CN113667137A - Preparation method and application of two-dimensional metal-organic framework material - Google Patents

Preparation method and application of two-dimensional metal-organic framework material Download PDF

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CN113667137A
CN113667137A CN202111069462.5A CN202111069462A CN113667137A CN 113667137 A CN113667137 A CN 113667137A CN 202111069462 A CN202111069462 A CN 202111069462A CN 113667137 A CN113667137 A CN 113667137A
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organic framework
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framework material
sodium hydroxide
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仲崇立
关璐
乔志华
赵新
杨紫博
岑喜喜
奥德
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Tianjin Polytechnic University
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Abstract

The invention discloses a preparation method and application of a two-dimensional metal-organic framework material, wherein the preparation method is to use 4-chloro-isophthalic acid as a ligand and react with Al in aluminum nitrate3+And (3) coordination, namely obtaining the metal organic framework material by a solvothermal synthesis method. The obtained metal organic framework material CACl-10(180) belongs to a two-dimensional metal organic framework, has excellent alkaline stability and is stable in a sodium hydroxide solution with the pH value of 14 for 24 hours, and has priority on methaneAdsorption effect, and the mixed matrix membrane prepared by using the adsorbent as the filler of the mixed matrix membrane can be used for separating CH in unconventional natural gas4/N2. The metal-organic framework material has strong stability, good crystallinity, simple preparation process and wide applicability.

Description

Preparation method and application of two-dimensional metal-organic framework material
Technical Field
The invention relates to the technical field of metal-organic framework materials, in particular to a preparation method and application of a two-dimensional metal-organic framework material.
Background
The metal-organic framework (MOF) is a novel porous material, and a coordination polymer with a periodic network structure, which is assembled by inorganic metal ions and organic ligands, has the characteristics of high porosity, high specific surface area, adjustable pore size and the like, and has wide application prospects in the aspects of gas separation, electrochemistry, catalysis, medicine and the like.
A two-dimensional metal organic framework (2D MOF) material is an emerging metal organic framework material. Compared with common metal organic framework materials, the metal organic framework material has more active sites, and the active sites can increase the interaction opportunities with substrate molecules, so that the metal organic framework material has more advantages in catalysis, sensing and gas separation.
According to the reports of relevant documents, many polymers have good film forming capability and stability and are alkaline. However, the effect of these polymers on gas separation when formed into films alone is still to be improved. In addition, most MOF materials are difficult or poorly film-forming alone. These all affect the gas separation effect, and it is difficult to realize industrialization of gas separation.
The invention adopts a solvothermal method to prepare a two-dimensional metal-organic framework CACl-10(180) with strong alkali stability, and the metal framework can be used as a filler to be mixed with polyvinyl amine with alkalinity to prepare a mixed matrix membrane. CACl-10(180) is used as a novel two-dimensional MOF material, the preparation process is simple, the crystallinity is good, the yield is high, and the mixed matrix membrane prepared by mixing with polyvinylamine is expected to realize industrial separation of methane and nitrogen.
Disclosure of Invention
The invention aims to solve the problems that a metal-organic framework material is unstable to an alkaline environment and is difficult to realize the technology of industrially separating gas, and provides a two-dimensional metal-organic framework material CACl-10(180) with strong alkali stability, and the metal-organic framework material CACl-10 and the two-dimensional metal-organic framework material CACl-180 form a mixed matrix membrane with polyvinylamine to realize the possibility of industrially separating gas.
