Preparation method and application of two-dimensional multi-stage pore MOF material with self-repairing capability
By forming hierarchical pores and grafting UPy-NCO monomers into two-dimensional MOF materials, self-healing is achieved through quadruple hydrogen bonds, which solves the problem of easy collapse of nanostructures in two-dimensional MOF materials during long-term use and improves electrochemical performance and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU UNIV
- Filing Date
- 2024-12-20
- Publication Date
- 2026-06-23
AI Technical Summary
Two-dimensional MOF materials are prone to nanostructure collapse during long-term use, which leads to the covering of active sites and a decline in electrochemical performance. Although the addition of existing conductive ligands has improved the situation, the specific capacitance retention rate is still low.
By using amphiphilic block copolymers as templates, mesopores are formed in MOF materials. The addition of doped ligand 2,6-diaminopyridine forms hierarchical pores. Combined with UPy-NCO monomer grafting, self-healing is achieved through quadruple hydrogen bonding, thereby enhancing the stability of the material.
It improves the electrochemical cycling performance and stability of two-dimensional MOF materials, and the materials can restore their structure through self-repair after damage, thus extending their service life.
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Figure CN122255489A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of nanocomposite materials technology, specifically to a method for preparing a two-dimensional hierarchical porous MOF material with self-healing capabilities and its application. Background Technology
[0002] Metal-organic frameworks (MOFs) are typical porous crystalline materials constructed by orderly splicing organic connectives between metal nodes. The unique framework and pore structure of MOFs determine their unique properties such as large specific surface area, high porosity, and chemical tunability.
[0003] With their unique advantages, MOFs have shown broad application prospects in gas storage, adsorption separation, biology, and catalysis. In particular, two-dimensional MOFs, due to their exposed active sites, possess supercapacitor performance and capacitance surpassing that of traditional materials, thus being regarded as a novel class of electrode materials. (SEUNG-JAE S, JAMIE WG, CHLOE JB, et al. Metal-Organic Framework Supercapacitors: Challenges and Opportunities. Advanced Functional Materials, 2023)
[0004] However, due to their unique spatial structure, two-dimensional MOF materials experience nanostructure collapse and active site coverage during prolonged use, leading to a decline in electrochemical performance. To improve material stability, conductive ligands are added. Mayank K et al. used an ultrasonic method to combine reduced graphene oxide (rGO) with MOFs, obtaining a Cu-MOF-rGO composite material. The introduction of rGO significantly reduced the impedance at 10 Ag. -1 After 4000 cycles at a current density, the specific capacitance retention is still 82%. (MAYANK KS, ANOOP KG, SARATHKUMAR K, et al. A new hierarchically porous Cu-MOF composited with rGO as an efficient hybrid supercapacitor electrode material. Journal of Energy Storage, 2021)
[0005] Although the addition of conductive ligands improves the stability of MOF materials, their specific capacitance retention is still low. Therefore, it is necessary to find other methods to improve the stability of materials, such as optimization on the MOF bulk. Summary of the Invention
[0006] In view of the problems existing in the prior art, the purpose of this invention is to provide a method for preparing a two-dimensional hierarchical porous MOF material with self-healing ability and its application.
[0007] In the preparation method of the two-dimensional hierarchical porous MOF material of the present invention, the inventors utilize the strong tunability of MOF materials, employing an amphiphilic block copolymer as a template agent, followed by washing away the template agent to form mesopores in the MOF material. During MOF synthesis, the doped ligand 2,6-diaminopyridine is added, and the difference in ligand structure is utilized to form larger defect pores. These pores, along with the mesopores and micropores in the MOF, form hierarchical pores, making the active sites more easily exposed. Simultaneously, the addition of more amino groups to the MOF matrix allows for the introduction of more UPy-NCO monomers.
[0008] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:
[0009] In a first aspect of the present invention, a method for preparing a two-dimensional hierarchical porous MOF material with self-healing capability is provided, comprising the following steps:
[0010] 1) Dissolve the metal salt and the amphiphilic block copolymer template agent in a solvent and stir for 2 hours to obtain solution A;
[0011] 2) The substrate material GO was sonicated in deionized water for 4 hours to form solution B;
[0012] 3) Add an organic ligand to solution A, with or without adding a doped ligand. When adding a doped ligand, use 2,6-diaminopyridine as the doped ligand. Then mix and stir with solution B for 2 hours to form solution C.
