereof, but is not limited thereto.
  • the metal salt may be a metal nitrate or a hydrate thereof.
  • the metal may be at least one selected from the group consisting of Cu, Zn, Fe, Ni, Zr, Cr, Sc, Co, Ti, (Mn), vanadium (V), aluminum (Al), magnesium (Mg), gallium (Ga), indium (In), yttrium (Y), niobium (Nb) At least one metal selected from the group consisting of tantalum (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag) and cadmium (Cd).
  • the metal salt may be a metal salt of a metal ion having a divalent or trivalent charge derived from the metal.
  • the molar ratio of the metal salt to the organic ligand precursor may be 1:20 to 20: 1, more specifically 5: 1 to 10: 1.
  • Metal-Organic Structure The molar ratio of the metal salt to the organic ligand precursor may be appropriately selected depending on the kind of the metal salt and the organic ligand precursor used.
  • the metal ion dissociated from the metal salt may be exchanged with the metal ion present in the form of a metal salt together with the anionic polymer in step 1), or with the crosslinkable metal salt administered in step 1-1).
  • the exchanged metal ions combine with the organic ligands already distributed around to form metal-organic structure crystals.
  • the ligand is dispersed in the matrix and then the metal- Can be generated within a short time.
  • metal-organic structure crystals were formed from 5 minutes after the addition of the metal salt (FIG. 4). It has also been observed that the metal-organic structure crystals are uniformly formed from the surface point to the core point of the sphere.
  • the anionic polymer of the present invention can well disperse an organic ligand having a negative charge through a functional group exhibiting a negative charge in the matrix.
  • the metal ion of the crosslinkable metal salt may serve to link the anionic polymer with the organic ligand, and thereby the organic ligand can be uniformly dispersed in the polymer.
  • the metal ion is added in step 2) to exchange it with the dissociated metal ion in the cross-linkable metal salt, the dissociated metal ion in the cross-linkable metal salt is evenly dispersed in the matrix, so that the exchanged metal ion is also dispersed evenly 14). Therefore, the resulting metal-organic structure crystals can be evenly dispersed. That is, unlike the post-production method in which it is difficult to disperse the crystals evenly in the matrix, it is possible to prepare the metal-organic structure to be distributed evenly by dispersing the ligands in advance and generating crystals.
  • the step 2) may be carried out at a room temperature of 20 to 25 ° C. As described above, since the heating process is not required, the reaction can be carried out at room temperature, so that the convenience of the process can be increased and energy consumption is not required.
  • the step 2) may be performed for 5 minutes to 60 minutes. Unlike the conventional metal-organic structure crystal formation method, the method of the present invention enables crystal structure formation in a short time.
  • the solvent of the solution of step 2) may be any solvent as long as it can dissolve the metal salt. Mixing of two or more solvents is also possible.
  • the solvent may be selected from the group consisting of methanol, ethanol, propanol, isopropanol, butanol, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), acetonitrile, chloroform, n-Hexane ), Benzene, toluene, xylene, diethyl ether, acetone, and water. More specifically, it may be ethanol, acetonitrile, water or a combination thereof.
  • the metal-organic structure produced by the method of the present disclosure may include a structural unit represented by the following formula (1).
  • M may be, for example, copper (Cu), zinc (Zn), iron (Fe), nickel (Ni), zirconium (Zr), chromium (Cr), scandium (Sc), cobalt (Co) Manganese (Mn), vanadium (V), aluminum (Al), magnesium (Mg), gallium (Ga), indium (In), yttrium (Y) At least one metal selected from the group consisting of tantalum (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag) and cadmium (Cd)
  • L is, for example, 1,4-benzenedicarboxylate (BDC), 2,5-dihydroxyterephthalate (DOBDC), 1,3,5- 1,3,5-benzenetricarboxlate (BTC), 1,1'-biphenyl-3,3 ', 5,5'-tetracarboxylate (1,1'-biphenyl-3,3 N, N ', N'-tetrakis (4-carboxyphenyl) -biphenyl-4,4'-diamine (N, 2-aminoterephthalate, 2-nitroterephthalate, 2-aminophenol, 2-aminoterephthalate, 2- 2-methylterephthalate, 2-haloterephthalate, azobenzene tetracarboxylate, 1,3,5-tricarboxyphenylbenzene (1,3,5-tri (4 2,6-naphthalene dicarboxylate (NDC), benzene-1,3,5-tribenzoate benzene-1,3,5-tribenzo
  • x is an integer of 2 to 6
  • y is an integer of 2 to 12;
  • the metal-organic structure [Cu 3 (BTC) 2] , [Cu 2 (BDC) 2], [Zn 3 (BTC) 2], [Zn 2 (BDC) 2], [Fe 3 (BTC ) 2 ], [Fe 2 (BDC) 2 ], [Ni 3 (BTC) 2 ], or Ni 2 (BDC) 2 .
