CN113083042B - Mixed matrix membrane based on MXene/ZIF-8 composite material and preparation method thereof - Google Patents

Mixed matrix membrane based on MXene/ZIF-8 composite material and preparation method thereof Download PDF

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CN113083042B
CN113083042B CN202110386877.9A CN202110386877A CN113083042B CN 113083042 B CN113083042 B CN 113083042B CN 202110386877 A CN202110386877 A CN 202110386877A CN 113083042 B CN113083042 B CN 113083042B
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zif
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CN113083042A (en
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李祥村
牟家微
代岩
贺高红
郑文姬
焉晓明
郭明钢
阮雪华
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Dalian University of Technology
Panjin Institute of Industrial Technology Dalian University of Technology DUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079—Manufacture of membranes comprising organic and inorganic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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    • B01D71/06—Organic material
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Abstract

The invention relates to the field of new material preparation, in particular to a mixed matrix membrane based on MXene/ZIF-composite material and a preparation method thereof, wherein the gas preparation step comprises the following steps: preparing MXene material, preparing ZIF-8 material, preparing polymer solution and preparing mixed matrix membrane; the invention provides a preparation method of a mixed matrix membrane for gas separation, which is prepared by compounding an MXene material and a ZIF-8 material to prepare a composite material and then blending the composite material with a polymer. It combines the high selectivity and dimensional stability of inorganic materials with the high permeability, mechanical stability and simplicity of the preparation process of polymeric materials.

Description

Mixed matrix membrane based on MXene/ZIF-8 composite material and preparation method thereof
Technical Field
The invention relates to the field of new material preparation, in particular to a mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof.
Background
With the increasing demand for energy in China, the separation and purification of hydrogen is one of the most critical steps for hydrogen energy. Among the various separation techniques, the membrane separation technique has the advantages of high separation efficiency, low energy consumption, simple operation, easy coupling with other processes, and the like.
CN105478019A discloses a composite metal hydrogen separation membrane, a preparation method thereof, and an application of the composite metal hydrogen separation membrane in dehydrogenation reaction, wherein the separation membrane comprises a porous stainless steel layer and a composite membrane of zinc oxide and palladium metal on the porous stainless steel layer. The composite metal hydrogen separation membrane provided by the invention can effectively separate hydrogen, improves the yield of reaction products of dehydrogenation reaction, has strong bonding effect between zinc oxide and palladium metal composite membrane and porous stainless steel, and effectively solves the sintering phenomenon of high-temperature metal palladium membrane. In addition, the preparation method of the composite metal hydrogen separation membrane provided by the invention is simple and easy to operate, and is beneficial to popularization and application.
CN110433672A discloses a non-coplanar polyimide gas separation membrane with large steric hindrance and a preparation method thereof, wherein the separation membrane is prepared by polymerizing diamine monomers with non-coplanar large steric hindrance structures and aromatic dianhydride monomers. The polyimide gas separation membrane has high permeability and high selectivity, and has good membrane forming property. The membrane can separate and recover hydrogen from hydrogen-containing gas and CO from carbon-containing and sulfur-containing gas2、H2The separation and recovery of S, and the oxygen enrichment or nitrogen enrichment of air and other fields have important application.
