CN115970501B - Method for rapidly preparing MOF/PEO mixed matrix membrane at room temperature by alkali induction - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 27
- 230000006698 induction Effects 0.000 title claims abstract description 9
- 239000003513 alkali Substances 0.000 title claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 38
- 238000005266 casting Methods 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000012670 alkaline solution Substances 0.000 claims abstract description 15
- 238000004132 cross linking Methods 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000013110 organic ligand Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 8
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000004280 Sodium formate Substances 0.000 claims description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 4
- 235000019254 sodium formate Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- 230000001939 inductive effect Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 15
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 71
- 239000012621 metal-organic framework Substances 0.000 description 31
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 19
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 19
- 239000007789 gas Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 9
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- 239000011259 mixed solution Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 4
- 239000012917 MOF crystal Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
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- 229920005597 polymer membrane Polymers 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
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- 239000002803 fossil fuel Substances 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A method for rapidly preparing MOF/PEO mixed matrix membrane at room temperature by alkali induction belongs to the technical field of membrane preparation, and comprises the following steps: 1) Preparing a casting solution containing a high-concentration MOF precursor and PEO prepolymer; 2) Preparing a MOF precursor/PEO film by adopting a photoinitiated polymerization crosslinking technology; 3) Placing the MOF precursor/PEO film in alkaline solution at room temperature, and rapidly converting the MOF precursor in the PEO matrix into MOF nanocrystalline through alkali induction; 4) The converted MOF/PEO mixed matrix membrane was washed and dried for gas separation. The method has the advantages of high film making speed, simple process and mild condition, MOF particles in the prepared mixed matrix film are uniformly dispersed, and the method is favorable for rapid mass transfer of gas molecules, and can be widely applied to separation of CO 2 mixed gas in gas separation.
Description
Technical Field
The invention mainly relates to a method for rapidly preparing a Metal Organic Framework (MOF)/polyethylene oxide (PEO) mixed matrix membrane at room temperature by alkali induction, which can be applied to separation of CO 2 in a gas separation process and belongs to the technical field of membranes.
Background
The use of fossil fuels to emit CO 2 results in a greenhouse effect, severely affecting the ecological environment. CO 2 in the flue gas of a coal-fired power plant is one of the important sources of CO 2 in the atmosphere, and thus capturing CO 2 from the flue gas is one of the paths for effectively controlling the concentration of CO 2 in the air. The current separation of CO 2 mainly uses chemical absorption processes, such as amine absorption, etc., to reduce the energy consumption, amine degradation and volatilization, and operation costs in the process of capturing CO 2 by the amine absorption method, which is a difficulty in this field. The development of a new CO 2 capturing process is beneficial to promoting industrialization.
The membrane separation technology becomes a promising alternative technology due to low energy consumption, simple operation and small occupied area, and the polymer membrane for CO 2 separation has the advantages of easy molding and amplification, breaks through the game effect between the inherent permeability and selectivity of the polymer membrane, improves the separation efficiency of the polymer membrane CO 2, and is beneficial to reducing the application cost of the membrane method CO 2 trapping industry. Therefore, the design and preparation of the high-separation-performance gas separation membrane for CO 2 separation are of great significance.
The mixed matrix membrane consists of dispersed inorganic/organic filler and continuous polymer matrix, and has the characteristics of good gas separation performance of the filler and easy processing of the polymer, thereby being an effective method for constructing the high-performance gas separation membrane. The MOF material has the advantages of high porosity, large specific surface area, adjustable structure and the like, and becomes a preferable material for preparing the mixed matrix membrane.
The MOF is dispersed in a polymer solution, and the mixed matrix membrane is obtained by solvent evaporation, which is the main method for preparing the current mixed matrix membrane. However, due to the differences in physicochemical properties between the MOF particles and the polymer matrix, the particles are susceptible to agglomeration, causing non-selective defects, thereby reducing the gas separation performance of the mixed matrix membrane. In order to solve the problem, researchers adopt physical/chemical modification to the polymer and the filler, so that the interfacial compatibility between the polymer and the filler is improved to a certain extent, and the dispersibility of the filler in the film is improved. Lv Yongqin topic group a polymer film was obtained by mixing PEO prepolymer with ZIF-8 precursor, heating at 65 ℃ for 2 hours for crosslinking, then melting the precursor salt for 5 hours under high temperature (120 ℃) conditions to achieve dispersion, and finally converting to obtain a mixed matrix film (Ma et al, j. Mater. Chem. A,2019,7,20293-20301). The study shows that nano particles grow in situ in the polymer film, so that the problems of poor filler dispersibility and interface compatibility can be solved, and the loading of the filler in the polymer matrix can be improved. If the MOF process is simplified and the film forming time is shortened, the MOF mixed matrix film is obtained under mild conditions, which is helpful to promote the practical application process of the film.
