CN111821952A - Preparation method of polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material - Google Patents
Preparation method of polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material, which comprises the following steps: (1) preparing a PVDF/GO binary fiber membrane; (2) preparing MOFs precursor solution: the MOFs material is Cu-BTC or ZIF-8, and a precursor solution of the Cu-BTC or ZIF-8 is prepared; (3) and (3) carrying out in-situ self-assembly growth on the MOFs by using the PVDF/GO fiber membrane to prepare the PVDF/GO/MOFs three-phase composite material. This method of combining electrospinning with MOFs can be used to produce textiles with good adsorption properties and to prepare individual protective clothing that can adsorb toxic substances such as volatile organic compounds.
Description
Technical Field
The invention relates to the field of polymer/metal organic framework composite materials, in particular to a preparation method of a polyvinylidene fluoride (PVDF)/Graphene Oxide (GO)/Metal Organic Framework (MOFs) three-phase composite material.
Background
How to make metal haveThe organic framework Materials (MOFs) have the advantages of high crystallinity, stable pore structure, good adsorption performance, high mechanical strength, self-support and the like, and are a key step for realizing the industrial application of the MOFs at present. Under appropriate conditions, the MOFs and functional materials with different properties or shapes are reasonably compounded to obtain a two-phase or multi-phase composite material, namely the MOFs composite material, which not only maintains the excellent properties of the original component material, but also can make up the defects of the MOFs in application, so that the problem of the MOFs in practical industrial application is hopefully solved. 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 the central metal ions of the MOFs, so that the MOFs crystal is 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 MOFs organic ligand, hydrogen bonds can be generated between hydrogen atoms in the hydroxyl groups of GO and oxygen atoms in the MOFs structure, and the two acting forces can enhance the bonding firmness degree between GO and MOFs. The MOFs and GO are effectively combined, and the crystallinity of the MOFs is expected to be improved and MOFs particles are fixed through the interface induction effect of functional groups on the surface of GO. 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 MOFs and improve the distribution condition of crystals when being used as a self-supporting carrier, and realizes the rapid transmission of gas. In conclusion, the ternary phase composite material is prepared by layer-by-layer self-assembly of the MOFs crystal with the electrostatic spinning film as the matrix and the GO as the structure directing agent, so that the 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 MOFs nano composite material with high adsorption performance, and the method has important significance for further realizing industrial application of the MOFs in the fields of gas adsorption separation and individual protection.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a PVDF/GO/MOFs three-phase composite material, which can comprehensively improve the MOFs in the aspects of morphological structure, stability, adsorption and separation performance and self-supporting performance.
The invention can be realized by the following technical scheme:
a preparation method of a polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material comprises the following steps:
(1) preparing a polyvinylidene fluoride/graphene oxide fiber membrane: dissolving polyvinylidene fluoride in N, N-dimethylformamide, adding graphene oxide, surfactant cetyl trimethyl ammonium bromide and acetone, performing ultrasonic and heating stirring to uniformly disperse the graphene oxide, standing at room temperature for one night, and blending by using an electrostatic spinning machine to form a composite fiber membrane; wherein the mass ratio of polyvinylidene fluoride, N-dimethylformamide, hexadecyl trimethyl ammonium bromide to acetone is 50: 315: 1: 135, the mass ratio of the graphene oxide to the polyvinylidene fluoride is 1: 1000,1: 200,1: 100,3: 100, namely the weight percentages of the graphene oxide in the polyvinylidene fluoride are respectively 0.1%, 0.5%, 1% and 3%;
(2) preparing a metal organic framework precursor solution: the metal organic framework material is Cu-BTC or ZIF-8, and a precursor solution of the Cu-BTC or ZIF-8 is prepared;
(3) preparing a polyvinylidene fluoride/graphene oxide fiber film in-situ growth metal organic framework crystal: cutting the composite fiber membrane obtained in the step (1) into small pieces, uniformly putting the small pieces into the metal organic framework precursor solution obtained in the step (2), ensuring that the composite fiber membrane is immersed, and putting the sealed reaction kettle into a drying oven at 100 ℃ for reaction for 7.5 hours; and (3) taking out the composite fiber membrane after the reaction is finished, washing the composite fiber membrane for 3-6 times by using absolute ethyl alcohol or methanol, and drying the composite fiber membrane overnight at 100 ℃ to obtain the polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material.
