CN112853759B - Metal organic framework core-shell fiber material and preparation method thereof - Google Patents

Metal organic framework core-shell fiber material and preparation method thereof Download PDF

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CN112853759B
CN112853759B CN202110152322.8A CN202110152322A CN112853759B CN 112853759 B CN112853759 B CN 112853759B CN 202110152322 A CN202110152322 A CN 202110152322A CN 112853759 B CN112853759 B CN 112853759B
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CN112853759A (en
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吴俊涛
郝志敏
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Beihang University
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Abstract

The invention discloses a metal organic framework core-shell fiber material and a preparation method thereof, belonging to the technical field of high polymer materials. According to the preparation method, the MOF particles are wrapped on the surface of the nanofiber material through the preparation steps of a precursor solution, the electrospinning nanofiber and the metal organic framework fiber material, so that the metal organic framework core-shell fiber material is prepared, the porosity and the specific surface area of the material can be effectively increased, the pore structure of the nanofiber is reserved, and the specific surface area of the composite fiber membrane is increased.

Description

Metal organic framework core-shell fiber material and preparation method thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a metal organic framework core-shell fiber material and a preparation method thereof.
Background
The Metal-Organic Framework (MOF) is a crystal material composed of Metal ions and Organic ligands, has the characteristics of large specific surface area, various structures and pores, adjustable functionality and the like, also shows excellent PM2.5 capturing and harmful gas adsorption capacity, and has potential application in the field of multifunctional air filtration. However, since MOFs are generally brittle powder crystalline materials, direct use often presents pipe plugging and recovery problems, and it is often necessary to grow or deposit MOFs onto fibers or mix them with polymers to form composite fibers for use in the air filtration field. In the fiber obtained by blending electrospinning, the polymer layer wraps the MOF particles, so that the specific surface area and active sites of the MOF particles are obviously reduced, and the MOF particles cannot effectively adsorb gas, while the MOF particles are used as the shell and the nanofiber particles are used as the core of the core-shell fiber material, so that the specific surface area and the active sites of the MOF particles are effectively reserved, and the effective adsorption of gas molecules and the efficient PM2.5 capture can be realized. In recent years, the preparation of MOF core-shell fiber materials has become the focus of research on novel air filtering materials, and the preparation method of ZIF @ PAN fiber capable of simultaneously adsorbing formaldehyde and efficiently filtering PM2.5 is reported in the journal of Material chemistry (J.Mater.chem.A., 2018,6, 15807-)2Introduced into polyacrylonitrile PAN, and then PAN/Co (AC)2Preparation of a Metal organic framework core-Shell fiber Material by immersion in 2-methylimidazole, but from PAN/Co (AC)2The conversion to ZIF @ PAN is slow in rate and long in reaction time (10 h); the Journal of Membrane Science 581 (2019)252-261) reported that ZIF core-shell fiber materials can be made by controlling crystallization through back diffusionThe preparation time is shortened to 0.5h, and the prepared ZIF @ SiO2The material also has excellent formaldehyde/PM multifunctional filtering performance, but the back diffusion needs a special interface diffusion device, and although the preparation time is short, the size of the fiber membrane is also greatly limited. At present, although the MOF core-shell fiber has been successfully prepared by in-situ growth, atomic layer deposition, seed growth, two-phase interface diffusion, supramolecular assembly, metal oxide phase conversion and other methods, the methods often have the problems of low preparation efficiency, complex preparation process, equipment size limitation, material waste and the like, and large-scale and rapid preparation is difficult to realize.
Therefore, how to provide a metal organic framework core-shell fiber material which is simple to operate, easy to produce in a large scale, high in porosity and large in specific surface area and a preparation method thereof are problems to be solved in the field.
Disclosure of Invention
The invention discloses a preparation method of a metal organic framework core-shell fiber material.