The invention adopts the following technical scheme: a preparation method of a two-dimensional metal-organic framework material is characterized by comprising the following steps:
preparing a 4-chloro-isophthalic acid solution of N, N-dimethylformamide with the concentration of 1 mol/L; dissolving 4-chloro-isophthalic acid in N, N-dimethylformamide and uniformly stirring; the volume of the above-mentioned solution of N, N-dimethylformamide and chlorometaphthalic acid was 1 mL;
preparing an aluminum nitrate solution with the concentration of 1 mol/L; dissolving aluminum nitrate in deionized water and uniformly stirring; the volume of the aluminum nitrate solution is 1 mL;
step three, putting the mixture of the light yellow 4-chloro-isophthalic acid solution of N, N-dimethylformamide and the aluminum nitrate solution obtained in the step one and the step two into a vacuum oven to be heated to 130 ℃, 140 ℃ and 180 ℃ respectively, and reacting for 12h to obtain crude products of white metal-organic frameworks CACl-10(130), CACl-10(140) and CACl-10 (180); the dosage of the 4-chloro-isophthalic acid and the aluminum nitrate is as follows according to the molar ratio of 4-chloro-isophthalic acid: aluminum nitrate was 1: 1;
step four, washing and centrifuging the crude products of the metal-organic framework materials CACl-10(130), CACl-10(140) and CACl-10(180) obtained in the step three for 1 day by using N, N-dimethylformamide, and aiming at washing off redundant 4-chloro-isophthalic acid; the centrifuge was washed with deionized water for 1 day in order to wash out the N, N-dimethylformamide. Finally, washing and centrifuging for three times by using methanol, and washing out impurities which are not completely removed;
step five, then putting the materials into a vacuum oven for drying for 5 hours at the temperature of 80 ℃, and aiming at removing methanol, finally obtaining metal organic framework materials CACl-10(130), CACl-10(140) and two-dimensional metal-organic framework materials CACl-10 (180); by adopting the steps and utilizing a solvothermal synthesis method, the Al-based metal-organic framework which has good crystallinity and high purity and takes 4-chloro-isophthalic acid as a ligand is obtained.
Furthermore, the two-dimensional metal-organic framework material CACl-10(180) has good alkaline stability, the appearance of the material is two-dimensional column shape, and the thickness of the material is 55 nm.
The invention adopts another technical scheme that: a method for testing the strong base stability of a two-dimensional metal-organic framework material is characterized by comprising the following steps:
preparing a sodium hydroxide solution with the concentration of pH 14, pH 13 and pH 12; the dosage is determined according to the mass ratio of the sodium hydroxide, namely pH is 14 sodium hydroxide solution: pH 13 sodium hydroxide solution: the pH of the sodium hydroxide solution is 12: 100:10: 1;
step two, testing the alkaline stability of metal-organic frameworks CACl-10(130), CACl-10(140) and CACl-10 (180); taking out a certain volume of sodium hydroxide solution in the step I, adding a small amount of CACl-10(130), CACl-10(140) and CACl-10(180) powder, and soaking for 24 hours, wherein the volume of the sodium hydroxide solution is 5-6 mL;
step three, the CACl-10(130), the CACl-10(140) and the CACl-10(180) soaked in the strong alkali solution in the step two are taken out to be washed and centrifuged for 3 to 4 times by deionized water, so that the sodium hydroxide is washed away;
step four, then putting the mixture into a vacuum oven to dry for 5 hours at the temperature of 60 ℃ to obtain white crystals; by the above method, the alkaline stability of CACl-10(130), CACl-10(140) and CACl-10(180) can be determined, i.e. CACl-10(180) can be stably stored in sodium hydroxide solution with pH 14 for 24h, CACl-10(130) can be instantly dissolved in sodium hydroxide solution with pH 14, CACl-10(140) is slowly dissolved, i.e. CACl-10(180) with the highest reaction temperature can be stably stored in sodium hydroxide solution with pH 14 for 24h, and the alkaline stability of CACl-10(130) and CACl-10(140) with reaction temperatures of 130 ℃ and 140 ℃ is lower than that of CACl-10 (180).
Further, Al in the ligand3+Reaction at high temperature to formWith AlOOH, the alkali resistance increases with increasing reaction temperature.
The invention adopts another technical scheme that: a mixed matrix membrane having a two-dimensional metal-organic framework material, characterized by: the raw materials used for the preparation of the organic polymer/metal organic composite material consist of an organic polymer, a metal organic framework material and an inorganic support body, wherein the dosage of the organic polymer and the metal organic framework material is as follows: the mass ratio of the metal organic framework material is 1: 2-5; the organic polymer is polyvinylamine, and the structural formula of the polyvinylamine is as follows:
Figure BDA0003259935990000031
wherein n is 300-1000; the inorganic support is a porous support layer with high flux and high hydrophilicity prepared by coating PDMS and PVA on a PSf membrane in sequence, and the concentration of PDMS used in the coating process is 0.4 wt%, and the concentration of PVA is 0.025 wt%.
