CN112316911B - Dual-functional metal organic framework membrane material and preparation method and application thereof - Google Patents

Dual-functional metal organic framework membrane material and preparation method and application thereof Download PDF

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CN112316911B
CN112316911B CN202011174851.XA CN202011174851A CN112316911B CN 112316911 B CN112316911 B CN 112316911B CN 202011174851 A CN202011174851 A CN 202011174851A CN 112316911 B CN112316911 B CN 112316911B
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organic framework
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metal
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CN112316911A (en
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马继平
李爽
李义华
周乾
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Guangda Institute Of Environmental Technology Qingdao Co ltd
Qingdao University of Technology
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Qingdao University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Abstract

The invention relates to a bifunctional metal organic framework membrane material and a preparation method and application thereof, belonging to the field of metal organic framework materials, wherein two functional organic ligands (tetrafluoroterephthalic acid and isonicotinic acid N-oxide) with carboxyl structures and metal zirconium are prepared into an F-functionalized positively charged metal organic framework material F-TMU-66+Then the granular F-TMU-66 is put into+Prepared with polyvinylidene fluoride to F-TMU-66+And (3) a membrane. On one hand, the material has F in a frame structure, and forms a stronger F-F acting force with a compound containing F, so that the problem of poor adsorption of a strong polar compound by the MOF is solved; on the other hand, the framework of the MOF has a positively charged structure, so that the limitation of the traditional MOF neutral framework is broken, and the application of the MOF neutral framework to the adsorption of anionic pollutants is expanded. More particularly, F-TMU-66 for film formation+The material not only keeps the high-efficiency selective adsorption of the metal organic framework material, but also is convenient to separate from the aqueous solution, and has good application prospect for removing and enriching the strong-polarity anionic pollutants in water.

Description

Dual-functional metal organic framework membrane material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal organic framework materials, and relates to a preparation method of a dual-functional metal organic framework membrane material.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Metal-organic frameworks (MOFs), abbreviated as MOFs, are a class of organic-inorganic hybrid nanoporous materials, which are currently one of the research hotspots and frontiers in the field of new materials. The metal-organic framework material is a three-dimensional network structure crystal formed by coordination bonding of aromatic acid or alkali of polydentate organic ligand containing nitrogen and oxygen and an inorganic metal center. The MOFs material combines an inorganic component and an organic component, so that compared with the traditional porous material, the MOFs material has many advantages, such as multiple types, strong functions, large porosity and specific surface area, strong pore size controllability and certain biocompatibility. Common classes of MOFs are the IRMOF series, ZIF series, MIL series, and UiO series. Among them, the UiO series is widely noticed because of its large specific surface area, good thermal stability and chemical stability. A typical UiO series MOFs-UiO-66 is a MOFs material with metal Zr as the metal center, and is composed of inorganic metal unit Zr6O4(OH)4Coordination with the carboxyl oxygen in the ligand forms both tetrahedral and octahedral types of pore cages. The special spatial configuration has great application prospect in various fields, particularly in the field of adsorption of pollutants in water.
However, when the solid particles of the MOFs are dispersed in water, solid-liquid separation is difficult, which limits the application of the MOFs in water pollutant adsorption. In order to solve the problem, the granular MOFs material is prepared into a film, so that the high-efficiency selective adsorption of the MOFs is reserved, and the time for separating the MOFs from the water phase is greatly shortened. The preparation method of the MOFs film mainly comprises an in-situ growth method, a seed crystal method and a mixed matrix method. The mixed matrix method is to embed the MOFs crystal particles into a polymer substrate containing polysulfone, polytetrafluoroethylene, polyvinylidene fluoride and the like. The preparation method of the MOFs membrane not only reserves the porous structure, high specific surface area and selectivity of the MOFs, but also has higher permeability and mechanical strength.
