A two-dimensional mesoporous MOF / Ti 3 C 2 T x Hybrid material, preparation method and application thereof

Abstract

The present invention provides a two-dimensional mesoporous MOF / Ti3C2T x hybrid material, a preparation method thereof and an application thereof. The hybrid material uses Ti3C2T x as a template, and amphiphilic block copolymers are in-situ self-assembled on the surface of Ti3C2T x to form micelle spheres, obtaining a micelle sphere / Ti3C2T x composite; further, through the coordination effect between the hydrophilic segments of the micelle spheres and metal ions, the nucleation and growth of MOF are induced, and the micelle spheres are removed to obtain a two-dimensional mesoporous MOF / Ti3C2T x hybrid material. The preparation method disclosed by the present invention is easy to scale up production. The prepared two-dimensional mesoporous MOF / Ti3C2T x hybrid material not only has a high specific surface area and more exposed active sites, but also has a hierarchical pore structure of mesopores and micropores, and the mesopore proportion is 30-50%. This material can be used as an electrode material for supercapacitor energy storage and has excellent electrochemical performance.

Description

Technical Field

[0001] The present invention relates to the technical field of nanocomposite materials, and particularly relates to a two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material. Background Art

[0002] In recent years, metal-organic framework materials (MOFs) have developed rapidly, with ultra-high porosity and specific surface area, great structural diversity and tunable functionality, and are easy to be precisely designed at the molecular level, showing great potential in the energy storage field. Especially two-dimensional MOFs, with open active sites and high specific surface area, excellent capacitive storage performance has been successively reported, becoming a research hotspot of supercapacitors.

[0003] However, in practical applications, two-dimensional MOF sheets are prone to agglomeration and stacking, resulting in the coverage of active sites and the decrease of specific surface area, leading to low electrochemical performance. To improve the structural stability of two-dimensional MOFs, overcome agglomeration, and improve conductivity, introducing a conductive template to construct two-dimensional MOF hybrid materials has been proved to be an effective method. Bai et al. introduced graphene oxide (GO) when preparing two-dimensional MOFs, and synthesized a series of 2D-2D M-TCPP (M = Cu, Co, Ni) / GO hybrid materials. The specific capacitance of Ni-TCPP / GO is 2.1 and 6.9 times that of pure Ni-TCPP nanosheets and GO respectively. GO can not only prevent the agglomeration of MOF nanosheets, but also act as a micro current collector to accelerate charge transfer, improving the electrochemical performance (J Mater Chem A, 2019, 7, 9086-9098).

[0004] However, the inherent microporous property of MOF materials restricts the full utilization of their active sites and high surface area, and the electrochemical performance is limited. Summary of the Invention

[0005] Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material and its preparation method. Based on the rich micropores of MOFs, a mesoporous structure is introduced to form a new electrolyte diffusion channel, improve the ion diffusion path, increase the diffusion rate and diffusion ability, effectively utilize the rich micropores, open active sites and high specific surface area of MOFs, and enhance its electrochemical performance.

[0006] Another purpose of the present invention is also to provide a two-dimensional mesoporous MOF / Ti 3 C 2 T xApplication of Hybrid Materials in Supercapacitors.

[0007] The present invention achieves the above technical objectives through the following technical means.

[0008] In order to achieve the above technical objectives, the technical solution adopted by the present invention is as follows:

[0009] A preparation method of a two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material, characterized in that first, the surface functional groups of Ti 3 C 2 T x are used to induce the in-situ self-assembly of amphiphilic block copolymers to form micelle spheres, and further, through the coordination between the hydrophilic segments of the micelle spheres and metal ions, the nucleation and growth of two-dimensional MOF are induced; finally, the micelle spheres are removed to form mesopores, and a two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material is obtained.

[0010] Furthermore, the size of the mesopores is regulated by the degree of polymerization of the hydrophobic segments of the amphiphilic block copolymer, and the degree of polymerization of the hydrophobic segments is 70-250.

[0011] Furthermore, the amphiphilic block copolymer is polystyrene-b-polyethylene oxide, polystyrene-b-poly(vinylpyridine), or poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide); the metal salt is one or two of zinc, copper nitrates, acetates, or chlorides.

