CN112808031A - Two-dimensional nanoscale ZIF-90/C3N4Preparation method of mixed matrix membrane of nano-sheet composite material - Google Patents
Two-dimensional nanoscale ZIF-90/C3N4Preparation method of mixed matrix membrane of nano-sheet composite material Download PDFInfo
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Abstract
The invention discloses a two-dimensional nanoscale ZIF-90/C3N4A preparation method of a mixed matrix membrane of a nano-sheet composite material belongs to the technical field of membrane separation. Firstly, the invention prepares the nano-scale C by an acid etching method3N4The nano-sheet is taken as a template, and then a large number of continuous ZIF-90 nano-particles are grown on the surface of the nano-sheet by adopting an in-situ growth technology to obtain the two-dimensional nano-ZIF-90/C3N4The preparation method uses two-dimensional nanoscale ZIF-90/C3N4The nano-sheet composite material is used as a filler, and is beneficial to constructing ZIF-90 continuous in the gas diffusion direction (vertical direction)The channel reduces the gas mass transfer resistance and improves the CO content of the mixed matrix membrane2Permeation rate and CO2/N2And (4) selectivity.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a two-dimensional nanoscale ZIF-90/C-based membrane3N4A method for preparing a nano-sheet composite material mixed matrix film.
Background
In recent years, under the double pressure of the aggravation of greenhouse effect and the shortage of energy sources, economic and effective CO is generated2Trapping technology becomes increasingly important. Compared with CO produced by amine method, pressure swing adsorption, low temperature separation and the like2Separation techniques, membrane separation techniques, have received much attention because of their advantages such as economy, low consumption, good recovery effect, and high degree of couplability.
The gas separation membrane can be mainly divided into an organic membrane and an inorganic membrane according to different materials, and the organic membrane is widely applied to the fields of hydrogen recovery, nitrogen enrichment, light hydrocarbon recovery and the like. However, currently available organic membranes generally have low separation performance and are severely limited by the "tradeoff" effect between selectivity and permeability, making them incapable of combining high selectivity with high permeability. The inorganic membrane has ultrahigh selective separation performance, but the disadvantages of being fragile, expensive in cost and difficult to prepare in batches severely limit the industrial application of the inorganic membrane.
The development of the mixed matrix membrane is an effective method for breaking through the upper limit limitation of an organic membrane, and the method combines the advantages of an inorganic material and an organic material, integrates the advantages of the inorganic material and the organic material, avoids the disadvantages, and has the characteristics of higher gas separation performance, simple preparation process, plasticization resistance and the like. MOFs (e.g., ZIF-8, ZIF-90, etc.) are a hybrid porous material composed of inorganic metal nodes coordinated with multivalent organic molecules, and have been widely used in recent years for the research of mixed matrix membranes due to their high porosity, uniformly adjustable pore structure and rich chemical functions. However, even though MOFs have a rich pore structure that provides some free volume for the passage of gases, its disordered dispersion in the membrane matrix does not fully exploit its advantages. Therefore, the construction of the MOFs continuous channel which is beneficial to gas diffusion is very important for improving the mixed matrix membrane.
In addition, some MOFs have a "respiratory effect", which is usually caused by unstable rotation of the ligand, for example ZIF-8, which requires only 0.36kcal/mol of energy for ligand rotation, resulting in a cage with pores
Can be expanded all the time, so that the gas sieving effect is reduced. Compared with ZIF-8, the ZIF-90 has higher ligand rotation energy (14.1kcal/mol) and more stable structure, so that the ZIF-90 is selected as a main filling material in the invention in order to fundamentally solve the problem caused by the respiratory effect from the filler.
Disclosure of Invention
Based on the defects of the prior art of the mixed matrix membrane, the invention aims to prepare the two-dimensional nanoscale ZIF-90/C3N4A mixed matrix membrane of a nanosheet composite.
