High-conductivity two-dimensional conductive metal-organic framework material with double carbazole, preparation method and application thereof

Abstract

The application relates to a high-conductivity double-carbazole type two-dimensional conductive metal organic framework material, a preparation method and application thereof, and belongs to the field of metal organic framework materials. Three double-carbazole type two-dimensional conductive metal organic framework materials Cu-DCA-MOF, Cu-DCPy-MOF and Cu-DCPt-MOF are prepared, all of which have a special "rotor-stator" structure, and are obtained by coordination polymerization of double-carbazole type ligands and metal ions. Due to the special "rotor-stator" structure of the double-carbazole type ligands, the three materials have high crystallinity and high conductivity, and have important significance in enriching the types and structural diversity of two-dimensional conductive metal organic framework materials. In addition, the double-carbazole type two-dimensional conductive metal organic framework materials with high conductivity can be applied in potassium ion batteries, and provide a new idea and solution for the development of positive electrode materials of the potassium ion batteries.

Description

Technical Field

[0001] This invention belongs to the field of metal-organic framework materials, specifically relating to a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material, its preparation method, and its application in potassium-ion battery cathode materials. Background Technology

[0002] Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) are emerging two-dimensional multifunctional crystalline materials that self-assemble from conjugated organic linkers and metal ions through a planar quadrilateral coordination mode, exhibiting a graphene-like sheet structure. Due to the strong orbital hybridization between metal ions and ligands, and the open one-dimensional channels, 2D c-MOFs not only inherit the characteristics of traditional 3D MOFs (tunable porosity, multifunctional structure, and abundant active sites), but also possess photoelectric activity and excellent conductivity. To date, the development of 2D conductive metal-organic frameworks has mainly focused on planar ligands with π-conjugation derived from benzene, benzo[a]phenanthrene, coumarin, tetrabenzo[a]naphthalene, and phthalocyanine, which suffers from drawbacks such as cumbersome synthesis steps and a limited variety of ligand cores. Furthermore, larger planar ligand cores further lead to problems such as lower metal density and longer distances between metal ions in 2D conductive metal-organic frameworks. Therefore, developing a ligand with good solubility and simple synthesis steps to prepare high-metal-density two-dimensional conductive metal-organic framework materials is an urgent problem to be solved.

[0003] Bicarbazole derivatives are nonplanar compounds composed of two carbazole units and an aromatic core, as shown in formula (X):

[0004]

[0005] The two carbazole units in this bis-carbazole derivative are almost coplanar, while the aromatic core exhibits a certain degree of torsion relative to the two carbazole units. This unique structure is called a "rotor-stator" configuration, where the two carbazole units of the bis-carbazole derivative can be considered as the "stator," and the aromatic core (such as benzene) can be considered as the "rotor." This non-planar structure gives them excellent solubility in a variety of organic solvents. Furthermore, the coplanarity of the two carbazole units allows for expansion, potentially forming two-dimensional network structures. Therefore, based on these advantages, integrating bis-carbazole units into 2D c-MOFs can solve the problem of poor solubility of organic ligands and enrich the variety and structural diversity of 2D c-MOF materials. Moreover, the conductivity of 2D c-MOFs can be tuned by changing the "rotor." However, constructing two-dimensional bis-carbazole metal-organic framework materials remains a significant challenge. Summary of the Invention

[0006] To overcome the shortcomings of the prior art, the purpose of this invention is to provide a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material, its preparation method, and its application in secondary battery cathode materials.

