CN116284825A - Two-dimensional mesoporous MOF/Ti 3 C 2 T x Hybrid material, preparation method and application thereof - Google Patents
Two-dimensional mesoporous MOF/Ti 3 C 2 T x Hybrid material, preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/14—Carbides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention provides a two-dimensional mesoporous MOF/Ti 3 C 2 T x Hybrid material, preparation method and application thereof, wherein the hybrid material adopts Ti 3 C 2 T x As template, inducing amphiphilic block copolymer in Ti by functional group 3 C 2 T x Surface in-situ self-assembly to form micelle spheres to obtain micelle spheres/Ti 3 C 2 T x A complex; further through coordination between micelle sphere hydrophilic chain segments and metal ions, MOF nucleation and growth are induced, micelle spheres are removed, and the two-dimensional mesoporous MOF/Ti is obtained 3 C 2 T x A hybrid material. The invention disclosesThe preparation method of the (C) is easy for mass production, and the prepared two-dimensional mesoporous MOF/Ti 3 C 2 T x The hybrid material not only has higher specific surface area and more exposed active sites, but also has a mesoporous and microporous hierarchical pore structure, wherein the content of the mesoporous and microporous hierarchical pore structure is 30-50%, and the hybrid material can be used as an energy storage electrode material of a super capacitor and has excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of nano composite materials, in particular to a two-dimensional mesoporous MOF/Ti 3 C 2 T x A hybrid material.
Background
In recent years, metal organic framework Materials (MOFs) are rapidly developed, have ultrahigh porosity and specific surface area, huge structural diversity and functional adjustability, are easy to accurately design at the molecular level, and have great development potential in the energy storage field. In particular, two-dimensional MOFs, which have open active sites and high specific surface areas, are reported in succession as excellent capacitive storage properties, and are becoming a research hotspot of supercapacitors.
However, in practical application, the two-dimensional MOFs sheet layers are easy to agglomerate and stack, so that active sites are covered, the specific surface area is reduced, and the electrochemical performance is lower. In order to improve the structural stability of the two-dimensional MOFs, overcome agglomeration and improve conductivity, the introduction of a conductive template to construct a two-dimensional MOFs hybrid material proves to be an effective method. When Bai et al prepare two-dimensional MOFs, graphene Oxide (GO) is introduced, a series of 2D-2D M-TCPP (M=Cu, co, ni)/GO hybrid materials are synthesized, wherein the specific capacities of Ni-TCPP/GO are 2.1 and 6.9 times that of pure Ni-TCPP nano-sheets and GO respectively, and GO can prevent the agglomeration of MOFs nano-sheets, plays roles of a micro-current collector and accelerating charge transmission, and improves the electrochemical performance (J Mater Chem A,2019,7,9086-9098).
However, the inherent microporous nature of MOFs materials makes their active sites and high surface area underutilized, and electrochemical performance is limited.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a two-dimensional mesoporous MOF/Ti 3 C 2 T x Hybrid material and preparation method thereof, and mesoporous structure is introduced on the basis of rich micropores of MOFs to form new structureThe electrolyte diffusion channel improves ion diffusion path, diffusion rate and diffusion capacity, so that micropores rich in MOFs, open active sites and high specific surface area are effectively utilized, and electrochemical performance of the MOFs is improved.
Another object of the present invention is also to provide a two-dimensional mesoporous MOF/Ti 3 C 2 T x The application of the hybrid material in the super capacitor.
The present invention achieves the above technical object by the following means.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
two-dimensional mesoporous MOF/Ti 3 C 2 T x A process for producing a hybrid material, characterized by using Ti as a first component 3 C 2 T x The surface functional group induces the amphiphilic block copolymer to self-assemble in situ to form micelle spheres, and further induces the nucleation and growth of the two-dimensional MOF through the coordination action between the hydrophilic chain segment of the micelle spheres and metal ions; finally removing micelle spheres to form mesopores to obtain the two-dimensional mesoporous MOF/Ti 3 C 2 T x A hybrid material.
Further, the mesoporous size is regulated and controlled through the polymerization degree of the hydrophobic chain segment of the amphiphilic block copolymer, and the polymerization degree of the hydrophobic chain segment is 70-250.
