CN116059839A - Preparation method of flexible electrospun fiber supported metal organic framework film - Google Patents
Preparation method of flexible electrospun fiber supported metal organic framework film Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the field of gas membrane separation, and provides a preparation method of a flexible electrospun fiber supported metal organic framework membrane. The electrostatic spinning technology is utilized to realize seed implantation and provide sufficient MOFs growth nucleation sites. The method combines a one-step method strategy to realize the heteroepitaxial growth of the seed crystal, and the electrospun nanofiber is used as a substrate material to prepare the metal organic frame film. MOFs grow tightly throughout the fiber, balancing basal flexibility with MOFs rigidity. MOF modulation using a mixed ligand strategy "one-step" method S Thereby modulating MOF S The prepared MOFs polycrystalline film is used for efficiently and selectively sieving gas molecules by virtue of the pore size special for MOFs and the pore size of Kong Long. In comparison with the prior artMOF prepared on AAO or like substrates S The membrane is easy to amplify, has lower cost, simple preparation process and good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of gas membrane separation, and mainly discloses a method for realizing seed crystal embedded cloth by utilizing an electrostatic spinning technology, simultaneously utilizing electrospun nanofibers as a flexible support substrate, combining a one-step strategy to design a metal organic frame membrane which is easy to amplify and has no defects, and utilizing a specific window size of a metal organic frame to realize efficient screening of gas molecules.
Background
At present, the gas separation has great application prospect in aspects of human production, living and the like. The membrane separation method is an indispensable core technology in energy and chemical systems, can effectively improve the conversion efficiency in the gas separation process and reduce the emission of pollutants. The membrane separation method has remarkable advantages compared with other traditional separation methods such as pressure swing adsorption, cryogenic separation and the like, and is particularly characterized in that the membrane separation method has the advantages of simple operation process, energy conservation, high efficiency, low energy consumption, easy coupling with other processes and the like.
The gas membrane separation technology mainly utilizes the mass transfer rate difference of gas micromolecules in a membrane to realize separation, and the core component is a membrane material with high permeability and high selectivity. Conventional gas separation membranes can be divided into three general categories: polymer films, inorganic films, and hybrid films. Polymeric films are currently the main type of commercial film with easy processability, excellent mechanical strength, good reproducibility and low cost. Common materials are Polyimides (PI), polysulfones (PSF), polycarbonates (PC), cellulose Acetates (CA), and the like. However, conventional polymer membrane materials cannot break through the "trade-off" limitation, and the permeability and selectivity cannot be compromised. The inorganic membrane has high separation performance and good stability, and can be applied under severe conditions such as high temperature, high pressure and the like. Inorganic membrane materials include ceramic, glass, metal and molecular sieve membranes, and metal ionsOr Metal Organic Frameworks (MOFs) formed by bridging clusters with organic ligands S ) A polycrystalline film. The inorganic membrane has brittle texture, a good supporting substrate is needed in the preparation process, the cost is high, the preparation conditions are complex, and the membrane material with large area, stability and good separation performance is difficult to prepare. Hybrid membranes are novel membrane materials that researchers integrate both polymer and inorganic membrane types, combining the properties of both inorganic materials and polymer matrices: the inorganic filler provides additional gas adsorption sites and preferential diffusion paths, enhancing the permeation of the polymer film material.
The MOFs polycrystalline film has the characteristics of regular pore structure, high surface area, modifiable property and the like, so that the MOFs polycrystalline film has high-efficiency gas separation performance. The Beijing university of industry Xie Yabo et al prepared a metal organic framework membrane application gas separation (CN201510444805. X), belonging to the technical field of membrane separation. Use of porous metallic nickel as MOF S The film growth substrate is subjected to a series of treatments such as dipping high temperature and the like to modify the cobaltosic oxide nanowire, and then organic ligand and metal ions are subjected to solvothermal reaction to grow MOF (metal oxide film) on the nanowire-modified nickel substrate through coordination S Continuous compact polycrystalline film capable of high-efficiency H 2 /CO 2 And (5) separating. The invention provides a novel preparation method of a metal organic framework membrane, which has simple process, and the MOFS membrane prepared by the method can be used for gas separation. Most MOFs today S Polycrystalline films are based on hard substrates such as alpha-alumina (AAO), porous metallic nickel, etc., and the benefit of using a hard substrate is that it is possible to balance the substrate with the MOF as much as possible S Rigidity difference between polycrystalline films, convenient operation and easy preparation of ultrathin and stable MOF S A polycrystalline film. But this results in MOF S The film manufacturing cost is greatly increased, and industrial scale-up is difficult due to the limitation of the substrate.