In the PVDF/GO/MOFs three-phase composite material, a PVDF material is selected for electrostatic spinning to form the nanofiber, the nanofiber has the advantages of small diameter, large specific surface area, easy surface functionalization and the like, the nanofiber can be directly and continuously prepared through electrostatic spinning, the efficiency is higher, and the large-scale application is facilitated. MOFs asThe porous material has the advantages of various structures, large specific surface area, adjustable pore size, modifiable framework and the like, and can be well applied to gas adsorption and separation. However, the specific application of the MOFs material in many fields is limited due to the defects of low mechanical strength, poor humidity stability, powdery solid finished product and the like. Under appropriate conditions, MOFs and functional materials with different properties or shapes are reasonably compounded, and the obtained two-phase or multi-phase composite material, namely the MOFs composite material, not only maintains the excellent properties of the original composition material, but also can make up the defects of the MOFs in respective application, so that the difficult problems encountered in the actual industrial application of the MOFs are hopefully solved. 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 MOFs (metal-organic frameworks), so that the 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 MOFs organic ligand, hydrogen bonds can be generated between hydrogen atoms in the hydroxyl groups of GO and oxygen atoms in the MOFs structure, and the two acting forces can enhance the bonding firmness degree between GO and MOFs. The effective combination of the MOFs and GO is expected to improve the crystallinity of the MOFs and fix the MOFs particles through the interface induction effect of the 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 MOFs and improve the distribution condition of crystals when being used as a self-supporting carrier, and realizes the rapid transmission of gas.
Further, the MOFs material is Cu-BTC, and the preparation method of the precursor solution in the step (2) comprises the following steps: trimesic acid (H)3BTC) with absolute ethanol and copper nitrate Cu (NO)3)2Dissolving with deionized water respectively, performing ultrasonic treatment for 2 hr, mixing the two solutions, and stirring for 0.5 hr; wherein are all H3BTC and Cu (NO)3)2In a molar ratio of 1: 1, the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1.
further, the MOFs material is ZIF-8, and the preparation method of the precursor solution in the step (2)The method comprises the following steps: 2-methylimidazole (2-Hmim) and zinc nitrate Zn (NO)3)2·6H2Dissolving O in methanol respectively, performing ultrasonic treatment for 2 hours, mixing the two solutions, and finally performing ultrasonic treatment for 2 hours under stirring; among them, 2-Hmim and Zn (NO)3)2·6H2The molar ratio of O is 8: 1.
the preparation method of the PVDF/GO/MOFs three-phase composite material has the following beneficial effects:
firstly, the PVDF/GO/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 PVDF and GO serving as the matrix material.
Secondly, PVDF/GO electrostatic spinning is used as a matrix to provide a large number of growth sites for MOFs materials, and the interface induction effect of GO surface functional groups improves the crystallinity of the MOFs and fixes MOFs particles. The specific surface area and porosity of the three-phase composite material are simultaneously enhanced by GO and 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, individual protection and the like.
Drawings
FIG. 1 is an SEM image of PVDF/GO/ZIF-8 three-phase composites with different GO contents.
FIG. 2 is an SEM image of PVDF/GO/Cu-BTC three-phase composites with different GO contents.
FIG. 3 is N for different materials2Adsorption isotherms.
FIG. 4 is a PVDF/GO/ZIF-8 three-phase composite vs. CO for different GO contents2Adsorption condition (2).
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.
