CN108441982B - Preparation method of graphene/metal organic framework composite fiber - Google Patents
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Abstract
The invention discloses a preparation method of graphene/metal organic framework composite fibers, wherein the graphene/metal organic framework composite fibers are obtained by compounding graphene oxide and MOF crystal powder, and the preparation method comprises the following steps: mixing graphene oxide dispersion liquid with the concentration of 0.1-100 mg/mL and MOF crystal powder under a closed condition, uniformly stirring to obtain spinning solution, and performing wet spinning on the spinning solution to prepare graphene oxide/MOF composite fibers with the diameter of 20-50 micrometers, namely the graphene/metal organic framework composite fibers; the feeding mass ratio of the MOF crystal powder to the graphene oxide is (0.1-10): 1. the preparation method disclosed by the invention is simple to operate, mild in condition, adjustable in morphology, controllable in structure and uniform in component distribution, reserves the structural integrity of the graphene oxide and MOF crystals, has the excellent performances of the graphene oxide and the MOF, and can be used for batch or industrial production.
Description
Technical Field
The invention relates to the field of composite material synthesis, in particular to a preparation method of graphene/metal organic framework composite fibers.
Background
The graphene fiber is a continuous assembly material formed by graphene which is closely and orderly arranged along the axial direction. At present, methods such as a one-dimensional limited hydrothermal assembly method, a template-assisted chemical vapor deposition method, a wet spinning method, a dry spinning method, a film twisting method and the like have been developed to prepare graphene fibers. The wet spinning method has the advantages of being simple in operation, high in efficiency, good in continuity, easy to amplify and the like, and is the most classical method for preparing the graphene fibers.
Metal-organic frameworks (MOFs) are periodic porous framework materials, which are mainly formed by coordination of Metal ions/ion clusters and organic ligands through complexation. MOF materials have great potential in gas storage, chemical separation, selective catalysis, and drug delivery. In addition, porous metal oxides, porous carbon composites, and the like prepared from MOFs as precursors are also widely used in clean energy storage and conversion systems, such as fuel cells, supercapacitors, and lithium batteries.
Graphene has high conductivity and high theoretical surface area, and is an ideal electrode material. In recent years, flexible electronic devices have attracted much attention, and research and development of flexible electrode materials have become more important. Compared with the traditional two-dimensional and three-dimensional graphene composite material, the graphene composite fiber has the characteristics of high mechanical strength, high conductivity, high flexibility and the like, and is an attractive novel carbon-based fiber. The graphene/MOF composite fiber can have the structural advantages of all components, has the structural characteristics of fiber materials, and has good application prospects in the fields of energy, environment, flexible devices and the like. Therefore, the development of a simple, mild and universal method has important significance in constructing the graphene/MOF composite fiber with controllable morphology and structure and uniform component distribution.
Disclosure of Invention
The invention aims to overcome the problems of low mechanical strength, conductivity and flexibility of two-dimensional and three-dimensional graphene composite materials in the prior art, and provides a preparation method of graphene/metal organic framework composite fibers.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the graphene/metal organic framework composite fiber is characterized in that the graphene/metal organic framework composite fiber is obtained by compounding graphene oxide and MOF crystal powder. The method is almost applicable to all MOF crystals, and the preparation method of the MOF crystals can be obtained by consulting the literature, for example, Fe-MOF, ZIF-8, Co-MOF, Ni-MOF and Cu-MOF crystals can be synthesized by a solvothermal method; during the mixing with the graphene oxide, one MOF may be added, or two or more MOFs may be added.