Preparation of MOFs that are easily scalable, low cost S Films are highly desirable and this can be well addressed by using polymeric substrates as the substrate. Preparation of continuous defect-free MOFs directly on polymeric substrates S The surface functionalization and seed pre-implantation of the support are the support surfaces, since the layers are very difficultDirect nucleation and growth MOF S Two main methods of layering. Seed epitaxial growth is a process in which a seed layer is introduced onto the surface of a support by some physical means, followed by a secondary growth to form a dense MOF S A method of forming a film. With the help of seeds, the nucleation bottleneck in the film preparation process is overcome, and the difficulty of heterogeneous nucleation is greatly reduced. The electrostatic spinning is an assembly process from top to bottom, has the advantages of continuous fiber, adjustable thickness, easy amplification, good mechanical strength and the like, has large fiber gap and has good air permeability. Therefore, the electrostatic spinning has the potential of realizing the pre-embedding of the seed crystals and ensuring the quantity and distribution of the seed crystals.
Therefore, we propose to use the electrostatic spinning technology to realize seed implantation, and combine the one-step strategy to realize the heteroepitaxial growth of the seed, so as to construct the metal organic frame film with the electrospun nanofiber as the flexible substrate material. Spinning polymer precursor solutions and MOFs S The seed crystal is blended for electrostatic spinning, and the high-density fiber structure can ensure the number and distribution of the seed crystal, thereby being beneficial to the nucleation growth of the subsequent crystal film. The excellent mechanical properties of electrospun fibers provide skeletal support for the crystalline film, MOF S MOF through fiber growth S Tightly fixed, balancing substrate flexibility with MOF S Is a rigid part of the steel sheet. Meanwhile, the electrospun fiber support template can be freely regulated and amplified according to experimental design, so that the MOF easy to amplify and low in cost is prepared S A polycrystalline film. Electrospun fibrous substrates can be grown into different types of MOFs via solvothermal reaction "one-shot" processes S Polycrystalline membranes, combined with mixed ligands, and the like, can be used for MOF S The pore diameter structure and the physical and chemical environment are properly regulated so as to achieve the selective screening of target gas and MOF S The macroporous structure has good gas permeation rate. In conclusion, the flexible electrospun fiber supporting metal-organic framework film has good industrial application prospect.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art metal-organic frame film, an object of the present invention is to design a metal-organic frame film supported by flexible electrospun fibers, which is buried by electrospun fibersSeed and act as MOF S Flexible framework support for membrane growth, construction of defect-free MOFs polycrystalline membranes, and utilization of MOFs S The porous structure of the (2) is used for efficiently selecting and sieving target gas molecules.
The invention designs a flexible electrospun fiber self-supporting metal organic frame membrane, which comprises a substrate supporting material, namely a certain amount of nanofiber mats. MOF synthesis using solvothermal S The material is used as seed crystal and doped into spinning solution, and is superposed and electrospun on the substrate supporting material to obtain doped MOF S The nanofiber mat of the seed crystals was then subjected to a vacuum drying process to completely remove the solvent. Fiber voids were reduced by flat plate hot pressing and placed vertically in MOF S In the precursor growth solution, the growth proportion of metal salt and ligand is regulated and controlled, and MOF is grown by controlling the reaction time through solvothermal reaction S Polycrystalline membranes, equilibrated MOFs under suitable reaction conditions S Nucleation and growth, and reduction of grain boundary defects. Slowly cooling to take out membrane material and cleaning MOF deposited on surface S And (3) particles. Electrospun fibers as a base material can improve MOF to some extent S Mechanical strength of the film. MOFs prepared using this method S The membrane has excellent gas sieving performance and MOF S The pore structure of (2) provides a rapid path for the transfer of gas molecules. Simultaneous MOF S The specific pore size can be selected to screen gas molecules, such as the pore size of ZIF-8 (0.34 nm) for CO 2 /N 2 The molecules are effectively screened, so that the gas selectivity of the membrane is improved. In growth of MOF S MOF can be regulated by combining mixed ligand strategy in one-step method in membrane process S Thereby modulating MOF S Pore size and pore cage size. Therefore, the constructed flexible electrospun fiber supported metal organic framework membrane can realize high-efficiency selective permeation of gas molecules, and MOF is regulated by controlling synthesis conditions S Permeability and selectivity of the membrane material. Compared with MOF prepared by AAO or other substrates S The membrane is easy to amplify, has lower cost, and has simple preparation process and good industrial application advantage.
