CN114177788A - ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof - Google Patents
ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof Download PDFInfo
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- 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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- B01D71/56—Polyamides, e.g. polyester-amides
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Abstract
The invention provides a ZIF-8 tube modified ultrathin nano composite membrane, and a preparation method and application thereof. The preparation method of the ZIF-8 tube modified ultrathin nano composite membrane comprises the following steps: firstly, preparing zinc-ethylene glycol, then preparing a ZIF-8 tube by taking the zinc-ethylene glycol as a precursor, then adding the ZIF-8 tube into a polyether sulfone porous substrate, and finally preparing a polyamide selection layer by taking the polyether sulfone filter membrane as the substrate. The addition of the ZIF-8 increases a porous channel of the polyether sulfone membrane, and the hollow ZIF-8 tube provides an additional one-dimensional nano channel, so that the water flux of the TFN membrane is greatly improved compared with that of the TFC membrane under the condition that the retention rate of the dye is not reduced, the limitations of the water flux and the retention rate of the TFC membrane are effectively broken through, and a new method is provided for preparing the ultrathin nano composite membrane.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a ZIF-8 tube modified ultrathin nano composite membrane, a preparation method and application thereof.
Background
Water is a source of life and is one of the important resources on which humans live and develop socially. However, with the rapid growth of population and the rapid development of industrialization in recent years, problems such as water resource shortage and water pollution have arisen. Therefore, the development of efficient water treatment technology is a basic approach to solve the water resource shortage and pollution. The membrane separation technology has the advantages of simple operation, energy conservation, high efficiency and low cost, and is rapidly developed in the field of water treatment. Ultra-thin composite membranes (TFCs) formed by interfacial polymerization on polymeric substrates are one type of membrane material that has been commercialized for water treatment. One of the key problems encountered with TFC membranes in water treatment, however, is the tradeoff between water flux and rejection.
Disclosure of Invention
The invention aims to provide an ultrathin nanometer composite membrane modified by a ZIF-8 tube, a preparation method and application thereof, wherein the water flux of the membrane can be obviously improved after the ZIF-8 tube is added.
The invention is realized by the following steps: the ZIF-8 pipe modified ultrathin nano composite membrane comprises a polyether sulfone substrate at the bottom and a polyamide selection layer at the top, wherein a ZIF-8 pipe is added in the polyether sulfone substrate. The ZIF-8 tube is prepared by taking zinc-glycol as a precursor.
The invention provides a preparation method of an ultrathin nanometer composite membrane modified by a ZIF-8 tube, which specifically comprises the following steps:
(1) preparing a zinc-glycol precursor: dissolving anhydrous zinc acetate in ethylene glycol, reacting under a stirring state, centrifuging, and washing to obtain a zinc-ethylene glycol precursor;
(2) preparing a ZIF-8 tube: dissolving the zinc-glycol precursor obtained in the step (1) in N, N-dimethylformamide, and carrying out ultrasonic stirring to obtain a solution A; dissolving 2-methylimidazole in N, N-dimethylformamide to obtain a solution B; adding the solution B into the solution A and fully stirring to uniformly mix the solution B and the solution A to obtain a solution C; transferring the solution C into a reaction kettle for reaction, cooling to room temperature, centrifuging, washing and drying to obtain a ZIF-8 tube;
(3) preparing a polyether sulfone substrate: ultrasonically stirring and dispersing the ZIF-8 tube obtained in the step (2) in N, N-dimethylacetamide, then sequentially adding polyether sulfone, finally adding polyvinylpyrrolidone, and stirring at room temperature to obtain a solution D; ultrasonically treating the solution D and standing to remove bubbles; scraping the solution D by using a film scraping device, soaking the film in deionized water for phase conversion, finally taking out the film, and drying at room temperature to obtain a polyether sulfone substrate;
(4) preparation of a polyamide selection layer: dissolving anhydrous piperazine in deionized water to obtain a solution E; dissolving trimesoyl chloride in n-hexane to obtain a solution F; and (4) pouring the solution E and the solution F on the polyether sulfone substrate obtained in the step (3) in sequence, standing, pouring out the redundant solution, and drying in an oven to obtain the ZIF-8 tube modified ultrathin nano composite membrane.