[0013] 4) Pour solution C into a watch glass and evaporate at 60°C for 3 hours; then place it in a drying oven at 100°C and react for 24 hours.
[0014] 5) Centrifuge the reaction product, and after washing, soaking and drying, obtain MOF material with template agent removed;
[0015] 6) Dissolve the UPY-NCO unit in a solvent to obtain solution D;
[0016] 7) Disperse the MOF material obtained in step 5) in a solvent at 90℃, then add the solution D obtained in step 6) to it to obtain a mixed system E, add the catalyst dibutyltin dilaurate to it, and then raise the temperature to 90-150℃ and stir for 18-24h.
[0017] 8) Centrifuge the reaction product, wash and dry it to obtain a two-dimensional hierarchical porous MOF material.
[0018] Further, in step 1), the metal salt is one or two of the nitrates, acetates or chlorides of zinc, copper, nickel, cobalt, iron, titanium, and zirconium.
[0019] Furthermore, in step 1), the content of the metal salt in solution A is 5-15 mg / ml.
[0020] Further, in step 1), the template agent is an amphiphilic block copolymer PS. 70 -b-PEO 114 .
[0021] Further, in step 3), the organic ligand is one or two of 2-aminoterephthalic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,5-dihydroxyterephthalic acid, and 2,5-diaminoterephthalic acid.
[0022] Further, in steps 1)-3), the mass ratio of metal salt, amphiphilic block copolymer, organic ligand, doped ligand and GO is 1:(0.2-0.5):(1.0-2.5):(0-0.3):(0.3-0.5).
[0023] Further, in step 6), the preparation method of the UPY-NCO unit is as follows: UPY and HDI are mixed at a mass ratio of 1:(9-10), and then the mixture is reacted at 100°C under N2 protection for 15 hours. After the reaction is completed, the reaction product is washed with n-hexane and then dried to obtain the UPY-NCO unit.
[0024] Further, in step 7), the mass ratio of UPY-NCO unit to basic MOF material is 1:(0.8~1.2).
[0025] Further, the solvent used in step 1) is a mixed solvent of methanol and tetrahydrofuran (THF) in a volume ratio of 1:1; the soaking solvent used in step 5) is dichloromethane (CH2Cl2), and the washing solvent is a mixed solvent of methanol and tetrahydrofuran (THF) in a volume ratio of 1:1; the solvent used in steps 6) and 7) is N,N-dimethylformamide (DMF).
[0026] In the method of this invention, UPY-NCO supramolecular polymers are grafted onto organic ligands and doped ligands in a mesoporous MOF material after template removal. Since the main ligand 2-aminoterephthalic acid has only one amino group, and the doped ligand 2,6-diaminopyridine has two amino groups, adding more doped ligands will graft more UPY-NCO, introducing more quadruple hydrogen bonds. The UPY system can form dimers through quadruple hydrogen bonds, thus obtaining a cross-linked network. When the MOF structure is damaged, the structure can be restored through dynamic hydrogen bonding, obtaining a MOF material with self-healing capabilities.
[0027] In a second aspect of the invention, the application of a self-healing two-dimensional hierarchical porous MOF material prepared by the method described in the first aspect in supercapacitors is also provided. After grafting UPy-NCO monomers, quadruple hydrogen bonds are introduced. When the nanostructure of the material is damaged after prolonged use, the quadruple bonds enable dynamic self-repair of the material, thereby improving its cycle stability and extending its service life.
[0028] The present invention has the following beneficial effects:
[0029] 1. In the method of the present invention, no surfactant is added when preparing the basic MOF material with two-dimensional structure. Instead, a petri dish is used to induce solvent evaporation, which promotes the growth of MOF crystal structure in a sheet-like two-dimensional form. Figure 1 The image shows the SEM image of the ungrafted (H-Cu-MOF@GO-3) from Example 3. Figure 1 It can be seen that the basic MOF material structure is two-dimensional. Figure 2 These are SEM images of the grafted (H-Cu-MOF@GO-UPy-NCO-3) from Example 3. Figure 2 It can be seen that after grafting UPY, the material crosslinks into a network-like structure.