CN110108091B provides a hydrogen separation membrane that inlays modified cryrogenic liquefaction system to STAR propane dehydrogenation technology, belongs to petrochemical technical field. The system starts from the composition characteristics of dehydrogenation reaction products, introduces a hydrogen membrane separation unit after a shallow cooling unit, and utilizes the selectivity of a membraneThe majority of the hydrogen is separated by permeation and then further pressurized and cryogenically liquefied to further separate propane and propylene from the remaining non-condensable components. By embedding the improved cryogenic liquefaction system in the hydrogen membrane separation unit, the compression load can be obviously reduced while high-concentration hydrogen is obtained, the total compression energy consumption can be reduced by 8-24%, the heat exchange load of the cryogenic unit can be reduced by 80-86%, the purity of the byproduct hydrogen can be improved to 99 mol% from 82 mol%, and the requirements of hydrogen consumption devices such as hydrocracking and the like in a refining enterprise are met. Under the optimal working condition, the 35 ten thousand tons of STAR process can save the compression energy consumption by 1020kW and produce qualified hydrogen 16198Nm3/h。
The research of the polymer membrane for gas separation is early, and the advantages of low preparation cost, mature preparation process and the like become large-area application in industry. However, the performance of the polymer material itself is limited by the upper limit of Robeson, and it is difficult to achieve both excellent permeability and excellent gas separation performance. The inorganic membrane material has regular pore channels and adjustable pore diameter and affinity, realizes separation by virtue of size screening and a surface diffusion mechanism, and can overcome the trade-off effect. However, the inorganic membrane has high preparation cost, is easy to have defects in the preparation process, is difficult to prepare on a large scale, and further limits the application of the inorganic membrane in gas separation. The hybrid matrix membrane combines the high selectivity and dimensional stability of inorganic materials with the high permeability, mechanical stability of polymeric materials and the ease of the preparation process, which has become H2The research hotspot in the field of separation membranes. The new material MXene in recent years is expected to play an important role in the field of gas separation due to the multilayer two-dimensional structure and strong surface modifiability. ZIF-8 is a crystalline material with high specific surface area, porosity and unsaturated sites, and is used for separating H2Has good application prospect.
Disclosure of Invention
In order to solve the problems, the invention provides a mixed matrix membrane based on an MXene/ZIF-8 composite material and a preparation method thereof.
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding 200-400 mesh MXene into a hydrofluoric acid solution, and adding 7.5-20mL of 40-50wt% hydrofluoric acid per gram of MXene; heating to 40-80 ℃ and stirring for 6-24h at the stirring speed of 100-500 rpm;
(2) centrifuging the solution obtained in the step (1) at a centrifugation rate of 5000-10000rpm, washing with deionized water, and then discarding the supernatant, wherein the step is repeated 4-10 times until the pH = 6-7;
(3) freeze-drying the precipitate obtained in the step (2) for 24-48h to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:8-16: 500-700; sealing the cup mouth with a preservative film after mixing, and stirring for 12-18h with a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in the step (b) at a centrifugation speed of 8000-10000rpm, and washing the obtained precipitate with N, N-dimethylformamide, wherein the step is repeated for 5-6 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying for 5-20h in an oven at the temperature of 40-60 ℃ to obtain a ZIF-8 material;
step three, preparing a polymer solution, dissolving 0.1-5 parts by mass of polymer particles and 0.1-0.5 part by mass of synergist into 3.33-16.67 parts by mass of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain the polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained MXene and the obtained ZIF-8 into the obtained polymer solution, stirring for 1-5h, and performing ultrasonic treatment for 3-5 min; then pouring the obtained solution into a glass culture dish, putting the glass culture dish into an oven, standing the glass culture dish at 65-75 ℃ for 24-48h, and then transferring the obtained membrane into a vacuum oven to remove the solvent for 24-72h at the temperature of 65-75 ℃.
The preparation method of the synergist comprises the following steps:
according to the weight portion, 10-17 portions of zinc acrylate, 2-5 portions of 4-vinylbenzo-18-crown ether-6, 1.7-4.5 portions of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 200 portions of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is raised and the mixture is stirred to 60-70 ℃, 1.2-2.4 portions of benzoyl peroxide are added for reaction for 0.5-2h, and then reduced pressure distillation is carried out to remove water, thus obtaining the synergist.
And (3) carrying out polymerization reaction on zinc acrylate, 4-vinyl benzo-18-crown ether-6, 1-allyl-3-methylimidazole bromine salt to obtain the synergist. The equation for the partial reaction in the polymerization reaction is schematically shown below:
Figure 650077DEST_PATH_IMAGE001
Figure 367498DEST_PATH_IMAGE002
the MXene is Ti3AlC2Or Nb2AlC or Ti3C2Or TiNbC or V2Al2C。
The polymer is polyether copolyamide or polysulfone or polyether sulfone or polyimide or ethyl cellulose.
The MXene and ZIF-8 are mixed according to the mass ratio of 1: 7-12.
The concentration of the MXene casting solution is 0.2-0.7 wt%.
The mixed matrix membrane is a gas separation membrane for hydrogen separation.