Further, since the polymer polyvinylamine is a polar polymer, CH, the mixed matrix membrane having a support obtained as described above4Is a nonpolar analysis with polar bonds, and PVAm can adsorb CH according to the similar compatibility principle4(ii) a In addition, the metal-organic framework filler pair CH4Also has adsorption capacity. Thus, the mixed matrix membrane has preferential adsorption of CH4Has the advantages of simple process and low cost. Final CH4Has a permeability rate of 1647.99barrer, CH4/N2The selectivity of (A) was 3.1.
Furthermore, in the preparation process of the metal organic framework in the mixed matrix membrane, the cited ligand is 4-chloro-isophthalic acid, and the dosage of the ligand is as follows: the mass ratio of the 4-chloroisophthalic acid is 3.7: 2; the dosage of the organic polymer and the metal organic framework material in the mixed matrix membrane is as follows: the mass ratio of the organic polymer is 1:4, and the organic polymer is polyvinylamine.
Further, the mixed matrix membrane is the synergistic effect of CACl-10(180) and polyvinylamine, and the obtained mixed matrix membrane is enhanced to CH4/N2Selectivity of (2). Final CH4Has a permeability of 1647.99barrer, CH4/N2The selectivity of (A) was 3.1.
The invention adopts another technical scheme that: a preparation method of a mixed matrix membrane with a two-dimensional metal-organic framework material is characterized by comprising the following steps:
step one, mixing a metal-organic framework material with an organic polymer solution with the mass percentage concentration of 0.5%, and ultrasonically stirring for 12 hours to obtain a uniformly mixed casting solution; controlling the ultrasonic frequency to be 40kHz in the ultrasonic mixing process, carrying out ultrasonic treatment for 10min, and then controlling the rotating speed to be 200r/min, and stirring for 12 h;
step two, sequentially coating PDMS and PVA on a PSf membrane to prepare a high-flux and high-hydrophilicity porous support layer (MPSf membrane), wherein the concentration of PDMS used in the coating process is 0.4 wt%, and the concentration of PVA is 0.025 wt%;
and step three, coating the membrane casting solution on an MPSf supporting layer by using a scraper with the thickness of 300 microns, and then drying for 3-4 hours in a constant temperature and humidity box with the temperature of 30 ℃ and the RH of 40% to obtain a mixed matrix membrane with the thickness of 1 micron.
Furthermore, the metal-organic framework adopted in the method belongs to a two-dimensional nano material as a filler, the interaction with an organic polymer is strong, the preparation process of the mixed matrix membrane is simple, the metal-organic framework material and the organic polymer solution are uniformly mixed only by ultrasound and then blade-coated, and the method has the characteristics of simple preparation process and convenience in operation.
Further, in the third step, drying is performed in a constant temperature and humidity chamber at 30 ℃ and 40% RH, in order to prevent defects in the final film formation by slowly evaporating the solvent, i.e., the aqueous solution of ethanol.
Furthermore, the finally obtained mixed matrix membrane has the advantages of uniform surface, large flux of separated gas and high selectivity. The mixed matrix membrane obtained above was paired with CH4The invention has excellent adsorption effect, and the inventor of the invention performs gas separation test on a mixed matrix membrane by using a soap bubble method, wherein the mixed matrix membrane can realize CH4/N2Separation of (4). The mixed matrix membrane obtained above can therefore be used for the separation of methane and nitrogen in unconventional natural gas.
The innovation point of the invention is that the MOF material is a two-dimensional MOF material with strong alkali stability and can stably exist in a sodium hydroxide solution with the pH value of 14 for 24 h. And the material can be prepared into a mixed matrix membrane, and few two-dimensional MOF materials can be prepared into the mixed matrix membrane and are used for CH4/N2The separation effect of (2) is good.
