CN114307693B - Preparation method of MOFs and polymer bicontinuous mixed matrix membrane - Google Patents
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Abstract
The invention belongs to the technical field of gas membrane separation, and provides a preparation method of a MOFs and polymer bicontinuous mixed matrix membrane. Adding inorganic metal salt particles into an electrospinning polymer for electrostatic spinning, calcining to convert into metal oxide fibers, taking oxide nanofibers as a self-sacrificial template, growing MOFs in situ through coordination-replication, maintaining the balance between template dissolution and MOFs nucleation, and converting the metal oxide nanofiber mat into the MOFs nanofiber mat. Functional micromolecules with low molecular weight are polymerized into gaps of the MOFs nanofibers in situ to construct a compact high-permeability MOFs/PDA mixed matrix gas separation membrane. The MOFs/PDA can provide a low-resistance rapid transmission path, selective screening of gas molecules is realized, and the prepared gas separation membrane has the characteristics of high permeability, high selectivity and high mechanical strength, so that the application prospect of the membrane is wider.
Description
Technical Field
The invention belongs to the technical field of gas membrane separation, and mainly designs a MOFs and polymer bicontinuous mixed matrix membrane, constructs a long-range continuous low-resistance channel for gas molecule transfer, and improves the gas permeability of the mixed matrix membrane.
Background
The membrane separation technology is a novel high-efficiency separation technology applied to industrial production, has the advantages of high efficiency, easy coupling and the like compared with the traditional separation method, requires relatively low operation energy in the separation process, is a competitive separation method, is concerned, and has the core of preparing a separation membrane material with high separation performance.
The conventional polymer film material has an obvious 'trade-off' phenomenon, and the permeability and the selectivity cannot be considered at the same time; inorganic membranes generally have good separation performance and high stability, but are expensive to manufacture. Thus, in the field of gas separation, the concept of mixed matrix membranes has been proposed, which is a reasonable compromise between the two types. Inorganic fillers provide additional gas adsorption sites and preferential diffusion paths, and theoretically, both high permeability and high selectivity can be achieved. Metal organic framework compounds (MOFs) are inorganic-organic hybrid materials with porous structures formed by coordination self-assembly of metal ions and organic ligands, are novel fillers for preparing mixed matrix membranes, and have the advantages of developed pore structures, high specific surface areas, adjustable pore sizes, easy functionalization and the like, so that people pay extensive attention to the metal organic framework compounds. In the conventional MOFs mixed matrix membrane, due to the poor interface compatibility between filler MOFs and a polymer matrix, the filler content is low and the filler is dispersed, so that gas molecules are short-circuited in the transmission process and mainly take the polymer, and the permeability of the gas is difficult to improve. Therefore, how to construct continuous MOFs transfer channels in the mixed matrix membrane is crucial to improving the gas permeability of the membrane.