[0012] Furthermore, it specifically includes the following steps:

[0013] (1) Dissolve the amphiphilic block copolymer and Ti 3 C 2 T x in solvents respectively to prepare solutions, mix the two solutions, and stir for 10 minutes to obtain solution A;

[0014] (2) Dissolve the metal salt in a solvent, add it to solution A, and stir for 10 minutes to form a mixed solution B;

[0015] (3) Dissolve 2-aminoterephthalic acid and polyvinylpyrrolidone (PVP) in a solvent, add it to the mixed solution B to obtain a reaction system, and react at 30-120 °C for 2-20 h;

[0016] (4) Centrifuge the reaction product, wash to remove the micelle spheres, and dry to obtain a two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material;

[0017] Further, the solvent is one or more of tetrahydrofuran (THF), ethanol, deionized water, N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC).

[0018] Further, the mass ratio of the metal salt, 2-aminoterephthalic acid, and the block copolymer is 1:(1 - 0.5):(0.15 - 1);

[0019] The metal salt, Ti 3 C 2 The mass ratio of Tx, PVP is 1:(0.05 - 0.5):(0.5 - 3).

[0020] Further, the content of the metal salt in the reaction system is 0.5 - 1.5 mg / ml.

[0021] Further, in step (4), the method for removing the micelle spheres from the product by washing is: soaking in tetrahydrofuran or N,N-dimethylformamide for 6 - 10 h, and then washing with ethanol.

[0022] The two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material prepared by the preparation method is characterized in that the MOF is composited on the Ti 3 C 2 T x template in the form of in-situ assembly through hydrogen bonding and coordination bonding, and the hybrid material has micropores and mesopores, and the mesopore ratio can reach 30% - 50%.

[0023] The application of the two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material is characterized in that it is used as an electrode material for supercapacitors.

[0024] The present invention has the following beneficial effects:

[0025] Ti 3 C 2 T x is a typical two-dimensional nanomaterial of transition metal carbide or carbonitride (MXene), and T x represents surface groups (such as hydroxyl, oxygen, or fluorine). The present invention uses Ti 3 C 2 T x as a template, and through the hydrogen bonding of the surface functional groups of Ti 3 C 2 T x induces the amphiphilic block copolymer on the Ti3 C 2 T x Self-assembly occurs in situ on the surface to form micelle spheres. Further, the coordination between the hydrophilic segments in the micelle spheres and metal ions is utilized to induce the nucleation and growth of MOF. In Ti 3 C 2 T x hydrogen bonds and coordination bonds are formed among the template, copolymer micelle spheres, and MOF. The interactions among the components drive the ordered assembly of the hybrid material; after washing away the micelle spheres, mesopores are formed in the two-dimensional MOF / Ti 3 C 2 T x hybrid material. Moreover, the size of the mesopores can be regulated by the hydrophobic segments of the micelle spheres, enabling the controllable structure and adjustable properties of the hybrid material.

[0026] In the present invention, mesopores are introduced into the two-dimensional MOF hybrid structure, which not only fully exploits the respective characteristics of two-dimensional MOF, Ti 3 C 2 T x conductive template, and mesopores, but also maximally integrates the properties of each component. The two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material obtained in the present invention has good electrochemical performance. When used as an electrode material for supercapacitors, under the same conditions, the specific capacitance of the two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material of the present invention is 8 to 14 times that of a single MOF material and 3 to 6 times that of the MOF / Ti 3 C 2 T x composite material. Description of the Drawings

[0027] Figure 1 is the SEM image of two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -1 prepared in Example 1.

[0028] Figure 2 is the N 3 C 2 T x adsorption-desorption isotherm diagram of two-dimensional mesoporous Zn-MOF / Ti 2 -1 prepared in Example 1.

[0029] Figure 3 is the two-dimensional mesoporous Zn-MOF / Ti prepared in Example 1 3 C 2 T xPore size distribution diagram of -1.

[0030] Figure 4 is the two-dimensional mesoporous Cu-Zn-MOF / Ti prepared in Example 5 3 C 2 T x Galvanostatic charge-discharge curve of -5. Detailed implementation manners

[0031] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments, but the protection scope of the present invention is not limited thereto.