The invention discloses a preparation method of a PVDF/GO/MOFs three-phase composite material, which comprises the following steps:
(1) preparation of PVDF/GO fiber membranes: dissolving PVDF in DMF, adding GO, CTAB and acetone, performing ultrasonic and heating stirring to uniformly disperse the mixture, and blending the mixture into a binary composite fiber membrane by an electrostatic spinning machine; wherein the mass ratio of PVDF, DMF, CTAB and acetone is 50: 315: 1: 135, the mass ratio of GO to PVDF is 1: 1000,1: 200,1: 100,3: 100, respectively;
(2) preparing MOFs precursor solution: the MOFs material is Cu-BTC or ZIF-8, and a precursor solution of the Cu-BTC or ZIF-8 is prepared;
(3) preparing PVDF/GO fiber membrane in-situ growth MOFs: cutting the composite fiber membrane obtained in the step (1) into small pieces, uniformly placing the small pieces into the MOFs 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 100 ℃ for reaction for 7.5 hours or 6 hours; and (3) taking out the composite fiber membrane after the reaction is finished, washing the composite fiber membrane for 3-6 times by using absolute ethyl alcohol or methanol, and drying the composite fiber membrane overnight at 100 ℃ to obtain the PVDF/GO/MOFs three-phase composite material.
In the invention, the MOFs material is Cu-BTC, and the preparation method of the precursor solution in the step (2) comprises the following steps: h is to be3BTC with absolute ethanol and Cu (NO)3)2Dissolving with deionized water respectively, performing ultrasonic treatment for 2 hr, mixing the two solutions, and stirring for half an hour to obtain the final product; wherein the molar ratio of trimesic acid to copper nitrate is 1: 1, the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1. the MOFs material is ZIF-8, and the preparation method of the precursor solution in the step (2) comprises the following steps: 2-Hmim and Zn (NO)3)2·6H2Dissolving O in methanol respectively, performing ultrasonic treatment for 2 hours, mixing the two solutions, and stirring for 2 hours to obtain the product; wherein the molar ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 8: 1.
Example 1
The invention discloses a preparation method of a PVDF/GO/MOFs three-phase composite material, which comprises the following steps:
1. preparation of PVDF/GO fiber membranes
After 3 g of PVDF was dissolved in 18.9 g of DMF, 0.003 g of GO, 0.06 g of CTAB and 8.1 g of acetone were added and uniformly dispersed by ultrasonic and heating stirring, followed by standing at room temperature overnight.
Firstly, wrapping tin foil paper on a receiving roller of a spinning machine, adhering a joint by using an adhesive tape, then taking a 20 ml syringe, and grinding the middle part of a needle head of the syringe into a completely horizontal round pipe with abrasive paper. About 15 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 PVDF/GO binary fiber membrane took 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. Preparation of PVDF/GO/ZIF-8 three-phase composite material
(1) The spun binary fiber membrane is cut into the size of 0.5 cm multiplied by 0.5 cm, and about 0.12g is weighed.
(2) Preparing a precursor solution of ZIF-8: 1.2980 g of 2-Hmim was added to 30 ml of methanol and sonicated for 1 hour to mix 0.5866 g of Zn (NO)3)2·6H2O was added to 30 ml of methanol and sonicated for 0.5 hour, the two solutions were mixed and stirred uniformly for 2 hours, followed by sonication for 1 hour, and the mixture was poured into a 100 ml reaction vessel.
(3) And (3) putting the binary fiber membrane into the mixed solution to ensure that the fiber membrane is immersed, and putting the screwed reaction kettle into a drying oven at 90 ℃ for continuous reaction for 6 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carefully clamping the loaded fiber membrane, washing the fiber membrane for 4 times by using methanol, and drying the fiber membrane at 100 ℃ overnight to obtain the PVDF/GO/ZIF-8 three-phase composite material.
Example 2
The invention discloses a preparation method of a PVDF/GO/MOFs three-phase composite material, which comprises the following steps:
1. preparation of PVDF/GO fiber Membrane as in step 1 of example 1
2. Preparation of PVDF/GO/Cu-BTC composite material
(1) The spun fiber membrane was cut into 0.5 cm × 0.5 cm, and about 0.12g was weighed.
(2) Preparing a precursor solution of Cu-BTC: 0.84 g H3Adding BTC into 30 ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 2 hours after dissolving; 0.93 g of Cu (NO)3)2Adding 30 ml deionized water, stirring for half an hour, mixing the two solutions, fully stirring, and pouring into a 100 ml reaction kettle.
(3) Uniformly putting the mixture 1) into the mixture 2) to ensure that the fiber membrane is immersed, and putting the screwed reaction kettle into an oven at 100 ℃ for reaction for 7.5 hours.