Further, the amphiphilic block copolymer is polystyrene-b-polyethylene oxide, polystyrene-b-poly (vinylpyridine) and polyoxyethylene-polyoxypropylene-polyoxyethylene; the metal salt is one or two of nitrate, acetate or chloride of zinc and copper.
Further, the method specifically comprises the following steps:
(1) Amphiphilic block copolymer and Ti 3 C 2 T x Respectively dissolving in a solvent, preparing a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A;
(2) Dissolving metal salt in a solvent, adding the solvent into the solution A, and stirring for 10 minutes to form a mixed solution B;
(3) Dissolving 2-amino terephthalic acid and polyvinylpyrrolidone (PVP) in a solvent, adding the solvent into the mixed solution B to obtain a reaction system, and reacting for 2-20 h at 30-120 ℃;
(4) Centrifuging the reaction product, washing to remove micelle spheres, and drying to obtain the two-dimensional mesoporous MOF/Ti 3 C 2 T x A hybrid material;
further, the solvent is one or more of Tetrahydrofuran (THF), ethanol, deionized water, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMAC).
Further, the mass ratio of the metal salt to the 2-amino terephthalic acid to the block copolymer is 1: (1-0.5): (0.15-1);
the metal salt, ti 3 C 2 The mass ratio of Tx to PVP is 1: (0.05-0.5): (0.5-3).
Further, the content of the metal salt in the reaction system is 0.5-1.5 mg/ml.
Further, in the step (4), the method for removing micelle balls from the product by washing is as follows: soaking in tetrahydrofuran or N, N-dimethylformamide for 6-10 hr, and washing with ethanol.
The two-dimensional mesoporous MOF/Ti prepared by the preparation method 3 C 2 T x A hybrid material characterized in that MOF is composited on Ti through in-situ assembly by hydrogen bond and coordination bond 3 C 2 T x On the template, the hybrid material has micropores and mesopores, and the proportion of the mesopores can reach 30% -50%.
The two-dimensional mesoporous MOF/Ti 3 C 2 T x Use of a hybrid material, characterized by an electrode material for a supercapacitor.
The invention has the following beneficial effects:
Ti 3 C 2 T x is a typical two-dimensional nanomaterial of transition metal carbide or carbonitride (MXene), T x Represents a surface group (e.g., hydroxyl, oxygen or fluorine). The invention adopts Ti 3 C 2 T x As a template by Ti 3 C 2 T x Hydrogen bonding of surface functional groups induces amphiphilic block copolymers in Ti 3 C 2 T x The surface is self-assembled in situ to form micelle sphere, and the coordination effect of hydrophilic chain segment and metal ion in the micelle sphere is further utilized to induce MOF nucleation and growth in Ti 3 C 2 T x The templates, the copolymer micelle spheres and the MOFs form hydrogen bond and coordination bond effects, and the interaction among components drives the ordered assembly of the hybrid material; after the micelle balls are removed by washing, the two-dimensional MOF/Ti 3 C 2 T x Mesoporous is formed in the hybrid material. And the size of the mesopores can be regulated and controlled through the micelle sphere hydrophobic chain segments, so that the structure of the hybrid material is controllable and the performance is adjustable.
The invention introduces the mesoporous into the two-dimensional MOF hybridization structure, thereby not only fully playing the two-dimensional MOF and Ti 3 C 2 T x The conductive template and the mesoporous feature can also integrate the attribute of each component to the maximum, and the two-dimensional mesoporous MOF/Ti obtained by the invention 3 C 2 T x The hybrid material has better electrochemical performance. When being used as the electrode material of the super capacitor, the two-dimensional mesoporous MOF/Ti of the invention is under the same condition 3 C 2 T x The specific capacity of the hybrid material is 8-14 times that of single MOF material, which is MOF/Ti 3 C 2 T x 3-6 times of the composite material.
Drawings
FIG. 1 is a two-dimensional mesoporous Zn-MOF/Ti prepared in example 1 3 C 2 T x -SEM image of 1.
FIG. 2 is a two-dimensional mesoporous Zn-MOF/Ti prepared in example 1 3 C 2 T x N of-1 2 Adsorption-desorption isotherm plot.
FIG. 3 is a two-dimensional mesoporous Zn-MOF/Ti prepared in example 1 3 C 2 T x -1 pore size distribution profile.