Preferably, the preparation method of the graphene/metal organic framework composite fiber comprises the following steps: mixing the graphene oxide dispersion liquid with the concentration of 0.1-100 mg/mL and MOF crystal powder under a closed condition, uniformly stirring to obtain a spinning solution, and performing wet spinning on the spinning solution to prepare the graphene oxide/MOF composite fiber with the diameter of 20-50 micrometers, namely the graphene/metal organic framework composite fiber. (ii) a The charging mass ratio of the MOF crystal powder to the graphene oxide is (0.1-10): 1. the graphene oxide/MOF composite fiber with adjustable appearance, controllable structure and uniform component distribution is prepared by utilizing a simple mixing process and wet spinning, and the preparation method of the composite fiber is simple to operate, mild in condition, wide in source of used reagent instruments and capable of realizing batch or industrial production; the technical scheme of the invention adopts a wet spinning method, and wet spinning can be realized only by stirring and mixing two materials, namely MOF and graphene or graphene oxide; the solvent used in the method can be obtained in laboratories or industrial production, is low in price and wide in source, the used experimental equipment is convenient to operate, the structural integrity of the graphene oxide and the MOF crystal is kept in the synthesis process, and the method can effectively prevent the graphene oxide sheets and the MOF from agglomerating.
Preferably, the graphene oxide dispersion liquid is a graphene oxide aqueous solution or a graphene oxide DMF solution, and is preferably a graphene oxide DMF solution.
Preferably, the compounding manner of the graphene oxide surface and the MOF crystal powder in the graphene/metal organic framework composite fiber is one or two of the MOF crystal powder coated with graphene oxide or the MOF crystal powder uniformly loaded on the graphene oxide surface, specifically depending on the nature and the addition amount of the MOF crystal powder.
Preferably, the MOF crystal powder is selected from ZIF-8, Ni-MOF, Fe-MOF, MOF-5, Co-MOF or [ K ]2Sn2(bdc)3](H2O)XOne or more of them. Two or more MOF crystals can be added simultaneously, so that the graphene oxide/MOF composite fiber containing multiple MOF crystals is obtained.
Preferably, the wet spinning comprises the following steps: and continuously injecting the spinning solution into a coagulating bath through an injector, wherein the inner diameter of a needle head of the injector is 0.2-0.22mm, the outer diameter of the needle head of the injector is 0.2-0.6mm, and the length of the needle head of the injector is 10-15mm, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber.
Preferably, the charging mass ratio of the MOF crystal powder to the graphene oxide is (1-2): 1; the graphene oxide is flaky, and the transverse dimension of the graphene oxide is 0.1-100 mu m, preferably 40-50 mu m; the concentration of the graphene oxide dispersion liquid is 6-10 mg/mL.
Preferably, the coagulation bath is selected from 5% wt CaCl2Any one of water solution, ethanol solution of saturated potassium hydroxide or ethyl acetate.
Preferably, the coagulation bath is ethyl acetate.
Application of graphene/metal organic framework composite fiber prepared by the preparation method of the graphene/metal organic framework composite fiber in the fields of energy, environment or flexible devices.
By adopting the technical scheme of the invention, with the help of the properties of graphene oxide liquid crystal and based on the classical colloid liquid crystal theory, the one-dimensional graphene oxide/metal organic framework composite fiber is prepared by adding different types of MOF crystals and wet spinning, the graphene oxide/metal organic framework composite fiber prepared by uniformly attaching the MOF crystals to the surfaces of graphene oxide sheets of the fiber has a porous structure, the structural integrity of the graphene oxide and the MOF crystals is kept in the synthetic process, the composite fiber has the excellent performances of the graphene oxide and the MOF crystals, the excellent performances of the graphene oxide and the MOF crystals can be simultaneously exerted in the fields of catalysis, energy storage, sensing, adsorption and the like, the graphene oxide/metal organic framework composite fiber has certain flexibility, and the composite fiber has bright application prospect in flexible electronic devices
Therefore, the invention has the following beneficial effects: (1) the preparation method has the advantages of simple operation, mild condition, adjustable appearance, controllable structure and uniform component distribution; (2) the mass production or the industrial production can be realized; (3) the preparation method keeps the structural integrity of the graphene oxide and MOF crystals and has the excellent performances of the graphene oxide and the MOF crystals.