The invention relates to a mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, aiming at solving the problem that the selectivity and the permeability of the existing gas separation membrane cannot be obtained at the same time. The invention utilizes the special structure of the two-dimensional material MXene to lead the diffusion path of the gas in the membrane to be lengthened and bent, and the molecular sieving capability of the membrane is increased, thereby improving the selectivity; ZIF-8 is used because it has a high specific surface area, a large pore volume, and good thermal and chemical stability, and can effectively improve the permeability in the membrane. For gas, after passing through ZIF-8, the adsorption capacity is improved by virtue of the large pore volume and the specific surface areaMultiple CO2The gas achieves the separation effect, and then the gas is selected by MXene due to the lengthening and the tortuosity of the diffusion channel, so that the gas can be used for H2Has better selectivity, and the zinc acrylate, 4-vinyl benzo-18-crown ether-6, 1-allyl-3-methylimidazole bromine salt are subjected to polymerization reaction to obtain the synergist, so that the high permeability of the polymer matrix membrane can be improved, and the effects of improving the selectivity and the permeability are achieved.
Drawings
FIG. 1: SEM picture of ZIF-8/MXene mixed matrix membrane surface;
FIG. 2: SEM picture of ZIF-8/MXene mixed matrix membrane section;
FIG. 3: selection-permeation performance plots for mixed matrix membranes of different dope solution concentrations ZIF-8/MXene ratios prepared in example 4.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding 200 meshes of MXene into a hydrofluoric acid solution, and adding 7.5ml of hydrofluoric acid with the concentration of 40wt% per gram of MXene; heating to 40 ℃ and stirring for 6h, wherein the stirring speed is 100 rpm;
(2) centrifuging the solution obtained in (1) at a centrifugation rate of 5000rpm, washing with deionized water and then discarding the supernatant, and repeating the step 4 times until pH = 6;
(3) freeze-drying the precipitate obtained in the step (2) for 24 hours to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:8: 500; sealing the cup mouth with a preservative film after mixing, and stirring 12 with a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in (b) at a centrifugation rate of 8000rpm and washing the resulting precipitate with N, N-dimethylformamide, which step is repeated 5 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying in an oven at the temperature of 50 ℃ for 10 hours to obtain a ZIF-8 material;
step three, preparing a polymer solution, namely dissolving 0.1g of polymer particles and 0.1g of synergist in 3.33g of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain the polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained MXene and the obtained ZIF-8 into the obtained polymer solution, stirring for 3h, and performing ultrasonic treatment for 4 min; the resulting solution was then poured into a glass petri dish, placed in an oven at 70 ℃ for 36h, and the resulting membrane was then transferred to a vacuum oven to desolventize for 45h at 70 ℃.
The MXene is Ti3AlC2。
The polymer is polyether copolyamide.
The MXene and ZIF-8 are mixed according to the mass ratio of 1: 7.
the concentration of the MXene casting solution is 0.2 wt%.
The mixed matrix membrane is a gas separation membrane for hydrogen separation.
The preparation method of the synergist comprises the following steps:
adding 10g of zinc acrylate, 2g of 4-vinylbenzo-18-crown ether-6, 1.7g of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 100g of deionized water into a sealed high-pressure reaction kettle, introducing nitrogen, heating and stirring to 60 ℃, adding 1.2g of benzoyl peroxide, reacting for 0.5h, and then carrying out reduced pressure distillation to remove water g to obtain the synergist.
Example 2
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding 300-mesh MXene into a hydrofluoric acid solution, and adding 14.6mL of 45wt% hydrofluoric acid per gram of MXene; heating to 60 ℃ and stirring for 14h, wherein the stirring speed is 300 rpm;
(2) centrifuging the solution obtained in (1) at a centrifugation rate of 8000rpm, washing with deionized water and then discarding the supernatant, and repeating the step 6 times until pH = 6.5;
(3) freeze-drying the precipitate obtained in the step (2) for 36 hours to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:12: 600; sealing the cup mouth with a preservative film after mixing, and stirring for 15 hours by using a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in (b) at a centrifugation rate of 9000rpm, and washing the resulting precipitate with N, N-dimethylformamide, which was repeated 6 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying in an oven at the temperature of 50 ℃ for 12 hours to obtain a ZIF-8 material;
step three, preparing a polymer solution, namely dissolving 2g of polymer particles and 0.2g of synergist in 11.3g of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain the polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained MXene and the obtained ZIF-8 into the obtained polymer solution, stirring for 3h, and performing ultrasonic treatment for 4 min; the resulting solution was then poured into a glass petri dish, placed in an oven at 65 ℃ for 24h, and the resulting membrane was then transferred to a vacuum oven to desolventize for 24h at 65 ℃.