The technical scheme of the invention is as follows:
two-dimensional nanoscale ZIF-90/C3N4The preparation method of the mixed matrix membrane of the nano-sheet composite material comprises the following steps:
stripping nano-scale two-dimensional C by acid etching method3N4A nano-sheet growth template, and ZIF-90 nano-particles are grown on the surface of the nano-sheet by an in-situ growth method to form continuous MOTwo-dimensional nanoscale ZIF-90/C of F channel structure3N4A nanosheet composite; the method comprises the following specific steps:
(1) nanoscale two-dimensional C3N4The nano-sheet template is prepared by an acid etching method:
block C obtained by calcining Melamine3N4Using concentrated sulfuric acid to etch and insert, and ultrasonic auxiliary stripping method to separate from block C3N4In (iii) stripping to obtain two-dimensional C3N4Nanosheets.
Block C3N4The calcination conditions of (A) are as follows: air atmosphere, heating rate of 2-5 ℃/min, calcination temperature of 540-.
The volume ml of concentrated sulfuric acid and the block C3N4The mass g ratio is 10-20:1, the acid etching temperature is 25-40 ℃, and the acid etching time is 8-12 h.
The two dimensions C3N4The size of the nano-sheet is about 400-800 nm.
(2)ZIF-90/C3N4The nano-sheet composite material is prepared by two-dimensional reaction of nano-sheet composite material3N4In-situ growth on a nanosheet template to obtain:
in two dimensions C3N4Adding zinc acetate into the aqueous solution and carrying out ultrasonic treatment to fix Zn (II) on the two-dimensional C3N4Forming fixed growth sites on the surfaces of the nano sheets, replacing a methanol solution system, and adding the solution into an imidazole-2-formaldehyde methanol solution to enable the ZIF-90 nano particles to grow in situ on the two-dimensional C3N4Obtaining two-dimensional nano-sized ZIF-90/C on the surface3N4A nanosheet composite.
Two-dimensional C3N4The concentration of the nano-sheet aqueous solution is 0.1-2mg/L, and the zinc acetate and the two-dimensional C in the solution are used3N4The mass ratio of the nano sheets is 24-72: 1.
during the conversion of the methanol solution system, the added methanol is equal to the original two-dimensional C3N4The volume of the aqueous solution of the nanosheets; the molar ratio of the imidazole-2-formaldehyde to the zinc acetate is 4-8: 1; two-dimensional C with Zn (II) growth3N4Mixing of nanosheets with methanolThe mixing volume ratio of the mixed solution to the imidazole-2-formaldehyde methanol solution is 1: 2-4.
The ultrasonic growth time of Zn (II) is 0.5-2h, and the growth time of ZIF-90 is 6-8 h.
ZIF-90 in two dimensions C3N4The particle size of the nano-sheets is 20-40 nm.
(3) Film preparation:
two-dimensional nanoscale ZIF-90/C3N4Adding the nano-sheet composite material into a Pebax-1657 matrix solution, stirring and ultrasonically dispersing the nano-sheet composite material into the matrix solution uniformly, pouring the prepared membrane casting solution into a culture dish, and casting in an oven to form a membrane.
The concentration of the Pebax-1657 matrix solution is 3-8 wt.%.
The two-dimensional nanoscale ZIF-90/C3N4The mass percentage of the nano-sheet composite material to the solute in the Pebax-1657 substrate solution is 5%, 10% or 20%, the oven drying time is 12-24h, and the vacuum oven drying time is 12-24 h.
The temperature of the oven or the vacuum oven in the film making process is 30-60 ℃ in the film making process.
The two-dimensional composite material can exist in a vertical form in a large amount in a matrix due to its nano-scale size.
Using two dimensions C3N4The nano-sheet is used as a growth template to prepare two-dimensional nano-sized ZIF-90/C with a continuous MOF channel structure3N4A nanosheet composite.