  • [Cu 3 (BTC) 2 ] 3 -dimensional MOF is typically referred to as HKUST-1 ( "A Chemically Functionalizable Nanoporous Material [Cu 3 (TMA) 2 (H 2 O) 3] n" represented by, Chui, 2-dimensional MOF represented by [Cu 2 (BDC) 2 ] can be expressed by the following formula: [Cu 2 (BDC) 2 ] MOF-2. ≪ / RTI > Further, the three-dimensional MOF represented by [Zn (BTC) 2 ] is referred to as Zn-HKUST-1.
  • the metal-organic structure containing matrix of the present disclosure may comprise from about 10 to about 50 weight percent, based on the total matrix weight, of the metal-organic structure. Specifically about 20 to about 45 weight percent, and more specifically about 30 to about 40 weight percent.
  • an organic ligand is first dispersed in an anionic polymer, followed by the addition of metal ions to the reaction (metal ion diffusion path; path B in FIG. 1).
  • metal ion diffusion path path A in FIG. 1
  • a method ligand diffusion path (path A in FIG. 1) in which metal ions are first dispersed in an anionic polymer and ligands are added thereto in a different order according to the present invention is also possible, but in this case, It is observed that a metal-organic structure is produced only on the surface of the sphere (Fig. 3). This is thought to be due to the difference in the size and charge of the metal ion and the organic ligand.
  • 1,3,5-benzenetricarboxylic acid was used as an organic ligand and Cu 2+ was used as a metal ion.
  • 1,3,5-benzenetricarboxylate is 7.9 ⁇ or 8.6 ⁇ in size, whereas it is only 0.87 ⁇ in Cu 2 + ion, so that there is a difference in diffusion rate in the matrix, and as a result As can be seen in FIGS. 3 and 4, the rate of crystal formation was different when the same time elapsed.
  • the method according to the present invention may further comprise steps 1-0) of preparing an anionic polymer-containing solution by mixing an anionic polymer and a flexible polymer before step 1).
  • the flexible polymer is not limited as long as it is a flexible polymer that can be mixed with an anionic polymer to provide the shape of a flexible membrane.
  • the flexible polymer may be selected from the group consisting of polyimide, polyacetylene, cellulose acetate, polysulfone, polyethylene oxide, poly (4-methylpentene-1), poly (2,6-dimethylphenylene oxide), polydimethylsiloxane, And may be selected from the group consisting of polyethylene, polyvinylidene chloride, polytetrafluoroethylene oxide, polyacrylonitrile, poly (vinyl alcohol), polystyrene, polyethylene glycol, poly (acrylamide) It is not.
  • the metal-organic structure according to the present invention may have a window size of about 4 to about 25 A, and the size of the metal-organic structure may be uniform.
  • the term "window” refers to the open portion of a metal-organic structure.
  • HKUST-1 is used as the metal-organic structure, which corresponds to a window size of 8.5 ANGSTROM (FIG. 18A).
  • the metal-organic structure has a specific window size depending on the kind of each metal and the organic ligand, thereby allowing the specific molecule (s) to selectively pass and / or adsorb.
  • the window size is unevenly grown during the crystal growth of the metal-organic structure, the selective adsorption of molecules due to the window size becomes difficult, and the selectivity is reduced.
  • the size of the window in the crystal of the grown structure grows uniformly although the crystal is grown before diffusing the crystal after the ligand is dispersed in advance and the metal ions are diffused to grow the crystal. (Fig. 17A-i and Experimental Example 4).
  • first monomolecular size (V1)” and “second monomolecular size (V2)” are the sizes of the first fluid and the second fluid, which are monomolecular forms, Exhibits a kinetic molecular size.