[0007] The present invention discloses a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material, the structural formula of which is shown in (III), (VI) or (IX):

[0008]

[0009]

[0010] The preparation method of the high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material Cu-DCA-MOF of the present invention comprises the following steps:

[0011] 1) Add 2,3,6,7-tetramethoxy-9H-carbazole, 9,10-dibromoanthracene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide to toluene, and then perform multiple freeze-degassing operations; wherein the molar ratio of 2,3,6,7-tetramethoxy-9H-carbazole, 9,10-dibromoanthracene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide is 100–110:40–35:5–10:2 5~35:55~60, the concentration of 2,3,6,7-tetramethoxy-9H-carbazole in toluene is 2~5 g / mL; then the reaction solution is heated to 100~120℃ and reacted for 60~80 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with dichloromethane, dried with anhydrous sodium sulfate, and finally purified by column chromatography to obtain 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I);

[0012] The reaction formula is as follows:

[0013]

[0014] 2) Under nitrogen protection, 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I) was dissolved in anhydrous dichloromethane and cooled in an ice-water bath for 8–15 minutes. Then, boron tribromide was added dropwise and the reaction was carried out for 10–15 hours. The molar ratio of 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I) to boron tribromide was 1:10–15. The reaction was quenched with deionized water, and the filter cake was washed with water and dried under vacuum to obtain 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II).

[0015] The reaction formula is as follows:

[0016]

[0017] 3) Place 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene(II) and copper nitrate trihydrate in a 35-45% (w / w) N,N-dimethylformamide aqueous solution and sonicate for 8-15 minutes, then react at 80-90°C for 60-80 hours; wherein the molar ratio of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene(II) to copper nitrate trihydrate is 1:2-2.5. The concentration of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) in the aqueous solution of N,N-dimethylformamide was 0.5-0.6 g / mL. After the reaction was completed, the mixture was cooled to room temperature, and the filtered product was washed with DMF, H2O and acetone until the filtrate was colorless. The product was then vacuum dried for 2-5 hours to obtain Cu-DCA-MOF, a biscarbazole-type two-dimensional conductive metal-organic framework material with high electrical conductivity, as shown in (III).

[0018]

[0019] The preparation method of the high-conductivity bis-carbazole type two-dimensional conductive metal-organic framework material Cu-DCPy-MOF of the present invention comprises the following steps:

[0020] 1) Add 2,3,6,7-tetramethoxy-9H-carbazole, 2,7-dibromopyrene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide to toluene, and then perform multiple freeze-degassing operations; wherein the molar ratio of 2,3,6,7-tetramethoxy-9H-carbazole, 2,7-dibromopyrene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide is 100–110:40–35:5–10:25 ~35:55~60, the concentration of 2,3,6,7-tetramethoxy-9H-carbazole in toluene is 2~5 g / mL; then the reaction solution is heated to 100~120℃ and reacted for 60~80 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with dichloromethane, dried with anhydrous sodium sulfate, and finally purified by column chromatography to obtain 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV);

[0021] The reaction formula is as follows:

[0022]

[0023] 2) Under nitrogen protection, 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV) was dissolved in anhydrous dichloromethane and cooled in an ice-water bath for 8–15 minutes. Then, boron tribromide was added dropwise and the reaction was carried out for 10–15 hours. The molar ratio of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV) to boron tribromide was 1:10–15. The reaction was quenched with deionized water, and the filter cake was washed with water and dried under vacuum to obtain 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V).

[0024] The reaction formula is as follows:

[0025]

[0026] 3) Place 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V) and copper nitrate trihydrate in a 35-45% N,N-dimethylformamide aqueous solution and sonicate for 8-15 minutes, then react at 80-90℃ for 60-80 hours; wherein the molar ratio of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V) to nitric acid trihydrate is 1:2-2. 5. The concentration of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) in the aqueous solution of N,N-dimethylformamide was 0.5-0.6 g / mL. After the reaction was completed, the mixture was cooled to room temperature, and the filtered product was washed with DMF, H2O and acetone until the filtrate was colorless. The product was then vacuum dried for 2-5 hours to obtain the biscarbazole type two-dimensional conductive metal-organic framework material Cu-DCPy-MOF, as shown in formula (VI).