In the step (1), the anhydrous zinc acetate is 4.0g, and the ethylene glycol is 100 mL; the reaction temperature of the obtained zinc-glycol precursor is 150 ℃, the stirring speed is 200r/min, the reaction time is 1h, and the washing mode is that the zinc-glycol precursor is washed by ethanol for 3 times.
In the step (2), the zinc-ethylene glycol precursor is 1.5g, the 2-methylimidazole is 0.5g, and the N, N-dimethylformamide is 30 mL; the ultrasonic stirring time of the obtained solution A is 50 min; stirring the obtained solution C for 10 min; the reaction temperature required for obtaining the ZIF-8 tube was 120 ℃ and the reaction time was 24 hours, the washing was performed by washing 3 times with ethanol, the drying temperature was 60 ℃ and the drying time was 12 hours.
In the step (3), the addition amount of the ZIF-8 pipe is 0.5-1.5 wt%; the mass fraction of the polyether sulfone is 14.49-14.71 wt%; the mass fraction of the polyvinylpyrrolidone is 1.96 wt%; the stirring time required for obtaining the solution D is 24 hours; the thickness of the film scraping device is 150 mu m; the time for the membrane to undergo phase inversion in water was 24h and the time for drying was 24 h.
In the step (4), the concentration of the anhydrous piperazine is 2 w/v%, and the residence time on the polyether sulfone substrate is 2 min; the concentration of trimesoyl chloride is 0.1 w/v%, and the residence time on the polyether sulfone substrate is 1 min; the drying temperature of the obtained ultrathin nano composite film is 60 ℃, and the drying time is 10 min.
The ZIF-8 tube modified ultrathin nano composite membrane prepared by the method has a good application effect in water treatment.
The invention has the beneficial effects that: aiming at the balance problem between water flux and rejection rate of a TFC membrane in water treatment, the invention provides a method for preparing an ultrathin nano composite membrane (TFN) by adding a ZIF-8 tube into a polyether sulfone substrate, which comprises the following steps: firstly preparing zinc-ethylene glycol, then preparing a ZIF-8 tube by taking the zinc-ethylene glycol as a precursor, then adding the ZIF-8 tube into a polyether sulfone porous substrate, and finally preparing a polyamide selection layer by taking the polyether sulfone filter membrane as the substrate. The addition of the ZIF-8 tube increases a porous channel of the polyether sulfone membrane, and the hollow ZIF-8 tube provides an additional one-dimensional nano channel, so that the water flux of the TFN membrane is greatly improved compared with that of the TFC membrane under the condition that the retention rate of the dye is not reduced, the limitations of the water flux and the retention rate of the TFC membrane are effectively broken through, and a new method is provided for preparing the ultrathin nano composite membrane.
Drawings
FIG. 1 is a graph showing the results of tests on ZIF-8 tubes prepared according to the present invention; wherein (a) is the X-ray diffraction pattern of a ZIF-8 tube; (b) is a scanning electron micrograph of a ZIF-8 tube; (c) is a transmission electron micrograph of a ZIF-8 tube.
FIG. 2 is a scanning electron microscope image of a cross-section of a polyethersulfone substrate prepared in accordance with the present invention; wherein (a) corresponds to comparative example 1; (b) corresponding to example 1; (c) corresponding to example 2; (d) corresponding to example 3.
FIG. 3 is a scanning electron microscope photograph of the surface of a selective layer of polyamide prepared according to the invention; wherein (a) corresponds to comparative example 1; (b) corresponding to example 1; (c) corresponding to example 2; (d) corresponding to example 3.
Detailed Description
The invention is further illustrated by the following examples, which are given by way of illustration only and are not intended to limit the scope of the invention in any way.
The procedures and methods not described in detail in the following examples are conventional methods well known in the art. The following examples all achieve the objects of the present invention.
Comparative example 1
(1) Preparing a zinc-glycol precursor: dissolving 4.0g of anhydrous zinc acetate in 100mL of glycol, reacting for 1h at the stirring speed of 200r/min and the temperature of 150 ℃, centrifugally separating the obtained product after the reaction is finished, and washing for 3 times by using ethanol to obtain a zinc-glycol precursor.