In the invention, MOF precursor is dissolved in solvent to obtain MOF precursor liquid with uniform high concentration, and then is uniformly mixed with PEO prepolymer to prepare casting film liquid. The PEO polymer film is formed by photoinitiated polymerization while the precursor is uniformly dispersed at a high concentration. MOF precursor/PEO films were placed in alkaline solution at room temperature and MOF crystals were grown using base induction to quickly prepare MOF/PEO mixed matrix films for CO 2 capture. The method greatly shortens the preparation time of the mixed matrix membrane, simplifies the operation flow, and effectively solves the problems of uneven distribution of the filler in the matrix, long preparation period, complex process and the like.
Disclosure of Invention
The invention aims to provide a method for rapidly preparing a MOF/PEO mixed matrix membrane at room temperature by alkali induction. The design idea of the invention is as follows: firstly, preparing a casting film solution containing a high-concentration MOF precursor and PEO prepolymer; preparing a PEO film containing a high concentration of MOF precursor (MOF precursor/PEO) by a method of photoinitiating prepolymer polymerization crosslinking; and then placing the MOF precursor/PEO film in an alkaline solution at room temperature, wherein the MOF precursor can be quickly converted into MOF crystals, and washing and drying to obtain the MOF/PEO mixed matrix film.
In order to achieve the above object, the present invention is realized by the following steps:
(1) Preparing a film casting solution containing a high-concentration MOF precursor, dissolving metal salt and an organic ligand in a solvent to prepare a high-concentration MOF precursor solution, dissolving PEO prepolymer and a photoinitiator in the solution, and uniformly stirring;
(2) Preparing the film casting solution prepared in the step (1) into a film by utilizing the characteristic of photoinitiated PEO prepolymer polymerization crosslinking, and then carrying out photocrosslinking to prepare a PEO film containing the MOF precursor, namely the MOF precursor/PEO film;
(3) Mixing an alkaline substance and a solvent to prepare an alkaline solution for inducing the MOF precursor to rapidly crystallize in the cross-linked polymer matrix, and placing the MOF precursor/PEO membrane obtained in the step (2) into the alkaline solution at room temperature to obtain the MOF/PEO mixed matrix membrane with MOF particles uniformly distributed in a short time.
Preferably, in the step (1), the metal salt is one of zinc nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate, and the organic ligand may be 2-methylimidazole, benzimidazole, terephthalic acid, trimesic acid and the like; the relation between the amount of the organic ligand and the amount of the metal salt can theoretically obtain the corresponding MOF. The concentration of the metal salt is 0.0008mol/L to 0.0153mol/L, and the concentration of the organic ligand in the synthetic solution is 0.002mol/L to 0.043mol/L.
Preferably, in the step (1), the solvent is one or two selected from water, methanol, ethanol, N-dimethylformamide, dimethyl sulfoxide, and the like.
Preferably, in step (1), the PEO prepolymer contains photocrosslinkable vinyl groups and has a molecular weight of between 200 and 2000.
Preferably, in step (1), the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, wherein the mass ratio between the photoinitiator and the PEO prepolymer is between 0.1% and 5%.
Preferably, in step (1), the mass ratio of metal salt to PEO prepolymer is 0.07 to 1.30:1.
Preferably, in the step (2), the photo-crosslinking is irradiated by ultraviolet light, and the irradiation time of the ultraviolet light is 10 seconds to 500 seconds; the optical density was 50mW/cm 2～600mW/cm2.
Preferably, in the step (3), the alkaline substance is ammonia water, sodium formate, sodium hydroxide, potassium hydroxide, or the like. The pH value of the alkaline solution is 8.0-13.
Preferably, in the step (3), the solvent is one or two selected from water, methanol, ethanol, dimethyl sulfoxide, and the like.
Preferably, in step (3), the synthesis time is 1 to 10 minutes.
Preferably, a MOF/PEO mixed matrix membrane is prepared using this method. The membrane can be used for CO 2 gas separation, and further applied to separation of CO 2/N2,CO2/H2, CO 2/CH4 and the like.