[0027]

[0028] The preparation method of the high-conductivity bis-carbazole type two-dimensional conductive metal-organic framework material Cu-DCPt-MOF of the present invention comprises the following steps:

[0029] 1) Add 2,3,6,7-tetramethoxy-9H-carbazole, 2,7-dibromo-4,5-dihydrophenanthrene-9,10-dione, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide to toluene and perform multiple freeze-degassing operations; wherein the molar ratio of 2,3,6,7-tetramethoxy-9H-carbazole, 2,7-dibromo-4,5-dihydrophenanthrene-9,10-dione, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide is 100–110:40–35:5. ~10:25~35:55~60, the concentration range of 2,3,6,7-tetramethoxy-9H-carbazole in toluene is 2~5 g / mL; then the reaction solution is heated to 100~120℃ and reacted for 60~80 hours. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with dichloromethane, dried with anhydrous sodium sulfate, and finally purified by column chromatography to obtain 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII);

[0030] The reaction formula is as follows:

[0031]

[0032] 2) Under nitrogen protection, 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII) was dissolved in anhydrous dichloromethane and cooled in an ice-water bath for 8–15 minutes. Then, boron tribromide was added dropwise and the reaction was carried out for 10–15 hours. The molar ratio of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII) to boron tribromide was 1:10–15. The reaction was quenched with deionized water, and the filter cake was washed with water and dried under vacuum to obtain 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII).

[0033] The reaction formula is as follows:

[0034]

[0035] 3) 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII) and copper nitrate trihydrate were placed in a 35-45% (w / w) N,N-dimethylformamide aqueous solution and sonicated for 8-15 minutes, then reacted at 80-90°C for 60-80 hours; wherein, 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII) and The molar ratio of nitric acid trihydrate is 1:2 to 2.5, and the concentration of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) in the N,N-dimethylformamide aqueous solution is 0.5 to 0.6 g / mL. After the reaction is completed, the mixture is cooled to room temperature, and the filtered product is washed with DMF, H2O and acetone until the filtrate is colorless. The product is then vacuum dried for 2 to 5 hours to obtain a biscarbazole-type two-dimensional conductive metal-organic framework material Cu-DCPt-MOF, as shown in formula (IX).

[0036]

[0037] Advantages of this invention:

[0038] The three biscarbazole-type two-dimensional conductive metal-organic framework materials included in this invention—Cu-DCA-MOF, Cu-DCPy-MOF, and Cu-DCPt-MOF—all possess a unique "rotor-stator" structure, obtained through coordination polymerization of biscarbazole ligands with metal ions. Due to the unique "rotor-stator" structure of the biscarbazole ligands, the resulting three biscarbazole-type two-dimensional conductive metal-organic framework materials exhibit high crystallinity and high conductivity, which is significant in enriching the variety and structural diversity of two-dimensional conductive metal-organic framework materials. Furthermore, the excellent conductivity and redox activity of nitrogen atoms in the carbazole molecule make biscarbazole-type two-dimensional conductive metal-organic framework materials an ideal choice for potassium-ion battery cathode materials. The introduction of this material is expected to effectively solve the problems of low capacity and poor stability commonly found in current potassium-ion battery cathode materials, thereby improving the overall performance and lifespan of the battery. By fully utilizing the characteristics of biscarbazole-type materials, new ideas and solutions can be provided for the development of potassium-ion battery cathode materials. Attached Figure Description

[0039] Figure 1 The 1H NMR spectrum of the compound shown in formula (II) is shown below.

[0040] Figure 2 The high-resolution mass spectrum of the compound shown in formula (II) is shown below.

[0041] Figure 3 The 1H NMR spectrum of the compound shown in formula (V) is shown below.

[0042] Figure 4 The high-resolution mass spectrum of the compound shown in formula (V) is shown below.

[0043] Figure 5 The 1H NMR spectrum of the compound shown in formula (VIII);

[0044] Figure 6 The high-resolution mass spectrum of the compound shown in formula (VIII) is shown below.