The electrostatic spinning is an assembly process from top to bottom, various fiber materials can be simply, conveniently and effectively prepared, and the fibers formed by spinning have the advantages of controllable thickness, continuous fibers, high specific surface area, easy surface modification and the like, and have good mechanical properties, so that the electrostatic spinning technology has the potential of being applied to gas separation. Sun Tianji the invention provides a preparation method of an electrospun nanofiber gas separation membrane (CN 202011243605.5). Aiming at the problems of poor selectivity and low mechanical property of polyethylene glycol series photo-cured polymer membranes, the nanofiber prepared by electrostatic spinning is used as a framework, the fiber is used as the framework in the membrane, a reinforced cement structure is constructed, and due to in-situ polymerization of a polymer, the nanofiber and the polymer have good cohesive force, so that the mechanical property of the membrane is greatly improved, but due to the fact that the nanofiber belongs to a pure polymer membrane, the air permeability of the membrane is low. Professor Zhang Xiuling of Beijing university of science and technology provides a preparation method of a metal salt assisted rapid growth metal organic framework derivative (CN 202110228812.1), the method comprises the steps of firstly adding metal salt and high molecular polymer into an organic solvent, obtaining a metal salt/high molecular nanofiber membrane by adopting an electrostatic spinning technology, then uniformly coating an organic ligand solution containing a metal organic framework MOFs required for growth on the metal salt/high molecular nanofiber membrane, and then realizing chemical bond combination of metal ions and ligands in nanofibers by adopting a hot pressing technology, so that the MOFs material uniformly grows on the nanofiber membrane, but the high load of the MOFs material cannot be ensured. Meanwhile, because the electrostatic spinning fiber networks have gap structures among themselves, so that serious air leakage is caused, spinning treatment is required to be carried out to densify the electrostatic spinning fiber networks so as to be applied to gas separation, and spinning hot pressing, a solvent fumigation method, polymer pouring and other modes are mostly adopted to fill polymer gaps so as to realize the compactness of the membrane at present. Therefore, the long-range continuity of the electrostatic spinning fibers is used as a framework to realize an ideal carrier of the MOFs, so that the long-range continuous MOFs fibers are formed, and a continuous low-resistance transmission channel is provided for gas transmission. In order to realize the compactness of the MOFs fiber membrane, functional micromolecules are adopted to be polymerized in situ in fiber gaps, and a novel MOFs and polymer bicontinuous mixed matrix membrane is obtained. Compared with the MOFs loaded by directly utilizing spinning doping, the MOFs loading capacity in the MOFs nanofiber mat prepared by coordination-replication is higher, the MOFs in the mixed matrix membrane is continuous in long range, and a low-resistance channel is provided for the transfer of gas molecules, so that the gas permeability of the membrane can be greatly improved; the selectivity of gas molecules can be ensured by adopting in-situ polymerized functional micromolecules; the compatibility between the MOFs filler and the polymer base material is enhanced by the in-situ polymerization method, and the gas selectivity of the film is further ensured; the skeleton structure of the fiber ensures that the gas separation membrane has good mechanical strength. In conclusion, the proposed MOFs and polymer bicontinuous mixed matrix membrane has the prospect of realizing the industrial requirement.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention aims to design a bicontinuous mixed matrix membrane of MOFs and polymer, which ensures high loading of MOFs filler, constructs a long-range continuous channel for gas molecule transfer, and improves permeability and selectivity.
The invention designs a novel MOFs and polymer bicontinuous mixed matrix gas separation membrane, which is characterized in that inorganic metal salt particles are added into Polyacrylonitrile (PAN) spinning solution for electrostatic spinning to obtain a metal salt doped nanofiber composite material, the metal salt doped nanofiber composite material is subjected to high-temperature calcination and converted into a metal oxide nanofiber mat, the flexibility of the metal oxide can be ensured to a certain extent by carrying the metal oxide through spinning, and the fragility of an inorganic crystal material is overcome through an electrostatic spinning technology. And then taking the oxide nanofiber as a self-sacrificial template, growing MOFs in situ through coordination-replication, maintaining the balance between template dissolution and MOFs nucleation under a proper reaction condition, and converting the metal oxide nanofiber mat into the MOFs nanofiber mat. The long-range continuous channel for transferring gas molecules is constructed by the method, so that a low-resistance high-speed channel can be provided for gas transmission. The MOFs have a developed pore structure, high porosity and specific surface area, and meanwhile, the pore size is adjustable and easy to functionalize, and the organic part can be better compatible with a polymer matrix, so that a low-resistance path can be provided for gas transmission. Then, small molecular monomers which are easy to polymerize are adopted to be polymerized in situ into gaps of the MOFs fibers to form a polymer matrix, so that a compact MOFs/polymer composite fiber gas separation membrane is constructed. The ultra-microporous structure of the MOFs and the long-range continuous structure of the fibers are used for providing a low-resistance and rapid transmission path for gas molecules together, so that the high air permeability of the gas separation membrane is ensured; meanwhile, the gas molecules are sieved by utilizing the specific pore size of MOFs, such as the micropore size (0.34 nm) of ZIF-8 to sieve CO 2 /N 2 The molecules are effectively screened, so that the gas selectivity of the membrane is improved; the small molecules such as dopamine are used for pouring and blocking holes, the small molecules simultaneously have abundant affinity groups such as hydroxyl groups and amino groups which are easy to adsorb with gas molecules, and the polymer filled in gaps among the fibers can also provide excellent mechanical properties for the gas separation membrane. Therefore, the constructed MOFs and polymer bicontinuous composite fiber gas separation membrane can realize independent adjustment on the permeability and selectivity of gas molecules, and has good superiority compared with a hybrid membrane prepared by directly doping fillers in a membrane casting solution.
