CN115253714B - Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof - Google Patents
Mixed matrix membrane doped with molybdenum disulfide nanosheet modified material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a mixed matrix membrane doped with molybdenum disulfide nanosheet modified materials, and a preparation method and application thereof. The preparation method comprises the following steps: firstly, weighing a polymer, dispersing the polymer into a solvent to prepare a solution with the concentration of 2-10wt% and uniformly dispersing the solution, and naming the solution as a casting solution; adding the molybdenum disulfide nanosheet modified material into a solvent for uniform dispersion, then dripping the molybdenum disulfide nanosheet modified material into a casting film liquid for uniform dispersion again, and preparing a mixed matrix film by adopting a solution casting method or coating the surface of a porous support film with the casting film liquid; wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1: (0.005-0.20). The invention has low raw material price, wide sources and simple and convenient synthesis, and the prepared mixed matrix membrane has easy membrane formation, easy processing and good affinity to acid gas; the prepared mixed matrix membrane has better CO 2 Permeability coefficient and CO 2 /N 2 Selectivity of CO 2 The field of trapping and separation.
Description
Technical Field
The invention relates to a mixed matrix membrane doped with molybdenum disulfide nanosheet modified materials, a preparation method and application thereof, and belongs to the technical field of chemical engineering gas separation membranes.
Background
Excessive emissions of greenhouse gases cause global warming and the like to a certain extent, wherein climate change has become serious worldwideOne of the issues is to reduce the emission of greenhouse gases to cope with climate warming. Fossil fuel as one of the main energy sources, CO emitted by combustion of fossil fuel 2 Accounting for a substantial portion of the total emissions. Wherein the power plant flue gas is CO 2 Long-term stable concentrated emission source, which emits CO 2 The amount accounts for 30-40% of the total discharge amount, and the CO of the flue gas is realized 2 Trapping, sealing and utilizing are important ways of reducing emission of greenhouse gases.
Current flue gas carbon capture is from the CO 2 And N 2 Separation and capture of CO from flue gases as the principal component 2 And to CO 2 And (5) carrying out a recycling process. The main methods for realizing carbon capture of flue gas at present are physical adsorption method, physical and chemical absorption method, low-temperature rectification method and O 2 /CO 2 Combustion, membrane separation, and the like. Compared with the traditional gas separation process, the membrane separation technology has simple preparation process, easy realization of automation and stable operation. From the energy consumption point of view, compared with distillation, separating CO 2 The process saves the heat production cost by about 90 percent by membrane separation, and is one of the methods for capturing the carbon dioxide with low energy cost.
The core of the membrane method carbon capture is to prepare a carbon capture membrane with excellent performance. The current separation membranes for carbon capture are mainly polymer membranes, inorganic membranes and mixed matrix membranes. (1) The polymer film has simple processing process and low cost, and is difficult to be compatible with high CO 2 Permeability and high CO 2 /N 2 Selectivity. Chinese patent CN201480062703 discloses that "membranes for flue gas separation comprising crosslinked, thermally rearranged poly (benzoxazole-co-imide) and methods for their preparation" relates to polyimide copolymer membranes, and that the crosslinked and thermally rearranged poly (benzoxazole-co-imide) copolymer membranes are applied to flue gas separation; chinese patent CN202110081505.5 discloses a structure, a preparation method and an application of a polyimide copolymer gas separation membrane with anti-plasticizing effect, and reports a polyimide copolymer gas separation membrane with anti-plasticizing effect for CO 2 In a separate application. (2) Inorganic membranes although having a high CO content 2 Permeability and high CO 2 /N 2 Selectivity but high preparation costThe membrane is fragile and difficult to realize industrial application. Chinese patent CN202110306364.2 discloses a method for high temperature CO 2 SDC/LNO-carbonate membrane for gas separation, membrane reactor and application thereof are provided, which can carry out CO at high temperature 2 And (5) separating. (3) The mixed matrix membrane can combine the advantages of the two, and has high CO of the electrodeless membrane 2 Permeability and high CO 2 /N 2 The selectivity and low cost and easy processability of polymer membranes are a membrane material with great potential for flue gas carbon capture. Chinese patent CN202210061121.1 discloses an aminated fluoro-cerium nano-sheet, a preparation method and application thereof, a mixed matrix membrane, a preparation method and application thereof, and a method for preparing the mixed matrix membrane by self-assembling amine compounds (including polyethyleneimine and the like) and fluoride salt, cerium salt and the like in an aqueous solution, and the mixed matrix membrane is applied to separating CO in flue gas 2 And N 2 . The carbon capture membranes of the above documents have been well developed, but the CO of polymer membranes 2 The permeability and selectivity are not high; the inorganic film has complex preparation process, difficult mass production and high cost; mixed matrix membrane in CO 2 The carbon trapping film has a great advantage in trapping, but no carbon trapping film suitable for industrial production has been developed yet.
Along with the promotion of double-carbon targets in China, the further research and development of excellent carbon trapping films suitable for industrial mass production is the key point of film method carbon trapping.
Disclosure of Invention
The invention aims to provide a mixed matrix membrane doped with molybdenum disulfide nanosheet modified materials, and a preparation method and application thereof.
The technical conception of the invention is as follows: compared with one-dimensional and three-dimensional materials, the two-dimensional material with an atomic precise structure has unique lamellar structure characteristics. The two-dimensional transition metal sulfide is a typical lamellar material, wherein the molybdenum disulfide layer has strong planar chemical bonds, so that the stability of the two-dimensional structure is ensured. The van der Waals forces between the layers are relatively weak, and the coupling is weak, and can be separated into single or few layers of material. According to the invention, the molybdenum disulfide nanosheet modified material is selected as the doping material of the mixed matrix film, and the ordered stacking between layers is easier to realize after a single-layer or less-layer nanosheet material is dispersed in the polymer matrix; the gaps between the sheets can effectively adjust the pores to obtain regular channels, which is beneficial to accurately separating gas; the specific surface area is larger, and more active sites are provided for adsorption and reaction.