  • kinetic diameter refers to the size of a molecule calculated based on molecular dynamics.
  • Molecular dynamics refers to a method of numerically solving Newton's equations of motion at the atomic and molecular level. It means finding out the position of all the atoms in the molecule as a function of time.
  • Molecular dynamics calculations are also used for theoretical computational simulation of ideal molecular structures that have not been experimentally created. It has been developed in theoretical physics and has recently been extensively used in materials science and life sciences.
  • the term "fluid” includes gas and liquid, and may exist in a monomolecular state.
  • selective adsorption of methylene blue and rhodamine 6G molecules present in a liquid state was confirmed, but it is well known in the art that a metal-organic structure can adsorb a substance in a gaseous state
  • the metal-organic structure according to the present invention is also capable of adsorption to gas molecules.
  • the metal-organic structure dispersed in the metal-organic structure-containing matrix of the present disclosure is not produced according to the post-production method of the conventional method, the crystallinity is excellent and the size of the window formed in the crystal structure is also constant. As a result, it is possible to selectively adsorb gas or liquid molecules according to such window size, since a crystal structure having a desired window size and a constant size of each window size can be generated.
  • a matrix containing such a metal-organic structure can be produced during manufacture, and the first fluid and the second fluid can be separated from each other.
  • Organic ligands are first dispersed in polymers using ionic polymers, especially anionic polymers, so that the metal-organic structure crystals are evenly dispersed in the matrix, and the bond between the polymer and the metal-organic structure An increased metal-organic structure containing matrix can be produced. In addition, it can be manufactured in a short time, and the heating process is not required, so the convenience of the process is increased and there is no energy consumption.
  • ionic polymers especially anionic polymers
  • Figure 1 schematically illustrates the difference in the matrix structure produced in the order of metal and ligand addition in the process of making the metal-organic structure containing matrix of the present disclosure.
  • Fig. 2 schematically shows a method for producing the metal-organic structure-containing matrix of the present disclosure in the order of metal and ligand addition.
  • Fig. 3 is a microscopic observation result of the matrix containing the metal-organic structure formed according to the reaction time in Comparative Example 1.
  • Fig. OM is the result of optical microscopy
  • SEM is the result of scanning electron microscopy and shows the change with time from the addition of BTC 3- ion.
  • Fig. OM is the result of optical microscopy and SEM is a scanning electron microscope, showing the change with time from the addition of Cu 2+ ion.
  • FIGS. 5A and 5B are views showing SEM images taken on the side of the membrane
  • FIGS. 5C and 5D are photographs of the membrane prepared according to Comparative Example 2
  • FIGS. 6A and 6B are SEM image observations taken on the side of the membrane
  • FIGS. 6C and 6D are cross-sectional views of the membranes prepared according to Example 2, The results of the SEM images observed at the top and bottom.
  • Example 7 is a SEM image of the surface and interior of the matrix prepared according to Comparative Example 3 and Example 3.
  • Fig. MD-MOR74-ALG is the result of Comparative Example 3
  • LD-MOR74-ALG is the result of Example 3.
  • FIG. 8A-C are enlarged views of the matrix prepared according to Example 1 by SEM.
  • Fig. 8A is a view near the surface
  • Fig. 8B is a point far from the surface
  • Fig. 8C is a result observed at a core point.
  • FIG. 11 is an XRD result of a membrane prepared according to Comparative Example 2 and a polymer membrane containing no metal-organic structure.
  • FIG. 13 shows XRD results of the matrix prepared according to Comparative Examples 3 and 3 and the crystal of Preparation Example 2.
  • FIG. 14 shows the results of SEM measurement and EDS analysis according to the reaction time of the matrix according to Example 1.
  • 15a-d show the absorbance of methylene blue and rhodamine 6G against UV-visible light.
  • 15A and 15B are absorption spectra corresponding to the concentrations of methylene blue and rhodamine 6G, respectively, and
  • FIGS. 15C and 15D are absorption bands of methylene blue and rhodamine 6G And the absorbance intensity according to the concentration.
  • FIGS. 16A to 16F are graphs showing the absorption peaks of methylene blue and rhodamine 6G of the spheres (Cu 2+ ALG) before loading the ligand in Comparative Example 1 and spheres (Ca 2+ ALG) before loading the copper ion in Example 1 .