[0030] 2. In the method of the present invention, the amphiphilic block copolymer (PS) 70 -b-PEO 114 UPY (2-urea-4[H]-pyrimidinone) is used as a template agent in MOF synthesis due to its high degree of polymerization. The template agent is then washed away with a solvent, forming mesopores within the MOF. Because the doped ligand is monodentate and structurally different from the host ligand, defect pores are formed. Combined with the micropores of the MOF itself, this creates a hierarchical pore structure, facilitating the exposure of active sites and increasing the material's electrical conductivity. UPY (2-urea-4[H]-pyrimidinone) is characterized by its strong dimerization constant (K0). dim >10 7 M -1UPY-NCO is endowed with reversible and self-complementary quadruple hydrogen bonds in oligomers or polymers, resulting in materials that often exhibit stimulus-responsive behavior or repairable properties, making them excellent candidates for dynamic materials design. UPY-NCO is grafted into MOF materials by reacting the amino or hydroxyl groups on organic ligands and doped ligands with isocyanate bonds, introducing self-healing quadruple hydrogen bonds. When the material structure is damaged, it can spontaneously repair itself through hydrogen bonds, restoring its original structure. Since the main ligand 2-aminoterephthalic acid has only one amino group and the doped ligand 2,6-diaminopyridine has two, adding more doped ligands will graft more UPY-NCO, introducing even more quadruple hydrogen bonds.
[0031] 3. This invention fully utilizes the high tunability of MOF materials by incorporating a GO substrate to construct a multi-level porous channel and grafting self-healing functional groups, maximizing the role of each component. As can be seen from the specific embodiments of this invention, the two-dimensional MOF material obtained by this invention exhibits better electrochemical cycling performance compared to existing materials. When used as an electrode material to form a capacitor, damage to the electrode material can be repaired by the electrode material itself rather than by other conditions, significantly improving the capacitor's lifespan. Attached Figure Description
[0032] Figure 1 This is a SEM image of H-Cu-MOF@GO-3 from Example 3.
[0033] Figure 2 This is a SEM image of H-Cu-MOF@GO-UPy-NCO-3 from Example 3.
[0034] Figure 3 This is a comparison chart of the cycling performance of H-Cu-MOF@GO-3 and H-Cu-MOF@GO-UPy-NCO-3 prepared in Example 3, H-Cu-MOF@GO-UPy-NCO-4 prepared in Example 4, and the two-dimensional Cu-MOF prepared in Comparative Example 1. Detailed Implementation
[0035] The present invention will now be described in detail with reference to the accompanying drawings.
[0036] The present invention and its embodiments are described below. This description is not restrictive, and actual embodiments are not limited thereto. In short, if those skilled in the art are inspired by this description and, without departing from the spirit of the invention, design similar structures and embodiments to this technical solution, such designs should fall within the protection scope of the present invention.
[0037] The materials used in this invention were purchased from the following sources:
[0038] PS 70 -b-PEO 114 All chemicals were purchased from Xi'an Qiyue Biotechnology Co., Ltd., and GO was purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd. Anhydrous ethanol, tetrahydrofuran, methanol, acetone, concentrated hydrochloric acid, 2-aminoterephthalic acid (H2BDC-NH2), 2,6-diaminopyridine (DAP), N,N-dimethylformamide (DMF), copper nitrate trihydrate, and polyvinylpyrrolidone K-30 (PVP) were purchased from Shanghai Hushi. 2-Amino-6-methylpyrimidin-4(1H)-one (UPY), hexamethylene diisocyanate (HDI), and dibutyltin dilaurate (DBTDL) were purchased from Maclean's. No further purification was performed on any of the chemicals used in the experiment.
[0039] The preparation method of UPy-NCO unit is based on the method described in the following literature: [1] Liang Zhaopeng. Design, preparation and performance study of self-healing polyurethane elastomer [D]. Jiangsu University, 2021. DOI:10.27170 / d.cnki.gjsuu.2021.002025. The specific method is as follows: 0.751g UPy is mixed with 7.064g HDI. Then the mixture is placed in a round-bottom flask with a condenser and stirred for 15h in an oil bath at 100℃ (N2 protection). 20ml n-hexane is added to the flask, the precipitate is filtered and washed 3 times with n-hexane (3*20ml) (qualitative filter paper), and then vacuum dried at 50℃ for 12h to obtain the UPy-NCO product.