[0032] Example 1

[0033] Dissolve 5 mg of amphiphilic block copolymer PS 150 -b-PEO 114 in 5 ml of N,N-dimethylformamide, then add 8.5 ml of deionized water to prepare a solution; dissolve 2 mg of Ti 3 C 2 T x in 1 ml of N,N-dimethylformamide to prepare a solution, mix the two solutions, and stir for 10 minutes to obtain solution A; add 10 mg of (CH 3 COO) 2 Zn dissolved in 5 ml of ethanol to the above solution A, stir for 10 min to obtain a mixed solution B; dissolve 10 mg of H 2 BDC-NH 2 and 30 mg of PVP in 5 ml of N,N-dimethylformamide, and then add it to the above mixture B to obtain a reaction system, stir and react at 35 °C for 2 h; after the reaction, centrifuge and wash, soak in tetrahydrofuran for 6 h, then wash twice with ethanol, and dry at 60 °C for 12 hours to obtain a hybrid material, and mark this sample as two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -1.

[0034] From Figure 2 it can be seen that the N 3 C 2 T x adsorption-desorption isotherm of the -1 composite material prepared in this example shows an obvious hysteresis loop when P / P 2 is 0.45-1.0, indicating the presence of mesopores in the material. From its pore size distribution 0 it can be seen that its pore size distribution is concentrated at 1.6 nm, 17.1 nm and 34.7 nm, and the proportion of mesopore volume is 41.9%, successfully introducing a large number of mesoporous structures. Figure 3 It can be seen that its pore size distribution is concentrated at 1.6 nm, 17.1 nm and 34.7 nm, and the proportion of mesopore volume is 41.9%, successfully introducing a large number of mesoporous structures.

[0035] Using the two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -1 prepared in this example as the electrode material of a supercapacitor, after making a supercapacitor, a three-electrode test system is adopted, where the Pt sheet is the auxiliary electrode, Ag / AgCl is the reference electrode, and the two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -1 sample is the working electrode. In a 3M KOH electrolyte, at a current density of 1 A / g, the specific capacitance of the sample is 251.3 F / g.

[0036] Example 2

[0037] Dissolve 10 mg of block copolymer (PS 102 -b-PEO 114 ) in 5 ml of N,N-dimethylformamide, then add 9 ml of deionized water to prepare a solution; dissolve 5 mg of Ti 3 C 2 T x in 1 ml of N,N-dimethylformamide to prepare a solution, mix the two solutions, and stir for 10 minutes to obtain solution A; add 20 mg of ZnCl 2 dissolved in 5 ml of N,N-dimethylformamide to the above solution, stir for 10 min to obtain a mixed solution B; dissolve 10 mg of H 2 BDC-NH 2 and 20 mg of PVP in 5 ml of N,N-dimethylformamide, and then add it to the above mixture B to obtain a reaction system, and stir and react at 120 °C for 10 h; after the reaction, centrifuge and wash, soak in N,N-dimethylformamide for 10 h, then wash twice with ethanol, and dry at 60 °C for 12 hours to obtain a hybrid material, and label this sample as two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -2.

[0038] Using the two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -2 prepared in this example as the electrode material of a supercapacitor, after making a supercapacitor, a three-electrode test system is adopted, where the Pt sheet is the auxiliary electrode, Ag / AgCl is the reference electrode, and the two-dimensional mesoporous Zn-MOF / Ti 3 C 2 T x -2 sample is the working electrode. In a 3M KOH electrolyte, at a current density of 1 A / g, the specific capacitance of the sample is 239.2 F / g.

[0039] Example 3

[0040] Dissolve 15 mg of block copolymer (PS 102 -b-PEO 114 ) in 5 ml of N,N-dimethylformamide, then add 9 ml of deionized water to prepare a solution; dissolve 5 mg of Ti 3 C 2 T x in 3 ml of N,N-dimethylformamide to prepare a solution, mix the two solutions, and stir for 10 minutes to obtain solution A; dissolve 30 mg of CuCl 2 in 5 ml of N,N-dimethylformamide and add it to the above solution, stir for 10 min to obtain a mixed solution B; dissolve 20 mg of H 2 BDC-NH 2 and 30 mg of PVP in a mixed solvent of 15 ml of DMF, 5 ml of ethanol and 5 ml of deionized water, and then add it to the above mixture B to obtain a reaction system, stir and react at 120 °C for 15 h; after the reaction, centrifuge and wash, soak in tetrahydrofuran for 8 h, then wash twice with ethanol, and dry at 60 °C for 12 hours to obtain a hybrid material, mark this sample as two-dimensional mesoporous Cu-MOF / Ti 3 C 2 T x -3.