The invention provides a mixed matrix membrane doped with molybdenum disulfide nanosheet modified materials, which is prepared from a polymer matrix, a molybdenum disulfide nanosheet modified material and a casting solution prepared by a solvent; the polymer matrix selected by the mixed matrix membrane is any one of polyether block amide, sulfonated polyether ether ketone, polyvinyl amine and polyvinyl alcohol; the molybdenum disulfide nanosheet modified material is any one of molybdenum disulfide/MIP-202 nanocomposite and molybdenum disulfide/L-cysteine nanocomposite, the solvent is any one of water, ethanol and water mixed solvent, N-dimethylacetamide and N, N-dimethylformamide, and the ethanol and water mixed solvent refers to mixed solution with the volume percentage of 50-90% of ethanol.
The preparation method of the molybdenum disulfide/MIP-202 nanocomposite comprises the following steps:
(1) Preparation of molybdenum disulfide nanosheets
Weighing 5-200 g molybdenum disulfide, placing in a tube furnace, heating at constant temperature for 2-24h under the conditions that the clean air flow rate ranges from 30-500 mL/min and the temperature ranges from 200-350 ℃, naturally cooling, taking out the product, and naming the product A. Weighing a product A to prepare an aqueous solution with the concentration of 2-40 mg/ml, and adding analytically pure NaOH particles, wherein the mass ratio of the product A to the NaOH is 1: (0.5-5), magnetically stirring the mixed solution at the rotation speed of 100-1000 rpm and the temperature of 15-60 ℃ for 1-12 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at the temperature of 100-400 ℃ for 2-24h, cooling to 25 ℃, taking out, centrifuging the obtained solution at the rotation speed of 6000-12000 rpm for 10-180 min, washing the lower layer precipitate in a centrifuge tube with a mixture of ethanol and water with equal mass for 3-5 times, and then drying in a vacuum oven at the temperature of 60-100 ℃ for 8-24 h, thus obtaining the molybdenum disulfide nanosheets named as a product B.
(2) Preparation of molybdenum disulfide/MIP-202 nano composite material
The mass ratio of the molybdenum disulfide nano material to MIP-202 is (0.1:10): (0.1-10) grinding and mixing to prepare the molybdenum disulfide/MIP-202 nanocomposite.
The preparation method of the molybdenum disulfide/L-cysteine nanocomposite comprises the following steps:
(1) Preparation of molybdenum disulfide nanosheets
Weighing 5-200 g molybdenum disulfide, placing in a tube furnace, heating at constant temperature for 2-24h under the conditions that the clean air flow rate ranges from 30-500 mL/min and the temperature ranges from 200-350 ℃, naturally cooling, taking out the product, and naming the product A. Weighing a product A to prepare an aqueous solution with the concentration of 2-40 mg/ml, and adding analytically pure NaOH particles, wherein the mass ratio of the product A to the NaOH is 1: (0.5-5), magnetically stirring the mixed solution at the rotation speed of 100-1000 rpm and the temperature of 15-60 ℃ for 1-12 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at the temperature of 100-400 ℃ for 2-24h, cooling to 25 ℃, taking out, centrifuging the obtained solution at the rotation speed of 6000-12000 rpm for 10-180 min, washing the lower layer precipitate in a centrifuge tube with a mixture of ethanol and water with equal mass for 3-5 times, and then drying in a vacuum oven at the temperature of 60-100 ℃ for 8-24 h, thus obtaining the molybdenum disulfide nanosheets named as a product B.
(2) Molybdenum disulfide/L-cysteine nanocomposite
Weighing the product B to prepare an aqueous solution with the concentration of 2-40 mg/ml, and carrying out ultrasonic treatment on the aqueous solution to obtain a molybdenum disulfide nanosheet dispersion liquid with the concentration of 0.5-12 h, and naming the molybdenum disulfide nanosheet dispersion liquid as a solution D; weighing L-cysteine to be dissolved in water, wherein the mass ratio of the product B to the L-cysteine is 1: (0.2-5), magnetically stirring at a rotation speed of 100-1000 rpm and a temperature of 15-60 ℃ for 0.5-12 h to obtain an L-cysteine solution, which is named as solution E; slowly dripping the solution E into the solution D twice, performing ultrasonic dispersion on the solution D for 1 to 24h under the conditions of ultrasonic frequency of 20 to 50 KHz and ultrasonic temperature of 15 to 40 ℃, mechanically stirring the solution E for 6 to 48 h to perform chemical reaction under the conditions of rotating speed of 50 to 300rpm and temperature of 15 to 60 ℃, centrifuging the obtained solution for 10 to 180 minutes within the rotating speed range of 6000 to 12000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 to 5 times, and then placing the solution in a vacuum oven at 60 to 100 ℃ for drying for 8 to 24h, thereby obtaining the molybdenum disulfide/L-cysteine nanocomposite, and the product is named as a product F.
The invention provides a preparation method of a mixed matrix film doped with molybdenum disulfide nanosheet modified materials, which comprises the following steps: weighing polymer, dissolving the polymer in solvent to prepare solution with concentration of 2-20wt% and uniformly dispersing, and naming the solution as polymer matrix dispersion; dispersing the molybdenum disulfide nanosheet modified material product F in a solvent for uniform dispersion, then dripping the product into a polymer matrix dispersion liquid, and uniformly dispersing again to prepare a casting film liquid; preparing a mixed matrix membrane by adopting a solution casting method to the casting solution or preparing the mixed matrix membrane by coating the casting solution on the surface of the porous support membrane; wherein, the mass ratio of the polymer matrix to the molybdenum disulfide nanosheet modified material is 1: (0.005-0.20).