[0040] Example 1
[0041] The preparation method of H-Cu-MOF@GO-UPy-NCO-1 is as follows:
[0042] 95mg Cu(NO3)2·3H2O and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was dissolved in 15 mL of deionized water and sonicated for 4 h to form solution B. 150 mg of H₂BDC-NH₂ was added to solution A, then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was then evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was discarded. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Cu-MOF@GO-1.
[0043] First, 80 mg of H-Cu-MOF@GO-1 was uniformly dissolved in 15 ml of DMF at 90°C with stirring. The solution was poured into a three-necked flask, and then 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (1-2 drops of dibutyltin dilaurate (DBTDL) catalyst were added to adjust the temperature to 90°C and the reaction was carried out with stirring.) The reaction was carried out under nitrogen protection for 20 h. Then, the solution was washed three times by centrifugation in ethanol and dried under vacuum at 30-40°C to obtain H-Cu-MOF@GO-UPy-NCO-1.
[0044] The two-dimensional H-Cu-MOF@GO-UPy-NCO-1 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Cu-MOF@GO-UPy-NCO-1 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 85.3%.
[0045] Example 2
[0046] The preparation method of H-Cu-MOF@GO-UPy-NCO-2 is as follows:
[0047] 95mg Cu(NO3)2·3H2O and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was dissolved in 15 mL of deionized water and sonicated for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 5 mg of 2,6-diaminopyridine were added to solution A. This mixture was then combined with solution B and stirred for 2 h before being poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. The product was dried after washing three times with CH₂Cl₂ before vacuum drying at 60 °C to obtain H-Cu-MOF@GO-2.
[0048] First, under stirring at 90°C, 80 mg of H-Cu-MOF@GO-2 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Cu-MOF-UPy-NCO-2.
[0049] The two-dimensional H-Cu-MOF@GO-UPy-NCO-2 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which the Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Cu-MOF@GO-UPy-NCO-2 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 86.8%.
[0050] Example 3
[0051] The preparation method of H-Cu-MOF@GO-UPy-NCO-3 is as follows:
[0052] 95mg Cu(NO3)2·3H2O and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was dissolved in 15 mL of deionized water and sonicated for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 10 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B and stirred for 2 h before being poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Cu-MOF@GO-3.
[0053] First, under stirring at 90°C, 80 mg of H-Cu-MOF@GO-3 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Cu-MOF@GO-UPy-NCO-3.
[0054] The two-dimensional H-Cu-MOF@GO-UPy-NCO-3 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Cu-MOF@GO-UPy-NCO-3 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 88.4%.
[0055] Example 4
[0056] The preparation method of H-Cu-MOF@GO-UPy-NCO-4 is as follows:
[0057] 95mg Cu(NO3)2·3H2O and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was dissolved in 15 mL of deionized water and sonicated for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 20 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B and stirred for 2 h before being poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Cu-MOF@GO-4.
[0058] First, under stirring at 90°C, 80 mg of H-Cu-MOF@GO-4 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Cu-MOF@GO-UPy-NCO-4.
[0059] The two-dimensional H-Cu-MOF@GO-UPy-NCO-4 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which the Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Cu-MOF@GO-UPy-NCO-4 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance of the sample was retained at 90.0%.
[0060] Example 5
[0061] The preparation method of H-Zn-MOF@GO-UPy-NCO-1 is as follows:
[0062] Mix 70mg (CH3COO)2Zn and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was dissolved in 15 mL of deionized water and sonicated for 4 h to form solution B. 150 mg of H₂BDC-NH₂ was added to solution A. The mixture was then combined with solution B and stirred for 2 h before being poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Zn-MOF@GO-1.
[0063] First, under stirring at 90°C, 80 mg of H-Zn-MOF@GO-1 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Zn-MOF@GO-UPy-NCO-1.
[0064] The two-dimensional H-Zn-MOF@GO-UPy-NCO- prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Zn-MOF@GO-UPy-NCO-1 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 86.5%.
[0065] Example 6
[0066] The preparation method of H-Zn-MOF@GO-UPy-NCO-2 is as follows:
[0067] Mix 70mg (CH3COO)2Zn and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was sonicated in 15 mL of deionized water for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 5 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Zn-MOF@GO-2.
[0068] First, under stirring at 90°C, 80 mg of H-Zn-MOF@GO-2 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Zn-MOF@GO-UPy-NCO-2.