(2) Preparing a ZIF-8 tube: dissolving 1.5g of zinc-glycol precursor obtained in the step (1) in 30mL of N, N-dimethylformamide, and ultrasonically stirring for 50min to obtain a solution A; dissolving 0.5g of 2-methylimidazole in 30mL of N, N-dimethylformamide to obtain a solution B; adding the solution B into the solution A, and fully stirring for 10min to uniformly mix the solution B and the solution A to obtain a solution C; and (3) transferring the solution C into a reaction kettle, reacting at the temperature of 120 ℃ for 24h, cooling to room temperature, centrifuging to separate the obtained product, washing with ethanol for 3 times, and drying at the temperature of 60 ℃ for 12h to obtain a ZIF-8 tube.
The prepared ZIF-8 tube was tested, and the results are shown in fig. 1. In FIG. 1, (a) is an X-ray diffraction pattern of a ZIF-8 tube, and from the pattern (a), characteristic peaks of 011, 002, 112, 022, 013, and 222 appeared, and these characteristic peaks were in agreement with those in the literature, demonstrating that the substance was ZIF-8. In FIG. 1, (b) is a scanning electron microscope image of a ZIF-8 tube, and (c) is a transmission electron microscope image of a ZIF-8 tube, and as can be seen from (b) and (c) in FIG. 1, the ZIF-8 tube has a hollow structure, a length of 2 to 3 μm, and a diameter of 250 nm.
(3) Preparing a polyether sulfone substrate: ultrasonically stirring and dispersing the ZIF-8 tube obtained in the step (2) in N, N-dimethylacetamide, wherein the addition amount of the ZIF-8 tube is 0 wt%, then adding polyether sulfone one by one, finally adding polyvinylpyrrolidone, and stirring at room temperature for 24 hours to obtain a solution D, wherein the mass fraction of the polyether sulfone in the solution D is 14.71 wt%, and the mass fraction of the polyvinylpyrrolidone in the solution D is 1.96 wt%; ultrasonically treating the solution D and standing to remove bubbles; and (3) scraping the solution D by using a 150-micron scraping device, soaking the membrane in deionized water for 24h for phase conversion, finally taking out the membrane, and drying at room temperature for 24h to obtain the polyether sulfone substrate.
SEM testing of the polyethersulfone substrate produced gave the results shown in figure 2 (a), from which it can be seen that the polyethersulfone substrate consisted of a lower, thicker, porous layer and an upper, thinner, dense layer.
(4) Preparation of a polyamide selection layer: dissolving anhydrous piperazine in deionized water to obtain a solution E, wherein the concentration of the anhydrous piperazine is 2 w/v%; dissolving trimesoyl chloride in n-hexane to obtain a solution F, wherein the concentration of the trimesoyl chloride is 0.1 w/v%; pouring the solution E on the polyether sulfone substrate obtained in the step (3), and pouring out the redundant solution after staying for 2 min; pouring the solution F on a polyether sulfone substrate, and pouring out the redundant solution after the solution F stays for 1 min; and then drying in an oven at 60 ℃ for 10min to obtain the ultrathin composite film.
The result of SEM test of the polyamide selective layer prepared in this step is shown in fig. 3 (a), and it can be seen that the polyamide selective layer has a typical ridge structure.
Example 1
(1) Preparing a zinc-glycol precursor: dissolving 4.0g of anhydrous zinc acetate in 100mL of glycol, reacting for 1h at the stirring speed of 200r/min and the temperature of 150 ℃, centrifugally separating the obtained product after the reaction is finished, and washing for 3 times by using ethanol to obtain a zinc-glycol precursor.
(2) Preparing a ZIF-8 tube: dissolving 1.5g of zinc-glycol precursor obtained in the step (1) in 30mL of N, N-dimethylformamide, and ultrasonically stirring for 50min to obtain a solution A; dissolving 0.5g of 2-methylimidazole in 30mL of N, N-dimethylformamide to obtain a solution B; adding the solution B into the solution A, and fully stirring for 10min to uniformly mix the solution B and the solution A to obtain a solution C; and (3) transferring the solution C into a reaction kettle, reacting at the temperature of 120 ℃ for 24h, cooling to room temperature, centrifuging to separate the obtained product, washing with ethanol for 3 times, and drying at the temperature of 60 ℃ for 12h to obtain a ZIF-8 tube.