FIG. 4 is a two-dimensional mesoporous Cu-Zn-MOF/Ti prepared in example 5 3 C 2 T x -5 constant current charge-discharge curve graph.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1
5mg of amphiphilic block copolymer PS 150 -b-PEO 114 Dissolving in 5ml of N, N-dimethylformamide, and adding 8.5ml of deionized water to prepare a solution; will 2mg Ti 3 C 2 T x Dissolving in 1ml of N, N-dimethylformamide to prepare a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A; 10mg (CH) 3 COO) 2 Dissolving Zn in 5ml ethanol, adding into the solution A, and stirring for 10min to obtain a mixed solution B; 10mg H 2 BDC-NH 2 Dissolving 30mg PVP in 5ml of N, N-dimethylformamide, adding the mixture into the mixture B to obtain a reaction system, and stirring the reaction system at 35 ℃ for 2 hours; centrifugal washing after the reaction is finished, soaking for 6 hours by tetrahydrofuran, washing twice by ethanol, drying for 12 hours at 60 ℃ to obtain a hybrid material, and marking the hybrid material as a two-dimensional mesoporous Zn-MOF/Ti 3 C 2 T x -1。
As can be seen from FIG. 2, the two-dimensional mesoporous Zn-MOF/Ti prepared in this example 3 C 2 T x -1N of the composite material 2 Adsorption-desorption isotherms at P/P 0 Obvious hysteresis loops appear at 0.45-1.0, which indicates that mesoporous exists in the material, and the pore size distribution diagram 3 shows that the pore size distribution is concentrated at 1.6nm, 17.1nm and 34.7nm, the volume ratio of the mesoporous is 41.9%, and a large amount of mesoporous structures are successfully introduced.
The two-dimensional mesoporous Zn-MOF/Ti prepared in the embodiment 3 C 2 T x -1 as electrode material of super capacitor, after the super capacitor is manufactured, adopting a three-electrode test system, wherein Pt sheet is used as auxiliary electrode, ag/AgCl is used as reference electrode, and two-dimensional mesoporous Zn-MOF/Ti 3 C 2 T x -1 sample was working electrode with a current density of 1A/g and a specific capacity of 251.3F/g in 3m koh electrolyte.
Example two
10mg of block copolymer (PS) 102 -b-PEO 114 ) Dissolving in 5ml of N, N-dimethylformamide, and adding 9ml of deionized water to prepare a solution; 5mg of Ti 3 C 2 T x Dissolved in 1ml of N, N-dimethylformamide to prepareMixing the two solutions, and stirring for 10 minutes to obtain a solution A; 20mg of ZnCl 2 Dissolving in 5ml of N, N-dimethylformamide, adding into the solution, and stirring for 10min to obtain a mixed solution B; 10mg H 2 BDC-NH 2 Dissolving 20mg PVP in 5ml of N, N-dimethylformamide, adding into the mixture B to obtain a reaction system, and stirring at 120 ℃ for reaction for 10 hours; after the reaction is finished, centrifugally washing, soaking for 10 hours by using N, N-dimethylformamide, washing twice by using ethanol, drying for 12 hours at 60 ℃ to obtain a hybrid material, and marking the hybrid material as two-dimensional mesoporous Zn-MOF/Ti 3 C 2 T x -2。
The two-dimensional mesoporous Zn-MOF/Ti prepared in the embodiment 3 C 2 T x -2 as electrode material of super capacitor, after the super capacitor is manufactured, adopting a three-electrode test system, wherein Pt sheet is used as auxiliary electrode, ag/AgCl is used as reference electrode, and two-dimensional mesoporous Zn-MOF/Ti 3 C 2 T x -2 samples were working electrodes with a current density of 1A/g and a specific capacity of 239.2F/g in 3m koh electrolyte.