[0041] Use the two-dimensional mesoporous Cu-MOF / Ti 3 C 2 T x -3 prepared in this example as a supercapacitor electrode material. After making a supercapacitor, use a three-electrode test system, where the Pt sheet is the auxiliary electrode, Ag / AgCl is the reference electrode, and the two-dimensional mesoporous Cu-MOF / Ti 3 C 2 T x -3 sample is the working electrode. In a 3M KOH electrolyte, at a current density of 1 A / g, the specific capacitance of the sample is 267.1 F / g.

[0042] Example 4

[0043] Dissolve 10 mg of block copolymer (PS 200 -b-P4VP 100 ) in 10 ml of N,N-dimethylformamide, then add 1 ml of deionized water to prepare a solution; dissolve 2 mg of Ti 3 C 2 T x in 5 ml of N,N-dimethylformamide to prepare a solution, mix the two solutions, and stir for 10 minutes to obtain solution A; dissolve 10 mg of ZnCl 2 and 10 mg of CuCl2 Dissolve it in 5 ml of N,N-dimethylformamide and add it to the above solution, stir for 10 min to obtain a mixed solution B; add 15 mg of H 2 BDC-NH 2 and 50 mg of PVP are dissolved in 5 ml of N,N-dimethylformamide, and then added to the above mixture B to obtain a reaction system, and stirred at 100 °C for 20 h; after the reaction is completed, centrifuge and wash, soak in tetrahydrofuran for 10 h, then wash twice with ethanol, and dry at 60 °C for 12 hours to obtain a hybrid material, mark this sample as two-dimensional mesoporous Cu-Zn-MOF / Ti 3 C 2 T x -4.

[0044] Take the two-dimensional mesoporous Cu-Zn-MOF / Ti 3 C 2 T x -4 prepared in this example as the electrode material of a supercapacitor. After making a supercapacitor, a three-electrode test system is adopted, where the Pt sheet is the auxiliary electrode, Ag / AgCl is the reference electrode, and the two-dimensional mesoporous Cu-Zn-MOF / Ti 3 C 2 T x -4 sample is the working electrode. In a 3M KOH electrolyte solution, when the current density is 1 A / g, the specific capacitance of the sample is 320.6 F / g.

[0045] Example 5

[0046] Dissolve 5 mg of block copolymer (PS 90 -b-PEO 114 ) in 4 ml of N,N-dimethylformamide, and then add 8.4 ml of deionized water to prepare a solution; dissolve 3 mg of Ti 3 C 2 T x in 1 ml of N,N-dimethylformamide to prepare a solution. Mix the two solutions and stir for 10 minutes to obtain solution A; dissolve 10 mg of ZnCl 2 and 10 mg of CuCl 2 in 5 ml of ethanol and add it to the above solution, stir for 10 min to obtain a mixed solution B; dissolve 20 mg of H 2 BDC-NH 2 and 20 mg of PVP in 5 ml of N,N-dimethylformamide, and then add it to the above mixture B to obtain a reaction system, and stir at 120 °C for 20 h; after the reaction is completed, centrifuge and wash, soak in tetrahydrofuran for 10 h, then wash twice with ethanol, and dry at 60 °C for 12 hours to obtain a hybrid material, mark this sample as two-dimensional mesoporous

[0047] Cu-Zn-MOF / Ti 3 C 2 T x -5。

[0048] Using the two-dimensional mesoporous Cu-Zn-MOF / Ti prepared in this example 3 C 2 T x -5 as the electrode material of the supercapacitor, after making the supercapacitor, a three-electrode test system is adopted, where the Pt sheet is the auxiliary electrode, Ag / AgCl is the reference electrode, and the two-dimensional mesoporous Cu-Zn-MOF / Ti 3 C 2 T x -5 sample is used as the working electrode, and its galvanostatic charge-discharge curve is tested in 3M KOH electrolyte with a current density of 1 A / g. According to Figure 4 It can be seen that the charge storage mechanism of the hybrid material includes electric double layer and pseudocapacitance. The electric double layer mainly results from the adsorption of micropores and mesopores, and the pseudocapacitance originates from the redox reaction of active sites. According to the discharge curve, the specific capacitance of the sample is calculated to be 338.2 F / g.