(4) After the reaction is finished, cooling the reaction kettle to room temperature, carefully clamping the loaded fiber membrane, repeatedly washing the fiber membrane with absolute ethyl alcohol for several times, and drying the fiber membrane at 100 ℃ overnight to obtain the PVDF/GO/Cu-BTC three-phase composite material.
Example 3
The preparation method and the test method are the same as example 1, except that the amount of GO is 0.015 g, namely the mass ratio of GO to PVDF is 0.5%.
Example 4
The preparation method and the test method are the same as example 2, except that the amount of GO is 0.015 g, namely the mass ratio of GO to PVDF is 0.5%.
Example 5
The preparation method and the test method are the same as example 1, except that the amount of GO is 0.03 g, namely the mass ratio of GO to PVDF is 1%.
Example 6
The preparation method and the test method are the same as in example 2, except that the amount of GO is 0.03 g, i.e., the mass ratio of GO to PVDF is 1%.
Example 7
The preparation method and the test method are the same as example 1, except that the amount of GO is 0.09 g, i.e., the mass ratio of GO to PVDF is 3%.
Example 8
The preparation method and the test method are the same as example 2, except that the amount of GO is 0.09 g, i.e., the mass ratio of GO to PVDF is 3%.
Comparative example 1
The preparation method and the test method are the same as example 1, except that the amount of GO is 0 g.
Comparative example 2
The preparation method and the test method are the same as example 2, except that the amount of GO is 0 g.
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 an SEM image of a PVDF/GO/ZIF-8 three-phase composite material with different GO contents, wherein FIG. 1(a) is PVDF/ZIF-8 (comparative example 1); FIG. 1(b) is PVDF/GO (0.1%)/ZIF-8 (example 1); FIG. 1(c) is PVDF/GO (1%)/ZIF-8 (example 5); FIG. 1(d) is PVDF/GO (3%)/ZIF-8 (example 7);
FIG. 2 is an SEM image of a PVDF/GO/Cu-BTC three-phase composite material with different GO contents, and FIG. 2(a) is a PVDF/Cu-BTC (comparative example 2); FIG. 2(b) is PVDF/GO (0.1%)/Cu-BTC (example 2); FIG. 2(c) is PVDF/GO (0.5%)/Cu-BTC (example 4); FIG. 2(d) is PVDF/GO (3%)/Cu-BTC (example 8);
FIG. 3 is N for PVDF, PVDF/GO (0.5%)/Cu-BTC (example 4) and PVDF/GO (0.5%)/ZIF-8 (example 3)2Adsorption isotherms;
FIG. 4 shows the PVDF/GO/ZIF-8 three-phase composite material with different GO contents (0%, 0.1%, 0.5%, 1% and 3%) versus CO2The adsorption cases of (a) correspond to comparative example 1, example 3, example 5 and example 7, respectively.
It can be observed from FIG. 1 that with the addition of GO, the fiber surface becomes rough and the ZIF-8 crystals growing on the fiber surface become dense. The ZIF-8 crystals were present in greater amounts in example 1 than in comparative example 1, primarily because with the addition of GO more growth sites were available for nucleated self-assembly of ZIF-8 crystals. However, as GO content increased to 1% and 3%, more nucleation sites were available on the fiber surface for crystal growth, so that the same amount of ZIF-8 uniformly grew on more fiber surface, resulting in more crystal defects.
As can be seen from FIG. 2, when Cu-BTC crystals were tried to be supported on the surface of the binary fiber membrane, Cu-BTC existed only in the interstitial spaces of the composite fiber membrane, and the crystal grains were larger than those of ZIF-8, and the number of crystals was smaller. When the content of GO in the binary fiber membrane is 3%, the Cu-BTC crystals are in long columnar shapes and the size of the Cu-BTC crystals is far larger than the diameter of the fibers, which indicates that the Cu-BTC crystals cannot be loaded on the surfaces of the fibers.