Because the mutual combination of the charged metal center and the organic ligand of the MOFs material presents electric neutrality, the selective adsorbability of the MOFs material to the strong polar ionic compound is greatly limited, and the application development of the MOFs material to the strong polar ionic compound in a water environment is hindered. Functional metal organic framework materials are novel MOFs materials reported in recent years, and are expected to solve the problem, but the preparation and application research of the functional metal organic framework materials are still in the initial stage.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and seeks to design a preparation method of a bifunctional metal-organic framework membrane material, wherein the preparation method prepares a metal-organic framework membrane material into a membrane, and simultaneously functionalizes MOFs to enable the MOFs to simultaneously have F atoms and anion exchange groups.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, a method for preparing a bifunctional metal-organic framework membrane material is provided, which comprises:
tetrafluoroterephthalic acid and isonicotinic acid N-oxide are taken as ligands to be self-assembled with metal salt to form F functional positively charged metal organic framework material F-TMU-66+；
With F-TMU-66+PVDF (polyvinylidene fluoride) is taken as a matrix, and a mixed matrix membrane method is adopted on a polypropylene plate to prepare F-TMU-66+Mixing the matrix film;
subjecting said F-TMU-66 to+The mixed matrix membrane is impregnated in acid to form F-TMU-66 with ion exchange groups+·Cl-And mixing the matrix membrane, and washing to be neutral to obtain the dual-functional metal organic framework membrane material.
The invention carries out functional treatment on the traditional MOFs material, so that the material has a group for adsorbing strong polar ionic compounds, thereby efficiently, quickly and specifically adsorbing pollutants.
In a second aspect of the invention, there is provided a bifunctional metal-organic framework membrane material prepared by any of the above-described methods.
The bifunctional metal organic framework membrane material has the advantages that: on the one hand, the framework structure has F atoms, and forms stronger F-F acting force with F-containing compoundsThe problem of poor adsorption of strong polar compounds by the MOF is solved; on the other hand, the framework of the MOF has a positively charged structure, so that the limitation of the traditional MOF neutral framework is broken, and the application of the MOF neutral framework to the adsorption of anionic pollutants in the environment is expanded. More particularly, F-TMU-66 for film formation+The material not only keeps the high-efficiency selective adsorption of the metal organic framework material, but also is convenient to separate from the aqueous solution, and has good application prospect for removing and enriching the strong-polarity anionic pollutants in water.
In a third aspect of the invention, the application of the above bifunctional metal-organic framework membrane material in adsorption/enrichment, analysis/detection of perfluorinated compounds is provided.
The bifunctional metal organic framework membrane material has high-efficiency selective adsorption and is convenient to separate from an aqueous solution, so that the bifunctional metal organic framework membrane material is expected to be widely applied to sewage treatment.
The invention has the beneficial effects that:
(1) on one hand, the material has F atoms in a frame structure, and forms a strong F-F acting force with a compound containing F, so that the problem of poor adsorption of a strong polar compound by the MOF is solved; on the other hand, the framework of the MOF has a positively charged structure, so that the limitation of the traditional MOF neutral framework is broken, and the application of the MOF neutral framework to the adsorption of anionic pollutants in the environment is expanded.
(2) F-TMU-66 film-formed by the invention+The material not only keeps the high-efficiency selective adsorption of the metal organic framework material, but also is convenient to separate from the aqueous solution, and has good application prospect for removing and enriching the strong-polarity anionic pollutants in water.
(3) The preparation method is simple, convenient to operate, high in practicability and easy to popularize.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a Scanning Electron Microscope (SEM) image according to example 1 of the present invention, wherein FIGS. 1A and 1B,FIG. 1B shows a granular type of bifunctional F-TMU-66+FIG. 1C and FIG. 1D show a bifunctional F-TMU-66+The matrix membrane was mixed.
FIG. 2 is an infrared spectrum (A: F-TMU-66) according to example 1 of the present invention+Mixed matrix membrane, B: F-TMU-66+C, C: pure polyvinylidene fluoride membranes).
FIG. 3 is an X-ray diffraction chart (A: F-TMU-66) according to example 1 of the present invention+，B： F-TMU-66+Mixed matrix membranes).
FIG. 4 shows a bifunctional F-TMU-66 of example 3 of the present invention+·Cl-The mixed matrix membrane detects the chromatogram of the perfluorinated compound.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
A preparation method of a bifunctional metal organic framework membrane material specifically comprises the following steps:
the method comprises the following steps: preparation of F-functionalized positively charged metal organic framework material F-TMU-66+：
(1) Dissolving tetrafluoroterephthalic acid, isonicotinic acid N-oxide and zirconium tetrachloride in N, N-Dimethylformamide (DMF) solution together, and fully stirring for dissolving;
(2) reacting the mixture prepared in the step (1) in a solvent thermal reaction kettle at the temperature of 100 ℃ and 150 ℃ for 20-28 h;
(3) heating the solventCooling the reaction kettle to room temperature, washing the product with DMF and acetone for 4 times, and drying in an oven at 120 ℃ for 24 hours to obtain the F functional positively charged metal organic framework material F-TMU-66+Standby;
step two: preparation of F-TMU-66+Mixed matrix membranes
(1) The prepared F-TMU-66+Dispersing in acetone, ultrasonic dispersing for 5-15min, dissolving polyvinylidene fluoride (PVDF) in DMF, adding the solution of PVDF in DMF to F-TMU-66+Ultrasonic and fully mixing for 5-15 min;
(2) volatilizing acetone from the mixed solution prepared in the step (1) by adopting a rotary evaporation method, and spreading the rest mixed solution on a polypropylene plate drop by drop; heating polypropylene in an oven at 50-80 deg.C to volatilize solvent to obtain F-TMU-66+The matrix membrane was mixed.