MXene is Nb2AlC。
The polymer is polysulfone.
The MXene and ZIF-8 are mixed according to the mass ratio of 1: 10.
the concentration of the MXene casting solution is 0.5 wt%.
The mixed matrix membrane is a gas separation membrane for hydrogen separation.
The preparation method of the synergist comprises the following steps:
12g of zinc acrylate, 3g of 4-vinylbenzo-18-crown ether-6, 2.8g of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 130g of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is increased to 63 ℃, 1.7g of benzoyl peroxide is added for reaction for 1 hour, and then water g is removed through reduced pressure distillation to obtain the synergist.
Example 3
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding MXene of 400 meshes into a hydrofluoric acid solution, and adding MXene per gram into 20mL of hydrofluoric acid with the concentration of 50 wt%; heating to 80 ℃ and stirring for 24h at a stirring speed of 500 rpm;
(2) centrifuging the solution obtained in (1) at a centrifugation rate of 10000rpm, washing with deionized water, and then discarding the supernatant, wherein the step is repeated 10 times until the pH = 7;
(3) freeze-drying the precipitate obtained in the step (2) for 48 hours to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:16: 700; sealing the cup mouth with a preservative film after mixing, and stirring for 18 hours with a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in the step (b) at a centrifugation speed of 10000rpm, and washing the obtained precipitate with N, N-dimethylformamide, wherein the step is repeated for 5-6 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying the precipitate in an oven at the temperature of 60 ℃ for 20 hours to obtain a ZIF-8 material;
step three, preparing a polymer solution, namely dissolving 5g of polymer particles and 0.5g of synergist in 16.67g of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain the polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained MXene and the obtained ZIF-8 into the obtained polymer solution, stirring for 5h, and carrying out ultrasonic treatment for 5 min; the resulting solution was then poured into a glass petri dish, placed in an oven at 75 ℃ for 48h, and the resulting membrane was then transferred to a vacuum oven to desolventize for 72h at 75 ℃.
The MXene is Ti3C2。
The polymer is polyether sulfone.
The MXene and ZIF-8 are mixed according to the mass ratio of 1: 12.
the concentration of the MXene casting solution is 0.7 wt%.
The mixed matrix membrane is a gas separation membrane for hydrogen separation.
The preparation method of the synergist comprises the following steps:
15g of zinc acrylate, 4g of 4-vinylbenzo-18-crown ether-6, 3.7g of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 170g of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is increased to 67 ℃, 2.1g of benzoyl peroxide is added for reaction for 1.5h, and water g is removed through reduced pressure distillation to obtain the synergist.
The embodiment of the invention has the advantages that the selective permeability performance of the mixed matrix membrane for hydrogen/nitrogen mixed gas is realized under the pressure of 0.25 MPa; the test results of the above examples are shown in the following table:
H2/N2 Selectivity
example 1 13.8
Example 2 15.7
Example 3 16.9
Example 4
Preparation of mixed matrix membranes: 0.106g of N, N-dimethylformamide solution of MXene prepared in example 1, 1.06g of N, N-dimethylformamide solution of ZIF-8 prepared in example 1 and the PI solution prepared in example 1 are mixed to obtain a casting solution with the MXene filler concentration of 0.5wt% and the ZIF-8 filler concentration of 5wt%, and after the solution is fully mixed, the casting solution is subjected to ultrasonic treatment with the power of 30w for 5 min; and repeating the steps, changing the content of the ZIF-8 filler and preparing the casting solution with different filler concentrations. The mass of the needed N, N-dimethylformamide solution of MXene is 0.108g, 0.1085g and 0.111g respectively; the solutions of ZIF-8 in N, N-dimethylformamide were 1.512g, 1.736g and 2.22g, respectively; the ZIF-8 filler concentration in the prepared casting solution is 7wt%, 8wt% and 10 wt%; pouring the prepared sample into a glass culture dish leveled by a level meter, drying for 24 hours at 70 ℃, and then putting the sample into a vacuum oven for drying for 24 hours at the temperature of 65 ℃; and testing the selection-permeability performance of the ZIF-8/MXene mixed matrix membranes with different membrane casting liquid concentrations on hydrogen/nitrogen, hydrogen/methane and hydrogen/carbon dioxide.