[0049] Example 6

[0050] Dissolve 30 mg of block copolymer (P123) in 5 ml of tetrahydrofuran, then add 10 ml of deionized water to prepare a solution; dissolve 3 mg of Ti 3 C 2 T x in 1 ml of N,N-dimethylformamide to prepare a solution. Mix the two solutions and stir for 10 minutes to obtain solution A; add 30 mg of Cu(OAc) 2 ·H 2 O dissolved in 5 ml of ethanol to the above solution and stir for 10 min to obtain a mixed solution B; dissolve 30 mg of H 2 BDC-NH 2 and 90 mg of PVP in 5 ml of N,N-dimethylformamide, and then add it to the above mixture B to obtain a reaction system. Stir and react at 80 °C for 15 h; after the reaction, centrifuge and wash, soak in tetrahydrofuran for 6 h, then wash twice with ethanol, and dry at 60 °C for 12 hours to obtain a hybrid material, and label this sample as two-dimensional mesoporous Cu-MOF / Ti 3 C 2 T x -6。

[0051] Using the two-dimensional mesoporous Cu-MOF / Ti prepared in this example 3 C 2 T x-6 was used as the electrode material of the supercapacitor. After the supercapacitor was fabricated, a three-electrode test system was adopted, where the Pt sheet was the auxiliary electrode, Ag / AgCl was the reference electrode, and the two-dimensional mesoporous Cu-MOF / Ti 3 C 2 T x -6 sample was the working electrode. In a 3M KOH electrolyte with a current density of 1 A / g, the specific capacitance of the sample was 278.5 F / g.

[0052] Comparative Example 1: Preparation of pure Zn-MOF for comparison with the Example

[0053] Dissolve 30 mg of H 2 BDC-NH 2 and 50 mg of PVP in a mixed solvent of 15 ml of DMF, 5 ml of ethanol and 5 ml of water, and stir for 10 min. Add 30 mg of (CH 3 COO) 2 Zn to the above solution, sonicate for 30 min, then react at 120 °C for 18 hours. After the reaction, centrifuge and wash, wash twice with N,N-dimethylformamide and ethanol respectively, and dry at 60 °C for 12 hours to obtain the pure Zn-MOF sample.

[0054] Using the pure Zn-MOF prepared in this comparative example as the electrode material of the supercapacitor, after the supercapacitor was fabricated, a three-electrode test system was adopted. In a 3M KOH electrolyte with a current density of 1 A / g, the specific capacitance of the sample was 24 F / g.

[0055] Comparative Example 2: Preparation of Zn-MOF / Ti 3 C 2 T x Preparation of the composite material

[0056] Dissolve 30 mg of H 2 BDC-NH 2 and 40 mg of PVP in a mixed solvent of 15 ml of DMF, 5 ml of ethanol and 5 ml of water, and stir for 10 min. Add 30 mg of (CH 3 COO) 2 Zn to the above solution and stir for 10 min. Dissolve 3 mg of Ti 3 C 2 T x in 1 ml of N,N-dimethylformamide to prepare a solution, add it to the above solution, and stir for 10 min to obtain a reaction system. React at 120 °C for 15 hours. After the reaction, centrifuge and wash, wash twice with N,N-dimethylformamide and ethanol respectively, and dry at 60 °C for 12 hours to obtain Zn-MOF / Ti 3 C 2 Tx Composite material sample.

[0057] Taking the Zn-MOF / Ti3C2Tx composite material prepared in this comparative example as the supercapacitor electrode material, after making a supercapacitor, using a three-electrode test system, in a 3M KOH electrolyte, the current density is 1 A / g, and the specific capacitance of the sample is 65 F / g.