The technical scheme of the invention is as follows:
a preparation method of a flexible electrospun fiber supported metal organic framework film comprises the following steps:
(1) Preparation of high density MOF by electrospinning technique S Seed nanofiber substrate
Construction of high density MOFs using superposition electrospinning S The nanofiber substrate of the seed crystal is combined with hot pressing operation to reduce the fiber gap; the specific operation is as follows:
preparing MOFs-free doped electrospinning solution A: adding the electrostatic spinning polymer into a spinning solvent, and stirring at normal temperature to completely dissolve the electrostatic spinning polymer to obtain an electrostatic spinning solution A;
preparing MOFs doped electrospinning solution B: MOF (Metal oxide film) of S Adding the particles and the electrostatic spinning polymer into a spinning solvent, stirring at normal temperature and carrying out water bath ultrasonic treatment to enable MOF S The particles are completely dispersed, the polymer is completely dissolved to obtain an electrospun solution B, and the MOF is controlled S The mass ratio of the particles to the polymer is 1:3-5;
preparation of doped MOFs S Nanofiber substrate of seed: the two spinning solutions after preparation are subjected to superposition electrospinning, and the electrospinning solution A is subjected to electrospinning to obtain an electrospun fiber support substrate (the receiving amount of the aluminum foil per unit area is 1 ml/dm) 2 ) Immediately replacing the electrospun solution B to be overlapped on the A after the electrospinning is finished to carry out electrospinning, and controlling the volume ratio of the electrospun solution A to the electrospun solution B to be 4:1 to obtain the nanocomposite fiber; vacuum drying the nano composite fiber to remove residual solvent, and hot-pressing to reduce fiber gaps to obtain doped MOF S A nanofiber substrate of seed crystals;
(2) The MOFs polycrystalline film with no defects and adjustable pore size is prepared by a one-step method, and is constructed by combining solvothermal reaction with a seed crystal epitaxial growth strategy;
the doped MOF obtained in the step (1) is subjected to S Cutting the nanofiber substrate of the seed crystal to a required size, fixing by using a Teflon bracket, and then vertically placing the nanofiber substrate in the prepared MOFs growth solution to ensure that the nanofiber substrate is completely immersed by the growth solution; regulating the temperature to 60-120 ℃ and the growth time to 1-3h; after the solution is cooled to room temperature, the solution is slowly taken out and washed by deionized water for 3-5 times followed by 3-5 washes with methanol to treat the surface deposited MOF S Particles; the resulting MOF is then subjected to S And placing the film sample in a low-temperature refrigerator to enable the sample to be completely frozen and firm, and then performing freeze drying to ensure that volatile solvents are removed, so as to obtain the flexible electrospun fiber-supported metal-organic framework film.
The spinning solvent is water, N-dimethylformamide, absolute methanol, absolute ethanol or dimethyl sulfoxide.
The MOF S The particles are ZIF-7, ZIF-8, ZIF-9, ZIF-67 and NH 2 -ZIF-8。
The electrostatic spinning polymer is poly [1- (trimethylsilyl) ] -propyne, polyacrylonitrile, polyvinylidene fluoride, polybenzimidazole, polyvinyl alcohol, polyetherimide, polyethylene oxide and polyamide.