Compared with the existing metal organic framework material, the metal organic framework material has the following beneficial effects: (1) the metal organic framework is prepared by adopting a solvent thermal synthesis method, so that the metal organic framework material is convenient to operate and simple in preparation process. (2) Since the carboxyl functional group of the metal framework material is destroyed by high temperature in the preparation process, the metal framework can be kept stable in a sodium hydroxide solution with pH 14 under the condition that the framework structure of the metal framework can be kept not to collapse. (3) As the metal organic framework material is a two-dimensional nano rod-shaped material, more active sites on the surface of the metal organic framework material adsorb CH4。
The metal organic framework material obtained by the preparation method has preferential CH adsorption4The mixed matrix membrane obtained by using the same as a framework material, and the final CH4Has a permeation rate of 1647.99Barrer, CH4/N2The selectivity of (A) was 3.1. For the future wide application in the industrial separation of CH4/N2Providing a vast base.
Drawings
FIG. 1 is a scanning electron microscope image of a metal-organic framework material CACl-10(180) of the present invention.
FIG. 2 is a transmission electron microscope image of the metal-organic framework material CACl-10(180) of the present invention.
FIG. 3 is an XRD spectrum of the metal organic framework material CACl-10(180) of the present invention.
FIG. 4 is an infrared spectrum of the metal organic framework material CACl-10(180) of the present invention.
FIG. 5 shows N in the metal organic framework material CACl-10(180) of the present invention2Adsorption isotherm plot.
FIG. 6 is an XRD spectrum of the metal organic framework material CACl-10(140) of the present invention.
FIG. 7 shows an IR spectrum of CACl-10(140) of the metal-organic framework material of the present invention.
FIG. 8 shows N in the metal organic framework material CACl-10(140) of the present invention2Adsorption isotherm plot.
FIG. 9 is a scanning electron micrograph of the surface of the mixed matrix membrane of the present invention.
FIG. 10 is a scanning electron micrograph of a cross section of the mixed matrix membrane of the present invention.
Detailed Description
The technical solution of the present invention is further described below by referring to several specific embodiments and the accompanying drawings. The model of the equipment used in the embodiments of the present invention and the information of the manufacturer are as follows: a vacuum oven with the model of DHG-9053-A, Shanghai sperm macro implementation Equipment Co., Ltd; x-ray diffractometer (XRD) model D2 PHASER, manufactured by Bruker, Germany; fourier Infrared Spectroscopy (FT-IR) model TENSOR II, produced by Bruker, Germany; scanning Electron Microscope (SEM) model Drop Shape Analyzer100, produced by Bruker, Germany; transmission Electron Microscope (TEM) model Hitachi H7650, manufactured by HITACHI corporation of Japan.
The raw material information used in the examples of the present invention is as follows: 4-chloro-isophthalic acid, 95% in specification, available from Shanghai Bide pharmaceutical Co., Ltd; aluminum nitrate nonahydrate, 99.5% in specification, purchased from shanghai sann chemical technology ltd; sodium hydroxide, 97% in specification, purchased from shanghai sahn chemical technology ltd; n, N-Dimethylformamide (DMF) and methanol, which are analytically pure and purchased from chemical reagents of national drug group, Inc.;
the performance test method of the invention comprises the following steps: CH of Mixed matrix Membrane obtained in Each example of the present invention4See the literature (X.Yu, Z.Wang, Z.Wei, S.Yuan, J.ZHao, J.Wang, and S.Wang.novel derivative amino connecting with film composite polymers for CO2Journal of Membrane Science,2010,362, 265-278) and the apparatus used for the determination was a gas chromatograph of the type (HP7890, Porapak N)Manufactured by agilent corporation, usa.
CH of Mixed matrix Membrane obtained in Each example of the present invention4/N2See the literature (Koros W J, Ma Y H, Shimidzu. T. terminolobus for membranes and membrane processes (IUPAC Recommendations 1996) [ J]Pure appl. chem., 1996, 68 (7): 1479-1489), according to the IUPAC description of membranes and membrane separation processes, the two-component mixed gas separation factor is defined as the ratio of the gas composition on the permeate side to the gas composition in the retentate gas, i.e.:
Figure BDA0003259935990000061
CH of Mixed matrix Membrane obtained in Each example of the present invention4/N2And the above CO2/CH4The selectivity of (A) was determined in the same manner except that the CO used in the test was the same2By changing to CH4Is a handle CH4By changing to N2And when calculating, the CO in the formula is used2Corresponding value is correspondingly changed into CH4Corresponding value, CH4The corresponding value is correspondingly converted into N2The corresponding value.