[0069] The two-dimensional H-Zn-MOF@GO-UPy-NCO-2 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Zn-MOF@GO-UPy-NCO-2 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 87.1%.
[0070] Example 7
[0071] The preparation method of H-Zn-MOF@GO-UPy-NCO-3 is as follows:
[0072] Mix 70mg (CH3COO)2Zn and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was dissolved in 15 mL of deionized water and sonicated for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 10 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Zn-MOF@GO-3.
[0073] First, under stirring at 90°C, 80 mg of H-Zn-MOF@GO-2 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Zn-MOF@GO-UPy-NCO-3.
[0074] The two-dimensional H-Zn-MOF@GO-UPy-NCO-3 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Zn-MOF@GO-UPy-NCO-3 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 88.6%.
[0075] Example 8
[0076] The preparation method of H-Zn-MOF@GO-UPy-NCO-4 is as follows:
[0077] Mix 70mg (CH3COO)2Zn and 20mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was sonicated in 15 mL of deionized water for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 20 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. The product was dried after washing three times with CH₂Cl₂ before vacuum drying at 60 °C to obtain H-Zn-MOF@GO-4.
[0078] First, under stirring at 90°C, 80 mg of H-Zn-MOF@GO-2 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Zn-MOF@GO-UPy-NCO-4.
[0079] The two-dimensional H-Zn-MOF@GO-UPy-NCO-3 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Zn-MOF@GO-UPy-NCO-3 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 86.9%.
[0080] Example 9
[0081] The preparation method of H-Ni / Co-MOF@GO-UPy-NCO-1 is as follows:
[0082] Mix 45 mg NiCl2·6H2O with 45 mg CoCl2·6H2O and 20 mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was sonicated in 15 mL of deionized water for 4 h to form solution B. 150 mg of H₂BDC-NH₂ was added to solution A. The mixture was then combined with solution B and stirred for 2 h before being poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Ni / Co-MOF@GO-1.
[0083] First, under stirring at 90°C, 80 mg of H-Ni / Co-MOF@GO-1 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Ni / Co-MOF@GO-UPy-NCO-1.
[0084] The two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-1 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-1 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 84.3%.
[0085] Example 10
[0086] The preparation method of H-Ni / Co-MOF@GO-UPy-NCO-2 is as follows:
[0087] Mix 45 mg NiCl2·6H2O with 45 mg CoCl2·6H2O and 20 mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was sonicated in 15 mL of deionized water for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 5 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Ni / Co-MOF@GO-2.
[0088] First, under stirring at 90°C, 80 mg of H-Ni / Co-MOF@GO-2 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Ni / Co-MOF@GO-UPy-NCO-2.
[0089] The two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-2 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-2 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 84.9%.
[0090] Example 11
[0091] The preparation method of H-Ni / Co-MOF@GO-UPy-NCO-3 is as follows:
[0092] Mix 45 mg NiCl2·6H2O with 45 mg CoCl2·6H2O and 20 mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was sonicated in 15 mL of deionized water for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 10 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Ni / Co-MOF@GO-3.
[0093] First, under stirring at 90°C, 80 mg of H-Ni / Co-MOF@GO-3 was uniformly dissolved in 15 ml of DMF and poured into a three-necked flask. Then, 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Ni / Co-MOF@GO-UPy-NCO-3.
[0094] The two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-3 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-3 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 85.6%.
[0095] Example 12
[0096] The preparation method of H-Ni / Co-MOF@GO-UPy-NCO-2 is as follows:
[0097] Mix 45 mg NiCl2·6H2O with 45 mg CoCl2·6H2O and 20 mg PS 70 -b-PEO 114 The copolymer was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v) and stirred for 2 h to obtain solution A. 30 mg of GO was sonicated in 15 mL of deionized water for 4 h to form solution B. 150 mg of H₂BDC-NH₂ and 20 mg of 2,6-diaminopyridine were added to solution A. This was then mixed with solution B, stirred for 2 h, and poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the product was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v) and collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain H-Ni / Co-MOF@GO-4.
[0098] First, under stirring at 90°C, 80 mg of H-Ni / Co-MOF@GO-4 (90 mg) was uniformly dissolved in 15 ml of DMF. The solution was poured into a three-necked flask, and then 15 ml of DMF containing 85 mg of UPy-NCO was injected into the solution. (One to two drops of dibutyltin dilaurate (DBTDL) catalyst were added, and the temperature was adjusted to 90°C for stirring.) The reaction was carried out under nitrogen protection for 20 hours. The solution was then washed three times by centrifugation in ethanol and dried under vacuum at 30–40°C to obtain H-Ni / Co-MOF@GO-UPy-NCO-4.