The invention has the beneficial effects that: the flexible electrospun fiber self-supporting metal organic framework membrane prepared by the invention overcomes the conventional hard substrate MOF S The film has the disadvantages of difficult scale-up and low cost. Spinning polymer precursor solutions and MOFs using electrospun nanofibers as substrate support materials S The seed crystal is blended for electrostatic spinning, and the high-density fiber structure can ensure the number of the seed crystal and increase nucleation sites for crystal film growth. Excellent mechanical properties of electrospun fibers to improve film strength combined with MOF S Throughout fiber growth, with MOF S Tightly fixed, balancing substrate flexibility with MOF S Is a rigid part of the steel sheet. At the same time, the electrospun fiber can be amplified according to experimental design, thereby preparing the low-cost MOF S A polycrystalline film. Growth of different types of MOFs via solvothermal reaction "one-step" process S Polycrystalline film, MOF combined with various strategies such as mixed ligand S The pore diameter structure and the physical and chemical environment are properly regulated and controlled, so that the selective screening of target gas is achieved. The flexible electrospun fiber supported metal organic frame membrane has good industrial application prospect.
Drawings
FIG. 1 is an electron micrograph of a ZIF-8 seed doped nanofiber substrate of example 1.
FIG. 2 is the PAN/NH of example 1 2 -surface electron microscopy of ZIF-8.
FIG. 3 is PAN/NH according to example 1 2 -cross-sectional electron microscopy of ZIF-8.
FIG. 4 is a cross-sectional electron micrograph of PAN/ZIF-67 of example 2.
FIG. 5 is a sectional electron micrograph of PAN/ZIF-8 of example 3.
FIG. 6 is a cross-sectional electron micrograph of a ZIF-8 film of the comparative example.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and technical schemes.
Example 1:
preparing a nanofiber substrate doped with ZIF-8 seed crystals:
the electrospinning solution A was prepared by adding 2g of Polyacrylonitrile (PAN) to 20ml of N, N-Dimethylformamide (DMF) solvent, stirring for 24 hours and performing water bath ultrasonic treatment for 30 minutes to completely dissolve the solution to obtain the electrospinning solution A. Subsequently, an electrospinning solution B was prepared: 0.5g of ZIF-8 particles was added to 15ml of N, N-dimethylformamide solvent, stirred to dissolve completely and sonicated in a water bath for 30min to expel bubbles. Subsequently, 1.5g of polyacrylonitrile powder was added and stirred for 24 hours to complete a homogeneous solution to obtain an electrospun solution B. Electrospinning to prepare a ZIF-8 seed doped nanofiber substrate: 8mL of the electrospinning solution A solution was transferred to a 10mL disposable syringe, which was fixed on an electrospinning machine using a 23-gauge needle, and the aluminum foil-receiving fibers were wrapped on a receiver. The distance between the needle head and the receiver is adjusted to be 20cm, the injection speed is controlled to be 0.8mL/h, the rotating speed of the receiver is controlled to be 120r/h, the operating environment temperature is 25 ℃, the air humidity is 35%, the positive electrode voltage of the electrostatic spinning machine is set to be 17KV, and the negative electrode voltage is set to be-1.5 KV. Subsequently, 2ml of spinning solution B was transferred to a 10ml disposable syringe using a 19 gauge needle, spinning solution B was changed immediately after spinning solution a was completed, and the remaining electrospinning conditions were unchanged and the resulting nanofiber mat was vacuum dried at 60 ℃ for 6 hours to remove residual DMF solvent. FIG. 1 is an electron micrograph of a nanofiber substrate prepared with ZIF-8 seed crystals.