Drawings
FIG. 1 is a diagram of a graphene oxide/metal organic framework composite fiber entity in the invention.
FIG. 2 is a scanning electron micrograph of Fe-MOF (a, b) crystals.
FIG. 3 is a scanning electron micrograph of Co-MOF (a, b) crystals.
FIG. 4 is a scanning electron microscope image of the graphene oxide/Fe-MOF composite fiber, wherein the component mass ratio is Fe-MOF: GO =3:2(a, b).
FIG. 5 is a scanning electron microscope image of the graphene oxide/Co-MOF composite fiber, wherein the component mass ratio is Fe-MOF: GO =3:2(a, b).
FIG. 6 is a scanning electron microscope image of a graphene oxide/Fe-MOF/Co-MOF composite fiber, wherein the component mass ratio is Fe-MOF: Co-MOF: GO =3:3:4(a, b).
FIG. 7 is a flow chart of a process for preparing graphene oxide/metal organic framework composite fibers
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to the following examples and drawings, but the embodiments of the present invention are not limited thereto. The reagents used in the invention are all obtained by conventional experiments or on the market.
Example 1:
a preparation method of graphene/metal organic framework composite fibers comprises the following steps:
(1) preparation of Fe-MOF crystal powder: 50mL of N, N-dimethylformamide was added to a 100 mL reaction flask at room temperature, and 0.83 g of terephthalic acid and 1.215 g of anhydrous ferric chloride were added under magnetic stirring, and after completely dissolving, the mixture was reacted for 12 hours in an oil bath at 100 ℃. After the reaction, the reaction mixture was centrifuged at low speed (15 min, room temperature, 4000 rpm), the supernatant was removed, and the reaction mixture was washed with ethanol and centrifuged 3 times. Vacuum drying the obtained product at 60 ℃ for 24h to finally obtain Fe-MOF crystal powder;
(2) preparation of graphene/metal organic framework composite fiber graphene oxide DMF solution and Fe-MOF crystal powder are sequentially added into a centrifugal tube with the size of 5 mL, and the initial feeding ratio of the raw materials is controlled as follows: the graphene oxide solution has the concentration of 6.7 mg/mL, and the transverse size of a graphene oxide sheet is 50 micrometers; 30 mg of Fe-MOF crystal powder, wherein the adding mass ratio of the graphene oxide to the Fe-MOF crystal powder is 2: 3; and continuously mixing the obtained mixture for 2min under a closed condition by magnetic stirring to obtain GO/Fe-MOF composite gel, namely spinning solution, and further performing wet spinning on the spinning solution, wherein the specific steps are as follows: and continuously injecting the spinning solution into an ethyl acetate coagulating bath through an injector, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber with the diameter of 25 microns.
Samples in the examples were selected for characterization and analysis, and the test results were as follows:
FIG. 2(a, b) is an SEM picture of the Fe-MOF crystal powder obtained in example 1, and from FIG. 2 (b), it can be seen that the Fe-MOF crystals obtained are polygonal spindles with a transverse dimension of several hundred nanometers. Fig. 4(a, b) is the surface morphology of the graphene oxide/metal organic framework composite fiber obtained in example 1, fig. 4 (a) shows the overall morphology of the fiber, and it can be seen that the one-dimensional structure is formed by overlapping a large number of GO sheets, and Fe-MOF crystals are uniformly attached on the one-dimensional structure, and the fiber thickness is 25 μm; FIG. 4 (b) is an enlarged partial view of FIG. 4 (a), from which it is evident that the GO sheets are transparent, illustrating that the GO sheets do not agglomerate, further demonstrating that this self-supporting porous structure is built up from a large number of single GO sheets; the Fe-MOF crystals fully spread the surface of the GO sheet, and the phenomenon of Fe-MOF agglomeration is not found, so that the uniform composition of the Fe-MOF crystals and the GO sheet is intuitively proved, and a one-dimensional fiber structure is successfully obtained.