Compared with the prior art, the invention has the following advantages:
Compared with other preparation methods, the method has the advantages that the PEO polymer film is formed, meanwhile, the precursor with high concentration is uniformly dispersed, and the MOF precursor is quickly crystallized in situ in the PEO matrix by utilizing alkali induction, so that the problems of uneven distribution of filler in the polymer matrix and poor interface compatibility are effectively solved, and the quick preparation of the mixed matrix film is realized. The preparation process is simple to operate, high in repeatability, free of heating and low in energy consumption. In addition, the method is suitable for in-situ construction of mixed matrix membranes of MOF crystals of different types to be applied to separation and trapping of CO 2, and has excellent application potential.
Drawings
FIG. 1 is a synthetic route diagram of the base-induced room temperature rapid preparation of metal organic framework/polymer mixed matrix membranes of the present invention.
FIG. 2 is an infrared spectrum of a ZIF-8/PEO film prepared in example 1 of the present invention.
FIG. 3 is a nuclear magnetic resonance spectrum of ZIF-8/PEO films prepared in example 1 of the present invention.
FIG. 4 is a field emission scanning electron micrograph of a cross section of a ZIF-8/PEO film prepared in example 1 of the present invention.
Detailed Description
The following specific embodiments are used to illustrate the technical solution of the present invention, but the scope of the present invention is not limited thereto:
example 1
The metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, the solvent of the casting solution is a mixed solvent of methanol and ethanol, and ammonia water and methanol are used for preparing an alkaline solution to obtain the ZIF-8/PEO mixed matrix membrane. The preparation method comprises the following steps:
Step 1: 1g of zinc nitrate hexahydrate, 0.6g of 2-methylimidazole, 2.23g of PEO prepolymer (molecular weight: 700), 0.02g of a photoinitiator, 0.41g of methanol and 0.23g of ethanol were placed in a flask, and the flask was sufficiently stirred at room temperature and irradiated with a red laser lamp, and no significant Tyndall effect was observed, thereby obtaining a desired casting solution.
Step 2: and (3) transferring the casting solution by using a liquid transferring gun, controlling the thickness of the casting solution, initiating PEO prepolymer polymerization crosslinking by using ultraviolet light, wherein the ultraviolet light density is 50mW/cm 2, the illumination time is 500 seconds, and then taking out the crosslinked ZIF-8 precursor/PEO film from the glass sheet.
Step 3: the ZIF-8 precursor/PEO membrane was placed in 100mL of a mixed solution of ammonia water and methanol, wherein the ammonia water content was 20% by volume, the reaction time was 10 minutes, and the ZIF-8/PEO mixed matrix membrane was obtained at room temperature.
The ZIF-8/PEO membranes obtained above were tested for the bulk separation performance of the CO 2/N2 system. Test conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and the volume ratio of CO 2 to N 2 in the raw material gas is 1:1. Test results: the permeability coefficient of CO 2 was 890Barrer and the CO 2/N2 selectivity was 47.
Example 2
The metal salt is cobalt nitrate hexahydrate, the organic ligand is 2-methylimidazole, the solvent of the casting solution is methanol, and ammonia water, methanol and water are used for preparing an alkaline solution to obtain the ZIF-67/PEO mixed matrix membrane. The preparation method comprises the following steps:
step 1: 1g of cobalt nitrate hexahydrate, 0.6g of 2-methylimidazole, 1.52g of PEO prepolymer (molecular weight: 2000), 0.02g of a photoinitiator and 0.41g of methanol were placed in a flask and stirred well at room temperature until no significant Tyndall effect was observed by irradiation with a red laser lamp, thereby obtaining a desired casting solution.
Step 2: and (3) transferring the casting solution by using a liquid transferring gun, controlling the thickness of the casting solution, initiating PEO prepolymer polymerization crosslinking by using ultraviolet light, wherein the ultraviolet light density is 600mW/cm 2, the illumination time is 10 seconds, and then taking out the crosslinked ZIF-67 precursor/PEO film from the glass sheet.
Step 3: the ZIF-67 precursor/PEO film was placed in 100mL of a mixed solution of ammonia water, methanol and water, wherein the ammonia water content was 10% by volume, the reaction time was 1 minute, and the ZIF-67/PEO mixed matrix film was obtained at room temperature.
The ZIF-67/PEO membranes obtained above were tested for gas separation performance of the CO 2/N2 system. Test conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and the volume ratio of CO 2 to N 2 in the raw material gas is 1:1. Test results: the permeability coefficient of CO 2 was 1567Barrer and the CO 2/N2 selectivity was 41.