Step three: preparation of ion-exchanged F-TMU-66+·Cl-Mixed matrix membranes
(1)F-TMU-66+The membrane is placed in hydrochloric acid solution and soaked for 10 to 15 hours to form F-TMU-66 with ion exchange groups+·Cl-The matrix membrane was mixed.
(2) F-TMU-66+·Cl-The mixed matrix membrane is washed by ultrapure water for a plurality of times until the washing liquid is neutral.
In some embodiments, there are two functional organic ligands with carboxyl structures, tetrafluoroterephthalic acid and isonicotinic acid N-oxide. In addition to both having a carboxyl functional group for linking to the metal center, the two ligands have different chemical functional groups, respectively, forming an organic ligand containing an F atom and an organic ligand containing a pyridyl group. The MOF material prepared by the method has the advantages of dual functions of F formation and positive charge and electrification.
In some embodiments, the coordinating metal is zirconium and the particle size of the MOF particles is 300-400 nm. The granular bifunctional metal organic framework material is prepared into a film by adopting a mixed matrix membrane method, so that the aim of quickly separating the granular bifunctional metal organic framework material from a water sample is fulfilled.
In some embodiments, zirconium tetrachloride is combined with tetrafluoroterephthalic acid and isonicotinic acidThe mol ratio of the N-oxide is 1 (5-12) to (1-3) to form the F-functional positively charged metal organic framework material F-TMU-66 through self-assembly+And the ligand and the metal zirconium are reacted completely, so that the utilization rate of raw materials is improved.
In some embodiments, F-TMU-66+The mass ratio of the PVDF to the mixture is (1-3) to (3-5) to form F-TMU-66+And the mixed matrix membrane is convenient for subsequent loading of anion exchange groups.
In some embodiments, the concentration of PVDF/is 1% -5%, which allows the PVDF to be dispersed in DMF sufficiently to facilitate the dispersion of PVDF with F-TMU-66+And (3) mixing.
The bifunctional metal organic framework membrane material is applied to enrichment analysis of perfluorinated compounds in water.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1:
the preparation method of the bifunctional metal organic framework membrane material comprises the following steps:
the method comprises the following steps: preparation of F-functionalized positively charged metal organic framework material F-TMU-66+：
(1) Dissolving 1.39g of tetrafluoroterephthalic acid, 0.278g of isonicotinic acid N-oxide and 0.24g of zirconium tetrachloride in N, N-Dimethylformamide (DMF) solution, and fully stirring for dissolving;
(2) reacting the mixture prepared in the step (1) in a solvothermal reaction kettle at 120 ℃ for 24 hours;
(3) cooling the solvothermal reaction kettle to room temperature, washing the product with DMF and acetone for 4 times, and drying in an oven at 120 ℃ for 24 hours to obtain the F functionalized positively charged metal organic framework material F-TMU-66+Standby;
step two: preparation of F-TMU-66+Mixed matrix membranes
(1) The prepared F-TMU-66+Dispersing in acetone (mass concentration of 0.6%), ultrasonic dispersing for 10min, dissolving polyvinylidene fluoride (PVDF) in DMF, and dissolving PVDF in DMF solution(the mass concentration is 5.3 percent) is added with F-TMU-66+In the acetone solution, fully mixing for 10min by ultrasonic wave, and performing F-TMU-66+The mass ratio of the PVDF to the PVDF is 3: 10;
(2) volatilizing acetone from the mixed solution prepared in the step (1) by adopting a rotary evaporation method, and spreading the rest mixed solution on a polypropylene plate drop by drop; heating polypropylene in 70 deg.C oven to volatilize solvent to obtain F-TMU-66+The matrix membrane was mixed.