(3) Preparing a polyether sulfone substrate: ultrasonically stirring and dispersing the ZIF-8 tube obtained in the step (2) in N, N-dimethylacetamide, wherein the addition amount of the ZIF-8 tube is 0.5 wt%, then adding polyether sulfone one by one, finally adding polyvinylpyrrolidone, and stirring at room temperature for 24 hours to obtain a solution D, wherein the mass fraction of the polyether sulfone in the solution D is 14.63 wt%, and the mass fraction of the polyvinylpyrrolidone in the solution D is 1.96 wt%; ultrasonically treating the solution D and standing to remove bubbles; and (3) scraping the solution D by using a 150-micron scraping device, soaking the membrane in deionized water for 24h for phase conversion, finally taking out the membrane, and drying at room temperature for 24h to obtain the polyether sulfone substrate.
The polyethersulfone substrate prepared in this step was subjected to SEM test and the results are shown in fig. 2 (b), from which it can be seen that the polyethersulfone substrate comprised of a lower, thicker, porous layer and an upper, thinner, dense layer, the polyethersulfone substrate prepared in this example had a wider finger-like pore structure and a microporous structure as compared to the polyethersulfone substrate prepared in comparative example 1.
(4) Preparation of a polyamide selection layer: dissolving anhydrous piperazine in deionized water to obtain a solution E, wherein the concentration of the anhydrous piperazine is 2 w/v%; dissolving trimesoyl chloride in n-hexane to obtain a solution F, wherein the concentration of the trimesoyl chloride is 0.1 w/v%; pouring the solution E on the polyether sulfone substrate obtained in the step (3), and pouring out the redundant solution after staying for 2 min; pouring the solution F on a polyether sulfone substrate, and pouring out the redundant solution after the solution F stays for 1 min; and then drying in an oven at 60 ℃ for 10min to obtain the ultrathin nano composite film.
The result of SEM test of the polyamide selection layer prepared in this step is shown in fig. 3 (b), and it can be seen that the polyamide selection layer has a typical ridge structure, and the ridge structure of the polyamide selection layer prepared in this example becomes larger and more than that of the polyamide selection layer prepared in comparative example 1.
Example 2
(1) Preparing a zinc-glycol precursor: dissolving 4.0g of anhydrous zinc acetate in 100mL of glycol, reacting for 1h at the stirring speed of 200r/min and the temperature of 150 ℃, centrifugally separating the obtained product after the reaction is finished, and washing for 3 times by using ethanol to obtain a zinc-glycol precursor.
(2) Preparing a ZIF-8 tube: dissolving 1.5g of zinc-glycol precursor obtained in the step (1) in 30mL of N, N-dimethylformamide, and ultrasonically stirring for 50min to obtain a solution A; dissolving 0.5g of 2-methylimidazole in 30mL of N, N-dimethylformamide to obtain a solution B; adding the solution B into the solution A, and fully stirring for 10min to uniformly mix the solution B and the solution A to obtain a solution C; and (3) transferring the solution C into a reaction kettle, reacting at the temperature of 120 ℃ for 24h, cooling to room temperature, centrifuging to separate the obtained product, washing with ethanol for 3 times, and drying at the temperature of 60 ℃ for 12h to obtain a ZIF-8 tube.
(3) Preparing a polyether sulfone substrate: ultrasonically stirring and dispersing the ZIF-8 tube obtained in the step (2) in N, N-dimethylacetamide, wherein the addition amount of the ZIF-8 tube is 1.0 wt%, then adding polyether sulfone one by one, finally adding polyvinylpyrrolidone, and stirring at room temperature for 24 hours to obtain a solution D, wherein the mass fraction of the polyether sulfone in the solution D is 14.56 wt%, and the mass fraction of the polyvinylpyrrolidone in the solution D is 1.96 wt%; ultrasonically treating the solution D and standing to remove bubbles; and (3) scraping the solution D by using a 150-micron scraping device, soaking the membrane in deionized water for 24h for phase conversion, finally taking out the membrane, and drying at room temperature for 24h to obtain the polyether sulfone substrate.