The technical scheme of the invention is as follows:
a preparation method of a MOFs and polymer bicontinuous mixed matrix membrane comprises the following steps:
(1) MOFs nano-fiber pad prepared by adopting electrostatic spinning technology
Adding inorganic metal salt particles into N, N-dimethylformamide, stirring and carrying out water bath ultrasound to completely disperse the inorganic metal salt particles in the N, N-dimethylformamide; adding polyacrylonitrile (Mw =150,000) into the reaction system, controlling the mass ratio of the inorganic metal salt to the polyacrylonitrile to be 1:1, and stirring at normal temperature until the polyacrylonitrile is completely dissolved to obtain a spinning solution; then adopting an electrostatic spinning process to obtain the metal salt doped nano composite fiber; vacuum drying the nano composite fiber to remove residual solvent, putting the nano composite fiber in a muffle furnace, and calcining the nano composite fiber for 3 hours at the high temperature of 500 ℃ to obtain a metal oxide fiber pad; then, taking the metal oxide fiber mat as a self-sacrifice template, carrying out hydrothermal reaction for 5 hours at the temperature of 110 ℃, growing MOFs in situ by utilizing coordination-replication, and converting the metal oxide nanofiber mat into the MOFs nanofiber mat;
(2) Preparation of a bicontinuous mixed matrix membrane of MOFs and Polymer
Dopamine was used as the filler polymer small molecule: firstly, placing an MOFs nano-fiber pad in a dopamine solution with the concentration of 1-3g/L, adjusting the pH value to 8.5-9.0 by using a Tris-HCl buffer solution, placing at room temperature for 24 hours, taking out, and then fully oscillating and cleaning by using deionized water and ethanol; replacing a dopamine hydrochloride solution, repeatedly soaking for many times to ensure that dopamine micromolecules are fully polymerized on the MOFs nanofiber mat to obtain MOFs/PDA composite fibers, and then carrying out vacuum drying to ensure that volatile solvents are removed to obtain a fully polymerized MOFs/PDA composite fiber gas separation membrane;
polyethylene glycol diacrylate was used as the small molecule of the filler polymer: adding a photoinitiator 1-hydroxycyclohexyl phenyl ketone into polyethylene glycol diacrylate (Mw = 600) to prepare a polymer filling liquid, wherein the mass ratio of the 1-hydroxycyclohexyl phenyl ketone to the polyethylene glycol diacrylate is 1; stirring at room temperature in a dark environment, and adding the filling liquidDefoaming by ultrasonic treatment to discharge air bubbles; then, placing the MOFs nano-fiber pad obtained in the step (1) in an ultrafiltration cup, adding a polymer filling liquid into the ultrafiltration cup to ensure that the MOFs nano-fiber pad is completely immersed, and filling and permeating the polymer into fiber gaps of the MOFs nano-fiber pad; adjusting the air pressure to 0.05-0.1MPa, and introducing N 2 Increasing the internal pressure of ultrafiltration equipment, so that the polymer pore-plugging liquid permeates the MOFs nanofiber pad to obtain a wet MOFs @ PEGDA composite fiber pad, and then placing the wet MOFs @ PEGDA composite fiber pad on filter paper to suck dry residual pore-plugging liquid; and finally, placing the wet MOFs @ PEGDA composite fiber pad in an argon environment for photopolymerization for 3-5min to obtain the completely cured MOFs @ PEGDA composite fiber gas separation membrane.