In the preparation method, the specific operation of uniform dispersion is as follows: firstly, adopting an ultrasonic dispersing instrument to carry out ultrasonic dispersion for 1-12 h under the conditions of the ultrasonic frequency range of 20-50 KHz and the ultrasonic temperature range of 15-80 ℃, then adopting a magnetic stirrer to carry out stirring for 2-24h under the conditions of the temperature range of 15-80 ℃ and the rotating speed range of 100-1000 rpm, and finally adopting the ultrasonic wave to carry out ultrasonic defoaming for 0.5-2 h under the conditions of the ultrasonic frequency range of 20-50 KHz and the ultrasonic temperature range of 15-80 ℃.
In the preparation method, the specific operation of preparing the mixed matrix film by the solution casting method is as follows: the thickness of the wet film is controlled to be 100-1500 mu m; wherein the drying process of the film is carried out in a climatic chamber under the following drying conditions: drying 12-48 h at 20-80deg.C and relative humidity of 40-80%.
In the preparation method, the surface of the porous support film is coated with the film casting solution to prepare the mixed matrix film, and the thickness of the wet film is controlled to be 30-300 mu m; wherein the drying process of the film is carried out in a climatic chamber under the drying condition of 12-48 h at 20-80deg.C and relative humidity of 40-80%.
Further, the porous support membrane is a commercial microporous filter membrane, has a supporting function, has a molecular weight cutoff of 5000-50000, and is made of any one of polysulfone, polyethersulfone, polyvinylidene fluoride and polytetrafluoroethylene; the porous support membrane is soaked in a surfactant aqueous solution with the mass percent of 0.5-10% at the temperature of 20-50 ℃ for 24-72 h, and is cleaned and dried for later use; the surfactant is any one of sodium dodecyl sulfate, sodium dodecyl sulfate and ethylenediamine.
The invention provides a mixed matrix membrane doped with the molybdenum disulfide nanosheet modified material in CO 2 Is used for trapping and separating.
In the above application, the mixed matrix membrane is used for CO 2 During separation, the membrane is fixed in a membrane pool, the pressure range of the upstream side of the membrane is 0.1-1.0 MPa, the gas permeation test temperature is 25-160 ℃, the humidity of the upstream side gas is regulated and controlled by a humidifying tank, and the effective membrane area is 1-12 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Using high purity H on the downstream side of the membrane chamber 2 As a purge gas purge, the flow rate of the purge gas was controlled to 10-80 sccm at a pressure of 1 bar, and the downstream side components were detected by gas chromatography.
The invention has the beneficial effects that:
(1) The molybdenum disulfide nanosheet modified material is favorable for CO 2 The transferred active sites (e.g., vacancies, defects, and amino carriers) facilitate the build up of CO in the membrane 2 The CO of the mixed matrix film doped with the molybdenum disulfide nanosheet modified material is strengthened by the rapid transmission channel 2 Separation performance shows that the molybdenum disulfide nanosheet modified material is used in CO 2 The separation field has good application prospect;
(2) Compared with a pure film, the prepared mixed matrix film CO doped with the molybdenum disulfide nanosheet modified material 2 The separation performance is greatly improved and exceeds the Robeson upper limit in 2019, and the method has good long-time operation stability and good industrial application prospect.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Comparative example 1 preparation of pure polyether Block amide film
And (3) under the condition of reflux stirring at 80 ℃, the polyether block amide particles are placed into an ethanol/water (mass ratio is 70/30) mixed solvent to be dissolved, so that the mass fraction of the polyether block amide in the ethanol/water mixed solvent is ensured to be 8 wt%. Adding an equal mass ethanol/water mixed solvent under the conditions that the temperature range is 25 ℃ and the magnetic stirring rotating speed is 300rpm by adopting a magnetic stirrer, and carrying out ultrasonic defoaming 1 h under the conditions that the ultrasonic frequency range is 40 KHz and the ultrasonic temperature is 25 ℃ to obtain a uniform casting film solution with the concentration of 4 wt%. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to 900 mu m by using a film scraping device, putting the wet film into a climatic chamber, drying the wet film at the temperature of 50 ℃ for 12 h, and drying the wet film at the temperature of 70 ℃ for 12 h to obtain the pure polyether block amide film.
The prepared pure polyether block amide film is subjected to CO under the dry state and wet state conditions of 25 ℃ and 0.1 MPa of pressure difference 2 And N 2 And (5) testing the permeability of pure gas. Under dry conditions, CO was measured 2 Is 71 Barrer, CO 2 /N 2 The selectivity was 39; under wet condition, CO was measured 2 Has a permeability coefficient of 97 Barrer, CO 2 /N 2 The selectivity was 53.
Comparative example 2 preparation of Mixed matrix film doped with molybdenum disulfide nanosheets
10 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 4h, and the product is taken out and named as a product A. Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 10 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:2, magnetically stirring the mixed solution at the rotating speed of 300rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 220 ℃ for 6 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 15 min within the rotating speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with ethanol and water mixed solution with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h, thereby obtaining the molybdenum disulfide nano-sheet which is named as a product B.
And (3) under the condition of reflux stirring at 80 ℃, placing polyether block amide particles into an ethanol/water (mass ratio is 70/30) mixed solvent to be dissolved, and ensuring that the mass fraction of the polyether block amide in the ethanol/water mixed solvent is 8 wt percent to obtain the casting film liquid. Weighing a certain amount of product B, and adding the product B into an ethanol/water (the mass ratio is 70/30) mixed solvent, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.005, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 2 h under the conditions that the ultrasonic frequency range is 30 KHz and the ultrasonic temperature is 25 ℃, dripping the dispersion into the casting film liquid, firstly adopting the ultrasonic dispersing instrument to ultrasonically disperse 2 h under the conditions that the ultrasonic frequency is 20 KHz and the ultrasonic temperature is 30 ℃, and then adopting a magnetic stirrer to stir 2 h under the conditions that the temperature is 25 ℃ and the rotating speed is 300rpm, and repeating the steps for three times. Then ultrasonic defoaming is carried out on the mixture under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 25 ℃ for 1 h, thus obtaining the uniform casting film liquid. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to 900 mu m by using a film scraping device, placing the wet film in a climatic chamber, drying the wet film at the temperature of 50 ℃ for 12 h, and drying the wet film at the temperature of 70 ℃ for 12 h to obtain the mixed matrix film doped with molybdenum disulfide nano sheets.