Example 3
The metal salt is copper nitrate trihydrate, the organic ligand is terephthalic acid, the solvent of the casting solution is dimethyl sulfoxide, and ammonia water and water are used for preparing an alkaline solution to obtain the CuBDC/PEO mixed matrix membrane. The preparation method comprises the following steps:
Step 1: 0.5g of copper nitrate trihydrate, 0.4g of terephthalic acid, 2.23g of PEO prepolymer (molecular weight 200), 0.02g of photoinitiator and 0.41g of dimethyl sulfoxide are placed in a flask and stirred sufficiently at room temperature until no significant Tyndall effect is observed by irradiation with a red laser lamp, thus obtaining the desired casting solution.
Step 2: and (3) transferring the casting solution by using a liquid transferring gun, controlling the thickness of the casting solution, initiating PEO prepolymer polymerization crosslinking by using ultraviolet light, wherein the ultraviolet light density is 100mW/cm 2, the illumination time is 200 seconds, and then taking the crosslinked CuBDC precursor/PEO film out of the glass sheet.
Step 3: the CuBDC precursor/PEO film was placed in 100mL ammonia water and water mixed solution, wherein the ammonia water content was 10% by volume, and reacted for 3 minutes to obtain a CuBDC/PEO mixed matrix film at room temperature.
The gas separation performance of the CO 2/H2 system was tested on the CuBDC/PEO films obtained above. Test conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and the volume ratio of CO 2 to H 2 in the raw material gas is 1:1. Test results: the permeability coefficient of CO 2 was 430Barrer and the CO 2/H2 selectivity was 25.
Example 4
The metal salt is copper nitrate trihydrate, the organic ligand is trimesic acid, the solvent of the casting solution is dimethyl sulfoxide, ammonia water and water are used for preparing alkaline solution, and the CuBTC/PEO mixed matrix membrane is obtained. The preparation method comprises the following steps:
step 1: 0.5g of copper nitrate trihydrate, 0.4g of trimesic acid, 2.23g of PEO prepolymer (molecular weight 200), 0.02g of photoinitiator and 0.41g of dimethyl sulfoxide are placed in a flask, and stirred sufficiently at room temperature until no obvious Tyndall effect is observed by irradiation with a red laser lamp, thus obtaining the required casting solution.
Step 2: and (3) transferring the casting solution by using a liquid transferring gun, controlling the thickness of the casting solution, initiating PEO prepolymer polymerization crosslinking by using ultraviolet light, wherein the ultraviolet light density is 300mW/cm 2, the illumination time is 200 seconds, and then taking the crosslinked CuBTC precursor/PEO film out of the glass sheet.
Step 3: the CuBTC precursor/PEO film was placed in a 100mL ammonia water and water mixed solution, wherein the ammonia water content was 30% by volume, and reacted for 3 minutes to obtain a CuBTC/PEO mixed matrix film at room temperature.
The CuBTC/PEO membranes obtained above were tested for gas separation performance of the CO 2/CH4 system. Test conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and the volume ratio of CO 2 to CH 4 in the raw material gas is 1:1. Test results: the permeability coefficient of CO 2 was 730Barrer and the CO 2/CH4 selectivity was 31.
Example 5
The metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, the solvent of the casting solution is methanol, ammonia water and water are used for preparing alkaline solution, and the ZIF-8/PEO mixed matrix membrane is obtained. The preparation method comprises the following steps:
step 1: 1g of zinc nitrate hexahydrate, 0.6g of 2-methylimidazole, 1.51g of PEO prepolymer (molecular weight: 1000), 0.02g of a photoinitiator and 0.41g of methanol were placed in a flask, and stirred sufficiently at room temperature until no significant Tyndall effect was observed by irradiation with a red laser lamp, to obtain the desired casting solution.
Step 2: and (3) transferring the casting solution by using a liquid transferring gun, controlling the thickness of the casting solution, initiating PEO prepolymer polymerization crosslinking by using ultraviolet light, wherein the ultraviolet light density is 100mW/cm 2, the illumination time is 50 seconds, and then taking out the crosslinked ZIF-8 precursor/PEO film from the glass sheet.
Step 3: the ZIF-8 precursor/PEO film is placed in a mixed solution of 100mL of ammonia water and water, wherein the volume content of the ammonia water is 10%, and the mixed substrate film of the ZIF-8/PEO is obtained after reaction for 10 minutes at room temperature.
The ZIF-8/PEO membranes obtained above were tested for gas separation performance of the CO 2/N2 system. Test conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and the volume ratio of CO 2 to N 2 in the raw material gas is 1:1. Test results: the permeability coefficient of CO 2 was 1658Barrer and the CO 2/N2 selectivity was 37.