Preparation of PAN/NH 2 -ZIF-8 membrane: 2.57g Zn (NO) was weighed out 3 ) 2 ·6H 2 O is dissolved in 100m2.27g of 2-methylimidazole and 0.934g of 2-aminobenzimidazole were weighed out and dissolved in 100ml of absolute methanol, and then the two solutions were mixed and stirred uniformly to prepare MOF S Film growth solution. The ZIF-8 seed doped nanofiber substrate obtained by hot pressing was cut to 3cm by 3cm, vertically fixed on a Teflon stent, and then slowly immersed in MOF S In the growth liquid, the temperature is controlled to be 60 ℃ and the growth time is 2 hours. After the reaction is finished, the solution is naturally cooled to room temperature and is slowly taken out, and is washed by deionized water and methanol solution for 3 times, so as to ensure MOF deposited on the surface S The particles are removed. The PAN/NH obtained is then 2 Placing the ZIF-8 film sample in a low temperature refrigerator to freeze the sample completely, transferring to a freeze dryer for 12h to ensure volatile solvent removal to obtain PAN/NH 2 -ZIF-8 membrane. PAN/NH as shown in FIGS. 2 and 3, respectively 2 The surface electron microscope image and the section electron microscope image of the ZIF-8 can show that the crystal layer is compact and uniform and has no obvious defects.
Example 2:
preparing a nanofiber substrate doped with ZIF-67 seed crystals: first, preparing an electrospinning solution A: as in example 1. Then preparing an electrospinning solution B: 0.5g of ZIF-67 particles was added to 15ml of dimethyl sulfoxide solvent, stirred to dissolve completely and sonicated in a water bath for 30min to expel air bubbles. Subsequently, 1.5g of polyacrylonitrile powder was added and stirred for 24 hours to complete a homogeneous solution to obtain an electrospun solution B. Electrospinning to prepare a seed doped nanofiber substrate: as in example 1.
Preparation of PAN/ZIF-67 film: weigh 2.51g Co (NO) 3 ) 2 ·6H 2 O was dissolved in 100ml of absolute methanol, 2.8375g of 2-methylimidazole was weighed and dissolved in 100ml of absolute methanol, and then the two solutions were mixed into a large beaker and stirred uniformly to prepare MOF S Film growth solution. The ZIF-67 seed doped nanofiber substrate obtained by hot pressing was cut to 3cm by 3cm, vertically fixed on a Teflon stent, and then slowly immersed in MOF S In the growth liquid, the temperature is controlled to be 60 ℃ and the growth time is 2 hours. And after the reaction is finished, naturally cooling the solution to room temperature, slowly taking out, and cleaning with deionized water and methanol solution for 3 times to ensure that deposited particles on the surface are removed. Will thenAnd placing the obtained PAN/ZIF-67 film sample in a low-temperature refrigerator to enable the sample to be completely frozen, and transferring the sample into a freeze dryer for 12 hours to ensure that volatile solvents are removed, so as to obtain the PAN/ZIF-67 film. FIG. 4 is a cross-sectional electron microscope image of PAN/ZIF-67.
Example 3:
preparing a nanofiber substrate doped with ZIF-8 seed crystals: as in example 1.
Preparation of PAN/ZIF-8 film: 2.57g Zn (NO) was weighed out 3 ) 2 ·6H 2 O was dissolved in 100ml of absolute methanol, 2.8375g of 2-methylimidazole was weighed and dissolved in 100ml of absolute methanol, and then the two solutions were mixed and stirred uniformly to prepare MOF S Film growth solution. The ZIF-8 seed doped nanofiber substrate obtained by hot pressing was cut to 3cm by 3cm, vertically fixed on a Teflon stent, and then slowly immersed in MOF S In the growth liquid, the temperature is controlled to be 60 ℃ and the growth time is 2 hours. And after the reaction is finished, naturally cooling the solution to room temperature, slowly taking out, and cleaning with deionized water and methanol solution for 3 times to ensure that deposited particles on the surface are removed. And then placing the obtained PAN/ZIF-8 film sample in a low-temperature refrigerator to enable the sample to be completely frozen, and transferring the sample into a freeze dryer for 12 hours to ensure that volatile solvents are removed, so as to obtain the PAN/ZIF-8 film. FIG. 5 is a cross-sectional electron microscope image of PAN/ZIF-8.
Comparative example:
comparative reference was made without superposition electrospinning to make ZIF-8@pan film: directly electrospinning 10ml ZIF-8@PAN nanofiber mats, and carrying out hot pressing treatment to reduce fiber gaps. MOF growth was then performed to prepare ZI F-8 membranes. As shown in FIG. 6, which is a cross-sectional electron microscope image of the ZIF-8 film, the thickness of the ZIF-8 crystal layer exceeds 10 mu m, and the crystal boundary is not obvious, so that the permeation flux is seriously affected.