CO is carried out on the prepared mixed matrix membrane doped with molybdenum disulfide nanosheets under the dry condition that the temperature is 25 ℃ and the pressure difference is 0.1 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Is 165 Barrer, CO 2 /N 2 The selectivity was 71.
Comparative example 3: the preparation of a pure Sulfonated Polyetheretherketone (SPEEK) membrane is as follows:
sulfonated polyetheretherketone was added to N, N-dimethylacetamide, wherein the mass fraction of the polymer matrix in the solution was 10 wt%. Stirring 24h under the magnetic stirring condition with the temperature of 35 ℃ and the rotating speed of 500 rpm, and standing and defoaming 24h at the temperature of 25 ℃ to prepare uniform casting film liquid; casting the casting solution on a clean flat plate to form a film, controlling the thickness of a wet film to be 600 mu m, drying 12 h in a vacuum drying oven at 80 ℃, heating to 100 ℃ to further dry 12 h, and uncovering the film for later use.
The CO of the prepared pure SPEEK film is measured under the conditions of 25 ℃ and the pressure of 0.1 MPa and wet state 2 The permeability coefficient was 304 Barrer (1 barrer=10 -10 cm 3 (STP) cm·cm -2 ·s -1 ·cmHg -1 )，CO 2 /N 2 The selectivity was 32.
Example 1 preparation of a Mixed matrix Membrane of doped molybdenum disulfide/MIP-202 nanocomposite
10 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 8 h, and the product is taken out and named as a product A. Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 10 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:2.5, magnetically stirring the mixed solution at the speed of 300rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal treatment at 220 ℃ for 6 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 15 min within the speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare NaOH hydrothermal oxygen etched molybdenum disulfide, and the product is named as a product B.
The L-aspartic acid is weighed and dispersed in deionized water to prepare a solution with the concentration of 280 mg/ml, and the solution is magnetically stirred for 2 h under the conditions of the rotating speed of 300rpm and the temperature of 25 ℃ and named as solution C; zirconium tetrachloride is weighed and dissolved in deionized water to prepare a solution with the concentration of 230 mg/ml, and the solution is named solution D after ultrasonic dispersion of 1 h under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 30 ℃. Solution D was added dropwise to solution C and magnetically stirred at a speed of 200 rpm and a temperature of 25℃for 2 h. Putting the mixed solution into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, carrying out hydrothermal reaction at 200 ℃ for 12 h, cooling to 25 ℃, taking out, centrifuging the obtained solution for 15 min within the rotating speed range of 7500 rpm, soaking the lower white precipitate in a centrifuge tube with ethanol, centrifuging every 12 h to replace the ethanol for 6 times, and drying in a vacuum oven at 25 ℃ for 24h to obtain MIP-202.
The mass ratio of the product A to the MIP-202 is 7.5:2.5 grinding and mixing to prepare a product E.
And (3) under the condition of reflux stirring at 80 ℃, putting polyether block amide particles into an ethanol/water (mass ratio is 70/30) mixed solvent to dissolve, and ensuring that the mass fraction of polyether block amide in the ethanol/water mixed solvent is 8 wt percent to obtain the polymer matrix dispersion liquid. Weighing a certain amount of product E, and adding the product E into an ethanol/water (the mass ratio is 70/30) mixed solvent, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.02, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 6 h under the conditions that the ultrasonic frequency range is 40 KHz and the ultrasonic temperature is 25 ℃, dripping the dispersion into polymer matrix dispersion liquid, firstly adopting the ultrasonic dispersing instrument to ultrasonically disperse 2 h under the conditions that the ultrasonic frequency range is 40 KHz and the ultrasonic temperature is 25 ℃, then adopting a magnetic stirrer to stir 8 h under the conditions that the temperature range is 25 ℃ and the rotating speed range is 300rpm, and then carrying out ultrasonic bubble removal 1 h under the conditions that the ultrasonic frequency range is 30 KHz and the ultrasonic temperature is 25 ℃ to obtain uniform casting film liquid. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to 900 mu m by using a film scraping device, placing the wet film in a climatic chamber, drying the wet film at the temperature of 40 ℃ for 12 h, and drying the wet film at the temperature of 80 ℃ for 12 h to obtain the molybdenum disulfide/MIP-202 nanocomposite doped mixed matrix film.
CO is carried out on the mixed matrix film of the prepared molybdenum disulfide/MIP-202 nano composite material under the wet condition that the temperature is 25 ℃ and the pressure difference is 0.1 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Is 205 Barrer, CO 2 /N 2 The selectivity was 86.
Example 2 preparation of a Mixed matrix Membrane of doped molybdenum disulfide/MIP-202 nanocomposite
10 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 4h, and the product is taken out and named as a product A. Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 15 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:3, magnetically stirring the mixed solution at the rotation speed of 200 rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 220 ℃ for 6 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 15 min within the rotation speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare NaOH hydrothermal oxygen etched molybdenum disulfide, and the product is named as a product B.
The L-aspartic acid is weighed and dispersed in deionized water to prepare a solution with the concentration of 280 mg/ml, and the solution is magnetically stirred for 2 h under the conditions of the rotating speed of 300rpm and the temperature of 25 ℃ and named as solution C; zirconium tetrachloride is weighed and dissolved in deionized water to prepare a solution with the concentration of 230 mg/ml, and the solution is named solution D after ultrasonic dispersion of 1 h under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 30 ℃. Solution D was added dropwise to solution C and magnetically stirred at a speed of 200 rpm and a temperature of 25℃for 2 h. Putting the mixed solution into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, carrying out hydrothermal reaction at 110 ℃ for 24h, cooling to 25 ℃, taking out, centrifuging the obtained solution for 20 min within the rotating speed range of 7500 rpm, soaking the lower white precipitate in a centrifuge tube with ethanol, centrifuging every 12 h to replace the ethanol for 6 times, and drying in a vacuum oven at 25 ℃ for 24h to obtain MIP-202.