  • FIGS. 16A and 16D are absorption spectra of methylene blue and rhodamine 6G of the spheres (Ca 2+ ALG) before the addition of copper ions in Example 1 with time
  • FIGS. 16B and 16E are graphs showing absorption spectra of the ligands
  • FIG. 16C and FIG. 16F are graphs showing absorption spectra of methylene blue and rhodamine 6G with respect to time (Cu 2+ ALG) The results are shown in Fig.
  • FIGS. 17A-i show the absorbance of methylene blue and rhodamine 6G of spheres (LD-HK-ALG) of Comparative Example 1 and spheres of Example 1 (MD-HK-ALG).
  • FIGS. 17A and 17D are absorption spectra of methylene blue and rhodamine 6G, respectively, according to time of the spheres (MD-HK-ALG) of Example 1, (LD-HK-ALG) of Comparative Example 1 and the spheres of Example 1 (MD-HK-ALG) were measured in the same manner as in Example 1, ) Of methylene blue and rhodamine 6G, respectively The results are shown in Fig.
  • 17G is a graph showing absorption spectra of methylene blue and rhodamine 6G according to time in Example 1 (MD-HK-ALG), and FIG. (LD-HK-ALG) of Comparative Example 1 and methylene blue of the spheres of Example 1 (MD-HK-ALG), and the absorption spectrum of methylene blue and Rhodamine 6G Each of Rhodamine 6G And the change in concentration with time
  • FIG. 18A shows the window size of HKUST-1 crystal
  • FIG. 18B shows methylene blue
  • FIG. 18C shows the molecular size of rhodamine 6G together with their respective molecular structures.
  • FIG. 20A and 20B show results of thermogravimetric analysis of Comparative Examples 1 and 1, respectively.
  • Fig. 20A shows the results of the sphere of Example 1
  • Fig. 20B shows the results of the sphere of Comparative Example 1.
  • % used to denote the concentration of a particular substance is intended to include solids / solids (wt / wt), solid / liquid (wt / The liquid / liquid is (vol / vol)%.
  • TAA Triethylamine amine
  • H 4 DOBDC 2,5-dihydroxyterephthalic acid
  • Rhodamine 6G Purity: 99%, manufactured by Aldrich.
  • DW Deionized distilled water
  • Comparative Example 1 Preparation of HK-ALG spheres dispersed in BTC 3- ligand (LD-HK-ALG)
  • 0.5 M BTC 3 - solution (5 mL) was prepared by mixing H 3 BTC and TEA stoichiometrically in a 1: 3 mixture in a 1: 1 mixture of H 2 O and EtOH. After 1 hour of drying of the Cu 2+ ALG spherical solid, it was immersed in the 0.5 M BTC 3 - solution. BTC 3- ligand reacted with Cu 2+ in the Cu 2+ ALG. The reaction was carried out at room temperature and the changes during the reaction were observed at 5, 10, 20, 30, and 60 minutes after the reaction. The results are shown in FIG.
  • Example 1 Preparation of Cu 2+ ion dispersed HK-ALG spheres (MD-HK-ALG)
  • H 3 BTC and TEA were mixed stoichiometrically in a ratio of 1: 3 to prepare a 0.5 M BTC 3 - aqueous solution.
  • a BTC 3 -containing Na + ALG solution was prepared by mixing 1 mL of the 0.5 M BTC 3- aqueous solution and 9 mL of 5.0 wt% Na + ALG aqueous solution.
  • the BTC 3 -containing Na + ALG solution was then added dropwise to the 0.5 M Ca (NO 3 ) 2 solution using a Pasteur pipette. The dropwise droplet immediately became a white solid spherical shape (see FIG. 4).
  • Ca 2+ ALG Ca 2+ ALG
  • a solution of 0.5 M BTC 3 was prepared by mixing H 3 BTC and TEA 1 to 3 in deionized distilled water.
  • the elastic polymer membrane was immersed in the 0.5 M BTC 3 solution to react the BTC 3- ligand with Cu 2+ ions. The reaction was allowed to proceed at room temperature for 30 minutes. After washing with deionized distilled water, the membrane was dried at ambient conditions and at room temperature and cut to 4 x 6 cm 2 size before use.