Example 1
A metal-organic framework material, CACl-10(180), prepared by a process comprising the steps of:
1g of 4-chloro-isophthalic acid (0.5mmol) was dissolved in 5mL of N, N-dimethylformamide and stirred for 30min until the solution became a uniform pale yellow solution. 1.9g of aluminum nitrate nonahydrate solid (0.5mmol) was dissolved in 5mL of deionized water and stirred for 30min until the solution was colorless and transparent. Then, the uniformly stirred 4-chloro-m-phthalic acid solution of the N, N-dimethylformamide and the aluminum nitrate solution are mixed and stirred for 60min until the mixed solution is uniform. Then the uniformly stirred mixed solution is placed in an autoclave and placed in a vacuum oven to react for 12 hours at 180 ℃. After the reaction is finished, a crude CACl-10(180) product is obtained. The crude product was then washed with excess N, N-dimethylformamide (30mL), centrifuged for 2 days, and the unreacted 4-chloro-isophthalic acid was removed. The product after washing with N, N-dimethylformamide was then washed with excess deionized water (30mL) and centrifuged for 1 day to remove N, N-dimethylformamide. Finally, the cells were centrifuged 3 times with excess methanol (30 mL). The white crystals after washing centrifugation were then dried in a vacuum oven at 60 ℃ for 5h to remove methanol. Final to white CACl-10 (180).
Example 2
A metal-organic aggregate material CACl-10(180) by a method comprising:
4.1g,0.41g and 0.041g of 97% sodium hydroxide solid (1mol) were weighed, dissolved in small beakers with a small amount of distilled water, respectively, and the sodium hydroxide solution in the beakers was transferred to 100mL volumetric flasks, the beakers and glass rods were rinsed 2-3 times with distilled water, and the rinses were also transferred to 100mL volumetric flasks. Distilled water was added to the flask until 2-3 cm from the mark. Distilled water was added dropwise with a dropper until the liquid level reached the scale mark. The lid was closed and shaken upside down to give sodium hydroxide solutions having a pH of 14, 13 and 12, respectively. 1g of the solid CACl-10(180) was soaked in 5mL of sodium hydroxide solution at pH 14, pH 13 and pH 12 for 24 h. The soaked CACl-10(180) was then centrifuged to remove residual sodium hydroxide by washing with 10mL of deionized water. And finally, putting the washed and centrifuged solid in an oven at 60 ℃ for drying.
When the measurement is performed by using a scanning electron microscope and a transmission electron microscope in the above example 1, CACl-10(180) is obtained as a two-dimensional columnar material. By X-ray diffractometer, Fourier infrared spectrometer and N2Adsorption test the assay of example two showed that CACl-10 was stable at pH 14 in sodium hydroxide for 24 h.
The metal-organic framework material obtained in example 1, i.e. CACl-10(180), was used for CH4/N2The preparation of the selectively separated mixed matrix membrane comprises the following specific steps:
(1) dissolving 0.06g of metal-organic framework material CACl-10(180) in 5g of ethanol solution, halving uniformly, mixing with 5g of organic polymer polyvinylamine solution with the mass percentage concentration of 0.5%, performing ultrasonic treatment at 40kHz for 10min, controlling the rotating speed at 200r/min, and stirring for 12h to obtain a casting solution which is uniformly mixed.
(2) PDMS and PVA are coated on a PSf membrane in sequence to prepare a high-flux and high-hydrophilicity porous support layer (MPSf membrane), and the concentration of PDMS used in the coating process is 0.4 wt%, and the concentration of PVA is 0.025 wt%.
(3) Coating the membrane casting solution on an MPSf supporting layer by using a coating method and a scraper with the thickness of 300 mu m, then drying for 3-4h in a constant temperature and humidity box with the temperature of 30 ℃ and the RH of 40 percent, and volatilizing ethanol to obtain a mixed matrix membrane PVAm-CACl-10 (80%)/PMsf, thereby obtaining the thickness of 1 mu m.
The CH of the PVAm-CACl-10(180) (80%)/PMsf mixed matrix membrane obtained above was subjected to gas chromatography4Rate and CH4/N2The results are given in the following table:
CH4penetration Rate (GPU) CH4/N2Selectivity of (2)
PMSF film 447.56 2.28
PVAm-CACl-10(180) (80%)/PMsf membrane 1647.99 3.1
Note: the above PMSF film is the inorganic support of the mixed matrix film.