The mass ratio of the product A to the MIP-202 is 5:5 grinding and mixing to prepare a product E.
And (3) under the condition of reflux stirring at 80 ℃, putting polyether block amide particles into an ethanol/water (mass ratio is 70/30) mixed solvent to dissolve, and ensuring that the mass fraction of the polyether block amide in the ethanol/water mixed solvent is 10wt percent to obtain the polymer matrix dispersion liquid. Weighing a certain amount of product E, and adding the product E into an ethanol/water (the mass ratio is 70/30) mixed solvent, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.06, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 2 h under the conditions that the ultrasonic frequency range is 30 KHz and the ultrasonic temperature is 25 ℃, dripping the dispersion into polymer matrix dispersion liquid, firstly adopting the ultrasonic dispersing instrument to ultrasonically disperse 2 h under the conditions that the ultrasonic frequency range is 30 KHz and the ultrasonic temperature is 25 ℃, and then adopting a magnetic stirrer to stir 2 h under the conditions that the temperature range is 25 ℃ and the rotating speed range is 300 rpm; then ultrasonic defoaming is carried out on the film under the conditions of ultrasonic frequency range of 30 KHz and ultrasonic temperature of 25 ℃ for 1 h, thus obtaining the uniform film casting solution. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to 900 mu m by using a film scraping device, placing the wet film in a climatic chamber, drying the wet film at the temperature of 50 ℃ for 12 h, and drying the wet film at the temperature of 70 ℃ for 12 h to obtain the molybdenum disulfide/MIP-202 nanocomposite doped mixed matrix film.
CO is carried out on the prepared molybdenum disulfide/MIP-202 nano composite material mixed matrix membrane under the wet condition that the temperature is 25 ℃ and the pressure difference is 0.6 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Is 218 Barrer, CO 2 /N 2 The selectivity was 75.
Example 3 preparation of a Mixed matrix Membrane of doped molybdenum disulfide/MIP-202 nanocomposite
10 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 4h, and the product is taken out and named as a product A. Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 10 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:2, magnetically stirring the mixed solution at the rotating speed of 300rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 220 ℃ for 6 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 30 min within the rotating speed range of 6000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare NaOH hydrothermal oxygen etched molybdenum disulfide, and the product is named as a product B.
The L-aspartic acid is weighed and dispersed in deionized water to prepare a solution with the concentration of 350 mg/ml, and the solution is magnetically stirred at the rotation speed of 100 rpm and the temperature of 25 ℃ for 12 h and named as solution C; zirconium tetrachloride is weighed and dissolved in deionized water to prepare a solution with the concentration of 3500 mg/ml, and the solution is named solution D after ultrasonic dispersion of 1 h under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 30 ℃. Solution D was added dropwise to solution C and magnetically stirred at a speed of 200 rpm and a temperature of 25℃for 2 h. Putting the mixed solution into a stainless steel high-pressure reaction kettle with polytetrafluoroethylene lining, carrying out hydrothermal reaction at 120 ℃ for 24h, cooling to 25 ℃, taking out, centrifuging the obtained solution for 15 min within the rotating speed range of 7500 rpm, soaking the lower white precipitate in a centrifuge tube with ethanol, centrifuging every 12 h to replace the ethanol for 6 times, and drying in a vacuum oven at 25 ℃ for 24h to obtain MIP-202.
The mass ratio of the product A to the MIP-202 is 5:5 grinding and mixing to prepare a product E.
And (3) under the condition of reflux stirring at 80 ℃, putting polyether block amide particles into an ethanol/water (mass ratio is 70/30) mixed solvent to dissolve, and ensuring that the mass fraction of polyether block amide in the ethanol/water mixed solvent is 8 wt percent to obtain the polymer matrix dispersion liquid. Weighing a certain amount of product E, and adding the product E into an ethanol/water (the mass ratio is 70/30) mixed solvent, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.06, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 2 h under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 25 ℃, dripping the dispersion into polymer matrix dispersion liquid, firstly adopting the ultrasonic dispersing instrument to ultrasonically disperse 2 h under the conditions that the ultrasonic frequency range is 30 KHz and the ultrasonic temperature is 25 ℃, then adopting a magnetic stirrer to stir 6 h under the conditions that the temperature is 25 ℃ and the rotating speed is 300rpm, and finally carrying out ultrasonic defoaming under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 25 ℃ to obtain uniform casting film liquid. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to be 600 mu m by a film scraping device, placing the wet film in a climatic chamber, drying the wet film at the temperature of 50 ℃ for 12 h, and drying the wet film at the temperature of 70 ℃ for 12 h to obtain the molybdenum disulfide/MIP-202 nanocomposite doped mixed matrix film.
The prepared mixed matrix film of the doped molybdenum sulfide/MIP-202 nano composite material is subjected to CO under the wet condition of the temperature of 80 ℃ and the pressure difference of 0.1 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Has a permeability coefficient of 785 Barrer, CO 2 /N 2 The selectivity was 39.
Example 4 preparation of Mixed matrix Membrane of molybdenum disulfide/L-cysteine nanocomposite
10 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 4h, and the product is taken out and named as a product A. Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 10 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:2, magnetically stirring the mixed solution at the rotating speed of 300rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 220 ℃ for 6 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 15 min within the rotating speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare NaOH hydrothermal oxygen etched molybdenum disulfide, and the product is named as a product B.