  • Example 2 Preparation of Cu 2+ ion dispersed HK- (ALG + PVA) membrane (MD-HK- (ALG + PVA) M )
  • H 3 BTC and TEA were mixed stoichiometrically in a ratio of 1: 3 to prepare a 0.5 M BTC 3 - aqueous solution.
  • the BTC 3 -containing Na + ALG solution was prepared by mixing 5 mL of the 0.5 M BTC 3- aqueous solution and 5 mL of the 5.0 wt% Na + ALG aqueous solution.
  • PVA powder was dissolved in deionized distilled water in separate vials to prepare 5.0 wt% PVA aqueous solution.
  • Lt; RTI ID 0.0 > 80 C < / RTI > for 6 hours to completely dissolve PVA.
  • the PVA solution was added to the BTC 3 -containing Na + ALG solution, which was dropped on a flat glass plate having a size of about 15 x 15 cm 2 and spread.
  • the 0.5 M Ca (NO 3 ) 2 solution was then sprayed onto the plate using a spray gun for 30 minutes.
  • the elastic polymer membrane obtained so that the BTC 3- ligand was contained sufficiently in the membrane was immersed in 0.5 M BTC 3- solution and this process was repeated two more times. After gently rinsing with deionized distilled water, the membrane was dried at room temperature for 1 hour.
  • 0.5 M Cu (NO 3 ) 2 solution was prepared by dissolving Cu (NO 3 ) 2 in a 1: 1 mixture of H 2 O and ACT.
  • the membrane was immersed in the 0.5 M Cu (NO 3 ) 2 solution at room temperature for 30 minutes to allow the BTC 3- ligand in the membrane to react with Cu 2+ ions. After washing with deionized distilled water, the membrane was dried at ambient conditions and at room temperature and cut to 4 x 6 cm 2 size before use.
  • a 0.5 M DOBDC 4 solution was prepared by mixing H 4 DOBDC and TEA stoichiometrically in a 1: 4 mixture in a 1: 1 mixture of H 2 O and EtOH. After 1 hour of drying of the Zn 2+ ALG spherical solid, it was immersed in the 0.5 M DOBDC 4- solution. DOBDC 4- ligand reacted with Zn 2+ in the Zn 2+ ALG. The reaction was carried out at room temperature for 30 minutes.
  • Example 3 Preparation of Zn 2+ ion dispersed MOF-74 (Zn) -ALG spheres (MD-MOF74-ALG)
  • H 4 DOBDC and TEA were stoichiometrically mixed in a ratio of 1: 4 to prepare a 0.5 M DOBDC 4- aqueous solution.
  • the DOBDC 4- -containing Na + ALG solution was prepared by mixing 1 mL of the 0.5 M DOBDC 4- aqueous solution and 9 mL of the 5.0 wt% Na + ALG aqueous solution.
  • the DOBDC 4- -containing Na + ALG solution was then added dropwise to the 0.5 M Ca (NO 3 ) 2 solution using a Pasteur pipette. The dropwise droplet immediately became a yellow solid sphere.
  • Ca 2+ ALG Ca 2+ ALG
  • a 0.5 M Zn (NO 3 ) 2 solution in a 1: 1 mixture of H 2 O and ACT was prepared. After drying the sphere for 1 hour, it was immersed in the 0.5 M Zn (NO 3 ) 2 solution.
  • the DOBDC 4- ligand in the Ca 2+ ALG was allowed to react with Zn 2+ . The reaction was carried out at room temperature for 30 minutes.
  • SEM Scanning Electron Microscope
  • EDS Energy dispersive X-ray spectroscopy
  • Thermogravimetric analysis (TGA): Q500 (TA Instruments) was used and was run under N 2 gas at a flow rate of 100 mL / min.
  • HKUST-1 crystals were formed only on the surface and its vicinity, and a structure having a core and a shell surrounding it was observed as an egg shape (FIG. 3).
  • HKUST-1 crystals were uniformly formed from the core point to the surface according to Example 1 (Fig. 4). In particular, it was confirmed that crystals were formed within 5 minutes after the reaction, and crystals could be formed within a short time, and it was confirmed that crystal sizes were uniformly generated.
