CN115970501A - Method for quickly preparing MOF/PEO mixed matrix membrane at room temperature through alkali induction - Google Patents
Method for quickly preparing MOF/PEO mixed matrix membrane at room temperature through alkali induction Download PDFInfo
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- 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
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 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
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- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical group CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
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- 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
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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
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Abstract
A method for rapidly preparing an 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 a PEO prepolymer; 2) Preparing an MOF precursor/PEO film by adopting a photo-initiated polymerization crosslinking technology; 3) Placing the MOF precursor/PEO film in an alkaline solution at room temperature, and rapidly converting the MOF precursor in the PEO matrix into MOF nanocrystals through alkali induction; 4) The converted MOF/PEO mixed matrix membrane is washed and dried for gas separation. The method has the advantages of high membrane preparation speed, simple process and mild conditions, and MOF particles in the prepared mixed matrix membrane are uniformly dispersed, thereby being beneficial to the rapid mass transfer of gas molecules and being widely applied to gas separationCO 2 And (5) separating the mixed gas.
Description
Technical Field
The invention mainly relates to a method for quickly preparing a Metal Organic Framework (MOF)/polyethylene oxide (PEO) mixed matrix membrane at room temperature by alkali induction, wherein the membrane can be applied to CO in a gas separation process 2 Belonging to the technical field of membranes.
Background
CO emissions using fossil fuels 2 Causing greenhouse effect and seriously influencing ecological environment. CO in flue gas of coal-fired power plant 2 Is CO in the atmosphere 2 Of the flue gas, thus capturing CO from the flue gas 2 Is effective in controlling CO in air 2 One of the paths of concentration. Current CO 2 Mainly utilizes chemical absorption process, such as amine absorption, etc. to reduce the CO capture by amine absorption method 2 The problems of energy consumption, amine degradation and volatilization, operation cost and the like of the process are difficult points in the field. Development of novel CO 2 The trapping process is favorable for promoting the industrialization of the method.
The membrane separation technology is a promising alternative technology due to low energy consumption, simple operation and small occupied area, and CO is 2 The polymer membrane for separation has the advantages of easy molding and amplification, breaks through the game effect between the inherent permeability and selectivity of the polymer membrane, and improves the CO content of the polymer membrane 2 Separation efficiency, and is favorable for reducing CO in membrane method 2 Trapping the application cost of the industry. Therefore, the gas separation membrane with high separation performance is designed and prepared for CO 2 The separation is of great significance.
The mixed matrix membrane is composed of dispersed inorganic/organic fillers and a continuous polymer matrix, and has the characteristics of good gas separation performance of the fillers and easy processing of the polymer, so that the mixed matrix membrane becomes an effective method for constructing a 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 preferred material for preparing the mixed matrix membrane.
The dispersion of MOFs in polymer solutions, and the acquisition of mixed matrix membranes by solvent evaporation is currently the main method of mixed matrix membrane preparation. However, due to the differences in physicochemical properties between the MOF particles and the polymer matrix, the particles are prone to agglomeration, causing non-selective defects, thereby reducing the gas separation performance of the mixed matrix membrane. In order to solve the problem, researchers modify the polymer and the filler physically/chemically, 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 task group obtains a mixed matrix membrane by mixing a PEO prepolymer with a ZIF-8 precursor, heating at 65 ℃ for 2 hours to crosslink the mixture to obtain a polymer membrane, then melting the precursor salt at a high temperature (120 ℃) for 5 hours to realize dispersion, and finally converting the precursor salt to obtain the mixed matrix membrane (Ma et al, j. The research shows that the in-situ growth of the nano particles in the polymer film can solve the problems of poor filler dispersibility and interface compatibility and simultaneously improve the loading capacity of the filler in the polymer matrix. If the process of in-situ generation of the MOF in the polymer can be simplified, the film forming time can be shortened, and the MOF mixed matrix film can be obtained under mild conditions, which is beneficial to promoting the practical application process of the film.
In the invention, the MOF precursor is dissolved in a solvent to obtain uniform MOF precursor liquid with high concentration, and then the uniform MOF precursor liquid is uniformly mixed with PEO prepolymer to prepare the casting solution. The PEO polymer film is formed by photo-initiated polymerization, and the precursor with high concentration is uniformly dispersed. The MOF precursor/PEO film is placed in an alkaline solution at room temperature, alkali is utilized to induce the MOF to grow in a crystallized manner, and the MOF is rapidly prepared and used for CO 2 Trapped MOF/PEO mixed matrix membranes. The method greatly shortens the preparation time of the mixed matrix membrane, simplifies the operation process, 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 quickly 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 solution containing a high-concentration MOF precursor and a PEO prepolymer; preparing a PEO film containing a high concentration of MOF precursors (MOF precursor/PEO) by a method of photo-initiated prepolymer polymerization crosslinking; and then placing the MOF precursor/PEO film in an alkaline solution at room temperature, rapidly converting the MOF precursor into MOF crystals, and washing and drying to obtain the MOF/PEO mixed matrix film.