The product B is weighed and dispersed in water to prepare a solution with the concentration of 10 mg/ml, the ultrasonic treatment is carried out on the solution 2 h, and the molybdenum disulfide nanosheet dispersion is named as solution D; weighing L-cysteine to be dissolved in water, wherein the mass ratio of the product B to the L-cysteine is 1:1.5 magnetically stirring 2. 2 h at a rotation speed of 300rpm and a temperature of 25 ℃ to obtain an L-cysteine solution, which is named as a solution E; slowly dripping the solution E into the solution F twice, performing ultrasonic dispersion for 2 h under the conditions of ultrasonic frequency of 30 KHz and ultrasonic temperature of 25 ℃, mechanically stirring for 24h under the conditions of rotating speed of 200 rpm and temperature of 25 ℃ to perform chemical reaction, centrifuging the obtained solution for 15 min within the rotating speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare the L-cysteine modified molybdenum disulfide, and naming the product F.
And (3) under the condition of reflux stirring at 80 ℃, putting polyether block amide particles into an ethanol/water (mass ratio is 70/30) mixed solvent to dissolve, and ensuring that the mass fraction of the polyether block amide in the ethanol/water mixed solvent is 10wt percent to obtain the polymer matrix dispersion liquid. Weighing a certain amount of product F, and adding the product F into an ethanol/water (the mass ratio is 70/30) mixed solvent, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.015, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 2 h under the conditions of an ultrasonic frequency range of 30 KHz and an ultrasonic temperature of 25 ℃, dripping the dispersion into a polymer matrix dispersion liquid, firstly adopting the ultrasonic dispersing instrument to ultrasonically disperse 2 h under the conditions of the ultrasonic frequency of 30 KHz and the ultrasonic temperature of 25 ℃, then adopting a magnetic stirrer to stir 2 h under the conditions of the temperature of 25 ℃ and the rotating speed of 300rpm, and then carrying out ultrasonic defoaming 1 h under the conditions of the ultrasonic frequency of 30 KHz and the ultrasonic temperature of 25 ℃ to obtain the uniform casting film liquid. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to 900 mu m by using a film scraping device, putting the wet film into a climatic chamber, drying the wet film at the temperature of 50 ℃ for 12 h, and drying the wet film at the temperature of 70 ℃ for 12 h to obtain the mixed matrix film of the molybdenum disulfide/L-cysteine nano composite material.
CO is carried out on the mixed matrix film of the prepared molybdenum disulfide/L-cysteine doped nano composite material under the wet condition that the temperature is 25 ℃ and the pressure difference is 0.1 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Is 297 Barrer, CO 2 /N 2 The selectivity was 120.
Example 5 preparation of Mixed matrix film of molybdenum disulfide/L-cysteine nanocomposite
10 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 4h, and the product is taken out and named as a product A.
Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 10 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:2, magnetically stirring the mixed solution at the rotating speed of 300rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 220 ℃ for 6 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 15 min within the rotating speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare NaOH hydrothermal oxygen etched molybdenum disulfide, and the product is named as a product B.
The product B is weighed and dispersed in water to prepare a solution with the concentration of 10 mg/ml, ultrasonic treatment is carried out on the solution 2 h, and a NaOH hydrothermal oxygen etching molybdenum disulfide solution is obtained and is named as a solution D; weighing L-cysteine to be dissolved in water, wherein the mass ratio of the product B to the L-cysteine is 1:1.5 magnetically stirring 2. 2 h at a rotation speed of 300rpm and a temperature of 25 ℃ to obtain an L-cysteine solution, which is named as a solution E; slowly dripping the solution E into the solution D twice, performing ultrasonic dispersion on the solution D for 2 h under the conditions of ultrasonic frequency of 30 KHz and ultrasonic temperature of 25 ℃, mechanically stirring the solution at the speed of 200 rpm and the temperature of 25 ℃ for 24h to perform chemical reaction, centrifuging the obtained solution at the speed of 8000 rpm for 15 min, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare the L-cysteine modified molybdenum disulfide, and naming the product F.
And (3) under the condition of reflux stirring at 80 ℃, putting polyether block amide particles into an ethanol/water (mass ratio is 70/30) mixed solvent to dissolve, and ensuring that the mass fraction of polyether block amide in the ethanol/water mixed solvent is 8 wt percent to obtain the polymer matrix dispersion liquid. Weighing a certain amount of product F, and adding the product F into an ethanol/water (the mass ratio is 70/30) mixed solvent, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.015, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 2 h under the conditions that the ultrasonic frequency is 30 KHz and the ultrasonic temperature is 25 ℃, and dripping the dispersion into polymer matrix dispersion liquid; dispersing 2 h by an ultrasonic dispersing instrument under the conditions of ultrasonic frequency of 30 KHz and ultrasonic temperature of 25 ℃, stirring 2 h by a magnetic stirrer under the conditions of 25 ℃ and rotating speed of 300rpm, and removing foam 1 h by ultrasonic under the conditions of ultrasonic frequency of 30 KHz and ultrasonic temperature of 25 ℃ to obtain the uniform casting film liquid. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to 900 mu m by using a film scraping device, putting the wet film into a climatic chamber, drying the wet film at the temperature of 50 ℃ for 12 h, and drying the wet film at the temperature of 70 ℃ for 12 h to obtain the mixed matrix film of the molybdenum disulfide/L-cysteine nano composite material.
The prepared mixed matrix film of the doped molybdenum disulfide/L-cysteine nano composite material is heated at 25 ℃,CO is carried out under the wet condition with the pressure difference of 0.6 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Is 124 Barrer, CO 2 /N 2 The selectivity was 60.
Example 6 preparation of Mixed matrix Membrane of molybdenum disulfide/L-cysteine nanocomposite
The 20 g molybdenum disulfide is weighed and placed in a tube furnace to be directly heated to 350 ℃ under the air atmosphere, and is naturally cooled after being kept at 6 h, and the product is taken out and named as a product A. Weighing a product A, dispersing the product A in deionized water to prepare a solution with the concentration of 20 mg/ml, and adding analytically pure NaOH, wherein the mass ratio of the product A to the NaOH is 1:3, magnetically stirring the mixed solution at the rotating speed of 300rpm and the temperature of 25 ℃ for 2 h, filling the mixed solution into a stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 220 ℃ for 12 h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 20 min within the rotating speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then placing the washed solution in a vacuum oven at 80 ℃ for drying for 12 h, thereby preparing NaOH hydrothermal oxygen etched molybdenum disulfide, and the product is named as a product B.