The preparation method of the synergist comprises the following steps:
17g of zinc acrylate, 5g of 4-vinylbenzo-18-crown ether-6, 4.5g of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 200g of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is increased to 70 ℃, 2.4g of benzoyl peroxide is added for reaction for 2 hours, and water g is removed through reduced pressure distillation to obtain the synergist.
Comparative example 1
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding 200 meshes of MXene into a hydrofluoric acid solution, and adding 7.5ml of hydrofluoric acid with the concentration of 40wt% per gram of MXene; heating to 40 ℃ and stirring for 6h, wherein the stirring speed is 100 rpm;
(2) centrifuging the solution obtained in (1) at a centrifugation rate of 5000rpm, washing with deionized water and then discarding the supernatant, and repeating the step 4 times until pH = 6;
(3) freeze-drying the precipitate obtained in the step (2) for 24 hours to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:8: 500; sealing the cup mouth with a preservative film after mixing, and stirring 12 with a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in (b) at a centrifugation rate of 8000rpm and washing the resulting precipitate with N, N-dimethylformamide, which step is repeated 5 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying in an oven at the temperature of 50 ℃ for 10 hours to obtain a ZIF-8 material;
step three, preparing a polymer solution, namely dissolving 0.1g of polymer particles and 0.1g of synergist in 3.33g of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain the polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained MXene and the obtained ZIF-8 into the obtained polymer solution, stirring for 3h, and performing ultrasonic treatment for 4 min; the resulting solution was then poured into a glass petri dish, placed in an oven at 70 ℃ for 36h, and the resulting membrane was then transferred to a vacuum oven to desolventize for 45h at 70 ℃.
The preparation method of the synergist comprises the following steps:
adding 10g of zinc acrylate, 1.7g of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 100g of deionized water into a sealed high-pressure reaction kettle, introducing nitrogen, heating and stirring to 60 ℃, adding 1.2g of benzoyl peroxide, reacting for 0.5h, and then carrying out reduced pressure distillation to remove water g to obtain the synergist.
The MXene is Ti3AlC2。
The polymer is polyether copolyamide.
The MXene and ZIF-8 are mixed according to the mass ratio of 1: 7.
the concentration of the MXene casting solution is 0.2 wt%.
The mixed matrix membrane is a gas separation membrane for hydrogen separation.
Comparative example 2
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding 200 meshes of MXene into a hydrofluoric acid solution, and adding 7.5ml of hydrofluoric acid with the concentration of 40wt% per gram of MXene; heating to 40 ℃ and stirring for 6h, wherein the stirring speed is 100 rpm;
(2) centrifuging the solution obtained in (1) at a centrifugation rate of 5000rpm, washing with deionized water and then discarding the supernatant, and repeating the step 4 times until pH = 6;
(3) freeze-drying the precipitate obtained in the step (2) for 24 hours to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:8: 500; sealing the cup mouth with a preservative film after mixing, and stirring 12 with a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in (b) at a centrifugation rate of 8000rpm and washing the resulting precipitate with N, N-dimethylformamide, which step is repeated 5 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying in an oven at the temperature of 50 ℃ for 10 hours to obtain a ZIF-8 material;
step three, preparing a polymer solution, namely dissolving 0.1g of polymer particles in 3.33g of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain a polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained ZIF-8 into the obtained polymer solution, stirring for 3h, and then carrying out ultrasonic treatment for 4 min; the resulting solution was then poured into a glass petri dish, placed in an oven at 70 ℃ for 36h, and the resulting membrane was then transferred to a vacuum oven to desolventize for 45h at 70 ℃.