Example 6
The metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, the solvent of the casting solution is ethanol, and sodium formate and water are used for preparing an alkaline solution to obtain the ZIF-8/PEO mixed matrix membrane. The preparation method comprises the following steps:
step 1: 1g of zinc nitrate hexahydrate, 0.8g of 2-methylimidazole, 1.25g of PEO prepolymer (molecular weight: 700), 0.02g of a photoinitiator and 0.52g of ethanol were placed in a flask, and stirred sufficiently at room temperature until no significant Tyndall effect was observed by irradiation with a red laser lamp, to obtain the desired casting solution.
Step 2: and (3) transferring the casting solution by using a liquid transferring gun, controlling the thickness of the casting solution, initiating PEO prepolymer polymerization crosslinking by using ultraviolet light, wherein the ultraviolet light density is 200mW/cm 2, the illumination time is 400 seconds, and then taking out the crosslinked ZIF-8 precursor/PEO film from the glass sheet.
Step 3: the ZIF-8 precursor/PEO membrane was placed in a mixed solution of 100mL water and 0.4g sodium formate and reacted for 10 minutes to give a ZIF-8/PEO mixed matrix membrane at room temperature.
The ZIF-8/PEO membranes obtained above were tested for gas separation performance of the CO 2/N2 system. Test conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and the volume ratio of CO 2 to N 2 in the raw material gas is 1:1. Test results: the permeability coefficient of CO 2 was 2500Barrer and the CO 2/N2 selectivity was 37.
Claims (6)
1. A method for rapidly preparing a MOF/PEO mixed matrix membrane at room temperature by alkali induction, which is characterized by comprising the following steps:
(1) Preparing a film casting solution containing a high-concentration MOF precursor, dissolving metal salt and an organic ligand in a solvent to prepare a high-concentration MOF precursor solution, dissolving PEO prepolymer and a photoinitiator in the solution, and uniformly stirring;
(2) Preparing the film casting solution prepared in the step (1) into a film by utilizing the characteristic of photoinitiated PEO prepolymer polymerization crosslinking, and then carrying out photocrosslinking to prepare a PEO film containing the MOF precursor, namely the MOF precursor/PEO film;
(3) Mixing an alkaline substance and a solvent to prepare an alkaline solution for inducing the MOF precursor to rapidly crystallize in a cross-linked polymer matrix, and placing the MOF precursor/PEO film obtained in the step (2) into the alkaline solution at room temperature to obtain the MOF/PEO mixed matrix film with MOF particles uniformly distributed in a short time;
In the step (1), the metal salt is one of zinc nitrate hexahydrate, cobalt nitrate hexahydrate and copper nitrate trihydrate, and the organic ligand is 2-methylimidazole, benzimidazole, terephthalic acid and trimesic acid; the dosage relation of the organic ligand and the metal salt can theoretically obtain corresponding MOF; the concentration of the metal salt is 0.0008 mol/L-0.0153/mol/L, and the concentration of the organic ligand in the synthetic solution is 0.002 mol/L-0.043/mol/L;
In the step (1), the PEO prepolymer contains vinyl capable of undergoing photo-crosslinking reaction, and the molecular weight is 200-2000; in the step (1), the mass ratio of the metal salt to the PEO prepolymer is 0.07-1.30: 1, a step of;
In the step (3), the alkaline substance is ammonia water, sodium formate, sodium hydroxide or potassium hydroxide; the pH value of the alkaline solution is 8.0-13; in the step (3), the solvent is one or two of water, methanol, ethanol and dimethyl sulfoxide; in the step (3), the synthesis time is 1 to 10 minutes.
2. The method according to claim 1, wherein in the step (1), the solvent is one or a mixture of two of water, methanol, ethanol, N-dimethylformamide and dimethyl sulfoxide.
3. The method according to claim 1, wherein in the step (1), the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropionacetone, and wherein the mass ratio of the photoinitiator to the PEO prepolymer is 0.1% -5%.
4. The method according to claim 1, wherein in the step (2), the photocrosslinking is irradiated with ultraviolet light for 10 seconds to 500 seconds; the optical density was 50 mW/cm 2~600 mW/cm2.
5. A MOF/PEO mixed matrix membrane obtainable by the process according to any one of claims 1 to 4.
6. Use of a MOF/PEO mixed matrix membrane obtained according to the method of any one of claims 1 to 4 for the separation of CO 2/N2、CO2/H2 or CO 2/CH4.
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