The product B is weighed and dispersed in water to prepare a solution with the concentration of 15 mg/ml, the ultrasonic treatment is carried out on the solution 2 h, and the molybdenum disulfide nanosheet dispersion is named as solution D; weighing L-cysteine to be dissolved in water, wherein the mass ratio of the product B to the L-cysteine is 1:2 magnetically stirring 2 h at a rotation speed of 300rpm and a temperature of 25 ℃ to obtain an L-cysteine solution which is named as solution E; slowly dripping the solution E into the solution F twice, performing ultrasonic dispersion for 2 h under the conditions of ultrasonic frequency of 30 KHz and ultrasonic temperature of 25 ℃, mechanically stirring for 24h under the conditions of rotating speed of 200 rpm and temperature of 25 ℃ to perform chemical reaction, centrifuging the obtained solution for 15 min within the rotating speed range of 8000 rpm, washing the lower layer precipitate in a centrifuge tube with a mixed solution of ethanol and water with equal mass for 3 times, and then drying the solution in a vacuum oven at 80 ℃ for 12 h to prepare the L-cysteine modified molybdenum disulfide, and naming the product F.
And (3) under the condition of reflux stirring at 80 ℃, the sulfonated polyether-ether-ketone particles are placed into an ethanol/water (the mass ratio is 70/30) mixed solvent to be dissolved, so that the mass fraction of polyether block amide in an N, N-dimethylacetamide solvent is ensured to be 10wt%, and a polymer matrix dispersion liquid is obtained. Weighing a certain amount of product F, and adding the product F into a solvent of N, N-dimethylacetamide, wherein the mass ratio of the polymer to the molybdenum disulfide nanosheet modified material is 1:0.015, firstly adopting an ultrasonic dispersing instrument to uniformly disperse 2 h under the conditions of an ultrasonic frequency range of 30 KHz and an ultrasonic temperature of 25 ℃, dripping the dispersion into a polymer matrix dispersion liquid, firstly adopting the ultrasonic dispersing instrument to ultrasonically disperse 2 h under the conditions of the ultrasonic frequency of 30 KHz and the ultrasonic temperature of 25 ℃, then adopting a magnetic stirrer to stir 2 h under the conditions of the temperature of 25 ℃ and the rotating speed of 300rpm, and then carrying out ultrasonic defoaming 1 h under the conditions of the ultrasonic frequency of 30 KHz and the ultrasonic temperature of 25 ℃ to obtain the uniform casting film liquid. Casting the uniform casting solution on a clean polytetrafluoroethylene plate to form a film, controlling the thickness of the wet film to be 600 mu m by using a film scraping device, placing the wet film in a climatic chamber, firstly drying 12 h at 50 ℃ and then drying 12 h at 70 ℃ to obtain the molybdenum disulfide/L-cysteine nanocomposite mixed matrix film.
CO is carried out on the mixed matrix film of the prepared molybdenum disulfide/L-cysteine doped nano composite material under the wet condition that the temperature is 25 ℃ and the pressure difference is 0.1 MPa 2 And N 2 And (5) testing the permeability of pure gas. Measurement of CO 2 Is 315 Barrer, CO 2 /N 2 The selectivity was 58.
Compared with comparative examples 1 and 2, the mixed matrix film of the doped molybdenum disulfide/MIP-202 nanocomposite prepared in examples 1-3 has higher CO 2 Permeability coefficient and CO 2 /N 2 Selectivity of mixed matrix membrane is proved to have better CO 2 Separation performance. Compared with the comparative example 2 and the examples 1-3, the molybdenum disulfide/MIP-202 nano composite material has greatly improved gas separation performance of the mixed matrix membrane compared with the pure molybdenum disulfide nano sheet. Compared with comparative examples 1-3, the mixed matrix film of the doped molybdenum disulfide/L-cysteine nanocomposite prepared in examples 4-6 was CO 2 The separation performance is better. Polyether block amide was selected as the polymer in comparative example 1Comparison of pure films of composite matrices examples 4-5 select polyether block amide as the polymer matrix, mixed matrix film of doped molybdenum disulfide/L-cysteine nanocomposite, CO 2 The separation performance is greatly improved, the CO of the example 4 2 Permeability and CO 2 /N 2 Exceeds 2019 Robeson upper limit; compared with the mixed matrix film doped with molybdenum disulfide nanometer prepared in comparative example 2, the CO of the mixed matrix film doped with molybdenum disulfide/L-cysteine nanocomposite prepared in examples 4-5 2 The separation performance is better; comparative example 3 pure film with sulfonated polyetheretherketone as polymer matrix, mixed matrix film with molybdenum disulfide/L-cysteine nanocomposite doped with sulfonated polyetheretherketone as polymer matrix, co as example 6 2 The separation performance is greatly improved.
Although the present invention has been described above, the present invention is not limited to the above-described embodiment, which is merely illustrative and not restrictive, and many modifications may be made by those of ordinary skill in the art without departing from the spirit of the invention, which fall within the protection of the present invention.