Step three: preparation of ion-exchanged F-TMU-66+·Cl-Mixed matrix membranes
(1)F-TMU-66+The membrane is placed in hydrochloric acid solution (the concentration is 0.1mol/L) and soaked for 12 hours, so that F-TMU-66 with ion exchange groups is formed+·Cl-The matrix membrane was mixed.
(2) F-TMU-66+·Cl-The mixed matrix membrane is washed by ultrapure water for a plurality of times until the washing liquid is neutral.
The F-TMU-66 prepared in example 1 of the present invention was analyzed by scanning electron micrographs, X-ray diffraction patterns, and infrared spectrograms+And analyzing and explaining the morphological and structural characteristics of the mixed matrix membrane.
First, feature characterization
FIG. 1 is a Scanning Electron Microscope (SEM) image of a membrane material prepared by the present invention, wherein FIGS. 1A and 1B are granular bifunctional F-TMU-66+FIG. 1C and FIG. 1D show a bifunctional F-TMU-66+·Cl-The matrix membrane was mixed. The bifunctional type MOF crystals with a spherical structure can be seen to have a diameter of about 300-400 nm. In FIG. 1C and FIG. 1D, the bifunctional F-TMU-66+·Cl-The configuration of the MOF crystals in the mixed matrix membrane did not change significantly, indicating that the process of preparing the mixed matrix membrane did not affect the framework structure of the MOF.
Second, infrared spectroscopic analysis
FIG. 2 shows F-TMU-66+·Cl-Infrared spectrum of mixed matrix membrane (A: F-TMU-66)+·Cl-Mixed matrix membrane, B: F-TMU-66+C, C: pure polyvinylidene fluoride membranes). Wherein 1180cm in the curve B and the curve C-1The absorption peak of (A) is due to F-TMU-66+And the presence of C-F bonds in the polyvinylidene fluoride structure. And F-TMU-66+·Cl-The C-F bonds in the structure of the membrane overlap, resulting in 1180cm in Curve A-1The absorption peak of (A) is significantly enhanced, which indicates that the synthesis of bifunctional MOFs has been successful. 1250cm in the curve A and the curve B-1The absorption peak of (a) was due to stretching vibrations of the N-O bond in the functional ligand isonicotinic acid N-oxide, indicating that the functional ligand isonicotinic acid N-oxide has been successfully incorporated into the MOF structure. The above results show that two functional ligands were successfully used for F-TMU-66+·Cl-In the preparation of mixed matrix membranes.
Second, XRD analysis
FIG. 3 is an X-ray diffraction chart (A: F-TMU-66)+，B： F-TMU-66+·Cl-Mixed matrix membrane) at 2 θ of 7.4, and a peak of 20.2 ° is F-TMU-66+Characteristic peak of series, F-TMU-66+·Cl-Mixing matrix membranes with F-TMU-66+The presence of these absorption peaks indicates that the process of mixed matrix membrane preparation has no impact on the crystal structure of the MOF.
In conclusion, the bifunctional F-TMU-66 with F atom and anion exchange group+·Cl-Mixed matrix membrane materials have been successfully prepared.
Example 2:
15mg of F-TMU-66 obtained in example 1+·Cl-The mixed matrix membrane material is used for adsorbing and enriching 15 perfluorinated compounds in water, the standard concentration is 25ng/L, the adsorption time is 30min, 6mL of 2% methanol ammonia water solution is adopted for elution, the elution time is 30min, the eluent is dried by nitrogen and then redissolved, detection is carried out through UPLC-MS/MS, the recovery rate of the 15 perfluorinated compounds (1. perfluorobutyric acid, 2. perfluorovaleric acid, 3. perfluorobutanesulfonic acid, 4. perfluorohexanoic acid, 5. perfluoroheptanoic acid, 6. perfluorohexanesulfonic acid, 7. perfluorooctanoic acid, 8. perfluorononanoic acid, 9. perfluorooctanesulfonic acid, 10. perfluorodecanoic acid, 11. perfluoroundecanoic acid, 12. perfluorodecanesulfonic acid, 13. perfluorododecanoic acid, 14. perfluorotridecanoic acid and 15. perfluorotetradecanoic acid) is between 62 and 118%, and the chromatogram is shown in FIG. 4.
Example 3
The difference from example 1 is that: in the step one (2), the mixture reacts for 28 hours in a solvent thermal reaction kettle at the temperature of 100 ℃.