The MXene is TiNbC.
The polymer is ethyl cellulose.
The mixed matrix membrane is a gas separation membrane for hydrogen separation.
Comparative example 3
A mixed matrix membrane based on MXene/ZIF-8 composite material and a preparation method thereof, the scheme is as follows:
step one, preparing MXene materials: (1) adding 200 meshes of MXene into a hydrofluoric acid solution, and adding 7.5ml of hydrofluoric acid with the concentration of 40wt% per gram of MXene; heating to 40 ℃ and stirring for 6h, wherein the stirring speed is 100 rpm;
(2) centrifuging the solution obtained in (1) at a centrifugation rate of 5000rpm, washing with deionized water and then discarding the supernatant, and repeating the step 4 times until pH = 6;
(3) freeze-drying the precipitate obtained in the step (2) for 24 hours to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, Zn2+The molar ratio of the 2-methylimidazole to the methanol is 1:8: 500; sealing the cup mouth with a preservative film after mixing, and stirring 12 with a magnetic stirrer;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in (b) at a centrifugation rate of 8000rpm and washing the resulting precipitate with N, N-dimethylformamide, which step is repeated 5 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying in an oven at the temperature of 50 ℃ for 10 hours to obtain a ZIF-8 material;
step three, preparing a polymer solution, namely dissolving 0.1g of polymer particles in 3.33g of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain a polymer solution;
step four, preparing a mixed matrix membrane: adding the MXene into the polymer solution, stirring for 3h, and performing ultrasonic treatment for 4 min; the resulting solution was then poured into a glass petri dish, placed in an oven at 70 ℃ for 36h, and the resulting membrane was then transferred to a vacuum oven to desolventize for 45h at 70 ℃.
The preparation method of the synergist comprises the following steps:
adding 10g of zinc acrylate, 2g of 4-vinylbenzo-18-crown ether-6 and 100g of deionized water into a closed high-pressure reaction kettle, introducing nitrogen, heating and stirring to 60 ℃, adding 1.2g of benzoyl peroxide, reacting for 0.5h, and then carrying out reduced pressure distillation to remove water g, thereby obtaining the synergist.
MXene is V2Al2C。
The polymer is polyimide.
The concentration of the MXene casting solution is 0.2 wt%.
The comparative example of the present invention passed the selection-permeation performance of the mixed matrix membrane for hydrogen/nitrogen mixed gas at a pressure of 0.25 MPa; the test results of the above examples are shown in the following table:
H2/N2 Selectivity
comparative example 1 9.8
Comparative example 2 4.5
Comparative example 3 12.2

Claims (7)

1. A preparation method of a mixed matrix membrane based on MXene/ZIF-8 composite material is characterized by comprising the following steps:
step one, preparing MXene materials: (1) adding 200-400 mesh MXene into a hydrofluoric acid solution, and adding 7.5-20mL of 40-50wt% hydrofluoric acid per gram of MXene; heating to 40-80 ℃ and stirring for 6-24h at the stirring speed of 100-500 rpm;
(2) centrifuging the solution obtained in the step (1) at a centrifugation rate of 5000-10000rpm, washing with deionized water, and then discarding the supernatant, wherein the step is repeated 4-10 times until the pH = 6-7;
(3) freeze-drying the precipitate obtained in the step (2) for 24-48h to obtain a dried multi-layer MXene material;
step two, preparing a ZIF-8 material: (a) mixing zinc nitrate hexahydrate, 2-methylimidazole and methanol together, wherein the molar ratio of Zn2+, 2-methylimidazole and methanol is 1:8-16: 500-700; sealing the cup mouth with a preservative film after mixing, and placing the mixture in a magnetic stirrer for stirring for 12-18 h;
(b) washing the precipitate obtained in the step (a) with an organic solvent N, N-dimethylformamide of a casting film;
(c) centrifuging the mixed solution obtained in the step (b) at a centrifugation speed of 8000-10000rpm, and washing the obtained precipitate with N, N-dimethylformamide, wherein the step is repeated for 5-6 times;
(d) placing the precipitate obtained in the step (c) in a clean glass culture dish, and drying for 5-20h in an oven at the temperature of 40-60 ℃ to obtain a ZIF-8 material;