SEM testing of the polyethersulfone substrate prepared in this step gave the results shown in fig. 2 (c), from which it can be seen that the polyethersulfone substrate comprised of a lower, thicker, porous layer and an upper, thinner, dense layer, the polyethersulfone substrate prepared in this example had a wider finger-like pore structure extending from the top to the bottom of the polyethersulfone cross-section than the polyethersulfone substrate prepared in comparative example 1.
(4) Preparation of a polyamide selection layer: dissolving anhydrous piperazine in deionized water to obtain a solution E, wherein the concentration of the anhydrous piperazine is 2 w/v%; dissolving trimesoyl chloride in n-hexane to obtain a solution F, wherein the concentration of the trimesoyl chloride is 0.1 w/v%; pouring the solution E on the polyether sulfone substrate obtained in the step (3), and pouring out the redundant solution after staying for 2 min; pouring the solution F on a polyether sulfone substrate, and pouring out the redundant solution after the solution F stays for 1 min; and then drying in an oven at 60 ℃ for 10min to obtain the ultrathin nano composite film.
The results of SEM test on the polyamide selection layer prepared in this step are shown in (c) of fig. 3, and it can be seen that the polyamide selection layer has a typical ridge structure, and the ridge structure of the polyamide selection layer prepared in this example becomes larger and more than that of the polyamide selection layer prepared in comparative example 1.
Example 3
(1) Preparing a zinc-glycol precursor: dissolving 4.0g of anhydrous zinc acetate in 100mL of glycol, reacting for 1h at the stirring speed of 200r/min and the temperature of 150 ℃, centrifugally separating the obtained product after the reaction is finished, and washing for 3 times by using ethanol to obtain a zinc-glycol precursor.
(2) Preparing a ZIF-8 tube: dissolving 1.5g of zinc-glycol precursor obtained in the step (1) in 30mL of N, N-dimethylformamide, and ultrasonically stirring for 50min to obtain a solution A; dissolving 0.5g of 2-methylimidazole in 30mL of N, N-dimethylformamide to obtain a solution B; adding the solution B into the solution A, and fully stirring for 10min to uniformly mix the solution B and the solution A to obtain a solution C; and (3) transferring the solution C into a reaction kettle, reacting at the temperature of 120 ℃ for 24h, cooling to room temperature, centrifuging to separate the obtained product, washing with ethanol for 3 times, and drying at the temperature of 60 ℃ for 12h to obtain a ZIF-8 tube.
(3) Preparing a polyether sulfone substrate: ultrasonically stirring and dispersing the ZIF-8 tube obtained in the step (2) in N, N-dimethylacetamide, wherein the addition amount of the ZIF-8 tube is 1.5 wt%, then adding polyether sulfone one by one, finally adding polyvinylpyrrolidone, and stirring at room temperature for 24 hours to obtain a solution D, wherein the mass fraction of the polyether sulfone in the solution D is 14.49 wt%, and the mass fraction of the polyvinylpyrrolidone in the solution D is 1.96 wt%; ultrasonically treating the solution D and standing to remove bubbles; and (3) scraping the solution D by using a 150-micron scraping device, soaking the membrane in deionized water for 24h for phase conversion, finally taking out the membrane, and drying at room temperature for 24h to obtain the polyether sulfone substrate.
SEM testing of the polyethersulfone substrate prepared in this step gave the results shown in fig. 2 (d), from which it can be seen that the polyethersulfone substrate comprised of a lower, thicker, porous layer and an upper, thinner, dense layer, the polyethersulfone substrate prepared in this example had a wider finger-like pore structure extending from the top to the bottom of the polyethersulfone cross-section than the polyethersulfone substrate prepared in comparative example 1.
(4) Preparation of a polyamide selection layer: dissolving anhydrous piperazine in deionized water to obtain a solution E, wherein the concentration of the anhydrous piperazine is 2 w/v%; dissolving trimesoyl chloride in n-hexane to obtain a solution F, wherein the concentration of the trimesoyl chloride is 0.1 w/v%; pouring the solution E on the polyether sulfone substrate obtained in the step (3), and pouring out the redundant solution after staying for 2 min; pouring the solution F on a polyether sulfone substrate, and pouring out the redundant solution after the solution F stays for 1 min; and then drying in an oven at 60 ℃ for 10min to obtain the ultrathin nano composite film.
