CN113976088A - Preparation method of polyamide 6/graphene oxide/iron-based metal organic framework three-phase composite material - Google Patents
Preparation method of polyamide 6/graphene oxide/iron-based metal organic framework three-phase composite material Download PDFInfo
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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Abstract
The invention discloses a preparation method of a polyamide 6/graphene oxide/iron-based metal organic framework three-phase composite material, which comprises the following steps: (1) preparing a PA6/GO binary fiber membrane; (2) preparing Fe-MOFs precursor solution: Fe-MOFs material is NH2MIL-53(Fe), preparation to obtain NH2-a precursor solution of MIL-53 (Fe); (3) PA6/GO spinning film in-situ self-assembly growth Fe-MOFs, and PA6/GO/Fe-MOFs three-phase composite materials. The method combining polymer electrostatic spinning and Fe-MOFs in-situ growth can be used for producing composite materials with good adsorption performance and adsorbing heavy metal ions in sewage or greenhouse gases such as carbon dioxide in air.
Description
Technical Field
The invention relates to the field of polymer/metal organic framework composite materials, in particular to a preparation method of a polyamide 6 (PA 6)/Graphene Oxide (GO)/iron-based metal organic framework (Fe-MOFs) three-phase composite material.
Background
How to enable the iron-based metal organic framework materials (Fe-MOFs) to have the advantages of high crystallinity, stable pore structure, good adsorption performance, high mechanical strength, self-support and the like is a key step for realizing the industrial application of the iron-based metal organic framework materials at present. As Fe-MOFs are in powder solid state, the application of many fields is still in the experimental stage. In recent years, the application research of Fe-MOFs opens up a brand new direction for the field of heavy metal adsorption. A large number of researches prove that Fe-MOFs have the characteristics of fast adsorption kinetics, large adsorption capacity, good selectivity, reusability and the like, are relatively ideal heavy metal adsorbents, and have very important significance in research and application. The Fe-MOFs and functional materials with different properties or shapes are reasonably compounded under proper conditions, and the obtained two-phase or multi-phase composite material, namely the Fe-MOFs composite material, not only maintains the excellent properties of the original component material, but also can make up the defects of the Fe-MOFs in the application, thereby hopefully solving the problems encountered in the practical industrial application of the Fe-MOFs. Graphene Oxide (GO) has a high specific surface area and abundant surface functional groups as a carbon functional material with excellent performance. Wherein the oxygen-containing group can form coordination with central metal ions of Fe-MOFs, so that Fe-MOFs crystals are guided to perform heterogeneous nucleation on the surface of GO and further grow; and on the GO basal planesp 2 And pi-pi conjugation exists between the region and an aromatic ring of the MOFs organic ligand, hydrogen atoms in the hydroxyl groups of GO and oxygen atoms in the Fe-MOFs structure can generate hydrogen bonds, and the two acting forces can enhance the bonding firmness degree between GO and Fe-MOFs. Efficient junction of Fe-MOFs and GOAnd the method is expected to improve the crystallinity of the Fe-MOFs and fix the Fe-MOFs particles through the interface induction effect of GO surface functional groups. Meanwhile, the electrostatic spinning polymer film formed by the micro-nano fibers has relatively high specific surface area and porosity, is soft and flexible, has certain mechanical strength, is expected to improve the stability of Fe-MOFs and improve the distribution condition of crystals as a self-supporting carrier, and realizes the rapid transmission of gas. The ferric nitrate containing Fe3+And iron nitrate is added into the spinning solution to ensure that the spinning membrane fiber has a crystallization site of the Fe-MOFs crystal before in-situ growth, so that the Fe-MOFs crystal is easier to load on the fiber, and the load rate of the Fe-MOFs crystal is improved. In conclusion, the ternary-phase composite material is prepared by layer-by-layer self-assembly by taking the electrostatic spinning film as a substrate and adding GO as a structure directing agent to regulate the Fe-MOFs crystal, so that the Fe-MOFs can be comprehensively improved in the aspects of morphological structure, stability, adsorption and separation performance and self-supporting performance, a strategy is provided for further preparing the Fe-MOFs nano composite material with high adsorption performance, and the method has important significance for further realizing the industrial application of the Fe-MOFs in gas adsorption separation and adsorption of heavy metal ions in sewage.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a PA6/GO/Fe-MOFs three-phase composite material, which can comprehensively improve the aspects of the shape structure, stability, adsorption and separation performance and self-supporting performance of Fe-MOFs.