  • the membranes according to Comparative Example 2 and Example 2 were observed with naked eyes and SEM, respectively (Figs. 5A-D and 6A-D). All were made of flexible polymer membranes, and a polymer membrane with a thickness of approximately 140 ⁇ appeared. In particular, the membrane according to Embodiment 2 confirmed that HKUST-1 crystals are uniformly generated even from any point of view.
  • Spheres prepared according to Example 1 were observed by SEM to further observe the HKUST-1 crystals positioned at each point in more detail (FIGS. 8A-C). It is confirmed that the crystals are homogeneously distributed from the core point to the surface point and the crystal sizes are similar. In addition, it was confirmed that the HKUST-1 crystal and the polymer matrix were well bonded.
  • the metal-organic structure-containing matrix prepared according to the method of the present invention has a uniform size of the metal-organic structure and is well bonded to the polymer matrix. It was also confirmed that the metal-organic structure crystals were uniformly dispersed in the matrix.
  • the XRD patterns of the spheres prepared according to Comparative Example 1 and Example 1 and the spheres prepared according to Preparation Example 1 were compared and shown in Figs. 9 and 10, respectively.
  • the XRD patterns of the state (Cu 2+ ALG) before the ligand was added in Comparative Example 1 and the state (Ca 2+ ALG) before the copper ion was introduced in Example 1 were also shown.
  • Comparing HKUST-1 crystals (HKUST-1 Powder) the matrices of Example 1 showed a nearly identical pattern, indicating that HKUST-1 crystals were well formed within the matrix produced by the method according to the present invention Respectively.
  • the XRD patterns of the membranes prepared according to Comparative Example 2 and Example 2 are also shown in Figs. 11 and 12, respectively.
  • the absorption spectra of the spheres (LD-HK-ALG) of Comparative Example 1 and the spheres of Example 1 (MD-HK-ALG) show that both adsorbed on MB but not adsorbed on rhodamine 6G (Figs. 17A-i).
  • the HKUST-1 structure and its window are uniformly formed in the matrix prepared according to Comparative Example 1 and Example 1.
  • the molecular sizes of the MB and rhodamine 6G and the sizes of the windows existing in the HKUST-1 structure are respectively 8.5 ANGSTROM, which is the window size existing in the HKUST-1 structure.
  • the HKUST-1 structure will be capable of selective adsorption according to molecular size through its window. However, if the HKUST-1 structure does not grow uniformly, the window size will be unstable, making selective adsorption difficult.
  • the matrix according to Example 1 prepared according to the present invention has grown to a structure having a uniform window size, thereby enabling selective adsorption different depending on the molecular size.
  • thermogravimetric analysis of each of the spheres according to Comparative Example 1 and Example 1 was performed (Fig. 20a-b). And the decomposition temperature ranges of the sphere according to Example 1 were 110 to 175 ° C, 175 to 285 ° C, and 285 to 380 ° C, respectively.
  • the first temperature interval is due to evaporation of solvent
  • the second temperature interval is due to alginate decomposition
  • the third temperature interval is due to the decomposition of HKUST-1 crystals.
  • the amount of HKUST-1 crystals generated based on this decomposition temperature interval can be deduced.

Abstract

L'invention concerne un procédé pour la préparation d'une matrice contenant un réseau métallo-organique (MOF), comprenant les étapes consistant à : 1) préparer une solution mélangée par mélange d'une solution de précurseur de ligand organique et d'une solution contenant un polymère anionique ; et 2) ajouter un sel métallique à la solution mélangée. De plus, la présente invention concerne une matrice contenant un MOF préparée selon le procédé de préparation et un adsorbant comprenant celle-ci. En outre, l'invention concerne un procédé pour la mise en œuvre d'une séparation de fluides à l'aide de la matrice contenant un MOF préparée selon le procédé de préparation.