The invention has the beneficial effects that: the mixed matrix membrane adopts two-dimensional nanoscale ZIF-90/C3N4The nano-sheet composite material is used as a filler, the nano-sheet template not only enables ZIF-90 to densely grow on the surface of the template to form a continuous channel, but also enables the continuous channel to be vertically distributed due to the nanoscale size, and compared with a large amount of transversely arranged micron-sized template materials, the nano-sheet composite material can greatly reduce CO2Gas diffusion resistance, and gas diffusion efficiency is improved.
Drawings
FIG. 1 is a two-dimensional nanoscale ZIF-90/C3N4Scanning electrode of nano-sheet composite materialMirror image.
FIG. 2 is a two-dimensional nanoscale ZIF-90/C3N4XRD spectrogram of the nano-sheet composite material.
FIG. 3 is a two-dimensional nanoscale ZIF-90/C doped3N4Film section electron microscope image of the nanosheet composite material Pebax-1657 mixed matrix film.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Preparation of two-dimensional C3N4Nanosheet: firstly, a certain amount of melamine is taken out of a crucible, the crucible is placed in a muffle furnace, the initial temperature is set to be 50 ℃, the heating rate is 3.5 ℃/min, the calcining temperature is set to be 550 ℃, the calcining time is 4 hours, and the yellow blocky C is obtained by natural cooling3N4It is then ground to a yellow powder for use. Weighing 1g of yellow block C3N4Putting the powder into a reagent bottle, measuring 20ml of concentrated sulfuric acid, and stirring for 8 hours at the temperature of 30 ℃ to obtain a light yellow viscous solution; then slowly adding the solution into 200ml of deionized water and stirring for 0.5h to obtain a diluent, and then carrying out ultrasonic treatment on the diluent for 1h to separate the lamella; centrifuging at 2500r/min for 10min to remove un-peeled bulk structure, collecting upper layer suspension, centrifuging at 10000r/min for 15min, washing the solution pH to about 7 to obtain two-dimensional C3N4Nanosheets.
Preparation of ZIF-90/C3N4Nano-sheet composite material: two-dimensional C to be obtained3N4Dissolving the nano-sheet in deionized water to obtain 0.5mg/ml of two-dimensional C3N4The aqueous nanosheet/suspension is then measured 40ml and added with 0.96g of zinc acetate, sonicated for 2h and then centrifuged at 9000r/min for 10min to yield a Zn (II) -grown two-dimensional C3N4And adding 40ml of methanol into the nanosheet, dissolving and converting into a methanol system. 1.69g of imidazole-2-carbaldehyde was weighed out and dissolved in 100ml of methanol, stirred for 1 hour at 60 ℃ in a water bath, filtered through a 0.22 μm pinhole filter to remove undissolved impurities and the solution was cooledCooling to room temperature. Then two-dimensional C with zinc ion sites grown3N4The nanosheet/methanol solution was poured rapidly into the imidazole-2-formaldehyde methanol solution and stirred at room temperature for 8 h. Finally, centrifuging the obtained solution at 9000r/min for 10min and repeatedly centrifuging and washing with methanol for 3 times to obtain ZIF-90/C3N4A nanosheet composite.
Preparation of Pebax solution: 3.09g of the Pebax-1657 particles were weighed into 100g of the ethanol/water (70/30) mixed solution, and condensed and refluxed at 80 ℃ for 4 hours to obtain a Pebax-based membrane solution, which was cooled to room temperature for use.
Preparation of mixed matrix membranes: ZIF-90/C with solute mass percent of 5%, 10% and 20% based on the used Pebax membrane liquid3N4Adding the nano-sheet composite material into 8g of Pebax base membrane solution, stirring for 2h, then dispersing by using ultrasound for 1h, removing bubbles, pouring the obtained mixed casting membrane solution into a plastic culture dish, placing in a 40 ℃ drying oven for 12h to form a membrane, finally transferring into a 40 ℃ vacuum drying oven for 24h, and removing the residual solvent.