step three, preparing a polymer solution, dissolving 0.1-5 parts by mass of polymer particles and 0.1-0.5 part by mass of synergist into 3.33-16.67 parts by mass of N, N-dimethylformamide solution, stirring for 2-5h, and transferring the solution into a container to obtain the polymer solution;
step four, preparing a mixed matrix membrane: adding the obtained MXene and the obtained ZIF-8 into the obtained polymer solution, stirring for 1-5h, and performing ultrasonic treatment for 3-5 min; then pouring the obtained solution into a glass culture dish, putting the glass culture dish into an oven, standing the glass culture dish at 65-75 ℃ for 24-48h, and then transferring the obtained membrane into a vacuum oven to remove a solvent for 24-72h at the temperature of 65-75 ℃;
the mixed matrix membrane is a gas separation membrane for hydrogen/nitrogen separation;
the preparation method of the synergist comprises the following steps:
according to the weight portion, 10-17 portions of zinc acrylate, 2-5 portions of 4-vinylbenzo-18-crown ether-6, 1.7-4.5 portions of 1-allyl-3-methylimidazolium bromide (CAS No. 31410-07-8) and 200 portions of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is raised and the mixture is stirred to 60-70 ℃, 1.2-2.4 portions of benzoyl peroxide are added for reaction for 0.5-2h, and then reduced pressure distillation is carried out to remove water, thus obtaining the synergist.
2. The method for preparing the mixed matrix membrane based on the MXene/ZIF-8 composite material, according to claim 1, wherein the mixed matrix membrane comprises the following steps:
the MXene is Ti3AlC2Or Nb2AlC or Ti3C2Or TiNbC or V2Al2C。
3. The method for preparing the mixed matrix membrane based on the MXene/ZIF-8 composite material, according to claim 1, wherein the mixed matrix membrane comprises the following steps:
the polymer is polyether copolyamide or polysulfone or polyether sulfone or polyimide or ethyl cellulose.
4. The method for preparing the mixed matrix membrane based on the MXene/ZIF-8 composite material, according to claim 1, wherein the mixed matrix membrane comprises the following steps: the MXene and ZIF-8 are mixed according to the mass ratio of 1: 7-12.
5. The method for preparing the mixed matrix membrane based on the MXene/ZIF-8 composite material, according to claim 1, wherein the mixed matrix membrane comprises the following steps: the preparation method of the synergist comprises the following steps:
12g of zinc acrylate, 3g of 4-vinylbenzo-18-crown ether-6, 2.8g of 1-allyl-3-methylimidazolium bromide and 130g of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is raised to 63 ℃, 1.7g of benzoyl peroxide is added for reaction for 1 hour, and then reduced pressure distillation is carried out to remove water, so as to obtain the synergist.
6. The method for preparing the mixed matrix membrane based on the MXene/ZIF-8 composite material, according to claim 1, wherein the mixed matrix membrane comprises the following steps: the preparation method of the synergist comprises the following steps:
15g of zinc acrylate, 4g of 4-vinylbenzo-18-crown ether-6, 3.7g of 1-allyl-3-methylimidazolium bromide and 170g of deionized water are added into a closed high-pressure reaction kettle, nitrogen is introduced, the temperature is raised to 67 ℃, 2.1g of benzoyl peroxide is added for reaction for 1.5h, and then reduced pressure distillation is carried out to remove water, so as to obtain the synergist.
7. The method for preparing the mixed matrix membrane based on the MXene/ZIF-8 composite material, according to claim 1, wherein the mixed matrix membrane comprises the following steps: the preparation method of the synergist comprises the following steps:
adding 17g of zinc acrylate, 5g of 4-vinylbenzo-18-crown ether-6, 4.5g of 1-allyl-3-methylimidazolium bromide and 200g of deionized water into a sealed high-pressure reaction kettle, introducing nitrogen, heating and stirring to 70 ℃, adding 2.4g of benzoyl peroxide, reacting for 2 hours, and then carrying out reduced pressure distillation to remove water, thereby obtaining the synergist.
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