And (3) carrying out steam chemical reduction on the graphene oxide/MOF composite fiber by hydrazine hydrate (95 ℃, 12 h) to obtain the graphene/MOF composite fiber. The conductivity of the fiber reaches 310S/m can be used as a super capacitor, electrochemical performance characterization is carried out on the GO/MOF composite fiber in a three-electrode system, and the result shows that: at 10 mV s-1The highest specific capacity of the composite fiber reaches 329.1F g at the scanning speed-1. The loose and porous structure of the graphene oxide/MOF composite fiber is beneficial to increasing the contact area between the material and the electrolyte solution, so that the permeation of the electrolyte solution is facilitated, and the better electrochemical performance is realized.
Example 2:
a preparation method of graphene/metal organic framework composite fibers comprises the following steps: the preparation method of the Fe-MOF crystal powder is the same as that of example 1, and then the graphene oxide DMF solution and the Fe-MOF crystal powder are sequentially added into a centrifugal tube with the size of 5 mL, and the initial charge ratio of each raw material is controlled as follows: the graphene oxide solution has the concentration of 6 mg/mL, and the transverse size of a graphene oxide sheet is 30 micrometers; 20 mg of Fe-MOF crystal powder, and the adding mass ratio of the graphene oxide to the Fe-MOF crystal powder is 1: 1; and continuously mixing the obtained mixture for 5min under a closed condition by magnetic stirring to obtain GO/Fe-MOF composite gel, namely spinning solution, and further performing wet spinning on the spinning solution, wherein the specific steps are as follows: and continuously injecting the spinning solution into an ethyl acetate coagulating bath through an injector, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber with the diameter of 50 microns.
Example 3:
a preparation method of graphene/metal organic framework composite fibers comprises the following steps: the preparation method of the Fe-MOF crystal powder is the same as that of example 1, and then the graphene oxide DMF solution and the Fe-MOF crystal powder are sequentially added into a centrifugal tube with the size of 5 mL, and the initial charge ratio of each raw material is controlled as follows: the graphene oxide solution has the concentration of 10mg/mL, and the transverse size of a graphene oxide sheet is 50 micrometers; 40 mg of Fe-MOF crystal powder, and the adding mass ratio of the graphene oxide to the Fe-MOF crystal powder is 1: 2; and continuously mixing the obtained mixture for 5min under a closed condition by magnetic stirring to obtain GO/Fe-MOF composite gel, namely spinning solution, and further performing wet spinning on the spinning solution, wherein the specific steps are as follows: and continuously injecting the spinning solution into an ethyl acetate coagulating bath through an injector, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber with the diameter of 30 microns.
Example 4:
a preparation method of graphene/metal organic framework composite fibers comprises the following steps:
(1) preparation of Co-MOF crystalline powder: a50 mL beaker was charged with a mixed solution of 20 mL of methanol and 20 mL of ethanol, and 725 mg of cobalt nitrate hexahydrate was dissolved in the mixed solution and stirred until completely dissolved. A mixed solution of 20 mL of methanol and 20 mL of ethanol was added to another 50mL beaker, and 821 mg of 2-methylimidazole was dissolved in the mixed solution, followed by stirring until complete dissolution. The solutions in the two beakers are mixed and stirred uniformly, and then the mixture is reacted for 24 hours at room temperature. After the reaction is finished, centrifuging (15 min, room temperature, 4000 rpm), removing supernatant, washing for 3 times by using methanol, and carrying out vacuum drying on the obtained product at 60 ℃ for 24h to finally obtain Co-MOF crystal powder;
(2) preparing graphene/metal organic framework composite fibers: sequentially adding a graphene oxide DMF solution and Co-MOF crystal powder into a centrifugal tube with the size of 5 mL, and controlling the initial feeding ratio of the raw materials as follows: the graphene oxide solution has the concentration of 6.7 mg/mL, and the transverse size of a graphene oxide sheet is 50 micrometers; 30 mg of Co-MOF crystal powder, wherein the adding mass ratio of the graphene oxide to the Co-MOF crystal powder is 2: 3; and continuously mixing the obtained mixture for 2min under a closed condition by magnetic stirring to obtain GO/Co-MOF composite gel, namely spinning solution, and further performing wet spinning on the spinning solution, wherein the specific steps are as follows: and continuously injecting the spinning solution into an ethyl acetate coagulating bath through an injector, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber with the diameter of 30 microns.