PCT/KR2018/016894 2018-01-02 2018-12-28 Procédé pour la préparation, in situ, d'un réseau métallo-organique à l'aide du réglage de la diffusion au sein d'un polymère ionique WO2019135565A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112473745A (zh) * 2020-11-27 2021-03-12 复旦大学 一种介孔金属有机骨架多中心催化剂及其制备方法和应用
CN113351174A (zh) * 2021-06-18 2021-09-07 东北电力大学 一种负载v/n掺杂纳米二氧化钛的hkust-1/cnf复合膜的制备方法及应用
CN115228303A (zh) * 2022-06-24 2022-10-25 青岛大学 一种超薄蜂窝状金属-有机骨架混合基质膜（MOF MMMs）及其制备方法
CN115739046A (zh) * 2022-11-15 2023-03-07 武汉大学 一种hkust-1/海藻酸盐凝胶颗粒复合材料及其制备方法和其应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110052650A1 (en) * 2008-04-01 2011-03-03 Centre National De La Recherche Scientifique - CNR S Porous crystalline hybrid solid for adsorbing and releasing gas of biological interest
US8764887B2 (en) * 2011-04-04 2014-07-01 Massachusetts Institute Of Technology Methods for electrochemically induced cathodic deposition of crystalline metal-organic frameworks
US9114348B2 (en) * 2008-04-29 2015-08-25 Universitetet I Oslo Metal organic framework compounds
US20150367294A1 (en) * 2013-01-28 2015-12-24 Council Of Scientific & Industrial Research Process for the preparation of mofs-porous polymeric membrane composites
CN105498695A (zh) * 2015-12-02 2016-04-20 南京师范大学 一种海藻酸钠-金属有机框架复合小球及其制备方法和应用
WO2016100847A2 (fr) * 2014-12-20 2016-06-23 Northwestern University Composites polymère-structures organométalliques
WO2017083467A1 (fr) * 2015-11-10 2017-05-18 Northwestern University Matériaux composites contenant des structures organométalliques encapsulées dans un polymère organique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110052650A1 (en) * 2008-04-01 2011-03-03 Centre National De La Recherche Scientifique - CNR S Porous crystalline hybrid solid for adsorbing and releasing gas of biological interest
US9114348B2 (en) * 2008-04-29 2015-08-25 Universitetet I Oslo Metal organic framework compounds
US8764887B2 (en) * 2011-04-04 2014-07-01 Massachusetts Institute Of Technology Methods for electrochemically induced cathodic deposition of crystalline metal-organic frameworks
US20150367294A1 (en) * 2013-01-28 2015-12-24 Council Of Scientific & Industrial Research Process for the preparation of mofs-porous polymeric membrane composites
WO2016100847A2 (fr) * 2014-12-20 2016-06-23 Northwestern University Composites polymère-structures organométalliques
WO2017083467A1 (fr) * 2015-11-10 2017-05-18 Northwestern University Matériaux composites contenant des structures organométalliques encapsulées dans un polymère organique
CN105498695A (zh) * 2015-12-02 2016-04-20 南京师范大学 一种海藻酸钠-金属有机框架复合小球及其制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHU, H ET AL.: "Alginate Hydrogel: A Shapeable and Versatile Platform for in Situ Preparation of Metal-organic Framework-polymer Composites", ACS APPL. MATER. INTERFACES, vol. 8, 2016, pages 17395 - 17401, XP055419542, DOI: doi:10.1021/acsami.6b04505 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112473745A (zh) * 2020-11-27 2021-03-12 复旦大学 一种介孔金属有机骨架多中心催化剂及其制备方法和应用
CN112473745B (zh) * 2020-11-27 2021-08-17 复旦大学 一种介孔金属有机骨架多中心催化剂及其制备方法和应用
CN113351174A (zh) * 2021-06-18 2021-09-07 东北电力大学 一种负载v/n掺杂纳米二氧化钛的hkust-1/cnf复合膜的制备方法及应用
CN115228303A (zh) * 2022-06-24 2022-10-25 青岛大学 一种超薄蜂窝状金属-有机骨架混合基质膜（MOF MMMs）及其制备方法
CN115228303B (zh) * 2022-06-24 2024-03-22 青岛大学 一种超薄蜂窝状金属-有机骨架混合基质膜（MOF MMMs）及其制备方法
CN115739046A (zh) * 2022-11-15 2023-03-07 武汉大学 一种hkust-1/海藻酸盐凝胶颗粒复合材料及其制备方法和其应用
CN115739046B (zh) * 2022-11-15 2024-01-16 武汉大学 一种hkust-1/海藻酸盐凝胶颗粒复合材料及其制备方法和其应用

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