As can be seen from the above table, the PVAm-CACl-10(180) (80%)/PMSF mixed matrix membrane of the present invention is paired with CH4/N2The selectivity of (A) is 3.1, and the separation performance of the catalyst on methane nitrogen is greatly improved compared with that of a pure inorganic support.
In conclusion, the invention provides a two-dimensional metal organic framework with strong base stability and application thereof. The preparation method adopts a solvothermal method, and has the advantages of strong stability, good crystallinity, high yield, simple preparation process and wide applicability. Is expected to become a metal-organic framework material for industrial application.
The above embodiments are merely to explain the technical solutions of the present invention in detail, and the present invention is not limited to the above embodiments, and it should be understood by those skilled in the art that all modifications and substitutions based on the above principles and spirit of the present invention should be within the protection scope of the present invention.

Claims (9)

1. A two-dimensional metal-organic framework material, characterized by: the preparation method of the two-dimensional metal-organic framework material comprises the following steps:
preparing a 4-chloro-isophthalic acid solution of N, N-dimethylformamide with the concentration of 1mol/L, dissolving the 4-chloro-isophthalic acid in the N, N-dimethylformamide and uniformly stirring;
step two, preparing an aluminum nitrate solution with the concentration of 1mol/L, dissolving the aluminum nitrate in deionized water and stirring uniformly;
step three, placing the mixture of the light yellow 4-chloro-isophthalic acid solution of N, N-dimethylformamide and the aluminum nitrate solution obtained in the step one and the step two in a vacuum oven for heating reaction for 12 hours to obtain white crystal precipitate;
step four, washing and centrifuging the white crystal precipitate obtained in the step three for 1 day by using N, N-dimethylformamide; washing and centrifuging for 1 day by using deionized water; finally washing and centrifuging for three times by using methanol;
step five, then putting the mixture into a vacuum oven to dry for 5 hours at the temperature of 80 ℃ to finally obtain a product; by adopting the steps and utilizing a solvothermal synthesis method, the Al-based metal-organic framework which has good crystallinity and high purity and takes 4-chloro-isophthalic acid as a ligand is obtained.
2. A metal-organic framework material according to claim 1, wherein: the preparation method of the metal-organic framework material comprises the following steps:
in the first step, the volume of the solution of the N, N-dimethylformamide-chloroisophthalic acid is 1 mL;
in the second step, the volume of the aluminum nitrate solution is 1 mL;
the dosage of the 4-chloro-isophthalic acid and the aluminum nitrate in the third step is as follows according to the mol ratio of the 4-chloro-isophthalic acid: aluminum nitrate was 1: 1.
3. a metal-organic framework material according to claim 2, wherein:
when the mixture is heated to 130 ℃ in a vacuum oven, the reaction is carried out to obtain a product CACl-10(130);
when the mixture is heated to 140 ℃ in a vacuum oven, the reaction is carried out to obtain a product CACl-10(140);
when heated to 180 ℃ in a vacuum oven, the reaction gives the product CACl-10 (180).
4. A method for testing the stability of strong bases of metal-organic framework material according to claim 3, characterized in that: the test method comprises the following steps:
step one, preparing a sodium hydroxide solution with the concentration of pH =14, pH =13 and pH = 12; the above dosage is based on the mass ratio of sodium hydroxide, pH =14 sodium hydroxide solution: pH =13 sodium hydroxide solution: pH =12 sodium hydroxide solution 100:10: 1;
secondly, testing the alkaline stability of the metal-organic framework material; taking out a certain volume of sodium hydroxide solution in the step I, adding a small amount of CACl-10(130), CACl-10(140) and CACl-10(180) powder, and soaking for 24 hours, wherein the volume of the sodium hydroxide solution is 5-6 mL;
step three, the CACl-10(130), the CACl-10(140) and the CACl-10(180) soaked in the strong alkali solution in the step two are taken out to be washed and centrifuged for 3 to 4 times by deionized water;
step four, then putting the mixture into a vacuum oven to dry for 5 hours at the temperature of 60 ℃ to obtain white crystals; by the above method, the alkaline stability of CACl-10(130), CACl-10(140) and CACl-10(180) can be determined, i.e. CACl-10(180) can be stably present in pH =14 sodium hydroxide solution for 24h, CACl-10(140) is slowly dissolved in pH =14 sodium hydroxide solution, CACl-10(130) is instantly dissolved in pH =14 sodium hydroxide solution.