The samples of the examples were selected for characterization and analysis and the results were as follows, FIG. 3 (a, b) is an SEM image of the Co-MOF crystal powder obtained in example 4, and as can be seen from FIG. 2 (b), the Co-MOF crystals obtained were polygonal and several hundred nanometers in lateral dimension. Fig. 5 (a, b) is the surface morphology of the graphene oxide/metal organic framework composite fiber obtained in example 4, fig. 5 (a) shows the overall morphology of the fiber, it can be seen that the one-dimensional structure is formed by overlapping a large number of GO sheets, Co-MOF crystals are uniformly attached on the one-dimensional structure, and the thickness of the fiber is 35 microns; fig. 5 (b) is a partial enlarged view of fig. 5 (a), from which it is apparent that the GO sheets are transparent, illustrating that no agglomeration of GO sheets occurs, further proving that this self-supporting porous structure is constructed by a large number of single-layer GO sheets, Co-MOF crystals have fully spread the surface of GO sheets, and no Co-MOF agglomeration is found, intuitively proving that Co-MOF crystals and GO sheets are uniformly compounded, and successfully obtaining a one-dimensional fibrous structure.
And (3) carrying out steam chemical reduction on the graphene oxide/MOF composite fiber by hydrazine hydrate (95 ℃, 12 h) to obtain the graphene/MOF composite fiber. The conductivity of the fiber reaches 308S/m, and the fiber can be used as a super capacitor to perform electrochemical performance table on GO/MOF composite fiber in a three-electrode systemAnd (4) marking, and displaying the following results: at 10 mV s-1The highest specific capacity of the composite fiber reaches 282.6F g at the scanning speed-1. The loose and porous structure of the graphene oxide/MOF composite fiber is beneficial to increasing the contact area between the material and the electrolyte solution, so that the permeation of the electrolyte solution is facilitated, and the better electrochemical performance is realized.
Example 5:
a preparation method of graphene/metal organic framework composite fibers comprises the following steps: sequentially adding a graphene oxide DMF solution, Fe-MOF crystal powder and Co-MOF crystal powder into a centrifugal tube with the size of 5 mL, and controlling the initial feeding ratio of the raw materials as follows: the graphene oxide solution has the concentration of 6.7 mg/mL, and the transverse size of a graphene oxide sheet is 50 micrometers; 15mg of Fe-MOF crystal powder, 15mg of Co-MOF crystal powder, and the adding mass ratio of the graphene oxide, the Fe-MOF crystal powder and the Co-MOF crystal powder is 4:3: 3; and (3) continuously mixing the obtained mixture for 2min under a closed condition by magnetic stirring to obtain a composite gel, namely spinning solution, and further performing wet spinning on the spinning solution, wherein the method specifically comprises the following steps: and continuously injecting the spinning solution into an ethyl acetate coagulating bath through an injector, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber with the diameter of 25 microns.
Samples in the examples were selected for characterization and analysis, and the test results were as follows:
the surface topography of the graphene oxide/metal organic framework composite fiber obtained in example 5 is shown in fig. 6 (a, b). FIG. 6 (a) shows the overall morphology of the fiber, and it can be seen that the one-dimensional structure is formed by overlapping a large number of GO sheets, and Co-MOF crystals and Fe-MOF crystals are uniformly attached thereon, and the fiber thickness is 40 μm. Fig. 6 (b) is a partial enlarged view of fig. 6 (a), from which it is evident that the GO sheets are transparent, illustrating that no agglomeration of the GO sheets has occurred, further demonstrating that this self-supporting porous structure is built up from a large number of single-layer GO sheets. The uniform composition of Co-MOF crystals, Fe-MOF crystals and GO sheets is intuitively proved, and a one-dimensional fiber structure is successfully obtained.