The results of SEM test on the polyamide selection layer prepared in this step are shown in fig. 3 (d), and it can be seen that the polyamide selection layer has a typical ridge structure, and the ridge structure of the polyamide selection layer prepared in this example becomes larger and more than that of the polyamide selection layer prepared in comparative example 1.
The experimental method comprises the following steps:
the ultra-thin composite membrane (denoted by M0) prepared in comparative example 1 and the ultra-thin nanocomposite membranes (denoted by M1, M2 and M3, respectively) prepared in examples 1 to 3 were subjected to a water flux test of the membrane and a dye-retention test of the membrane, and water treatment performance of the membrane was performed on a self-made permeation device, the device and N32The gas transmission pipelines are connected as driving force. The pressure difference between the two sides of the membrane is 0.3Mpa, the test condition is 25 ℃, and the effective separation area of the membrane is 7.5cm2. To ensure the reliability of the test, the data was stabilized for 30min before recording and each type of film was tested at least three times.
The results are given in the following table:
table 1 results of water flux and dye retention test of the membranes prepared in comparative example 1 and examples 1 to 3
Experimental results show that when the ZIF-8 pipe prepared by the method is added to a polyether sulfone substrate, the water flux of the membrane can be effectively improved.
Claims (8)
1. The ZIF-8 pipe modified ultrathin nano composite membrane is characterized by comprising a polyether sulfone substrate at the bottom and a polyamide selection layer at the top, wherein a ZIF-8 pipe is added in the polyether sulfone substrate.
2. The ZIF-8 tube-modified ultrathin nanocomposite membrane as claimed in claim 1, wherein the ZIF-8 tube is prepared using zinc-ethylene glycol as a precursor.
3. A preparation method of an ultrathin nanometer composite membrane modified by a ZIF-8 tube is characterized by comprising the following steps:
(1) preparing a zinc-glycol precursor: dissolving anhydrous zinc acetate in ethylene glycol, reacting under a stirring state, centrifuging, and washing to obtain a zinc-ethylene glycol precursor;
(2) preparing a ZIF-8 tube: dissolving the zinc-glycol precursor obtained in the step (1) in N, N-dimethylformamide, and carrying out ultrasonic stirring to obtain a solution A; dissolving 2-methylimidazole in N, N-dimethylformamide to obtain a solution B; adding the solution B into the solution A and fully stirring to uniformly mix the solution B and the solution A to obtain a solution C; transferring the solution C into a reaction kettle for reaction, cooling to room temperature, centrifuging, washing and drying to obtain a ZIF-8 tube;
(3) preparing a polyether sulfone substrate: ultrasonically stirring and dispersing the ZIF-8 tube obtained in the step (2) in N, N-dimethylacetamide, then sequentially adding polyether sulfone, finally adding polyvinylpyrrolidone, and stirring at room temperature to obtain a solution D; ultrasonically treating the solution D and standing to remove bubbles; scraping the solution D by using a film scraping device, soaking the film in deionized water for phase conversion, finally taking out the film, and drying at room temperature to obtain a polyether sulfone substrate;
(4) preparation of a polyamide selection layer: dissolving anhydrous piperazine in deionized water to obtain a solution E; dissolving trimesoyl chloride in n-hexane to obtain a solution F; and (4) pouring the solution E and the solution F on the polyether sulfone substrate obtained in the step (3) in sequence, standing, pouring out the redundant solution, and drying in an oven to obtain the ZIF-8 tube modified ultrathin nano composite membrane.
4. The method for preparing the ZIF-8 tube-modified ultrathin nanocomposite membrane as claimed in claim 3, wherein in the step (1), the anhydrous zinc acetate is 4.0g, and the ethylene glycol is 100 mL; the reaction temperature of the obtained zinc-glycol precursor is 150 ℃, the stirring speed is 200r/min, the reaction time is 1h, and the washing mode is that the zinc-glycol precursor is washed by ethanol for 3 times.