In order to achieve the purpose, the invention adopts the following technical scheme: (ii) a
A metal organic framework core-shell fiber material comprises an inner layer made of polymer electrospun nanofiber and an outer layer made of metal organic framework material;
preferably, the inner layer is polyimide electrospun nanofiber, and the outer layer is metal organic framework material;
a preparation method of a metal organic framework core-shell fiber material comprises the following steps:
(1) preparing a ZIF-8 precursor solution:
1) preparation of methanol solution: uniformly mixing methanol and water according to the volume ratio of (3: 7) - (7: 3) to obtain a methanol solution;
2) preparing a methanol zinc acetate solution: according to the volume mass ratio of the methanol solution to the zinc acetate of 1 ml: (0.04-0.16) g of zinc acetate is added into the methanol water solution and mixed evenly to obtain methanol zinc acetate solution;
3) preparing a precursor solution: weighing 2-methylimidazole with the mass 2.5 times that of zinc acetate, adding the 2-methylimidazole into the methanol zinc acetate solution, and stirring until the solution becomes milky white to obtain a precursor solution;
preferably, the stirring is slow stirring at a low speed;
preferably, the stirring time is 5 min;
(2) preparing the electrospun nanofiber:
electrospinning high-molecular polymer fibers to obtain electrospun nanofibers;
(3) preparing a metal organic framework fiber material:
and (3) immersing the electrospun nanofiber prepared in the step (2) into the precursor solution prepared in the step (1), taking out after waiting for 8-12 seconds, and then washing with deionized water until no obvious white liquid drops on the nanofiber membrane, thereby obtaining the metal organic framework fiber material.
Preferably, the deionized water washing step is as follows: immersing the membrane in deionized water, standing for several seconds, then extracting the membrane out of the solution until the color of the solution is not changed any more, replacing the deionized water, and repeating the steps twice;
preferably, in the step (2), the voltage of electrospinning is 15kV, and the environmental humidity is less than 40%;
preferably, the receiving distance is 15 cm;
preferably, in the step (2), the high molecular polymer fiber includes: soluble polyimide 6FD A-BDAF, polyacrylonitrile PAN and 7wt percent of PMDA-ODA type polyamic acid PAA;
preferably, in the step (2), the preparation of the soluble polyimide 6FDA-BDAF electrospun material comprises the following steps: dissolving soluble polyimide 6FDA-BDAF in N, N-dimethylacetamide with the mass being 10 times that of the soluble polyimide, and stirring the mixture at room temperature until the soluble polyimide is completely dissolved to obtain an electro-spinning solution;
preferably, in the step (2), the preparation of the polyacrylonitrile PAN electrospun material comprises the following steps: dissolving polyacrylonitrile PAN in N, N-dimethylformamide with the mass of 9 times, stirring at 60-80 ℃ until the polyacrylonitrile PAN is completely dissolved to obtain an electro-spinning solution;
preferably, in the step (2), the 7 wt% of PMDA-ODA type polyamic acid PAA can be directly used for electrospinning;
preferably, after the electrospinning in the step (2), further subsequent processing is required, and the steps are as follows: thermally imidizing the product obtained by electrospinning the 7 wt% PM DA-ODA type polyamide acid PAA for 2h at 300 ℃ to obtain electrospun nanofibers;
preferably, after the step (3) of immersing, the mixture is taken out after waiting for 8 to 12 seconds;
preferably, after immersion, it is taken out after waiting for 10 seconds.
In conclusion, the invention discloses a metal organic framework core-shell fiber material and a preparation method thereof, the invention has simple operation, mild preparation conditions and easy large-scale production, combines the advantages of high porosity, large specific surface area and the like of the metal framework structure material, and the prepared metal organic framework fiber material not only retains the pore structure of the nano fiber, but also further improves the specific surface area of the composite fiber membrane.