The invention can be realized by the following technical scheme: a preparation method of a polyamide 6/graphene oxide/iron-based metal organic framework composite material comprises the following steps:
(1) preparation of polyamide/graphene oxide spinning membrane: dissolving polyamide 6 in formic acid, adding graphene oxide and ferric nitrate, performing ultrasonic and heating stirring to fully dissolve the graphene oxide and ferric nitrate, uniformly dispersing the graphene oxide and ferric nitrate, standing the mixture at room temperature for 12 hours, and blending the mixture into a composite spinning film through an electrostatic spinning machine; wherein the mass percent of polyamide 6 and formic acid is 14-18%, the mass percent of graphene oxide and polyamide 6 is 0.3-0.5%, and the mass percent of ferric nitrate and polyamide 6 is 1.5-2.5%;
(2) preparing an iron-based metal organic framework precursor solution: the iron-based metal organic framework material is NH2-MIL-53(Fe) in a molar ratio of 1: adding 1 2-amino terephthalic acid and ferric nitrate into 20 ml of N, N-dimethylformamide, and carrying out ultrasonic treatment until the mixture is fully dissolved to obtain a metal organic framework precursor solution;
(3) preparing an in-situ grown iron-based metal organic framework crystal of a polyamide 6/graphene oxide fiber membrane: cutting the composite spinning membrane obtained in the step (1) into small pieces, uniformly placing the small pieces into the metal organic framework precursor solution obtained in the step (2) to ensure that the composite fiber membrane is immersed, and placing the sealed reaction kettle into a drying oven at 150 ℃ for reaction for 6 hours; and (3) taking out the composite spinning membrane, washing the composite spinning membrane for 3-6 times by using methanol, and then carrying out vacuum drying treatment for 8 hours at 100 ℃ to obtain the polyamide 6/graphene oxide/iron-based metal organic framework three-phase composite material.
In the step (1), the mass percentage of polyamide 6 to formic acid was 16%.
In the step (1), the mass percentage of the graphene oxide to the polyamide 6 is 0.4%.
In the step (1), the mass percentage of the ferric nitrate to the polyamide 6 was 2%.
In the PA6/GO/Fe-MOFs three-phase composite material, PA6 polymer is selected to be subjected to electrostatic spinning to form the nanofiber, the nanofiber has the advantages of small diameter, large specific surface area, easiness in functionalization of the surface and the like, and the nanofiber can be directly and continuously prepared through electrostatic spinning, so that the efficiency is higher, and the large-scale application is facilitated. Fe-MOFs as a porous material has the advantages of various structures, large specific surface area, adjustable pore channel size, modifiable framework and the like, and can be well applied to gas adsorption and separation. However, the Fe-MOFs material is still in experimental stage in many fields due to the defects of low mechanical strength, poor humidity stability, powdery solid finished product and the like. The Fe-MOFs and functional materials with different properties or shapes are reasonably compounded under proper conditions, and the obtained two-phase or multi-phase composite material, namely the Fe-MOFs composite material not only maintains the excellent properties of the original composition material, but also can make up the defects of the Fe-MOFs in respective applications, thereby hopefully solving the problem that the Fe-MOFs are actually compoundedDifficulties encountered in industrial applications. The graphene oxide has higher specific surface area and abundant surface functional groups, and oxygen-containing groups of the graphene oxide can form coordination with central metal ions of Fe-MOFs (metal organic frameworks), so that Fe-MOFs crystals are guided to perform heterogeneous nucleation on the GO surface and further grow; and on the GO basal planesp 2 And pi-pi conjugation exists between the region and an aromatic ring of the Fe-MOFs organic ligand, hydrogen atoms in the hydroxyl groups of GO and oxygen atoms in the Fe-MOFs structure can generate hydrogen bonds, and the two acting forces can enhance the bonding firmness degree between GO and Fe-MOFs. The effective combination of Fe-MOFs and GO is expected to improve the crystallinity of Fe-MOFs and fix Fe-MOFs particles through the interface induction effect of GO surface functional groups. Meanwhile, the electrostatic spinning polymer film formed by the micro-nano fibers has relatively high specific surface area and porosity, is soft and flexible, has certain mechanical strength, is expected to improve the stability of Fe-MOFs and the load condition of crystals as a self-supporting carrier, and realizes the rapid transmission of gas.