The MOFs particles in the MOFs nano-fiber mat are UiO-66 and UiO-66-NH 2 、ZIF-8、HKUST-1、ZIF-67、MIL-88B(Fe)。
The invention has the beneficial effects that: the MOFs and polymer bicontinuous mixed matrix gas separation membrane prepared by the invention is different from the traditional spinning polymer with low air permeability, ensures the high loading capacity of the MOFs filler, forms a long-range low-resistance transmission path for gas molecule transmission by using continuous MOFs, and improves the permselectivity of the membrane. The three-dimensional network structure of the MOFs fiber traverses the whole membrane, and provides a high-speed transmission channel for gas transmission. The MOFs nano-fiber formed by in-situ growth and conversion can realize selective screening of gas molecules due to high porosity and ideal pore diameter. The crosslinkable micromolecule polymerization is utilized to block the pores, so that the mechanical property of the membrane is enhanced. The prepared gas separation membrane has the characteristics of high permeability, high selectivity and high mechanical strength, so that the application prospect of the membrane is wider.
Drawings
FIG. 1 shows Zn (Ac) in example 2 ·2H 2 SEM image of O @ PAN composite electrospun fiber.
FIG. 2 is an SEM image of ZnO nanofibers in the examples.
FIG. 3 is an SEM image of ZIF-8 nanofibers in examples.
FIG. 4 is an SEM image of a ZIF-8@ PDA composite fiber in the example.
FIG. 5 is an SEM image of a ZIF-8@ PEGDA composite fiber in the example.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Examples
Preparing a ZIF-8 nanofiber material: 1.0g of Zn (Ac) 2 ·2H 2 The O metal salt particles are added into 10ml of N, N-Dimethylformamide (DMF) solvent, stirred to be completely dissolved, and water bath ultrasound is carried out for 15min to discharge air bubbles. Thereafter, 1.0g of Polyacrylonitrile (PAN) powder was added thereto, and stirred vigorously at room temperature for 24 hours to be completely dissolved. The resulting spinning solution was transferred to a 10mL disposable syringe using a 22 gauge needle and placed on an electrospinning apparatus. Controlling the injection speed to be 1mL/h, the distance between the needle and the receiver to be 18cm, the rotating speed of the receiver to be 80r/h, the operating environment temperature to be 20 ℃, the air humidity to be 40%, and regulating and controlling the positive voltage of the spinning instrument to be 16KV and the negative voltage to be 1.5KV. An aluminum foil paper is wrapped on the receiver for receiving the fibers. The resulting composite fiber was vacuum dried at 50 ℃ for 12h to remove the residual DMF solvent. FIG. 1 shows Zn (Ac) prepared by spinning 2 ·2H 2 As shown in an electron microscope image of the O @ PAN composite fiber, the diameter of the fiber is about 150-250 nm, and gaps exist among the fibers and the fibers are uniform in thickness. And then placing the composite fiber in a muffle furnace for high-temperature calcination, firstly heating to 200 ℃ at the speed of 1 ℃/min, keeping for 2 hours for pre-oxidation, aiming at maintaining the fiber structure not to be damaged, then heating to 500 ℃ at the speed of 1 ℃/min, keeping for 3 hours for calcination, and finally cooling to room temperature at the speed of 2 ℃/min to obtain the ZnO nanofiber mat, wherein the fibers have granular irregular crystals as shown in an electron microscope figure of figure 2. Finally, MOFs grows in situ through hydrothermal reaction, 50mg of ZnO nanofiber mat is placed in a 50ml reaction kettle, 0.2g of 2-methylimidazole and 20ml of DMF solvent which are uniformly stirred are poured into the ZnO nanofiber mat in an immersed mode, the ZnO nanofiber mat is maintained at 110 ℃ for 5 hours and is converted into the ZIF-8 nanofiber mat, and as shown in an electron microscope picture of figure 3, the diameter of the fiber is thicker than that of the ZnO nanofiber and a typical ZIF-8 granular crystal form appears.