Carrying out steam chemical reduction on the graphene oxide/MOF composite fiber by hydrazine hydrate (95 ℃, 12 h) to obtain the graphene oxide/MOF composite fibergraphene/MOF composite fibers. The conductivity of the fiber reaches 320S/m, the fiber can be used as a super capacitor, electrochemical performance characterization is carried out on the GO/MOF composite fiber in a three-electrode system, and the result shows that: at 10 mVs-1The highest specific capacity of the composite fiber reaches 321.2F g at the scanning speed-1. The loose and porous structure of the graphene oxide/MOF composite fiber is beneficial to increasing the contact area between the material and the electrolyte solution, so that the permeation of the electrolyte solution is facilitated, and the better electrochemical performance is realized.
In conclusion, the graphene oxide/metal organic framework composite fiber with uniformly distributed components and controllable morphology and structure can be successfully prepared by the method.
Claims (7)
1. The preparation method of the graphene/metal organic framework composite fiber is characterized in that the graphene/metal organic framework composite fiber is obtained by compounding graphene oxide and MOF crystal powder;
the method comprises the following specific steps:
mixing the graphene dispersion liquid and the MOF crystal powder under a closed condition, uniformly stirring to obtain a spinning solution, and performing wet spinning on the spinning solution to prepare graphene oxide/MOF composite fibers, namely the graphene oxide/metal organic framework composite fibers;
the charging mass ratio of the MOF crystal powder to the graphene oxide is (0.1-10) to 1;
the MOF crystal powder is selected from ZIF-8, Ni-MOF, Fe-MOF, MOF-5, Co-MOF or [ K ]2Sn2(bdc)3](H2O)XOne or more of the above;
the graphene oxide is flaky, and the transverse dimension of the graphene oxide is 0.1-100 micrometers;
the concentration of the graphene oxide dispersion liquid is 6-10 mg/mL;
the wet spinning method comprises the following steps: continuously injecting the spinning solution into a coagulating bath through an injector, and then carrying out vacuum filtration and natural drying to obtain the graphene oxide/MOF composite fiber;
the inner diameter of the needle head of the injector is 0.2-0.22mm, the outer diameter is 0.2-0.6mm, and the length is 10-15 mm;
the coagulating bath is selected from 5 wt% CaCl2Any one of water solution, ethanol solution of saturated potassium hydroxide or ethyl acetate.
2. The preparation method of the graphene/metal-organic framework composite fiber according to claim 1, wherein the diameter of the prepared graphene oxide/MOF composite fiber is 20-50 micrometers.
3. The method of claim 2, wherein the graphene oxide dispersion is an aqueous graphene oxide solution or a DMF (dimethyl formamide) graphene oxide solution.
4. The preparation method of the graphene/metal-organic framework composite fiber according to claim 2, wherein the graphene oxide surface and the MOF crystal powder in the graphene/metal-organic framework composite fiber are compounded in a manner that the MOF crystal powder coated with graphene oxide or the MOF crystal powder is uniformly loaded on the graphene oxide surface or on both the graphene oxide surface and the MOF crystal powder.
5. The preparation method of the graphene/metal-organic framework composite fiber according to any one of claims 2 and 3, wherein the charging mass ratio of the MOF crystal powder to the graphene oxide is (1-2): 1.
6. The method for preparing the graphene/metal-organic framework composite fiber according to claim 1, wherein the coagulating bath is ethyl acetate.
7. The graphene/metal-organic framework composite fiber prepared by the preparation method of the graphene/metal-organic framework composite fiber according to any one of claims 1, 3 or 6 is applied to the fields of energy, environment or flexible devices.
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