[0099] The two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-4 prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional H-Ni / Co-MOF@GO-UPy-NCO-4 sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance retention rate of the sample was 84.1%.
[0100] Comparative Example 1
[0101] The preparation method of pure two-dimensional Cu-MOF is as follows:
[0102] 95 mg of Cu(NO3)2·3H2O was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v), and then 10 mL of deionized water was added. The mixture was stirred for 2 h to obtain solution A. 150 mg of H2BDC-NH2 was added to solution A, and the mixture was stirred for another 2 h before being poured into a glass petri dish with a diameter of approximately 10 cm. The mixture was then evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the mixture was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v), and the product was collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH2Cl2 at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH2Cl2 and then dried to obtain a two-dimensional Cu-MOF.
[0103] The two-dimensional Cu-MOF prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which the Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional Cu-MOF sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance of the sample was retained at 78.1%.
[0104] Comparative Example 2
[0105] The preparation method of pure two-dimensional Zn-MOF is as follows:
[0106] 75 mg of (CH3COO)2Zn was dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v), and then 10 mL of deionized water was added. The mixture was stirred for 2 h to obtain solution A. 150 mg of H2BDC-NH2 was added to solution A, and stirring was continued for 2 h. The solution was then poured into a glass petri dish with a diameter of approximately 10 cm and evaporated at 60 °C for 3 h. The petri dish containing the reaction mixture was then heated in an oven at 100 °C for 24 h. After the reaction was complete, the mixture was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v), and the product was collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH2Cl2 at room temperature for 8 h, and then the solvent was removed. Before vacuum drying at 60 °C, the product was washed three times with CH2Cl2 and then dried to obtain a two-dimensional Zn-MOF.
[0107] The two-dimensional Zn-MOF prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which the Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional Zn-MOF sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance of the sample was 78.7%.
[0108] Comparative Example 3
[0109] The preparation method of pure two-dimensional Ni / Co-MOF is as follows:
[0110] 45 mg NiCl₂·6H₂O and 45 mg CoCl₂·6H₂O were dissolved in 10 mL of a mixed solvent (THF / methanol = 1:1 v / v), and then 10 mL of deionized water was added. The mixture was stirred for 2 h to obtain solution A. 150 mg H₂BDC-NH₂ was added to solution A, and the mixture was stirred for another 2 h. The solution was then poured into a glass petri dish with a diameter of approximately 10 cm and evaporated at 60 °C for 3 h. Subsequently, the petri dish containing the reaction mixture was heated in an oven at 100 °C for 24 h. After the reaction was completed, the mixture was washed twice with 30 mL of tetrahydrofuran / methanol (1:1 v / v), and the product was collected by centrifugation. The obtained MOF material was soaked in 20 mL of CH₂Cl₂ for 8 h at room temperature, and then the solvent was poured off. Before vacuum drying at 60 °C, the product was washed three times with CH₂Cl₂ and then dried to obtain a two-dimensional Ni / Co-MOF.
[0111] The two-dimensional Ni / Co-MOF prepared in this embodiment was used as the electrode material for a supercapacitor. After the supercapacitor was fabricated, a three-electrode testing system was adopted, in which a Pt sheet was used as the auxiliary electrode, Hg / HgO was used as the reference electrode, and the two-dimensional Ni / Co-MOF sample was used as the working electrode. The sample was subjected to electrochemical cycling in 1M KOH electrolyte at a current density of 2A / g. After 5000 cycles, the specific capacitance of the sample was 73.2%.
[0112] Table 1 shows the cycling performance of the supercapacitors in Examples 1-12 and the comparative examples.
[0113]
[0114]
[0115] Table 1 compares the electrochemical cycling stability of Examples 1-12 and the comparative example. It can be seen that the electrochemical cycling stability of the MOF materials in Examples 1-12, which incorporate a conductive substrate, construct hierarchical channels, and graft self-healing groups, is improved compared to the pure two-dimensional MOF material in the comparative example. The material obtained in this invention, when used as a supercapacitor material, exhibits high electrochemical stability, significantly improving the device's lifespan.