Example III
15mg of block copolymer (PS) 102 -b-PEO 114 ) Dissolving in 5ml of N, N-dimethylformamide, and adding 9ml of deionized water to prepare a solution; 5mg of Ti 3 C 2 T x Dissolving in 3ml of N, N-dimethylformamide to prepare a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A; 30mg of CuCl 2 Dissolving in 5ml of N, N-dimethylformamide, adding into the solution, and stirring for 10min to obtain a mixed solution B; 20mg H 2 BDC-NH 2 Dissolving 30mg PVP in a mixed solvent of 15ml DMF, 5ml ethanol and 5ml deionized water, adding the mixed solvent into the mixture B to obtain a reaction system, and stirring and reacting for 15h at 120 ℃; centrifugal washing after the reaction is finished, soaking for 8 hours by tetrahydrofuran, washing twice by ethanol, drying for 12 hours at 60 ℃ to obtain a hybrid material, and marking the hybrid material as a two-dimensional mesoporous Cu-MOF/Ti 3 C 2 T x -3。
The two-dimensional mesoporous Cu-MOF/Ti prepared in the embodiment 3 C 2 T x -3 asAfter the super capacitor electrode material is manufactured into the super capacitor, a three-electrode test system is adopted, wherein a Pt sheet is used as an auxiliary electrode, ag/AgCl is used as a reference electrode, and two-dimensional mesoporous Cu-MOF/Ti 3 C 2 T x -3 samples were working electrodes with a current density of 1A/g and a specific capacity of 267.1F/g in 3m koh electrolyte.
Example IV
10mg of block copolymer (PS) 200 -b-P4VP 100 ) Dissolving in 10ml of N, N-dimethylformamide, and adding 1ml of deionized water to prepare a solution; will 2mg Ti 3 C 2 T x Dissolving in 5ml of N, N-dimethylformamide to prepare a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A; 10mg ZnCl 2 And 10mg CuCl 2 Dissolving in 5ml of N, N-dimethylformamide, adding into the solution, and stirring for 10min to obtain a mixed solution B; will 15mg H 2 BDC-NH 2 Dissolving 50mg PVP in 5ml of N, N-dimethylformamide, adding the mixture into the mixture B to obtain a reaction system, and stirring and reacting for 20 hours at 100 ℃; centrifugal washing after the reaction is finished, soaking for 10 hours by tetrahydrofuran, washing twice by ethanol, drying for 12 hours at 60 ℃ to obtain a hybrid material, and marking the sample as two-dimensional mesoporous Cu-Zn-MOF/Ti 3 C 2 T x -4。
The two-dimensional mesoporous Cu-Zn-MOF/Ti prepared in the embodiment 3 C 2 T x -4 as electrode material of super capacitor, after the super capacitor is manufactured, adopting a three-electrode test system, wherein Pt sheet is used as auxiliary electrode, ag/AgCl is used as reference electrode, and two-dimensional mesoporous Cu-Zn-MOF/Ti 3 C 2 T x -4 samples were working electrodes with a current density of 1A/g and a specific capacity of 320.6F/g in 3M KOH electrolyte.
Example five
5mg of block copolymer (PS) 90 -b-PEO 114 ) Dissolving in 4ml of N, N-dimethylformamide, and adding 8.4ml of deionized water to prepare a solution; will 3mg Ti 3 C 2 T x Dissolving in 1ml of N, N-dimethylformamide to prepare a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A; 10mg ZnCl 2 And 10mg CuCl 2 Dissolving in 5ml ethanol, adding into the above solution, and stirring for 10min to obtain mixed solution B; 20mg H 2 BDC-NH 2 Dissolving 20mg PVP in 5ml of N, N-dimethylformamide, adding into the mixture B to obtain a reaction system, and stirring at 120 ℃ for reaction for 20 hours; centrifugal washing after the reaction is finished, soaking in tetrahydrofuran for 10 hours, washing with ethanol twice, drying at 60 ℃ for 12 hours to obtain a hybrid material, and marking the sample as two-dimensional mesoporous
Cu-Zn-MOF/Ti 3 C 2 T x -5。
The two-dimensional mesoporous Cu-Zn-MOF/Ti prepared in the embodiment 3 C 2 T x -5 as electrode material of super capacitor, after the super capacitor is manufactured, adopting a three-electrode test system, wherein Pt sheet is used as auxiliary electrode, ag/AgCl is used as reference electrode, and two-dimensional mesoporous Cu-Zn-MOF/Ti 3 C 2 T x The sample-5 is a working electrode, the constant current charge-discharge curve of the sample-5 is tested in 3M KOH electrolyte, the current density is 1A/g, the charge storage mechanism of the hybrid material comprises an electric double layer and a pseudo-capacitor, the electric double layer is mainly generated by adsorption of micropores and mesopores, the pseudo-capacitor is generated by oxidation-reduction reaction of active sites, and the specific capacity of the sample is calculated to be 338.2F/g according to the discharge curve.