5. The method of preparing the ZIF-8 tube-modified ultrathin nanocomposite membrane as claimed in claim 3, wherein in the step (2), the zinc-ethylene glycol precursor is 1.5g, the 2-methylimidazole is 0.5g, and the N, N-dimethylformamide is 30 mL; the ultrasonic stirring time of the obtained solution A is 50 min; stirring the obtained solution C for 10 min; the reaction temperature required for obtaining the ZIF-8 tube was 120 ℃ and the reaction time was 24 hours, the washing was performed by washing 3 times with ethanol, the drying temperature was 60 ℃ and the drying time was 12 hours.
6. The method for preparing the ZIF-8 tube-modified ultrathin nano-composite membrane as claimed in claim 3, wherein in the step (3), the addition amount of the ZIF-8 tube is 0.5 wt% -1.5 wt%; the mass fraction of the polyether sulfone is 14.49-14.71 wt%; the mass fraction of the polyvinylpyrrolidone is 1.96 wt%; the stirring time required for obtaining the solution D is 24 hours; the thickness of the film scraping device is 150 mu m; the time for the membrane to undergo phase inversion in water was 24h and the time for drying was 24 h.
7. The method for preparing the ZIF-8 tube-modified ultrathin nanocomposite membrane as claimed in claim 3, wherein in the step (4), the concentration of the anhydrous piperazine is 2 w/v%, and the residence time on the polyethersulfone substrate is 2 min; the concentration of trimesoyl chloride is 0.1 w/v%, and the residence time on the polyether sulfone substrate is 1 min; the drying temperature of the obtained ultrathin nano composite film is 60 ℃, and the drying time is 10 min.
8. Use of the ZIF-8 tube-modified ultra-thin nanocomposite membrane of any of the preceding claims 1 to 7 in water treatment.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209021A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material |
| CN104209022A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | High-flux polyamide/ZIF-8 nanofiltration composite film and preparation method thereof |
| US20180065105A1 (en) * | 2016-05-02 | 2018-03-08 | LiSo Plastics, L.L.C. | Multilayer polymeric membrane and process |
| CN112191111A (en) * | 2019-07-08 | 2021-01-08 | 中国科学院青岛生物能源与过程研究所 | Ionic liquid/metal organic framework ZIF-8 composite membrane and preparation method and application thereof |
| AU2020104003A4 (en) * | 2020-12-10 | 2021-02-18 | Ocean University Of China | Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof |
| CN113209841A (en) * | 2021-05-14 | 2021-08-06 | 武汉工程大学 | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof |
-
2021
- 2021-12-01 CN CN202111455619.8A patent/CN114177788A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104209021A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | Preparation method of aromatic polyamide film modified by ZIF-8 type metal-organic framework material |
| CN104209022A (en) * | 2014-09-03 | 2014-12-17 | 北京林业大学 | High-flux polyamide/ZIF-8 nanofiltration composite film and preparation method thereof |
| US20180065105A1 (en) * | 2016-05-02 | 2018-03-08 | LiSo Plastics, L.L.C. | Multilayer polymeric membrane and process |
| CN112191111A (en) * | 2019-07-08 | 2021-01-08 | 中国科学院青岛生物能源与过程研究所 | Ionic liquid/metal organic framework ZIF-8 composite membrane and preparation method and application thereof |
| AU2020104003A4 (en) * | 2020-12-10 | 2021-02-18 | Ocean University Of China | Metal-Organic Frameworks ZIF-Based Polyamide Mixed Matrix Membranes and Preparation Method Thereof |
| CN113209841A (en) * | 2021-05-14 | 2021-08-06 | 武汉工程大学 | Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIU ZIYI ET AL.: "A effective "precursor-transformation" rote toward high-yield synthrsis of ZIF-8 tubes" * |
| SAINA AKBARI ET AL.: "Improving water flux and salt rejection by a tradeoff between hydrophilicity and hydrophobicity of sublayer in TFC FO membrane" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115445455A (en) * | 2022-09-26 | 2022-12-09 | 大连理工大学 | Preparation method of ultra-thin mixed matrix asymmetric membrane with MOFs (metal-organic frameworks) in gradient distribution |
| CN115445455B (en) * | 2022-09-26 | 2023-11-21 | 大连理工大学 | Preparation method of MOFs gradient-distributed ultrathin mixed matrix asymmetric membrane |
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