[0116] Figure 3 This is a comparison of the cycling performance of H-Cu-MOF@GO-3 and H-Cu-MOF@GO-UPy-NCO-3 prepared in Example 3, H-Cu-MOF@GO-UPy-NCO-4 prepared in Example 4, and the two-dimensional Cu-MOF prepared in Comparative Example 1. Figure 3 As can be seen, compared with Comparative Example 1 (2D Cu-MOF), the specific capacitance of H-Cu-MOF@GO-3 with the addition of auxiliary ligand 2,6-diaminopyridine is increased by about 118%. At the same time, the cycling stability of the specific capacitance is significantly improved after grafting UPy-NCO. Furthermore, as the number of grafted UPy-NCO increases with the addition of auxiliary ligand, its cycling stability is further improved.
[0117] The embodiments described above are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments. Any obvious improvements, substitutions or modifications that can be made by those skilled in the art without departing from the essence of the present invention shall be protected by the present invention.
Claims
1. A method for preparing a two-dimensional hierarchical porous MOF material with self-healing capabilities, characterized in that, Includes the following steps: 1) Dissolve the metal salt and the amphiphilic block copolymer template agent in a solvent and stir for 2 hours to obtain solution A; 2) The substrate material GO was sonicated in deionized water for 4 hours to form solution B; 3) Add an organic ligand to solution A, with or without adding a doped ligand. When adding a doped ligand, use 2,6-diaminopyridine as the doped ligand. Then mix and stir with solution B for 2 hours to form solution C. 4) Pour solution C into a watch glass and evaporate at 60°C for 3 hours; then place it in a drying oven at 100°C and react for 24 hours. 5) Centrifuge the reaction product, and after washing, soaking and drying, obtain MOF material with template agent removed; 6) Dissolve the UPY-NCO unit in a solvent to obtain solution D; 7) Disperse the MOF material obtained in step 5) in a solvent at 90℃, then add the solution D obtained in step 6) to it to obtain a mixed system E, add the catalyst dibutyltin dilaurate to it, and then raise the temperature to 90-150℃ and stir for 18-24h. 8) Centrifuge the reaction product, wash and dry it to obtain a two-dimensional hierarchical porous MOF material.
2. The method according to claim 1, characterized in that, In step 1), the metal salt is one or two of the nitrates, acetates or chlorides of zinc, copper, nickel, cobalt, iron, titanium or zirconium.
3. The method according to claim 1, characterized in that, In step 1), the content of the metal salt in solution A is 5-15 mg / ml.
4. The method according to claim 1, characterized in that, In step 1), the template agent is an amphiphilic block copolymer PS. 70 -b-PEO 114 .
5. The method according to claim 1, characterized in that, In step 3), the organic ligand is one or two of 2-aminoterephthalic acid, 1,2,4,5-benzenetetracarboxylic acid, 2,5-dihydroxyterephthalic acid, and 2,5-diaminoterephthalic acid.
6. The method according to claim 1, characterized in that, In steps 1)-3), the mass ratio of metal salt, amphiphilic block copolymer, organic ligand, doped ligand and GO is 1:(0.2-0.5):(1.0-2.5):(0-0.3):(0.3-0.5).
7. The method according to claim 1, characterized in that, In step 6), the UPY-NCO unit is prepared as follows: UPY and HDI are mixed at a mass ratio of 1:(9-10), and the mixture is reacted at 100°C under N2 protection for 15 hours. After the reaction is completed, the reaction product is washed with n-hexane and then dried to obtain the UPY-NCO unit.
8. The method according to claim 1, characterized in that, In step 7), the mass ratio of UPY-NCO unit to basic MOF material is 1:(0.8~1.2).
9. The method according to claim 1, characterized in that, The solvent used in step 1) is a mixed solvent of methanol and tetrahydrofuran (THF) in a volume ratio of 1:1; the soaking solvent used in step 5) is dichloromethane (CH2Cl2), and the washing solvent is a mixed solvent of methanol and tetrahydrofuran (THF) in a volume ratio of 1:1; the solvent used in steps 6) and 7) is N,N-dimethylformamide (DMF).
10. The application of the self-healing two-dimensional hierarchical porous MOF material prepared by the method of any one of claims 1-9 in supercapacitors.