Example six
30mg of the block copolymer (P123) was dissolved in 5ml of tetrahydrofuran, and 10ml of deionized water was added thereto to prepare a solution; will 3mg Ti 3 C 2 T x Dissolving in 1ml of N, N-dimethylformamide to prepare a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A; 30mg Cu (OAc) 2 ·H 2 Dissolving O in 5ml of ethanol, adding into the solution, and stirring for 10min to obtain mixed solution B; 30mg H 2 BDC-NH 2 Dissolving the mixture with 90mg PVP in 5ml of N, N-dimethylformamide, adding the mixture into the mixture B to obtain a reaction system, and stirring the reaction system at 80 ℃ for 15 hours; centrifugal washing after the reaction is finished, soaking for 6 hours by tetrahydrofuran, washing twice by ethanol, drying for 12 hours at 60 ℃ to obtain a hybrid material, and marking the hybrid material as a two-dimensional mesoporous Cu-MOF/Ti 3 C 2 T x -6。
The two-dimensional mesoporous Cu-MOF/Ti prepared in the embodiment 3 C 2 T x -6 as electrode material of super capacitor, after the super capacitor is manufactured, adopting a three-electrode test system, wherein Pt sheet is used as auxiliary electrode, ag/AgCl is used as reference electrode, and two-dimensional mesoporous Cu-MOF/Ti 3 C 2 T x -6 samples were working electrodes with a current density of 1A/g and a specific capacity of 278.5F/g in 3m koh electrolyte.
Comparative example one: comparative example-preparation of pure Zn-MOF
30mg H 2 BDC-NH 2 With 50mg PVP in a mixed solvent of 15ml DMF, 5ml ethanol and 5ml water, stirring for 10min. 30mg (CH) 3 COO) 2 Zn is added into the solution, ultrasonic treatment is carried out for 30min, then the reaction is carried out for 18 hours at 120 ℃, centrifugal washing is carried out after the reaction is finished, N-dimethylformamide and ethanol are respectively used for 2 times, and the pure Zn-MOF sample is obtained after drying at 60 ℃ for 12 hours.
The pure Zn-MOF prepared in the comparative example is used as an electrode material of a super capacitor, a three-electrode test system is adopted after the super capacitor is manufactured, the current density is 1A/g in 3M KOH electrolyte, and the specific capacity of a sample is 24F/g.
Comparative example two: comparative example-Zn-MOF/Ti 3 C 2 T x Preparation of composite materials
30mg H 2 BDC-NH 2 With 40mg PVP in a mixed solvent of 15ml DMF, 5ml ethanol and 5ml water, stirring for 10min. 30mg (CH) 3 COO) 2 Zn is added into the solution and stirred for 10min, 3mg Ti is added 3 C 2 T x Dissolving in 1ml of N, N-dimethylformamide to prepare a solution, adding the solution into the solution, stirring for 10min to obtain a reaction system, reacting at 120 ℃ for 15 hours, centrifugally washing after the reaction is finished, washing with N, N-dimethylformamide and ethanol for 2 times respectively, and drying at 60 ℃ for 12 hours to obtain Zn-MOF/Ti 3 C 2 T x Composite samples.
The Zn-MOF/Ti3C2Tx composite material prepared in the comparative example is used as an electrode material of a super capacitor, a three-electrode test system is adopted after the super capacitor is manufactured, the current density is 1A/g in 3M KOH electrolyte, and the specific capacity of a sample is 65F/g.
Table 1 shows specific capacities of supercapacitors prepared by using the electrode materials as the products prepared in examples 1 to 6 and comparative examples, and two-dimensional mesoporous MOF/Ti obtained in examples 1 to 6 3 C 2 T x When the hybrid material is used as the electrode material of the super capacitor, the two-dimensional mesoporous MOF/Ti of the invention is prepared under the same condition 3 C 2 T x The specific capacity of the hybrid material is 8-14 times that of single MOF material, which is MOF/Ti 3 C 2 T x 3-6 times of the composite material. The invention introduces the mesoporous into the two-dimensional MOF hybridization structure, thereby not only fully playing the two-dimensional MOF and Ti 3 C 2 T x The conductive template and the mesoporous feature can also integrate the component attribute to the maximum, and has better electrochemical performance.