Preparing a ZIF-8/PDA mixed matrix membrane: preparing a dopamine solution with the concentration of 2g/L, regulating the pH value to 8.5 by using a Tris-HCl buffer solution, placing the ZIF-8 nanofiber mat in the dopamine hydrochloride solution, standing at room temperature for 24 hours, taking out, and then fully oscillating and cleaning by using deionized water and ethanol, wherein the operation is repeated for three times for 60s each time; replacing the dopamine hydrochloride solution, repeatedly soaking for 3 times to ensure that the dopamine micromolecules are fully polymerized in gaps of the ZIF-8 nano-fiber mat to obtain a ZIF-8/PDA mixed matrix membrane; and then, placing the ZIF-8/PDA mixed matrix membrane in a vacuum oven for vacuum drying for 5 hours to ensure that the volatile solvent is removed, and obtaining the fully polymerized ZIF-8/PDA mixed matrix membrane. The PDA micromolecules are polymerized in situ to fill gaps among the ZIF-8 fibers, and the fibers are uniformly distributed in the film. As can be seen from the SEM image of the cross section of the film in FIG. 4, DA small molecules are self-polymerized in situ to fill gaps among ZIF-8 nano fibers, and the fibers are uniformly distributed in the film.
Preparation of ZIF-8/PEGDA mixed matrix membrane: 12g of polyethylene glycol diacrylate (PEGDA) is weighed, 0.012g of 1-hydroxycyclohexyl phenyl ketone (HCPK) is added as a photoinitiator, the mixture is stirred for 2 hours under the normal temperature state in a dark environment, then the filling liquid is treated by ultrasound for 0.5 hour to be defoamed so as to discharge bubbles, and the mixture is cooled to the room temperature for standby. And (2) placing the ZIF-8 nanofiber pad in an ultrafiltration cup, then adding PEGDA polymer filling liquid into an ultrafiltration device to ensure that the ZIF-8 nanofiber pad is completely immersed, adjusting the air pressure to be 0.1MPa, carrying out ultrafiltration operation to enable the polymer film liquid to permeate into fiber gaps, and sucking the ZIF-8@ PEGDA composite fiber obtained by ultrafiltration with clean filter paper to dry redundant PEGDA solution on two sides. And finally, placing the ZIF-8@ PEGDA composite fiber permeated with PEGDA in an argon environment for ultraviolet polymerization for 3min to obtain the fully-cured ZIF-8@ PEGDA composite fiber gas separation membrane. As can be seen from the SEM (scanning Electron microscope) image of the cross section of the membrane in FIG. 5, the voids among the ZIF-8 nanofibers are filled by PEGDA in-situ photopolymerization, the fibers are uniformly distributed in the membrane, and the fiber structure can be seen.
The prepared MOFs and polymer bicontinuous mixed matrix gas separation membrane is used for measuring CO by adopting a constant-volume variable-pressure permeation device 2 And N 2 Gas separation performance of the components. ZIF-8 fibers provide a fast transport path for gas transport, but due to the presence of the "trade-off" effect, reduce the CO of the membrane 2 /N 2 Selectivity and increase of CO 2 The ZIF-8/PDA composite fiber gas separation membrane and the ZIF-8/PEGDA composite fiber gas separation membrane with high loading of ZIF-8 have wide practical application prospect in the aspect of improving the membrane permeability.