[0045] Figure 7 The powder X-ray diffraction pattern of the metal-organic framework material Cu-DCA-MOF described in formula (III);

[0046] Figure 8 The image is a scanning electron microscope image of the metal-organic framework material Cu-DCA-MOF described in formula (III);

[0047] Figure 9 The powder X-ray diffraction pattern of the metal-organic framework material Cu-DCPy-MOF described in formula (VI);

[0048] Figure 10 Here is a scanning electron microscope image of the metal-organic framework material Cu-DCPy-MOF described in formula (VI);

[0049] Figure 11 The powder X-ray diffraction pattern of the metal-organic framework material Cu-DCPt-MOF as described in formula (IX);

[0050] Figure 12 The image shows a scanning electron microscope image of the metal-organic framework material Cu-DCPt-MOF as described in formula (IX).

[0051] Figure 13 The conductivity curve of the metal-organic framework material Cu-DCA-MOF described in equation (III);

[0052] Figure 14 The conductivity curve of the metal-organic framework material Cu-DCPy-MOF described in equation (VI);

[0053] Figure 15 The conductivity curve of the metal-organic framework material Cu-DCPt-MOF described in equation (IX) is shown. Detailed Implementation

[0054] The present invention will be further described below with reference to specific embodiments and accompanying drawings.

[0055] Example 1

[0056] The preparation method of Cu-DCA-MOF, a two-dimensional conductive metal-organic framework material based on biscarbazole, includes the following steps:

[0057] 1) Synthesis of 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazol-9-yl)anthracene (I):

[0058] 2,3,6,7-Tetramethoxy-9H-carbazole (1.0 g, 3.5 mmol), 9,10-dibromoanthracene (470 mg, 1.4 mmol), palladium acetate (72 mg, 0.25 mmol), tri-tert-butylphosphine tetrafluoroborate (288 mg, 1.0 mmol), and sodium tert-butoxide (180 mg, 2.0 mmol) were added to a 250 mL round-bottom flask, followed by the addition of 60 mL of toluene, and the mixture was subjected to three freeze-drying degassing processes. The reaction mixture was heated to 110 °C and reacted for 72 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and finally purified by column chromatography (eluent: DCM) to give 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I) (520 mg, yield 50.0%).

[0059] The reaction formula is as follows:

[0060]

[0061] 2) Synthesis of 9,10-bis(2,3,6,7-hydroxy-9H-carbazol-9-yl)anthracene(II):

[0062] Under nitrogen protection, 1 gram of 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I) was dissolved in 100 mL of anhydrous dichloromethane. The mixture was cooled in an ice-water bath for 10 minutes, and 2 mL of boron tribromide was added dropwise. The reaction was allowed to proceed for 12 hours. The reaction was quenched with deionized water. The resulting filter cake was washed with water and dried under vacuum to give the black product 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) (782 mg, yield 92%).

[0063] The 1H NMR spectrum and high-resolution mass spectrum of 9,10-bis(2,3,6,7-hydroxy-9H-carbazol-9-yl)anthracene(II), (abbreviated as 8OH-DCA) are shown below. Figure 1 and Figure 2 This indicates that it was successfully synthesized.

[0064] The reaction formula is as follows:

[0065]

[0066] 3) Synthesis of Cu-DCA-MOF, a two-dimensional conductive metal-organic framework material based on biscarbazole:

[0067] 8OH-DCA(II) (12.7 mg, 0.02 mmol), copper nitrate trihydrate (14.5 mg, 0.06 mmol), 1 mL DMAc, and 4 mL H2O were added to a 10 mL Schlenk tube; the mixture was sonicated for 10 minutes and then reacted at 85 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed with DMF, H2O, and acetone until the filtrate was colorless. The filtrate was then dried under vacuum for 3 hours to obtain a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material Cu-DCA-MOF(III) (12.2 mg, yield 93.2%).