By N of FIG. 32The adsorption isotherm shows the N of PVDF/GO (0.5%) compared with pure PVDF and binary fiber membrane2Compared with an adsorption isotherm, the composite material PVDF/GO (0.5%)/ZIF-8 to N loaded with ZIF-82The adsorption capacity is improved, and the fact that the specific surface area and the porosity of the composite material can be increased by loading ZIF-8 on the surface of the composite fiber membrane is proved; and because the loading effect of the Cu-BTC is not obvious, the crystal amount of the Cu-BTC is less, and the adsorption amount of PVDF/GO (0.5%)/Cu-BTC to nitrogen is lower than that of PVDF/GO (0.5%)/ZIF-8, which is consistent with the results of attached figures 1 and 2.
As can be observed from FIG. 4, as the GO content increases, the three-phase composite PVDF/GO/ZIF-8 sample is aligned to CO2The adsorption capacity is increased, which proves that the addition of GO provides more growth sites for heterogeneous nucleation of ZIF-8 crystals, induces the in-situ self-assembly of the ZIF-8, improves the crystallinity of the ZIF-8, and improves the CO content of the composite material2The amount of adsorption of (3). But since the GO content added is not so much, it is useful to increase the CO of the composite2The adsorption effect is not obvious.
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 (3)
1. A preparation method of a polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material is characterized by comprising the following steps:
(1) preparing a polyvinylidene fluoride/graphene oxide fiber membrane: dissolving polyvinylidene fluoride in N, N-dimethylformamide, adding graphene oxide, surfactant cetyl trimethyl ammonium bromide and acetone, performing ultrasonic and heating stirring to uniformly disperse the graphene oxide, standing at room temperature for one night, and blending by using an electrostatic spinning machine to form a composite fiber membrane; wherein the mass ratio of polyvinylidene fluoride, N-dimethylformamide, hexadecyl trimethyl ammonium bromide to acetone is 50: 315: 1: 135, the mass ratio of the graphene oxide to the polyvinylidene fluoride is 1: 1000,1: 200,1: 100,3: 100, namely the mass of the graphene oxide accounts for 0.1%, 0.5%, 1% and 3% of the mass of the polyvinylidene fluoride;
(2) preparing a metal organic framework precursor solution: the metal organic framework material is Cu-BTC or ZIF-8, and a precursor solution of the Cu-BTC or ZIF-8 is prepared;
(3) preparing a polyvinylidene fluoride/graphene oxide fiber film in-situ growth metal organic framework crystal: cutting the composite fiber membrane obtained in the step (1) into small pieces, uniformly putting the small pieces into the metal organic framework precursor solution obtained in the step (2), ensuring that the composite fiber membrane is immersed, and putting the sealed reaction kettle into a drying oven at 100 ℃ for reaction for 7.5 hours or 6 hours; and (3) taking out the composite fiber membrane after the reaction is finished, washing the composite fiber membrane for 3-6 times by using absolute ethyl alcohol or methanol, and drying the composite fiber membrane overnight at 100 ℃ to obtain the polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material.
2. The preparation method of the polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material according to claim 1, characterized by comprising the following steps: the metal organic framework material is Cu-BTC, and the preparation method of the precursor solution in the step (2) comprises the following steps: respectively dissolving trimesic acid and absolute ethyl alcohol, and dissolving copper nitrate and deionized water, then carrying out ultrasonic treatment for 2 hours, then mixing the two solutions, and stirring for half an hour to obtain the compound; wherein the molar ratio of trimesic acid to copper nitrate is 1: 1, the volume ratio of the absolute ethyl alcohol to the deionized water is 1: 1.
3. the preparation method of the polyvinylidene fluoride/graphene oxide/metal organic framework three-phase composite material according to claim 1, characterized by comprising the following steps: the metal organic framework material is ZIF-8, and the preparation method of the precursor solution in the step (2) comprises the following steps: respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in methanol, performing ultrasonic treatment for 2 hours, mixing the two solutions, and stirring for 2 hours to obtain the compound zinc nitrate salt solution; wherein the molar ratio of the 2-methylimidazole to the zinc nitrate hexahydrate is 8: 1.
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| CN112316911A (en) * | 2020-10-28 | 2021-02-05 | 青岛理工大学 | Dual-functional metal organic framework membrane material and preparation method and application thereof |
| CN112657352A (en) * | 2020-11-30 | 2021-04-16 | 同济大学 | Polyamide thin film layer composite reverse osmosis film and preparation method and application thereof |
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