Claims (3)
1. A preparation method of a MOFs and polymer bicontinuous mixed matrix membrane is characterized by comprising the following steps:
(1) MOFs nano-fiber pad prepared by adopting electrostatic spinning technology
Adding inorganic metal salt particles into N, N-dimethylformamide, stirring and carrying out water bath ultrasound to completely disperse the inorganic metal salt particles in the N, N-dimethylformamide; adding polyacrylonitrile into the reaction system, controlling the mass ratio of the inorganic metal salt to the polyacrylonitrile to be 1:1, and stirring at normal temperature until the polyacrylonitrile is completely dissolved to obtain a spinning solution; then adopting an electrostatic spinning process to obtain the metal salt doped nano composite fiber; vacuum drying the nano composite fiber to remove residual solvent, putting the nano composite fiber in a muffle furnace, and calcining the nano composite fiber for 3 hours at the high temperature of 500 ℃ to obtain a metal oxide fiber pad; then, taking the metal oxide fiber mat as a self-sacrifice template, carrying out hydrothermal reaction for 5h at 110 ℃, growing MOFs in situ by utilizing coordination-replication, and converting the metal oxide nanofiber mat into the MOFs nanofiber mat;
(2) Preparation of a bicontinuous mixed matrix membrane of MOFs and Polymer
Dopamine was used as a small filling polymer molecule: firstly, placing an MOFs nano-fiber pad in a dopamine solution with the concentration of 1-3g/L, adjusting the pH value to 8.5-9.0 by using a Tris-HCl buffer solution, placing at room temperature for 24 hours, taking out, and then fully oscillating and cleaning by using deionized water and ethanol; replacing a dopamine hydrochloride solution, repeatedly soaking for many times to ensure that dopamine micromolecules are fully polymerized on the MOFs nanofiber mat to obtain MOFs/PDA composite fibers, and then carrying out vacuum drying to ensure that volatile solvents are removed to obtain a fully polymerized MOFs/PDA composite fiber gas separation membrane;
polyethylene glycol diacrylate was used as the small molecule of the filler polymer: adding photoinitiator 1-hydroxycyclohexyl phenyl ketone into polyethylene glycol diacrylate for polymerizationThe filling liquid comprises a filling material, wherein the mass ratio of 1-hydroxycyclohexyl phenyl ketone to polyethylene glycol diacrylate is 1; stirring uniformly at normal temperature in a dark environment, and then carrying out ultrasonic treatment and defoaming on the filling liquid to discharge air bubbles; then, placing the MOFs nano-fiber pad obtained in the step (1) in an ultrafiltration cup, adding a polymer filling liquid into the ultrafiltration cup to ensure that the MOFs nano-fiber pad is completely immersed, and filling and permeating the polymer into fiber gaps of the MOFs nano-fiber pad; adjusting the air pressure to 0.05-0.1MPa, and introducing N 2 Increasing the internal pressure of ultrafiltration equipment, so that the polymer pore-plugging liquid permeates the MOFs nanofiber pad to obtain a wet MOFs @ PEGDA composite fiber pad, and then placing the wet MOFs @ PEGDA composite fiber pad on filter paper to suck dry residual pore-plugging liquid; and finally, placing the wet MOFs @ PEGDA composite fiber pad in an argon environment for photopolymerization for 3-5min to obtain the completely cured MOFs @ PEGDA composite fiber gas separation membrane.
2. The method according to claim 1, wherein said MOFs particles in said MOFs nanofiber mat are UiO-66, uiO-66-NH 2 、ZIF-8、HKUST-1、ZIF-67、MIL-88B(Fe)。
3. The method of claim 1 or 2, wherein the polyethylene glycol diacrylate has a Mw =600; mw =150,000 for polyacrylonitrile.
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| CN115121135B (en) * | 2022-06-20 | 2024-02-27 | 西安交通大学 | Mixed matrix membrane, preparation method and application thereof, and space division nitrogen production device |
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