Table 1 specific capacities of supercapacitors of examples 1 to 6 and comparative examples
The examples are preferred embodiments of the present invention, but the present invention is not limited to the above-described embodiments, and any obvious modifications, substitutions or variations that can be made by one skilled in the art without departing from the spirit of the present invention are within the scope of the present invention.
Claims (10)
1. Two-dimensional mesoporous MOF/Ti 3 C 2 T x A process for producing a hybrid material, characterized by using Ti as a first component 3 C 2 T x The surface functional group induces the amphiphilic block copolymer to self-assemble in situ to form micelle spheres, and further induces the nucleation and growth of the two-dimensional MOF through the coordination action between the hydrophilic chain segment of the micelle spheres and metal ions; finally removing micelle spheres to form mesopores to obtain the two-dimensional mesoporous MOF/Ti 3 C 2 T x A hybrid material.
2. The two-dimensional mesoporous MOF/Ti of claim 1 3 C 2 T x The preparation method of the hybrid material is characterized in that the mesoporous size can be regulated and controlled through the polymerization degree of the hydrophobic chain segment of the amphiphilic block copolymer, and the polymerization degree of the hydrophobic chain segment is 70-250.
3. The two-dimensional mesoporous MOF/Ti of claim 1 3 C 2 T x The preparation method of the hybrid material is characterized in that the amphiphilic block copolymer is polystyrene-b-polyoxyethylene, polystyrene-b-poly (vinylpyridine) and polyoxyethylene-polyoxypropylene-polyoxyethylene; the metal salt is one or two of nitrate, acetate or chloride of zinc and copper.
4. The two-dimensional mesoporous MOF/Ti of claim 1 3 C 2 T x The preparation method of the hybrid material is characterized by comprising the following steps of:
(1) Amphiphilic block copolymer and Ti 3 C 2 T x Respectively dissolving in a solvent, preparing a solution, mixing the two solutions, and stirring for 10 minutes to obtain a solution A;
(2) Dissolving metal salt in a solvent, adding the solvent into the solution A, and stirring for 10 minutes to form a mixed solution B;
(3) Dissolving 2-amino terephthalic acid and polyvinylpyrrolidone (PVP) in a solvent, adding the solvent into the mixed solution B to obtain a reaction system, and reacting for 2-20 h at 30-120 ℃;
(4) Centrifuging the reaction product, washing to remove micelle spheres, and drying to obtain the two-dimensional mesoporous MOF/Ti 3 C 2 T x A hybrid material.
5. The two-dimensional mesoporous MOF/Ti as claimed in claim 4 3 C 2 T x The preparation method of the hybrid material is characterized in that the solvent is one or more of Tetrahydrofuran (THF), ethanol, deionized water, N-Dimethylformamide (DMF) and N, N-Dimethylacetamide (DMAC).
6. The two-dimensional mesoporous MOF/Ti as claimed in claim 4 3 C 2 T x The preparation method of the hybrid material is characterized in that the mass ratio of the metal salt to the 2-amino terephthalic acid to the block copolymer is 1: (1-0.5): (0.15-1);
the metal salt, ti 3 C 2 The mass ratio of Tx to PVP is 1: (0.05-0.5): (0.5-3).
7. The two-dimensional mesoporous MOF/Ti according to claim 6 3 C 2 T x The preparation method of the hybrid material is characterized in that the content of the metal salt in the reaction system is 0.5-1.5 mg/ml.
8. The two-dimensional mesoporous MOF/Ti as claimed in claim 4 3 C 2 T x The preparation method of the hybrid material is characterized in that in the step (4), the method for removing micelle balls from the product by washing is as follows: soaking in tetrahydrofuran or N, N-dimethylformamide for 6-10 hr, and washing with ethanol.
9. Two-dimensional mesoporous MOF/Ti prepared by the preparation method according to any one of claims 1 to 8 3 C 2 T x A hybrid material characterized in that MOF is composited on Ti through in-situ assembly by hydrogen bond and coordination bond 3 C 2 T x On the template, the hybrid material has micropores and mesopores, and the proportion of the mesopores reaches 30% -50%.
10. The two-dimensional mesoporous MOF/Ti of claim 9 3 C 2 T x Use of a hybrid material, characterized by an electrode material for a supercapacitor.
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