The preparation method of the PA6/GO/Fe-MOFs three-phase composite material has the following beneficial effects:
firstly, the PA6/GO/Fe-MOFs three-phase composite material prepared by the invention has stable physical and mechanical properties due to the nanofiber membrane formed by electrostatic spinning of the matrix material PA6 and GO.
Secondly, PA6/GO electrostatic spinning is used as a matrix, and ferric nitrate is added, so that a large amount of iron ions exist in the fiber before an in-situ growth experiment is carried out, a large amount of growth sites are provided for Fe-MOFs materials, the interface induction effect of GO surface functional groups improves the crystallinity of Fe-MOFs, and Fe-MOFs particles are fixed. The specific surface area and porosity of the three-phase composite material are simultaneously enhanced by GO and Fe-MOFs, and the adsorption performance of the material is enhanced.
Thirdly, the application prospect is wide, the preparation process is simple and the forming is convenient, and the prepared adsorption composite material has larger adsorption capacity and better flexibility and is suitable for the fields of gas adsorption separation, sewage adsorption of heavy metal ions and the like.
Drawings
FIG. 1 is an SEM image of different spun membrane fibers (PA6, PA6/GO, PA 6/GO/Fe).
FIG. 2 is SEM images of different composite materials PA6/Fe-MOFs, PA6/GO/Fe-MOFs, PA 6/GO/Fe/Fe-MOFs.
FIG. 3 is a graph of different composite material pairs N2Adsorption isotherm diagram of (1).
FIG. 4 is a graph of different composite materials vs. CO2Adsorption isotherm diagram of (1).
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the following detailed description is provided for the product of the present invention with reference to the examples.
Example 1
1. Preparation of spinning membrane:
dissolving 3 g of PA6 in 15.75 g of formic acid, adding 0.0612 g of GO and 0.0212 g of ferric nitrate, performing ultrasonic and heating stirring to uniformly disperse, and standing at room temperature for one night to obtain a PA6/GO/Fe spinning solution.
Firstly, wrapping tin foil paper on a receiving roller of a spinning machine, adhering a joint by using an adhesive tape, then taking a 10 ml syringe, and grinding the middle part of a needle head of the syringe into a completely horizontal round pipe with abrasive paper. About 8 ml of the spinning solution was then drawn up with a syringe and the syringe containing the spinning solution was fixed on an electrospinning machine. Clamping a connecting chuck of a positive high-voltage electrode at the front end part of a syringe needle, adjusting a push injection plate until the push injection plate just pushes out spinning solution in the syringe, setting a push injection distance and a push injection termination position, and setting a push injection rate. After the spinning solution starts to be injected and liquid drops just appear at the needle opening of the needle cylinder, a positive high-voltage switch and a negative high-voltage switch of the spinning machine are immediately and simultaneously turned on, and electrostatic spinning is started after positive voltage and negative voltage are adjusted to set values. Electrospinning a complete spun film takes approximately 24 hours. The prepared nanofiber film is finally attached to the tin foil paper on the surface of a receiving roller, the fiber film is carefully taken down and then placed in a 100 ℃ oven for drying for one night, and then the nanofiber film is taken out, dried and stored well.
2. Preparing a precursor solution: the iron-based metal organic framework material is NH2-MIL-53(Fe) in a molar ratio of 1: 1 2-Aminoterephthalic acid and ferric nitrate were added to 20 ml of DFully dissolving the mixture in MF (N, N-dimethylformamide) by ultrasonic for 2 hours to obtain Fe-MOFs precursor solution, and pouring the mixture into a 100 ml reaction kettle.
3. Preparing a composite material:
(1) the spun three kinds of spinning films are cut into 0.5 cm multiplied by 0.5 cm, and about 0.1g is weighed.
(2) And (3) putting the spinning membrane into a reaction kettle with the existing precursor solution to ensure that the spinning membrane is immersed, putting the screwed reaction kettle into an oven at 150 ℃, and continuously reacting for 6 hours.
(3) And (3) after the reaction is finished, cooling the reaction kettle to room temperature, clamping the loaded fiber membrane, washing for 4 times by using methanol, and putting the fiber membrane into an oven for vacuum drying at 100 ℃ overnight to obtain the PA6/GO/Fe/Fe-MOFs composite material.