[0068] like Figure 7 As shown, the powder X-ray diffraction pattern of the high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material Cu-DCA-MOF(III) confirms its successful synthesis. Furthermore, as... Figure 8 As shown, the scanning electron microscope image of Cu-DCA-MOF indicates that it has a rod-like morphology.

[0069] The reaction formula is:

[0070]

[0071] Example 2

[0072] The preparation method of Cu-DCPy-MOF, a two-dimensional conductive metal-organic framework material based on biscarbazole, includes the following steps:

[0073] 1) Synthesis of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazol-9-yl)pyrene (IV):

[0074] 2,3,6,7-Tetramethoxy-9H-carbazole (1.0 g, 3.5 mmol), 2,7-dibromopyrene (504 mg, 1.4 mmol), palladium acetate (72 mg, 0.25 mmol), tri-tert-butylphosphine tetrafluoroborate (288 mg, 1.0 mmol), and sodium tert-butoxide (180 mg, 2.0 mmol) were added to a 250 mL round-bottom flask, followed by the addition of 60 mL of toluene, and the mixture was subjected to three freeze-drying degassing processes. The reaction mixture was heated to 110 °C and reacted for 72 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, extracted with dichloromethane, and dried over anhydrous sodium sulfate. Finally, the product was purified by column chromatography (eluent: DCM) to give the yellow product 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV) (508 mg, yield 47.0%).

[0075] The reaction formula is as follows:

[0076]

[0077] 2) Synthesis of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazol-9-yl)pyrene (V):

[0078] Under nitrogen protection, 1 g of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV) was dissolved in 100 mL of anhydrous dichloromethane. The mixture was cooled in an ice-water bath for 10 minutes, and 2 mL of boron tribromide was added dropwise. The reaction was allowed to proceed for 12 hours. The reaction was quenched with deionized water, filtered, and the filter cake was washed with water and dried under vacuum to obtain the black product 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V) (812 mg, yield 95.0%).

[0079] The 1H NMR spectrum and high-resolution mass spectrum of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazol-9-yl)pyrene (V), (abbreviated as 8OH-DCPy) are shown below. Figure 3 and Figure 4 This indicates that it was successfully synthesized.

[0080] The reaction formula is as follows:

[0081]

[0082] 3) Synthesis of Cu-DCPy-MOF(VI), a two-dimensional conductive metal-organic framework material based on biscarbazole:

[0083] 8OH-DCPy(V) (11.9 mg, 0.02 mmol), copper nitrate trihydrate (14.5 mg, 0.06 mmol), 0.5 mL DMAc, and 4.5 mL H2O were added to a 10 mL Schlenk tube; the mixture was sonicated for 10 minutes and then reacted at 85 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed with DMF, H2O, and acetone until the filtrate was colorless. The filtrate was then vacuum dried for 3 hours to obtain a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material Cu-DCPy-MOF(VI) (12.3 mg, 86.1%).

[0084] like Figure 9 As shown, the powder X-ray diffraction pattern of the high-conductivity bis-carbazole type two-dimensional conductive metal-organic framework material Cu-DCPy-MOF(VI) confirms its successful synthesis. Furthermore, as... Figure 10 As shown, the scanning electron microscope image of Cu-DCPy-MOF indicates that it has a rod-like morphology.

[0085] The reaction formula is:

[0086]

[0087] Example 3

[0088] The preparation method of Cu-DCPt-MOF, a two-dimensional conductive metal-organic framework material based on biscarbazole, includes the following steps:

[0089] 1) Synthesis of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazol-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII):

[0090] 2,3,6,7-Tetramethoxy-9H-carbazole (1.0 g, 3.5 mmol), 2,7-dibromo-4,5-dihydrophenanthrene-9,10-dione (515 mg, 1.4 mmol), palladium acetate (72 mg, 0.25 mmol), tri-tert-butylphosphine tetrafluoroborate (288 mg, 1.0 mmol), and sodium tert-butoxide (180 mg, 2.0 mmol) were added to a 250 mL round-bottom flask, followed by the addition of 60 mL of toluene, and the mixture was subjected to three freeze-drying degassing cycles. The reaction mixture was heated to 110 °C and reacted for 72 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, extracted with dichloromethane, and dried over anhydrous sodium sulfate. Finally, the product was purified by column chromatography (eluent: DCM) to give the black product 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII) (848 mg, 63%).