In order to achieve the purpose, the invention is realized by adopting the following steps:
(1) Preparing a 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 a PEO prepolymer and a photoinitiator in the solution, and uniformly stirring;
(2) Utilizing the characteristic of photo-initiated PEO prepolymer polymerization crosslinking, preparing the casting solution prepared in the step (1) into a film, and then carrying out photo-crosslinking to prepare a PEO film containing MOF precursors, namely an MOF precursor/PEO film;
(3) And (3) mixing an alkaline substance and a solvent, preparing an alkaline solution for inducing the MOF precursor to rapidly crystallize in the cross-linked polymer matrix, and placing the MOF precursor/PEO film obtained in the step (2) in the alkaline solution at room temperature to obtain the MOF/PEO mixed matrix film with uniformly distributed MOF particles 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 can be 2-methylimidazole, benzimidazole, terephthalic acid, trimesic acid and the like; the dosage relation of the organic ligand and the metal salt is that the corresponding MOF can be obtained theoretically. 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.
Preferably, in the step (1), the solvent is one or a mixed solvent of two of water, methanol, ethanol, N-dimethylformamide and dimethyl sulfoxide, and the like.
Preferably, in step (1), the PEO prepolymer contains vinyl groups capable of undergoing a photocrosslinking reaction and has a molecular weight of 200 to 2000.
Preferably, in step (1), the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, wherein the mass ratio of the photoinitiator to the PEO prepolymer is 0.1-5%.
Preferably, in the step (1), the mass ratio of the metal salt to the PEO prepolymer is 0.07 to 1.30:1.
preferably, in the step (2), ultraviolet light is adopted for irradiation in the photocrosslinking, and the time of the ultraviolet light irradiation is 10 seconds to 500 seconds; the optical density is 50mW/cm 2 ～600mW/cm 2 。
Preferably, in the step (3), the alkaline substance is ammonia, 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 type of the solvent is one or a mixed solvent of two of water, methanol, ethanol, and dimethyl sulfoxide, and the like.
Preferably, in step (3), the synthesis time is 1 minute to 10 minutes.
Preferably, a MOF/PEO mixed matrix membrane can be prepared using this method. The membrane can be used for CO 2 Gas separation, further application to CO 2 /N 2 ，CO 2 /H 2 And CO 2 /CH 4 And the like.
Compared with the prior art, the invention has the following advantages:
compared with other preparation methods, the method for quickly preparing the metal organic framework/polyethylene oxide mixed matrix membrane at room temperature through alkali induction enables a high-concentration precursor to be uniformly dispersed while a PEO polymer membrane is formed, and enables an MOF precursor to be quickly crystallized in situ in the PEO matrix through alkali induction, so that the problems of nonuniform distribution of a filler in the polymer matrix and poor interface compatibility are effectively solved, and the quick preparation of the mixed matrix membrane 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 different types of MOF crystal in-situ construction of mixed matrix membranes for CO application 2 Has excellent application potential.
Drawings
FIG. 1 is a synthesis scheme for the rapid preparation of a metal organic framework/polymer mixed matrix membrane at room temperature by alkali induction according to 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 a ZIF-8/PEO membrane prepared in inventive example 1.
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 technical solution of the present invention is illustrated by the following specific examples, 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 membrane 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 photoinitiator, 0.41g of methanol and 0.23g of ethanol were placed in a flask, stirred well at room temperature, irradiated with a red laser lamp, and no significant Tyndall effect was observed, i.e., the desired casting solution was obtained.
Step 2: using a liquid-transfering gun to transfer the casting solution, controlling the thickness of the casting solution, and using ultraviolet light to initiate PEO prepolymer to polymerize and crosslink, wherein the ultraviolet light density is 50mW/cm 2 The light exposure time was 500 seconds, and the crosslinked ZIF-8 precursor/PEO film was then removed from the glass sheet.
And 3, step 3: and (3) placing the ZIF-8 precursor/PEO film into 100mL of a mixed solution of ammonia water and methanol, wherein the volume content of the ammonia water is 20%, the reaction time is 10 minutes, and obtaining the ZIF-8/PEO mixed matrix film at room temperature.