Comparative example 1:
dissolving 3 g of PA6 in 15.75 g of formic acid, performing ultrasonic treatment and heating stirring to uniformly disperse the solution, and standing the solution at room temperature for one night to prepare a PA6 spinning solution; the remaining procedure was the same as in example 1, giving a PA6/Fe-MOFs composite material.
Comparative example 2:
dissolving 3 g of PA6 in 15.75 g of formic acid, adding 0.0612 g of GO, ultrasonically stirring and heating to uniformly disperse the GO, and standing at room temperature for one night to prepare a PA6/GO spinning solution; the remaining steps were the same as in example 1, giving a PA6/GO/Fe-MOFs composite.
In order to evaluate the technical effects of the present invention, SEM test and gas (N) were performed on the samples obtained in the present invention2And CO2) The results of the adsorption test are shown in figures 1 to 4:
FIG. 1 is SEM images of three spinning films of PA6, PA6/GO and PA 6/GO/Fe. FIG. 1(a) is PA 6; FIG. 1(b) is PA 6/GO; FIG. 1(c) is PA 6/GO/Fe;
FIG. 2 is an SEM image of composite materials PA6/Fe-MOFs, PA6/GO/Fe-MOFs, PA6/GO/Fe/Fe-MOFs, FIG. 2(a) is PA 6/Fe-MOFs; FIG. 2(b) is PA 6/GO/Fe-MOFs; FIG. 2(c) is PA 6/GO/Fe/Fe-MOFs;
FIG. 3 shows N of the composite materials PA6/Fe-MOFs, PA6/GO/Fe-MOFs, PA6/GO/Fe/Fe-MOFs and Fe-MOFs crystals2Adsorption isotherms;
FIG. 4 shows three spinning films of PA6, PA6/GO and PA6/GO/Fe, PA6/Fe-MOFs (abbreviated as PA 6Y), PA6/GO/Fe-MOFs (abbreviated as PA 6/GOY), PA6/GO/Fe/Fe-MOFs (abbreviated as PA 6/GO/FeY) composite material and the pair of CO and Fe-MOFs crystals2Adsorption isotherm of (a).
The appearance characteristics of three spinning films can be observed from the attached figure 1, and the fiber diameters are in the order of: PA6> PA6/GO > PA 6/GO/Fe. The PA6/GO spinning membrane and the PA6/GO/Fe spinning membrane are added with GO, so that the viscosity of a spinning solution is greatly increased, and the liquid discharge speed on a syringe needle is slow in spinning. The fiber diameter of the PA6/GO spinning membrane is larger than that of the PA6/GO/Fe spinning membrane, and the reason for analyzing the fiber diameter is that a small amount of ferric nitrate possibly added into the spinning solution can further improve the viscosity of the spinning solution. Obvious beading phenomenon can be observed on a scanning electron microscope picture of the PA6/GO/Fe spinning film, but no beading appears on the surfaces of the PA6 spinning film and the PA6/GO spinning film, which indicates that the viscosity of the spinning solution of the PA6/GO/Fe spinning film is higher than that of the PA6/GO and PA 6.
As can be seen from the attached figure 2, after in-situ growth, the Fe-MOFs crystal is successfully loaded on the spinning film, and the morphological characteristics of the Fe-MOFs crystal can be clearly seen. The growth conditions of the PA6 in-situ growth film are not much different from those of the PA6/GO in-situ growth film and the PA6/GO/Fe in-situ growth film. However, most of crystals on the PA6 in-situ growth film are gathered on the surface, and Fe-MOFs crystals growing in the fiber are fewer, but gaps between the surfaces of the PA6/GO in-situ growth film and the PA6/GO/Fe in-situ growth film and the fiber are full of Fe-MOFs crystals, so that the Fe-MOFs crystals can be obviously observed to be loaded on the fiber in a scanning electron microscope image of the PA6/GO in-situ growth film.
As shown in FIG. 3, the amounts of nitrogen adsorbed by PA6/Fe-MOFs and PA6/GO/Fe-MOFs are slightly different, while the amounts of nitrogen adsorbed by PA6/GO/Fe/Fe-MOFs are slightly higher than those adsorbed by PA6/Fe-MOFs and PA 6/GO/Fe-MOFs. The addition of ferric nitrate enables a PA6/GO/Fe spinning film to have a crystallization site before in-situ growth, so that the crystal plays a role of anchoring, and Fe-MOFs crystals are better loaded on the spinning film, therefore, the loading rate of the Fe-MOFs crystals in PA6/GO/Fe/Fe-MOFs is higher than that of the Fe-MOFs crystals in PA6/GO/Fe-MOFs, and therefore, the adsorption capacity of PA6/GO/Fe/Fe-MOFs to nitrogen is stronger than that of PA6/Fe-MOFs and PA 6/GO/Fe-MOFs.