Example 4
The difference from example 1 is that: in the step one (2), the mixture reacts for 20 hours in a solvent thermal reaction kettle at the temperature of 150 ℃.
Example 5
The difference from example 1 is that: step two: preparation of F-TMU-66+Mixed matrix membranes
(1) The prepared F-TMU-66+Dispersing in acetone, ultrasonic dispersing for 5min, dissolving polyvinylidene fluoride (PVDF) in DMF, adding the DMF solution containing PVDF into F-TMU-66+Fully mixing the solution in the acetone solution for 5min by ultrasonic;
(2) volatilizing acetone from the mixed solution prepared in the step (1) by adopting a rotary evaporation method, and spreading the rest mixed solution on a polypropylene plate drop by drop; heating polypropylene in 50 deg.C oven to volatilize solvent to obtain F-TMU-66+The matrix membrane was mixed.
Example 6
The difference from example 1 is that: step two: preparation of F-TMU-66+Mixed matrix membranes
(1) The prepared F-TMU-66+Dispersing in acetone, ultrasonic dispersing for 15min, dissolving polyvinylidene fluoride (PVDF) in DMF, adding the DMF solution containing PVDF to F-TMU-66+Ultrasonic and fully mixing for 5-15 min;
(2) volatilizing acetone from the mixed solution prepared in the step (1) by adopting a rotary evaporation method, and spreading the rest mixed solution on a polypropylene plate drop by drop; heating polypropylene in an oven at 80 deg.C to volatilize the solvent to obtain F-TMU-66+The matrix membrane was mixed.
Example 7
The difference from example 1 is that: and step three (1), soaking for 10 hours.
Example 8
The difference from example 1 is that: and step three (1), soaking for 15 hours.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (9)

1. A preparation method of a bifunctional metal organic framework membrane material is characterized by comprising the following steps:
tetrafluoroterephthalic acid and isonicotinic acid N-oxide are taken as ligands to be self-assembled with metal salt to form F functional positively charged metal organic framework material F-TMU-66+；
With F-TMU-66+PVDF (polyvinylidene fluoride) is taken as a matrix, and a mixed matrix membrane method is adopted on a polypropylene plate to prepare F-TMU-66+Mixing the matrix film;
subjecting said F-TMU-66 to+The mixed matrix membrane is impregnated in acid to form F-TMU-66 with ion exchange groups+·Cl-Mixing the matrix membrane, and washing to be neutral to obtain the dual-functional metal organic framework membrane material;
the metal salt is a zirconium salt.
2. The method for preparing a bifunctional metal-organic framework membrane material according to claim 1, wherein the molar ratio of the zirconium salt to tetrafluoroterephthalic acid and isonicotinic acid N-oxide is 1:5-12: 1-3.
3. The method for preparing a bifunctional metal-organic framework membrane material of claim 1, wherein the F-TMU-66 is prepared by a method comprising a step of preparing a solution of the F-TMU-66, and a step of preparing a solution of the F-TMU-66+The particle size of (D) is 300-400 nm.
4. The method for preparing a bifunctional metal-organic framework membrane material of claim 1, wherein the F-TMU-66 is prepared by a method comprising a step of preparing a solution of the F-TMU-66, and a step of preparing a solution of the F-TMU-66+The mass ratio of the PVDF to the PVDF is 1-3: 3-5.
5. The method for preparing a bifunctional metal-organic framework membrane material as claimed in claim 1, wherein the self-assembly is performed by solvothermal synthesis under the conditions of 100-150 ℃ for 20-28 h.
6. The method for preparing a bifunctional metal-organic framework membrane material of claim 1, wherein the F-TMU-66 is prepared by a method comprising a step of preparing a solution of the F-TMU-66, and a step of preparing a solution of the F-TMU-66+Dispersing in acetone, dissolving PVDF in DMF, adding the solution of PVDF in DMF to F-TMU-66+And fully mixing the solution with the acetone solution for 5 to 15min by ultrasonic to obtain a mixed solution.
7. The method for preparing a bifunctional metal-organic framework membrane material of claim 6, wherein the concentration of the PVDF/DMF solution is 1% -5%.
8. A bifunctional metal-organic framework membrane material prepared by the method of any one of claims 1-7.
9. Use of the bifunctional metal-organic framework membrane material of claim 8 for adsorption/enrichment, analysis/detection of perfluorinated compounds.
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