Subjecting the ZIF-8/PEO membrane obtained above to CO 2 /N 2 And (4) testing the separation performance of the system. And (3) testing conditions are as follows: the temperature is 35 ℃, the pressure is 0.35MPa, and CO in the raw material gas 2 And N 2 1:1. And (3) testing results: CO 2 2 Has a permeability coefficient of 890Barrer 2 /N 2 The 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 photoinitiator, 0.41g of methanol were placed in a flask and stirred well at room temperature until irradiated with a red laser lamp, and no significant Tyndall effect was observed, i.e., the desired casting solution was obtained.
Step 2: using a liquid-transfering gun to transfer the casting solution, controlling the thickness of the casting solution, and using ultraviolet light to initiate PEO prepolymer to polymerize and crosslink, wherein the ultraviolet light density is 600mW/cm 2 Light exposure time of 10 seconds, followed by cross-linking of the ZIF-67 precursor/PEO film was removed from the glass sheet.
And step 3: and (3) placing the ZIF-67 precursor/PEO film into 100mL of a mixed solution of ammonia water, methanol and water, wherein the volume content of the ammonia water is 10%, the reaction time is 1 minute, and obtaining the ZIF-67/PEO mixed matrix film at room temperature.
Subjecting the ZIF-67/PEO membrane obtained above to CO 2 /N 2 And (5) testing the gas separation performance of the system. And (3) testing conditions are as follows: the temperature is 35 ℃, the pressure is 0.35MPa, and CO in the raw material gas 2 And N 2 1:1. And (3) testing results: CO 2 2 Has a permeability coefficient of 1567Barrer 2 /N 2 The 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, 0.41g of dimethyl sulfoxide were placed in a flask and stirred well at room temperature until irradiated with a red laser lamp, and no significant Tyndall effect was observed, i.e., the desired casting solution was obtained.
Step 2: using a liquid-transfering gun to transfer the casting solution, controlling the thickness of the casting solution, and using ultraviolet light to initiate PEO prepolymer to polymerize and crosslink, wherein the ultraviolet light density is 100mW/cm 2 The light exposure time was 200 seconds, and the crosslinked CuBDC precursor/PEO film was subsequently removed from the glass sheet.
And step 3: and (3) placing the CuBDC precursor/PEO film into 100mL of ammonia-water and water mixed solution, wherein the volume content of ammonia water is 10%, reacting for 3 minutes, and obtaining the CuBDC/PEO mixed matrix film at room temperature.
Subjecting the CuBDC/PEO film obtained above to CO 2 /H 2 And (5) testing the gas separation performance of the system. And (3) testing conditions are as follows: the temperature is 35 ℃, the pressure is 0.35MPa, and CO in the raw material gas 2 And H 2 1:1. And (3) testing results: CO 2 2 Has a permeability coefficient of 430Barrer 2 /H 2 SelectingThe sex 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, and ammonia water and water are used for preparing an alkaline solution to obtain the CuBTC/PEO mixed matrix membrane. 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 were placed in a flask and stirred well at room temperature until irradiated with a red laser lamp, and no significant Tyndall effect was observed, i.e., the desired casting solution was obtained.
Step 2: using a liquid-transfering gun to transfer the casting solution, controlling the thickness of the casting solution, and using ultraviolet light to initiate PEO prepolymer to polymerize and crosslink, wherein the ultraviolet light density is 300mW/cm 2 The illumination time was 200 seconds, and the crosslinked CuBTC precursor/PEO film was subsequently removed from the glass sheet.
And step 3: and (3) placing the CuBTC precursor/PEO film into 100mL of mixed solution of ammonia water and water, wherein the volume content of the ammonia water is 30%, reacting for 3 minutes, and obtaining the CuBTC/PEO mixed matrix film at room temperature.
Subjecting the CuBTC/PEO film obtained above to CO 2 /CH 4 And (5) testing the gas separation performance of the system. And (3) testing conditions: the temperature is 35 ℃, the pressure is 0.35MPa, and CO in the raw material gas 2 And CH 4 1:1. And (3) testing results: CO 2 2 Has a permeability coefficient of 730Barrer 2 /CH 4 The 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, and ammonia water 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, 0.6g of 2-methylimidazole, 1.51g of PEO prepolymer (molecular weight 1000), 0.02g of photoinitiator, 0.41g of methanol were placed in a flask and stirred well at room temperature until irradiated with a red laser lamp, and no significant Tyndall effect was observed, i.e., the desired casting solution was obtained.
Step 2: using a liquid-transfering gun to transfer the casting solution, controlling the thickness of the casting solution, and using ultraviolet light to initiate PEO prepolymer to polymerize and crosslink, wherein the ultraviolet light density is 100mW/cm 2 The light exposure time was 50 seconds, and the crosslinked ZIF-8 precursor/PEO film was then removed from the glass sheet.