5. A mixed matrix membrane having the two-dimensional metal-organic framework material CACl-10(180) of claim 3, characterized in that: the raw materials used for preparing the mixed matrix membrane consist of organic polymers, metal organic framework materials and inorganic supporting bodies;
the organic polymer and the metal-organic framework material are used according to the following ratio of the organic polymer: the mass ratio of the metal organic framework material is 1: 2-5;
the organic polymer is polyvinylamine, and the structural formula of the polyvinylamine is as follows:
Figure RE-979622DEST_PATH_IMAGE001
wherein n is 300-1000;
the inorganic support is a porous support layer with high flux and high hydrophilicity prepared by coating PDMS and PVA on a PSf membrane in sequence, and the concentration of PDMS used in the coating process is 0.4 wt%, and the concentration of PVA is 0.025 wt%.
6. The hybrid matrix membrane with a two-dimensional metal-organic framework material according to claim 5, wherein:
the mixed matrix membrane has preferential adsorption of CH4Advantage is its CH4Has a permeability rate of 1647.99barrer, CH4/N2The selectivity of (A) was 3.1.
7. The hybrid matrix membrane with a two-dimensional metal-organic framework material according to claim 5, wherein:
in the preparation process of the metal organic framework in the mixed matrix membrane, the introduced ligand is 4-chloro-isophthalic acid, and the dosage of the ligand is as follows: the mass ratio of the 4-chloroisophthalic acid is 3.7: 2; the dosage of the organic polymer and the metal organic framework material in the mixed matrix membrane is as follows: the mass ratio of the organic polymer is 1:4, and the organic polymer is polyvinylamine.
8. A method for preparing a mixed matrix membrane having a two-dimensional metal-organic framework material according to claim 7, characterized by comprising the steps of:
step one, mixing a metal-organic framework material with an organic polymer solution with the mass percentage concentration of 0.5%, and ultrasonically stirring for 12 hours to obtain a uniformly mixed casting solution;
coating PDMS and PVA on a PSf membrane in sequence to prepare a porous support layer with high flux and high hydrophilicity, namely an MPSf support layer;
and step three, coating the membrane casting solution on an MPSf supporting layer by using a scraper with the thickness of 300 microns, and drying for 3-4 hours in a constant temperature and humidity box with the temperature of 30 ℃ and the RH of 40% to obtain a mixed matrix membrane with the thickness of 1 micron.
9. The method for preparing a mixed matrix membrane with a two-dimensional metal-organic framework material according to claim 7, comprising the steps of:
controlling the ultrasonic frequency to be 40kHz in the ultrasonic mixing process in the first step, carrying out ultrasonic treatment for 10min, and then controlling the rotating speed to be 200r/min for stirring for 12 h;
in the second step, the concentration of PDMS used in the coating process is 0.4 wt%, and the concentration of PVA used in the coating process is 0.025 wt%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160361702A1 (en) * 2015-06-09 2016-12-15 The Regents Of The University Of California Polymer-metal organic framework materials and methods of using the same
CN109734957A (en) * 2019-01-04 2019-05-10 北京化工大学 A kind of preparation method of modified metal organic framework material and its material obtained
CN113150304A (en) * 2021-04-24 2021-07-23 天津工业大学 Mixed body metal-organic framework material and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160361702A1 (en) * 2015-06-09 2016-12-15 The Regents Of The University Of California Polymer-metal organic framework materials and methods of using the same
CN109734957A (en) * 2019-01-04 2019-05-10 北京化工大学 A kind of preparation method of modified metal organic framework material and its material obtained
CN113150304A (en) * 2021-04-24 2021-07-23 天津工业大学 Mixed body metal-organic framework material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LU GUAN 等: "Transforming 3D CAU-10-H into 2D Materials with High Base Stability for Membrane Separation", 《CHEMISTRY - AN ASIAN JOURNAL》 *

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