[0091] The reaction formula is as follows:

[0092]

[0093] 2) Synthesis of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazol-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII):

[0094] Under nitrogen protection, 1 gram of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII) was dissolved in 100 mL of anhydrous dichloromethane. The mixture was cooled in an ice-water bath for 10 minutes, and 2 mL of boron tribromide was added dropwise. The reaction was allowed to proceed for 12 hours. The reaction was quenched with deionized water, filtered, and the filter cake was washed with water and dried under vacuum to give the black product 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII) (813 mg, yield 95.0%).

[0095] The 1H NMR spectrum and high-resolution mass spectrum of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazol-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII), (abbreviated as 8OH-DCPt) are shown below. Figure 5 and Figure 6 This indicates that it was successfully synthesized.

[0096] The reaction formula is as follows:

[0097]

[0098] 4) Synthesis of Cu-DCPt-MOF(IX), a two-dimensional conductive metal-organic framework material based on biscarbazole:

[0099] 8OH-DCPt(VIII) (13.4 mg, 0.02 mmol), copper nitrate trihydrate (14.5 mg, 0.06 mmol), 0.5 mL DMAc, and 4.5 mL H2O were added to a 10 mL Schlenk tube; the mixture was sonicated for 10 minutes and then reacted at 85 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and washed with DMF, H2O, and acetone until the filtrate was colorless. The filtrate was then dried under vacuum for 3 hours to obtain a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material Cu-DCPt-MOF(IX) (13.5 mg, yield 88.1%).

[0100] like Figure 11 As shown, the powder X-ray diffraction pattern of the high-conductivity bis-carbazole type two-dimensional conductive metal-organic framework material Cu-DCPt-MOF(IX) confirms its successful synthesis. Furthermore, as... Figure 12 As shown, the scanning electron microscope image of Cu-DCPt-MOF indicates that it has a rod-like morphology.

[0101] The reaction formula is:

[0102]

[0103] Example 4

[0104] The conductivity properties of three biscarbazole-type two-dimensional conductive metal-organic framework materials were tested, including the following steps:

[0105] Three milligrams of biscarbazole-type two-dimensional conductive metal-organic framework materials (Examples 1 to 3) were pressed into cylinders with a diameter of 3 millimeters, wherein the thickness of Cu-DCA-MOF was 0.85 mm, the thickness of Cu-DCPy-MOF was 1.30 mm, and the thickness of Cu-DCPt-MOF was 0.74 mm. Subsequently, current-voltage curves were tested within a voltage range of -2.0 to 2.0 V. Figure 13 , Figure 14 and Figure 15 As shown, the electrical conductivities of Cu-DCA-MOF, Cu-DCPy-MOF, and Cu-DCPt-MOF prepared in Examples 1 to 3 are 0.124 S / m, 1.36 S / m, and 8.5 × 10⁻⁶ S / m, respectively. -4S / m. The results show that all prepared biscarbazole-type two-dimensional conductive metal-organic framework materials exhibit excellent conductivity. Furthermore, the experimental results show that the conductivity of the prepared 2D c-MOFs increases with the increase of the conjugation degree of the "rotor" structure. Although the conductivity of Cu-DCPt-MOF is lower than that of Cu-DCA-MOF and Cu-DCPy-MOF, the redox activity of Cu-DCPt-MOF is enhanced due to the introduction of carbonyl groups as active sites in the "rotor" structure. Therefore, all three are expected to play an important role in the application of cathode materials in potassium-ion batteries.