Example 2
Preparation of two-dimensional C3N4Nanosheet: firstly, putting a certain amount of melamine into a crucible, placing the crucible in a muffle furnace, setting the initial temperature to be 50 ℃, the heating rate to be 5 ℃/min, the calcining temperature to be 560 ℃ and the calcining time to be 4h, and naturally cooling to obtain yellow block C3N4It is then ground to a yellow powder for use. 1.5g of yellow block C are weighed3N4Putting the powder into a reagent bottle, measuring 20ml of concentrated sulfuric acid, and stirring at 35 ℃ for 12 hours to obtain a light yellow viscous solution; then slowly adding the solution into 200ml of deionized water and stirring for 0.5h to obtain a diluent, and then carrying out ultrasonic treatment on the diluent for 1h to separate the lamella; centrifuging at 2500r/min for 10min to remove un-peeled bulk structure, collecting upper layer suspension, centrifuging at 10000r/min for 15min, washing the solution pH to about 7 to obtain two-dimensional C3N4Nanosheets.
Preparation of ZIF-90/C3N4Nano-sheet composite material: the obtained C3N4Dissolving the nano-sheet in deionized water to obtain 2mg/ml of two-dimensional C3N4The aqueous nanosheet/suspension is then measured 20ml and 0.96g zinc acetate is added, sonicated for 1h and then centrifuged at 9000r/min for 10min to yield a Zn (II) -grown two-dimensional C3N4And adding 20ml of methanol into the nanosheet, dissolving and converting into a methanol system. 1.69g of imidazole-2-carbaldehyde was weighed out and dissolved in 60ml of methanol, stirred for 1 hour under a water bath condition at 60 ℃, and then filtered through a 0.22 μm pinhole filter to remove undissolved impurities and the solution was cooled to room temperature. Then two-dimensional C with zinc ion sites grown3N4The nanosheet/methanol solution was poured rapidly into the imidazole-2-formaldehyde methanol solution and stirred at room temperature for 6 h. Finally, centrifuging the obtained solution at 9000r/min for 10min and repeatedly centrifuging and washing with methanol for 3 times to obtain ZIF-90/C3N4A nanosheet composite.
Preparation of Pebax solution: 3.09g of the Pebax-1657 particles were weighed into 100g of the ethanol/water (70/30) mixed solution, and condensed and refluxed at 80 ℃ for 4 hours to obtain a Pebax-based membrane solution, which was cooled to room temperature for use.
Preparation of mixed matrix membranes: ZIF-90/C with solute mass percent of 5%, 10% and 20% based on the used Pebax membrane liquid3N4Adding the nano-sheet composite material into 8g of Pebax base membrane solution, stirring for 2h, then dispersing by using ultrasound for 1h, removing bubbles, pouring the obtained mixed casting membrane solution into a plastic culture dish, placing in a drying oven at 40 ℃ for 12h for membrane formation, finally transferring into a vacuum drying oven at 50 ℃ for 12h, and removing the residual solvent.
Example 3
Preparation of two-dimensional C3N4Nanosheet: firstly, putting a certain amount of melamine into a crucible, placing the crucible in a muffle furnace, setting the initial temperature to be 50 ℃, the heating rate to be 2 ℃/min, the calcining temperature to be 540 ℃ and the calcining time to be 4h, and naturally cooling to obtain yellow blocky C3N4It is then ground to a yellow powder for use. Weighing 1g of yellow block C3N4Putting the powder into a reagent bottle, measuring 20ml of concentrated sulfuric acid, and stirring for 12 hours at 25 ℃ to obtain a light yellow viscous solution; the solution was then slowly addedAdding 200ml deionized water, stirring for 0.5h to obtain a diluent, and performing ultrasonic treatment on the diluent for 1h to separate lamella; centrifuging at 2500r/min for 10min to remove un-peeled bulk structure, collecting upper layer suspension, centrifuging at 10000r/min for 15min, washing the solution pH to about 7 to obtain two-dimensional C3N4Nanosheets.