Drawings
FIG. 1: scanning Electron Microscope (SEM) pictures of 6FDA-BDAF and ZIF @ PI fiber materials;
FIG. 2: scanning Electron Microscope (SEM) pictures of the core-shell fiber material formed by taking the PMDA-ODA fiber as a template;
FIG. 3: scanning Electron Microscope (SEM) pictures of core-shell fiber materials formed by using PAN fibers as templates;
FIG. 4: a ZIF @ PI fiber material X-ray diffraction spectrum picture;
FIG. 5: BET test results of the 6FDA-BDAF fiber material and the ZIF @ PI fiber material;
FIG. 6: 6FDA-BDAF fiber material and ZIF @ PI fiber material PM2.5 filtering performance;
FIG. 7: 6FDA-BDAF fiber material and ZIF @ PI fiber material.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing a ZIF-8 precursor solution:
(1) methanol and water are mixed according to a volume ratio of 3: 7, uniformly mixing to obtain a methanol solution; according to the volume mass ratio of the methanol solution to the zinc acetate of 1 ml: adding 0.04g of zinc acetate into the methanol aqueous solution, and uniformly mixing to obtain a methanol zinc acetate solution; weighing 2-methylimidazole with the mass 2.5 times that of zinc acetate, adding the 2-methylimidazole into the methanol zinc acetate solution, and stirring for 5min until the solution turns to milky white to obtain a precursor solution 1;
(1) methanol and water are mixed according to a volume ratio of 7: 3, uniformly mixing to obtain a methanol solution; according to the volume mass ratio of the methanol solution to the zinc acetate of 1 ml: adding 0.16g of zinc acetate into the methanol aqueous solution, and uniformly mixing to obtain a methanol zinc acetate solution; weighing 2-methylimidazole with the mass 2.5 times that of zinc acetate, adding the 2-methylimidazole into the methanol zinc acetate solution, and stirring for 5min until the solution turns to milky white to obtain a precursor solution 2;
(1) uniformly mixing methanol and water according to the volume ratio of 1:1 to obtain a methanol solution; according to the volume mass ratio of the methanol solution to the zinc acetate of 1 ml: adding 0.08g of zinc acetate into the methanol aqueous solution, and uniformly mixing to obtain a methanol zinc acetate solution; weighing 2-methylimidazole with the mass 2.5 times that of the zinc acetate, adding the 2-methylimidazole into the methanol zinc acetate solution, and stirring for 5min until the solution turns milky white to obtain a precursor solution 3.
Example 2
Preparing the electrospun nanofiber:
(1) dissolving soluble polyimide 6FDA-BDAF in N, N-dimethylacetamide with the mass being 10 times that of the soluble polyimide, and stirring the solution at normal temperature until the soluble polyimide is completely dissolved to obtain an electro-spinning solution; transferring the electrospinning liquid into an electrostatic spinning device, taking an aluminum foil as a collector, carrying out electrospinning on a receiver and an injection port of a spinner at a distance of 15cm, a spinning voltage of 15kV, an environmental humidity of less than 40 percent and a temperature of 20 ℃ to obtain polyimide 6FDA-BDAF nanofiber;
(2) transferring 7 wt% of PMDA-ODA type polyamide acid (PAA) into an electrostatic spinning device, carrying out electrospinning under the conditions that an aluminum foil is used as a collector, the distance between a receiver and an injection port of a spinner is 15cm, the spinning voltage is 15kV, the environmental humidity is less than 40%, and the temperature is 30 ℃ to obtain PAA nano fibers, and carrying out hot imidization on the prepared PAA nano fiber film for 2 hours at the temperature of 300 ℃ to obtain polyimide PMDA-ODA nano fibers;
(3) dissolving polyacrylonitrile PAN in N, N-dimethylformamide with the mass of 9 times, stirring at 60-80 ℃ until the polyacrylonitrile PAN is completely dissolved to obtain an electro-spinning solution; and (3) transferring the electrospinning liquid into an electrostatic spinning device, and carrying out electrospinning under the conditions that an aluminum foil is used as a collector, the distance between a receiver and an injection port of a spinner is 15cm, the spinning voltage is 15kV, the environmental humidity is less than 40%, and the temperature is 25 ℃ to obtain the polyacrylonitrile PAN nanofiber.
Example 3
Preparing a metal organic framework fiber material:
(1) immersing polyimide 6FDA-BDAF nano-fiber into the precursor solution 1, taking out the polyimide after waiting for 8 seconds, immersing the membrane into deionized water, standing for a few seconds, then extracting the membrane out of the solution until the color of the solution is not changed, replacing the deionized water, repeating the steps twice until no obvious white liquid drops on the nano-fiber membrane, and naming the nano-fiber membrane as ZIF @ PI-0.5;
(2) immersing polyimide 6FDA-BDAF nano-fiber into the precursor solution 2, taking out the polyimide after waiting for 10 seconds, immersing the membrane into deionized water, standing for a few seconds, then extracting the membrane out of the solution until the color of the solution is not changed, replacing the deionized water, repeating the steps twice until no obvious white liquid drops on the nano-fiber membrane, and naming the nano-fiber membrane as ZIF @ PI-1;
(3) immersing polyimide 6FDA-BDAF nano-fiber into the precursor solution 3, taking out after waiting for 12 seconds, immersing the membrane into deionized water, standing for a few seconds, extracting the membrane out of the solution until the color of the solution is not changed, replacing the deionized water, repeating the steps twice until no obvious white liquid drops on the nano-fiber membrane, and naming the nano-fiber membrane as ZIF @ PI-2;
(4) and (2) immersing the polyimide PMDA-ODA nanofiber into the precursor solution 2, taking out the polyimide PMDA-ODA nanofiber after waiting for 10 seconds, immersing the membrane into deionized water, standing for a few seconds, then extracting the membrane out of the solution until the color of the solution is not changed, replacing the deionized water, repeating the steps twice until no obvious white liquid drips on the nanofiber membrane, and naming the polyimide PMDA-ODA nanofiber as ZIF @ PI (PMDA-ODA).