Claims (8)
1. A mixed matrix membrane doped with molybdenum disulfide nanosheet modified material is characterized in that: preparing a mixed matrix membrane from a membrane casting solution prepared from a polymer matrix, a molybdenum disulfide nanosheet modified material and a solvent; wherein, the mass ratio of the polymer matrix to the molybdenum disulfide nanosheet modified material is 1: (0.005-0.20); the polymer matrix selected by the mixed matrix membrane is any one of polyether block amide, sulfonated polyether ether ketone, polyvinyl amine and polyvinyl alcohol; the molybdenum disulfide nanosheet modified material is a molybdenum disulfide/MIP-202 nanocomposite, and the solvent is any one of water, ethanol and water mixed solvent, N-dimethylacetamide and N, N-dimethylformamide;
the preparation method of the molybdenum disulfide/MIP-202 nanocomposite comprises the following steps:
(1) Preparing molybdenum disulfide nanosheets:
weighing 5-200 g molybdenum disulfide, placing the molybdenum disulfide in a tube furnace, heating at constant temperature for 2-24h under the conditions that the clean air flow rate ranges from 30 to 500 mL/min and the temperature ranges from 200 to 350 ℃, naturally cooling, taking out the product, and naming the product A; weighing a product A to prepare an aqueous solution with the concentration of 2-40 mg/ml, and adding analytically pure NaOH particles, wherein the mass ratio of the product A to the NaOH is 1: (0.5-5), magnetically stirring the mixed solution at the rotation speed of 100-1000 rpm and the temperature of 15-60 ℃ for 1-12 h, filling the mixed solution into a high-pressure reaction kettle, carrying out hydrothermal reaction at the temperature of 100-400 ℃ for 2-24h, taking out the mixed solution after the temperature is reduced to 25 ℃, centrifuging the obtained solution for 10-180 min within the rotation speed range of 6000-12000 rpm, washing the lower layer precipitate in the centrifuge tube with the mixed solution of ethanol and water with the same mass for 3-5 times, and then drying the lower layer precipitate in a vacuum oven at the temperature of 60-100 ℃ for 8-24 h to prepare molybdenum disulfide nanosheets, which are named as a product B;
(2) Preparing molybdenum disulfide/MIP-202 nano composite material:
the molybdenum disulfide nanosheets prepared in the step (1) and MIP-202 are mixed according to the mass ratio of (0.1-10): (0.1-10) grinding and mixing to prepare the molybdenum disulfide/MIP-202 nanocomposite.
2. A method for preparing a mixed matrix film of the doped molybdenum disulfide nanosheet modified material of claim 1, which is characterized by comprising the following steps: weighing a polymer matrix, dissolving the polymer matrix in a solvent to prepare a solution with the concentration of 2-20wt% and uniformly dispersing the solution, and naming the solution as polymer matrix dispersion liquid; uniformly dispersing the molybdenum disulfide nanosheet modified material in a solvent, then dripping the molybdenum disulfide nanosheet modified material into a polymer matrix dispersion liquid, and uniformly dispersing again to prepare a casting film liquid; preparing a mixed matrix membrane by adopting a solution casting method to the casting solution or preparing the mixed matrix membrane by coating the casting solution on the surface of the porous support membrane; wherein, the mass ratio of the polymer matrix to the molybdenum disulfide nanosheet modified material is 1: (0.005-0.20).
3. The method for preparing the mixed matrix film of the doped molybdenum disulfide nanosheet modified material of claim 2, which is characterized by comprising the following steps: the specific operation of preparing the casting film liquid by re-uniform dispersion is that firstly, an ultrasonic dispersing instrument is adopted to carry out ultrasonic dispersion for 1-12 h under the conditions of the ultrasonic frequency range of 20-50 KHz and the ultrasonic temperature range of 15-80 ℃, then a magnetic stirrer is adopted to carry out stirring for 2-24 hours under the conditions of the temperature range of 15-80 ℃ and the rotating speed range of 100-1000 rpm, and finally, the ultrasonic frequency range of 20-50 KHz and the ultrasonic temperature range of 15-80 ℃ are adopted to carry out ultrasonic defoaming for 0.5-2 h, thus obtaining the uniform dispersion liquid.
4. The method for preparing the mixed matrix film of the doped molybdenum disulfide nanosheet modified material of claim 2, which is characterized by comprising the following steps: preparing a mixed matrix film by adopting a solution casting method, wherein the thickness of a wet film is controlled to be 100-1500 mu m; wherein the drying process of the film is carried out in a climatic chamber under the following drying conditions: drying 12-48 h at 20-80deg.C and relative humidity of 40-80%.
5. The method for preparing the mixed matrix film of the doped molybdenum disulfide nanosheet modified material of claim 2, which is characterized by comprising the following steps: coating a casting solution on the surface of the porous support film to prepare a mixed matrix film, and controlling the thickness of a wet film to be 30-300 mu m; wherein the drying process of the film is carried out in a climatic chamber under the following drying conditions: drying 12-48 h at 20-80deg.C and relative humidity of 40-80%.
6. The method for preparing the mixed matrix film of the doped molybdenum disulfide nanosheet modified material of claim 5, wherein the method comprises the following steps: the porous support membrane is a commercial microporous filter membrane, has a supporting function, has a molecular weight cutoff of 5000-50000, and is made of any one of polysulfone, polyethersulfone, polyvinylidene fluoride and polytetrafluoroethylene; the porous support membrane is soaked in a surfactant aqueous solution with the mass percent of 0.5-10% at the temperature of 20-50 ℃ for 24-72 h, and is cleaned and dried for later use; the surfactant used is any one of sodium dodecyl sulfate and sodium dodecyl sulfate.
7. A mixed matrix membrane of the doped molybdenum disulfide nanosheet modified material of claim 1In CO 2 Is used for trapping and separating.
8. The use according to claim 7, characterized in that: mixed matrix membranes for CO 2 During separation, the membrane is fixed in a membrane pool, the pressure range of the upstream side of the membrane is 0.1-1.0 MPa, the gas permeation test temperature is 25-160 ℃, the humidity of the upstream side gas is regulated and controlled by a humidifying tank, and the effective membrane area is 1-12 cm 2 The method comprises the steps of carrying out a first treatment on the surface of the Using high purity H on the downstream side of the membrane chamber 2 As a purge gas purge, the flow rate of the purge gas was controlled to 10-80 sccm at a pressure of 1 bar, and the downstream side components were detected by gas chromatography.
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