As can be observed from the attached FIG. 4, the adsorption amount of the three in-situ grown films to carbon dioxide is much higher than that of the three spinning films. Before in-situ growth, the adsorption amount of the three spinning membranes to carbon dioxide is relatively close, but the adsorption effect of the spinning membrane added with the graphene oxide and the ferric nitrate to the carbon dioxide is observed to be better than that of the PA6 pure spinning membrane. As the load factor of the Fe-MOFs crystals in PA6/GO/Fe/Fe-MOFs is higher than that of the Fe-MOFs crystals in PA6/GO/Fe-MOFs, FIG. 4 shows that the adsorption amount of carbon dioxide by PA6/GO/Fe/Fe-MOFs is higher than that of PA 6/GO/Fe-MOFs. In conclusion, ferric nitrate is added into the spinning solution, so that a PA6/GO/Fe spinning film can form a crystallization site before in-situ growth, an anchoring effect is achieved, and Fe-MOFs crystals can be better loaded on the spinning film, so that the loading rate of the Fe-MOFs crystals in PA6/GO/Fe/Fe-MOFs is higher than that of the Fe-MOFs crystals in PA 6/GO/Fe-MOFs.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner; as will be readily apparent to those skilled in the art from the disclosure herein, the present invention may be practiced without these specific details; however, those skilled in the art should appreciate that they can readily use the disclosed conception and specific embodiments as a basis for designing or modifying other structures for carrying out the same purposes of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (4)
1. A preparation method of a polyamide 6/graphene oxide/iron-based metal organic framework composite material is characterized by comprising the following steps:
(1) preparation of polyamide/graphene oxide spinning membrane: dissolving polyamide 6 in formic acid, adding graphene oxide and ferric nitrate, performing ultrasonic and heating stirring to fully dissolve the graphene oxide and ferric nitrate, uniformly dispersing the graphene oxide and ferric nitrate, standing the mixture at room temperature for 12 hours, and blending the mixture into a composite spinning film through an electrostatic spinning machine; wherein the mass percent of polyamide 6 and formic acid is 14-18%, the mass percent of graphene oxide and polyamide 6 is 0.3-0.5%, and the mass percent of ferric nitrate and polyamide 6 is 1.5-2.5%;
(2) preparing an iron-based metal organic framework precursor solution: the iron-based metal organic framework material is NH2-MIL-53(Fe) in a molar ratio of 1: adding 1 2-amino terephthalic acid and ferric nitrate into 20 ml of N, N-dimethylformamide, and carrying out ultrasonic treatment until the 2-amino terephthalic acid and the ferric nitrate are fully dissolved to obtain an iron-based metal organic framework precursor solution;
(3) preparing an in-situ grown iron-based metal organic framework crystal of a polyamide 6/graphene oxide fiber membrane: cutting the composite spinning membrane obtained in the step (1) into small pieces, uniformly placing the small pieces into the metal organic framework precursor solution obtained in the step (2) to ensure that the composite fiber membrane is immersed, and placing the sealed reaction kettle into a drying oven at 150 ℃ for reaction for 6 hours; and (3) taking out the composite spinning membrane, washing the composite spinning membrane for 3-6 times by using methanol, and then carrying out vacuum drying treatment for 8 hours at 100 ℃ to obtain the polyamide 6/graphene oxide/iron-based metal organic framework three-phase composite material.
2. The method for preparing the polyamide 6/graphene oxide/metal organic framework three-phase composite material according to claim 1, wherein in the step (1), the mass percentage of polyamide 6 and formic acid is 16%.
3. The method for preparing the polyamide 6/graphene oxide/metal organic framework three-phase composite material according to claim 1, wherein in the step (1), the mass percentage of the graphene oxide to the polyamide 6 is 0.4%.
4. The method for preparing the polyamide 6/graphene oxide/metal organic framework three-phase composite material according to claim 1, wherein in the step (1), the mass percentage of the ferric nitrate to the polyamide 6 is 2%.
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