[0106] The formula for calculating electrical conductivity is as follows:

[0107]

[0108] In potassium-ion battery applications, the high conductivity and good redox activity of the biscarbazole-type two-dimensional conductive metal-organic framework material prepared in this invention make it an ideal cathode material. The performance of potassium-ion batteries is mainly reflected in the following aspects: 1. The introduction of the biscarbazole-type material helps to improve the specific capacity of potassium-ion batteries, overcoming the problem of low capacity in traditional cathode materials. 2. The structural stability and conductivity of this material can effectively improve the cycle life of the battery and reduce capacity decay. 3. High conductivity allows potassium ions to migrate rapidly during charging and discharging, thereby improving the rate performance of the battery and meeting the needs of fast charging. 4. Potassium-ion batteries have better safety than lithium-ion batteries, and the stability of the biscarbazole-type material further enhances the safety performance of the battery. In summary, the biscarbazole-type two-dimensional conductive metal-organic framework material not only exhibits excellent conductivity but also provides new possibilities for the high-performance development of potassium-ion batteries.

[0109] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any modifications, simplifications or simplified modifications that do not depart from the design principles and construction strategies of the present invention are included within the protection scope of the present invention.

Claims

1. A high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material, characterized in that: The structural formulas are shown in (III), (VI), or (IX):

2. The preparation method of the high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material according to claim 1, comprising the following steps: 1) 2,3,6,7-Tetramethoxy-9H-carbazole, 9,10-dibromoanthracene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide were added to toluene, followed by multiple freeze-degassing reactions. The reaction solution was then heated to 100–120 °C and reacted for 60–80 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and finally purified by column chromatography to obtain 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I). The reaction formula is as follows: 2) Under nitrogen protection, 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)anthracene (I) was dissolved in anhydrous dichloromethane, cooled in an ice-water bath for 8–15 minutes, and then boron tribromide was added dropwise for 10–15 hours. The reaction was quenched with deionized water, and the resulting filter cake was washed with water and dried under vacuum to obtain 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II). The reaction formula is as follows: 3) 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) and copper nitrate trihydrate were placed in an aqueous solution of N,N-dimethylformamide with a mass concentration of 35-45% and sonicated for 8-15 minutes, and then reacted at 80-90℃ for 60-80 hours. After the reaction was completed, the mixture was cooled to room temperature, and the filtered product was washed with DMF, H2O and acetone until the filtrate was colorless. The product was then vacuum dried for 2-5 hours to obtain Cu-DCA-MOF, a biscarbazole-type two-dimensional conductive metal-organic framework material with high electrical conductivity, as shown in (III).

3. The method for preparing a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material as described in claim 2, characterized in that: In step 1), the molar ratio of 2,3,6,7-tetramethoxy-9H-carbazole, 9,10-dibromoanthracene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide is 100–110:40–35:5–10:25–35:55–60, and the concentration of 2,3,6,7-tetramethoxy-9H-carbazole in toluene is 2–5 g / mL; in step 2), 9,10-bis(2,3,6,7-tetramethoxy-9H-carbazole)... The molar ratio of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (I) to boron tribromide is 1:10-15; in step 3), the molar ratio of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) to copper nitrate trihydrate is 1:2-2.5, and the concentration of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) in the N,N-dimethylformamide aqueous solution is 0.5-0.6 g / mL.

4. The preparation method of the high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material according to claim 1, comprising the following steps: 1) 2,3,6,7-Tetramethoxy-9H-carbazole, 2,7-dibromopyrene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide were added to toluene, followed by multiple freeze-degassing reactions. The reaction solution was then heated to 100–120 °C and reacted for 60–80 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and finally purified by column chromatography to obtain 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV). The reaction formula is as follows: 2) Under nitrogen protection, 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV) was dissolved in anhydrous dichloromethane and cooled in an ice-water bath for 8–15 minutes. Then, boron tribromide was added dropwise and the reaction was carried out for 10–15 hours. The reaction was quenched with deionized water, and the filter cake was washed with water and dried under vacuum to obtain 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V). The reaction formula is as follows: 3) 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V) and copper nitrate trihydrate were placed in an aqueous solution of N,N-dimethylformamide with a mass concentration of 35-45% and sonicated for 8-15 minutes, and then reacted at 80-90℃ for 60-80 hours. After the reaction was completed, the mixture was cooled to room temperature, and the filtered product was washed with DMF, H2O and acetone until the filtrate was colorless. The product was then vacuum dried for 2-5 hours to obtain the biscarbazole type two-dimensional conductive metal-organic framework material Cu-DCPy-MOF, as shown in formula (VI).