Preparation of ZIF-90/C3N4Nano-sheet composite material: two-dimensional C to be obtained3N4Dissolving the nano-sheet in deionized water to obtain 1mg/ml of two-dimensional C3N4The aqueous nanosheet/suspension is then measured 40ml and added with 0.96g of zinc acetate, sonicated for 0.5h and then centrifuged at 9000r/min for 10min to yield a Zn (II) -grown two-dimensional C3N4And adding 40ml of methanol into the nanosheet, dissolving and converting into a methanol system. 2.535g of imidazole-2-carbaldehyde were weighed out and dissolved in 160ml of methanol, stirred for 1h at 60 ℃ in a water bath, filtered through a 0.22 μm pinhole filter to remove undissolved impurities and the solution was cooled to room temperature. Then two-dimensional C with zinc ion sites grown3N4The nanosheet/methanol solution was poured rapidly into the imidazole-2-formaldehyde methanol solution and stirred at room temperature for 6 h. Finally, centrifuging the obtained solution at 9000r/min for 10min and repeatedly centrifuging and washing with methanol for 3 times to obtain ZIF-90/C3N4A nanosheet composite.
Preparation of Pebax solution: 3.09g of the Pebax-1657 particles were weighed into 100g of the ethanol/water (70/30) mixed solution, and condensed and refluxed at 80 ℃ for 4 hours to obtain a Pebax-based membrane solution, which was cooled to room temperature for use.
Preparation of mixed matrix membranes: ZIF-90/C with solute mass percent of 5%, 10% and 20% based on the used Pebax membrane liquid3N4Adding the nano-sheet composite material into 8g of Pebax base membrane solution, stirring for 2h, then dispersing by using ultrasound for 1h, removing bubbles, pouring the obtained mixed casting membrane solution into a plastic culture dish, placing in a drying oven at 30 ℃ for 24h for membrane formation, finally transferring into a vacuum drying oven at 40 ℃ for 18h, and removing the residual solvent.
Example 4
The gas permeation test shows that the two-dimensional nanoscale ZIF-90/C-based material prepared in the embodiment3N4The nano-sheet composite material mixed matrix film is prepared by mixing CO at 25 ℃ under the test condition of 1bar2The permeability coefficient of the material can reach 125Barrer, CO2/N2The selectivity was 70.
The invention relates to a two-dimensional nanoscale ZIF-90/C3N4The nano-sheet composite material is prepared by preparing nano-scale two-dimensional C3N4The nano-sheet is taken as a template, and then a continuous MOF structure grows on the surface of the nano-sheet, and the method has the advantages that: the synthesis steps are simple, and the ZIF-90 can continuously grow on C3N4The nano-scale template on the surface of the nano-sheet ensures that the obtained MOF continuous structure can be vertically arranged in the membrane to form a gas channel in the vertical direction, thereby reducing the mass transfer resistance and greatly improving the CO2Increase the permeation rate of CO of the mixed matrix membrane2/N2And (4) selectivity.
Claims (10)
1. Two-dimensional nanoscale ZIF-90/C3N4The preparation method of the mixed matrix membrane of the nano-sheet composite material is characterized by comprising the following steps:
(1) nanoscale two-dimensional C3N4The nano-sheet template is prepared by an acid etching method:
block C obtained by calcining Melamine3N4Using concentrated sulfuric acid to etch and insert, and ultrasonic auxiliary stripping method to separate from block C3N4In (iii) stripping to obtain two-dimensional C3N4Nanosheets;
(2)ZIF-90/C3N4the nano-sheet composite material is prepared by two-dimensional reaction of nano-sheet composite material3N4In-situ growth on a nanosheet template to obtain:
in two dimensions C3N4Adding zinc acetate into the nanosheet aqueous solution and performing ultrasonic treatment to fix Zn (II) in two-dimensional C3N4Forming fixed growth sites on the surfaces of the nano sheets, and then growing the two-dimensional C of Zn (II)3N4Replacing the nanosheet with a methanol solution system, and adding into imidazole-2-formaldehyde methanol solution to makeZIF-90 nanoparticles grown in situ on two-dimensional C3N4Nanosheet obtaining two-dimensional nanoscale ZIF-90/C3N4A nanosheet composite;
(3) film preparation:
two-dimensional nanoscale ZIF-90/C3N4Adding the nano-sheet composite material into a Pebax-1657 matrix solution, stirring and ultrasonically dispersing the nano-sheet composite material into the matrix solution uniformly, pouring the prepared membrane casting solution into a culture dish, and casting in an oven to form a membrane.