(5) And (2) immersing polyacrylonitrile PAN nanofiber into the precursor solution 2, taking out the polyacrylonitrile PAN nanofiber after waiting for 10 seconds, immersing the membrane into deionized water, standing for a few seconds, taking the membrane out of the solution, replacing the deionized water until the color of the solution is not changed any more, repeating the steps twice until no obvious white liquid drips on the nanofiber membrane, and naming the polyacrylonitrile PAN nanofiber membrane as ZIF @ PAN.
Example 4
(1) The characteristics of the prepared ZIF @ PI fiber, the core-shell fiber material formed by taking the PMDA-ODA fiber as a template, the core-shell fiber material formed by taking the PAN fiber as a template and the 6FDA-BDAF fiber observed by a scanning electron microscope are shown as 1-3: the surface of a pure PI (6FDA-BDAF) fiber is smooth, after loading, the size of the fiber is increased, a layer of MOF particles is coated on the surface, and a ZIF @ PI fiber material taking the PI fiber as a core and the MOF particles as a shell is formed; the core-shell fiber material formed by taking PI (PMDA-ODA) and PAN fibers as templates has different MOF loading capacity on the fiber surface along with the change of surface chemical groups of the material;
(2) the ZIF @ PI fiber material is subjected to X-ray diffraction detection to detect the characteristics, the scanning speed is 2 DEG/min, the scanning interval is 5-50 DEG, and the result is shown as 4: the X-ray diffraction spectrum of the ZIF @ PI fiber is completely consistent with the fitted ZIF-8 crystal structure spectrum, which shows that ZIF-8 is successfully loaded on the fiber, wherein the peak with the strongest diffraction intensity (about 7.34 ℃) corresponds to the (011) crystal face of the ZIF-8 crystal;
(3) the 6FDA-BDAF fiber material and the ZIF @ PI fiber material are subjected to BET test, the atmosphere of nitrogen is tested, the pretreatment temperature is 180 ℃, the pretreatment time is 6 hours, and the result is shown in figure 5: the nitrogen adsorption and desorption curve of the pure PI (6FDA-BDAF) fiber is a type II isotherm, which shows that the fiber is of a surface nonporous structure, the pores formed by connecting the fiber are large, and the specific surface area is 8.51m2After MOF loading, the adsorption curve is changed from type II to type I isotherm due to the micropore filling effect of ZIF, and the specific surface area is remarkably increased to 500.26 m2/g。
(4) PM2.5 filtration performance detection is carried out on the 6FDA-BDAF fiber material and the ZIF @ PI fiber material, and a proper test environment (PM2.5 concentration is more than 200 mu g/m) is created by burning cigarettes in a closed space3) Measured using an aerosol detectorThe filtration efficiency E is obtained from the PM2.5 concentration before and after membrane filtration, the pressure drop Δ P of the membrane is obtained by measuring the pressure difference across the membrane by a pressure difference meter, and the quality factor QF can be obtained by calculating the formula QF ═ ln (1-E)/Δ P, and the result is shown in fig. 6: the pressure drop and the filtration efficiency of a pure PI (6FDA-BDAF) fiber membrane are low, namely 42Pa and 79.4 percent respectively, the filtration efficiency of the ZIF @ PI fiber membrane is remarkably improved to 98 percent along with the loading of ZIF-8, the pressure drop of the fiber membrane is also increased (68.5Pa) due to the loading of the ZIF, in order to better compare the comprehensive performance of the membrane, the quality factor is introduced, the quality factor of the PI fiber is 0.0376Pa-1, and the quality factor of the ZIF @ PI fiber is 0.0571Pa-1, so that the ZIF @ PI has more excellent comprehensive filtration performance;