And step 3: and (3) placing the ZIF-8 precursor/PEO film into 100mL of a mixed solution of ammonia water and water, wherein the volume content of the ammonia water is 10%, reacting for 10 minutes, and obtaining the ZIF-8/PEO mixed matrix film at room temperature.
Subjecting the ZIF-8/PEO membrane obtained above to CO 2 /N 2 And (5) testing the gas separation performance of the system. And (3) testing conditions are as follows: the temperature is 35 ℃, the pressure is 0.35MPa, and CO in the raw material gas 2 And N 2 1:1. And (3) testing results: CO 2 2 Has a permeability coefficient of 1658Barrer 2 /N 2 The 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 photoinitiator, and 0.52g of ethanol were placed in a flask and stirred well at room temperature until irradiated with a red laser lamp, and no significant Tyndall effect was observed, i.e., the desired dope solution was obtained.
Step 2: using a liquid-transfering gun to transfer the casting solution, controlling the thickness of the casting solution, and using ultraviolet light to initiate PEO prepolymer to polymerize and crosslink, wherein the ultraviolet light density is 200mW/cm 2 The light exposure time was 400 seconds, and the crosslinked ZIF-8 precursor/PEO film was then removed from the glass sheet.
And step 3: and (3) putting the ZIF-8 precursor/PEO membrane into a mixed solution of 100mL of water and 0.4g of sodium formate, reacting for 10 minutes, and obtaining the ZIF-8/PEO mixed matrix membrane at room temperature.
Subjecting the ZIF-8/PEO membrane obtained above to CO 2 /N 2 And (5) testing the gas separation performance of the system. And (3) testing conditions are as follows: the temperature is 35 ℃, the pressure is 0.35MPa, the raw material gasMiddle CO 2 And N 2 1:1. And (3) testing results: CO 2 2 Has a permeability coefficient of 2500Barrer 2 /N 2 The selectivity was 37.
Claims (10)
1. A method for rapidly preparing an MOF/PEO mixed matrix membrane at room temperature by alkali induction, which is characterized by comprising the following steps:
(1) Preparing a 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 a PEO prepolymer and a photoinitiator in the solution, and uniformly stirring;
(2) Utilizing the characteristic of photo-initiated PEO prepolymer polymerization crosslinking, preparing the casting solution prepared in the step (1) into a film, and then carrying out photo-crosslinking to prepare a PEO film containing MOF precursors, namely an MOF precursor/PEO film;
(3) And (3) mixing an alkaline substance and a solvent, preparing an alkaline solution for inducing the MOF precursor to rapidly crystallize in the cross-linked polymer matrix, and placing the MOF precursor/PEO film obtained in the step (2) in the alkaline solution at room temperature to obtain the MOF/PEO mixed matrix film with uniformly distributed MOF particles in a short time.
2. The method according to claim 1, wherein 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, trimesic acid, etc.; the dosage relation of the organic ligand and the metal salt is that the corresponding MOF can be obtained theoretically. 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.
3. The method according to claim 1, wherein in the step (1), the solvent is one or a mixed solvent of two of water, methanol, ethanol, N, N-dimethylformamide, dimethylsulfoxide, and the like.
4. The method of claim 1, wherein in step (1), the PEO prepolymer contains vinyl groups capable of undergoing a photocrosslinking reaction and has a molecular weight of 200 to 2000.
5. The method of claim 1, wherein in step (1), the photoinitiator is 2-hydroxy-4' - (2-hydroxyethoxy) -2-methylpropiophenone, wherein the mass ratio of the photoinitiator to the PEO prepolymer is 0.1% to 5%.
6. The method of claim 1, wherein in step (1), the mass ratio of the metal salt to the PEO prepolymer is from 0.07 to 1.30:1.
7. the method according to claim 1, wherein in the step (2), the photocrosslinking is irradiated with ultraviolet light for a time of 10 seconds to 500 seconds; the optical density is 50mW/cm 2 ～600mW/cm 2 。
8. The method according to claim 1, wherein in the step (3), the basic substance is ammonia, sodium formate, sodium hydroxide, potassium hydroxide, or the like. The pH value of the alkaline solution is 8.0-13; in the step (3), the type of the solvent is one or a mixed solvent of two of water, methanol, ethanol and dimethyl sulfoxide, and the like; in the step (3), the synthesis time is 1 to 10 minutes.
9. A MOF/PEO mixed matrix membrane obtained according to the method of any one of claims 1 to 8.
10. Use of a MOF/PEO mixed matrix membrane obtained according to the method of any of claims 1 to 8 for CO 2 Gas separation, further application to CO 2 /N 2 ，CO 2 /H 2 And CO 2 /CH 4 And the like.
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