2. The method of claim 1, wherein two-dimensional C is used3N4The nano-sheet is used as a growth template to prepare two-dimensional nano-sized ZIF-90/C with a continuous MOF channel structure3N4A nanosheet composite; the two dimensions C3N4The size of the nano-sheet is about 400-800 nm; ZIF-90 in two dimensions C3N4The particle size of the nano-sheets is 20-40 nm.
3. The process according to claim 1 or 2, wherein the block C is a block C3N4The calcination conditions of (A) are as follows: air atmosphere, heating rate of 2-5 ℃/min, calcination temperature of 540-.
4. The process according to claim 1 or 2, wherein the concentrated sulfuric acid used is in the form of a mixture of bulk C and volume ml of concentrated sulfuric acid3N4The mass g ratio is 10-20:1, the acid etching temperature is 25-40 ℃, and the acid etching time is 8-12 h.
5. The method of claim 1 or 2, two-dimensional C3N4The concentration of the nano-sheet aqueous solution is 0.1-2mg/mL, and the zinc acetate and the two-dimensional C in the solution are used3N4The mass ratio of the nano sheets is 24-72: 1; the added methanol is equal to the original two-dimensional C3N4The volume of the aqueous solution of the nanosheets; the molar ratio of the imidazole-2-formaldehyde to the zinc acetate is 4-8: 1; two-dimensional C with Zn (II) growth3N4The mixing volume ratio of the mixed solution of the nano-sheets and the methanol to the imidazole-2-formaldehyde methanol solution is 1: 2-4.
6. The method according to claim 1 or 2, wherein the Zn (ii) ultrasonic growth time is 0.5 to 2 hours and the ZIF-90 growth time is 6 to 8 hours.
7. The method of claim 1 or 2, wherein the concentration of the Pebax-1657 in the base solution is 3-8 wt.%.
8. The method of claim 1 or 2, wherein the two-dimensional nanoscale ZIF-90/C is prepared as described in claim 1 or 23N4The mass percentage of the nano-sheet composite material to the solute in the Pebax-1657 substrate solution is 5%, 10% or 20%, the oven drying time is 12-24h, and the vacuum oven drying time is 12-24 h.
9. The production method according to claim 1 or 2, wherein the temperature of the oven or the vacuum oven during film formation is 30 to 60 ℃.
10. The method according to claim 1 or 2, wherein the two-dimensional composite material is allowed to exist in a vertical form in a large amount in the matrix due to its nano-scale size.
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| CN114669317A (en) * | 2022-04-08 | 2022-06-28 | 国科温州研究院(温州生物材料与工程研究所) | Nano enzyme with multistage enzyme-linked reaction performance and preparation method and application thereof |
| CN117563432A (en) * | 2023-11-23 | 2024-02-20 | 西北师范大学 | Preparation of carbon nitride-based two-dimensional composite membrane and application of carbon nitride-based two-dimensional composite membrane in gas separation |
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| CN113976160B (en) * | 2021-11-12 | 2023-11-03 | 哈尔滨工业大学 | Preparation method and application of two-dimensional photocatalytic film with heterostructure |
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| CN114669317B (en) * | 2022-04-08 | 2023-09-26 | 国科温州研究院(温州生物材料与工程研究所) | Nano-enzyme with multistage enzyme-linked reaction performance, and preparation method and application thereof |
| CN117563432A (en) * | 2023-11-23 | 2024-02-20 | 西北师范大学 | Preparation of carbon nitride-based two-dimensional composite membrane and application of carbon nitride-based two-dimensional composite membrane in gas separation |
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