[0058] Table 1 shows the specific capacitances of the supercapacitors made with the products prepared in Examples 1-6 and the comparative example. The two-dimensional mesoporous MOF / Ti obtained in Examples 1-6 3 C 2 T x When the hybrid material is used as the supercapacitor electrode material, under the same conditions, the two-dimensional mesoporous MOF / Ti of the present invention 3 C 2 T x The specific capacitance of the hybrid material is 8-14 times that of the single MOF material and 3-6 times that of the MOF / Ti 3 C 2 T x composite material. The present invention introduces mesopores into the two-dimensional MOF hybrid structure, which not only gives full play to the respective characteristics of the two-dimensional MOF, Ti 3 C 2 T x conductive template and mesopores, but also maximally integrates the properties of each component, and has good electrochemical performance.

[0059] Table 1 Specific capacitances of the supercapacitors in Examples 1-6 and the comparative example

[0060]

[0061] The above embodiments are the preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Without departing from the essence of the present invention, any obvious improvements, substitutions or variations that those skilled in the art can make all fall within the protection scope of the present invention.

Claims

1. A preparation method of a two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material It is characterized in that It includes the following steps: (1) Dissolve the amphiphilic block copolymer and Ti 3 C 2 T x separately in a solvent to prepare solutions, mix the two solutions, stir for 10 minutes, and use Ti 3 C 2 T x surface functional groups to induce in-situ self-assembly of the amphiphilic block copolymer to form micelle spheres, obtaining solution A; (2) Dissolve the metal salt in a solvent, add it to solution A, and stir for 10 minutes to form a mixed solution B; (3) Dissolve 2-aminoterephthalic acid and polyvinylpyrrolidone in a solvent, add it to the mixed solution B to obtain a reaction system, react at 30-120 °C for 2-20 h, and induce the nucleation and growth of two-dimensional MOF through the coordination between the hydrophilic segments of the micelle spheres and metal ions; (4) Centrifuge the reaction product, soak it in tetrahydrofuran or N,N-dimethylformamide for 6 - 10 h, then wash it with ethanol to remove the micelle spheres to form mesopores, and obtain two-dimensional mesoporous MOF / Ti after drying. 3 C 2 T x The hybrid material has both micropores and mesopores, and the proportion of mesopores reaches 30% - 50%. The amphiphilic block copolymer is polystyrene-b-polyethylene oxide, polystyrene-b-poly(vinylpyridine), and polyethylene oxide-polypropylene oxide-polyethylene oxide, and the degree of polymerization of the hydrophobic segment is 70-250; The metal salt is one or two of nitrates, acetates or chlorides of zinc and copper; The mass ratio of the metal salt, 2-aminoterephthalic acid, and the block copolymer is 1:(1 to 0.5):(0.15 to 1); the mass ratio of the metal salt, Ti 3 C 2 Tx, and PVP is 1:(0.05 to 0.5):(0.5 to 3).

2. The preparation method of the two-dimensional mesoporous MOF / Ti hybrid material according to claim 1 3 C 2 T x hybrid material It is characterized in that The mesopore size is regulated by the degree of polymerization of the hydrophobic segment of the amphiphilic block copolymer.

3. The preparation method of the two-dimensional mesoporous MOF / Ti hybrid material according to claim 2 3 C 2 T x hybrid material It is characterized in that The solvent is one or more of tetrahydrofuran, ethanol, deionized water, N,N-dimethylformamide, and N,N-dimethylacetamide.

4. The preparation method of the two-dimensional mesoporous MOF / Ti 3 C 2 T x hybrid material It is characterized in that The content of the metal salt in the reaction system is 0.5-1.5 mg / ml.

5. Two-dimensional mesoporous MOF / Ti hybrid material prepared by the preparation method according to any one of claims 1-4 3 C 2 T x hybrid material It is characterized in that The MOF is compounded on the TiC template in the form of in-situ assembly through hydrogen bonds and coordination bonds, and the hybrid material has both micropores and mesopores, and the mesopore proportion reaches 30% - 50%. 3 C 2 T x template, and the hybrid material has both micropores and mesopores, and the mesopore proportion reaches 30% - 50%.

6. The application of the two-dimensional mesoporous MOF / Ti hybrid material according to claim 5 3 C 2 T x hybrid material It is characterized in that An electrode material for a supercapacitor.

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