(5) carrying out formaldehyde adsorption performance test on a 6FDA-BDAF fiber material and a ZIF @ PI fiber material, respectively weighing about 100mg of PI fiber and ZIF @ PI fiber, recording the weight, putting the PI fiber and the ZIF @ PI fiber into a volumetric flask, then adding a small amount of formaldehyde solution into the volumetric flask, sealing, putting the volumetric flask into a water bath kettle at 80 ℃, taking out the fiber after certain time, weighing the weight of the fiber after adsorbing formaldehyde again, wherein the difference value before and after adsorption is the formaldehyde adsorption amount of the fiber, and the result is shown in figure 7: the weight of the PI fiber is slowly increased in the first 120min, the total formaldehyde adsorption amount is low and is only 0.3mg (unit adsorption amount is 2.9mg/g) when the PI fiber reaches a saturated adsorption state, the formaldehyde adsorption amount of the ZIF @ PI fiber is remarkably improved after ZIF loading, and the total formaldehyde adsorption amount is 9.5mg (unit adsorption amount is 91.3mg) when the PI fiber reaches the saturated state.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to the above-described embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (7)

1. A preparation method of a metal organic framework core-shell fiber material is characterized by comprising the following steps:
(1) preparing a ZIF-8 precursor solution:
1) preparation of methanol solution: uniformly mixing methanol and water according to the volume ratio of (3: 7) - (7: 3) to obtain a methanol solution;
2) preparing a methanol zinc acetate solution: according to the volume mass ratio of the methanol solution to the zinc acetate of 1 ml: (0.04-0.16) g of zinc acetate is added into the methanol water solution and mixed evenly to obtain the methanol zinc acetate water solution;
3) preparing a precursor solution: weighing 2-methylimidazole with the mass 2.5 times that of zinc acetate, adding the 2-methylimidazole into a methanol zinc acetate aqueous solution, and stirring until the solution becomes milky white to obtain a precursor solution;
(2) preparing the electrospun nanofiber:
electrospinning high-molecular polymer fibers to obtain electrospun nanofibers;
(3) preparing a metal organic framework fiber material:
immersing the electrospun nanofiber prepared in the step (2) into the precursor solution prepared in the step (1), taking out after waiting for 8-12 seconds, and then washing with deionized water until no obvious white liquid drops on the nanofiber membrane, thereby obtaining the metal organic framework fiber material;
the high molecular polymer fiber includes: soluble polyimide 6FDA-BDAF, polyacrylonitrile PAN and 7 wt% of PMDA-ODA type polyamic acid PAA.
2. The preparation method of the metal organic framework core-shell fiber material according to claim 1, wherein in the step (2), the voltage of electrospinning is 15-17kV, and the environmental humidity is less than 40%.
3. The preparation method of the metal organic framework core-shell fiber material according to claim 2, wherein in the step (2), the preparation steps of the soluble polyimide 6FDA-BDAF electrospun material are as follows: dissolving the soluble polyimide 6FDA-BDAF in N, N-dimethylacetamide with the mass being 10 times that of the soluble polyimide, and stirring the mixture at room temperature until the soluble polyimide is completely dissolved to obtain the electro-spinning solution.
4. The method for preparing a metal organic framework core-shell fiber material according to claim 1, wherein in the step (2), the polyacrylonitrile PAN electrospun material is prepared by the following steps: dissolving polyacrylonitrile PAN in N, N-dimethylformamide with the mass of 9 times, stirring at 60-80 ℃ until the polyacrylonitrile PAN is completely dissolved, and obtaining the electro-spinning solution.
5. The method for preparing a metal organic framework core-shell fiber material according to claim 1, wherein in the step (2), the 7 wt% of PMDA-ODA type polyamic acid PAA can be directly used for electrospinning.
6. The preparation method of the metal organic framework core-shell fiber material according to claim 1, wherein after the electrospinning in the step (2), the subsequent treatment is required, and the steps are as follows: and (3) carrying out hot imidization on the product obtained by electrospinning the 7 wt% PMDA-ODA type polyamide acid PAA for 2h at the temperature of 300 ℃ to obtain the electrospun nanofiber.
7. A metal organic framework core-shell fiber material, characterized by being obtained by the preparation method of any one of claims 1 to 6.
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