5. The method for preparing a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material as described in claim 4, characterized in that: In step 1), the molar ratio of 2,3,6,7-tetramethoxy-9H-carbazole, 2,7-dibromopyrene, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide is 100–110:40–35:5–10:25–35:55–60, and the concentration of 2,3,6,7-tetramethoxy-9H-carbazole in toluene is 2–5 g / mL; in step 3), 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole) The molar ratio of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V) to nitric acid trihydrate is 1:10-15; in step 3), the molar ratio of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)pyrene (V) to nitric acid trihydrate is 1:2-2.5, and the concentration of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) in the N,N-dimethylformamide aqueous solution is 0.5-0.6 g / mL.

6. The preparation method of the high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material according to claim 1, comprising the following steps: 1) 2,3,6,7-Tetramethoxy-9H-carbazole, 2,7-dibromo-4,5-dihydrophenanthrene-9,10-dione, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide were added to toluene and subjected to repeated freeze-drying. The reaction solution was then heated to 100–120 °C and reacted for 60–80 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and finally purified by column chromatography to obtain 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII). The reaction formula is as follows: 2) Under nitrogen protection, 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII) was dissolved in anhydrous dichloromethane, cooled in an ice-water bath for 8–15 minutes, and then boron tribromide was added dropwise for 10–15 hours. The reaction was quenched with deionized water, filtered, and the resulting filter cake was washed with water and dried under vacuum to obtain 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII). The reaction formula is as follows: 3) 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII) and copper nitrate trihydrate were placed in a 35-45% N,N-dimethylformamide aqueous solution and sonicated for 8-15 minutes, and then reacted at 80-90℃ for 60-80 hours. After the reaction was completed, the mixture was cooled to room temperature, and the filtered product was washed with DMF, H2O and acetone until the filtrate was colorless. The product was then vacuum dried for 2-5 hours to obtain the biscarbazole type two-dimensional conductive metal-organic framework material Cu-DCPt-MOF, as shown in formula (IX).

7. The method for preparing a high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material as described in claim 6, characterized in that: In step 1), the molar ratio of 2,3,6,7-tetramethoxy-9H-carbazole, 2,7-dibromo-4,5-dihydrophenanthrene-9,10-dione, palladium acetate, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide is 100–110:40–35:5–10:25–35:55–60, and the concentration range of 2,3,6,7-tetramethoxy-9H-carbazole in toluene is 2–5 g / mL; in step 2), the molar ratio of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VII) to boron tribromide is 1: 12-15; In step 3), the molar ratio of 2,7-bis(2,3,6,7-tetramethoxy-9H-carbazole-9-yl)pyrene (IV) to boron tribromide is 1:10-15; In step 3), the molar ratio of 2,7-bis(2,3,6,7-tetrahydroxy-9H-carbazole-9-yl)-4,5-dihydrophenanthrene-9,10-dione (VIII) to nitric acid trihydrate is 1:2-2.5, and the concentration of 9,10-bis(2,3,6,7-hydroxy-9H-carbazole-9-yl)anthracene (II) in the N,N-dimethylformamide aqueous solution is 0.5-0.6 g / mL.

8. The application of the high-conductivity biscarbazole-type two-dimensional conductive metal-organic framework material as described in claim 1 in the cathode material of potassium-ion batteries.

Images