H for preparing MOFs membrane by adopting high-permeability gas permeation device 2 、N 2 、CH 4 、CO 2 The gas separation properties of the components were determined. Wherein the PAN/NH is prepared under the test condition of 25 ℃ and the pressure difference of two sides of the membrane of 0.1Mpa 2 -ZIF-8 membrane H 2 The penetration can reach 9.626 multiplied by 10 -7 mol·m -2 ·s -1 ·Pa -1 ，H 2 /CO 2 The ideal selectivity of (a) can reach 10.1, which exceeds 2008The upper limit of Robeson of the prepared flexible electrospun fiber supporting metal organic framework film is used for improving MOF S The method has wide prospect in the aspect of membrane industrial application.
Claims (4)
1. The preparation method of the flexible electrospun fiber supported metal organic framework film is characterized by comprising the following steps:
(1) Preparation of high density MOF by electrospinning technique S Seed nanofiber substrate
Construction of high density MOFs using superposition electrospinning S The nanofiber substrate of the seed crystal is combined with hot pressing operation to reduce the fiber gap; the specific operation is as follows:
preparing MOFs-free doped electrospinning solution A: adding the electrostatic spinning polymer into a spinning solvent, and stirring at normal temperature to completely dissolve the electrostatic spinning polymer to obtain an electrostatic spinning solution A;
preparing MOFs doped electrospinning solution B: MOF (Metal oxide film) of S Adding the particles and the electrostatic spinning polymer into a spinning solvent, stirring at normal temperature and carrying out water bath ultrasonic treatment to enable MOF S The particles are completely dispersed, the polymer is completely dissolved to obtain an electrospun solution B, and the MOF is controlled S The mass ratio of the particles to the polymer is 1:3-5;
preparation of doped MOFs S Nanofiber substrate of seed: carrying out superposition electrospinning on the two spinning solutions after preparation, and carrying out electrospinning on the electrospinning solution A to obtain an electrospun fiber supporting substrate, wherein the receiving amount of the aluminum foil per unit area is 1ml/dm 2 Immediately replacing the electrospun solution B to be overlapped on the A after the electrospinning is finished to carry out electrospinning, and controlling the volume ratio of the electrospun solution A to the electrospun solution B to be 4:1 to obtain the nanocomposite fiber; vacuum drying the nano composite fiber to remove residual solvent, and hot-pressing to reduce fiber gap to obtain doped MO F S A nanofiber substrate of seed crystals;
(2) The MOFs polycrystalline film with no defects and adjustable pore size is prepared by a one-step method, and is constructed by combining solvothermal reaction with a seed crystal epitaxial growth strategy;
the doped MOF obtained in the step (1) is subjected to S Cutting the nanofiber substrate of the seed crystal to a required size, and carrying out treatment by using a Teflon bracketFixing, and then vertically placing the mixture in the prepared MOFs growth liquid to ensure that the mixture is completely immersed by the growth liquid; regulating the temperature to 60-120 ℃ and the growth time to 1-3h; slowly taking out the solution after the solution is cooled to room temperature, washing with deionized water for 3-5 times, and then washing with methanol for 3-5 times to treat the MOF deposited on the surface S Particles; the resulting MOF is then subjected to S The film sample is placed in a low-temperature refrigerator to enable the sample to be completely frozen and firm, and then freeze drying is carried out to ensure that volatile solvents are removed, and the organic framework film supported by the electrospun fibers is obtained.
2. The method according to claim 1, wherein the spinning solvent is water, N-dimethylformamide, anhydrous methanol, anhydrous ethanol or dimethyl sulfoxide.
3. The method of claim 1, wherein the MOF S The particles are ZIF-7, ZIF-8, ZIF-9, ZIF-67 or NH 2 -ZIF-8。
4. The method according to claim 1, wherein the electrospun polymer is poly [1- (trimethylsilyl) ] -propyne, polyacrylonitrile, polyvinylidene fluoride, polybenzimidazole, polyvinyl alcohol, polyetherimide, polyethylene oxide or polyamide.
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