Two-dimensional conductive metal-organic frameworks based on amino-coordinated tricyclic quinazoline

Abstract

The invention discloses a tricyclic quinazoline-based two-dimensional conductive metal organic framework material based on amino coordination, the structure of which is shown in Formula I: #imgabs0# wherein M is Ni, Zn, Co or Cu; the synthesis steps are: dispersing 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer VI in an organic solvent to obtain a dispersion; and mixing the dispersion and a divalent metal ion M 2+ The aqueous solution is mixed, and an alkali aqueous solution is added to react to obtain the material. The synthesis steps of the material are simple, the reaction conditions are mild, and the material has good crystallinity, gas adsorption performance and excellent sodium ion battery cycle stability. The material obtained by the present invention is used as a positive electrode material for a sodium ion battery. The electrolyte solution is a 1.0M NaPF6 diethylene glycol dimethyl ether solution, the voltage range is 1.0 to 3.6V, and the scan rate is 1A g ‑1 It exhibits excellent cycling stability and Coulombic efficiency under the conditions of .

Description

Technical Field

[0001] The present invention belongs to the field of metal organic framework and metal ion battery, and specifically relates to Background Art

[0002] Although lithium-ion batteries have been widely used in the market, the limited lithium metal resources and the cost of mining and operation have greatly restricted the development of lithium-ion batteries. In recent years, sodium-ion batteries are one of the most promising alternatives to lithium-ion batteries due to their abundant resources, low cost, and electrochemical properties similar to those of lithium-ion batteries. Since the radius of sodium ions is larger than that of lithium ions, some materials suitable for lithium-ion batteries often show low rate performance, short life, and low energy density when used as electrode materials for sodium-ion batteries. Based on this, a class of metal-organic framework materials with pore size adaptation and rich active sites are designed and synthesized, which has a profound reference significance for improving the performance of sodium-ion batteries.

[0003] Metal-organic framework (MOF) is a long-range ordered porous crystalline material connected by coordination bonds. Metals with different coordination numbers such as copper, cobalt, nickel, iron and platinum can be introduced into the framework material. Often, the change of these metals will lead to completely different performance of the framework material. However, traditional metal-organic framework materials are electrical insulators. At present, two-dimensional conductive metal-organic frameworks are increasingly showing excellent electrochemical properties. The types of coordination are mainly amino, thiol and hydroxyl. Thanks to the designability and easy regulation of framework materials, two-dimensional conductive metal-organic frameworks have shown abundant application prospects in sensing, optoelectronics and spin electronics. Among them, the conductive mechanism of two-dimensional conductive metal-organic framework materials is mainly divided into promoting charge transfer through the effective energy overlap of metal orbitals and ligand orbitals in coordination bonds, and secondly, using the space provided by non-covalent interactions and orbital overlap to induce charge transfer at the spatial level. Benefiting from excellent conductive properties, such materials have certain application prospects in the field of metal ion batteries.

[0004] Two-dimensional conductive tricyclic quinazoline-based metal organic framework materials have good electrochemical activity. It has been reported that hydroxyl-coordinated tricyclic quinazoline-based metal organic framework materials are used in lithium-ion batteries and electrocatalytic carbon dioxide reduction. However, the synthesis of amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal organic framework materials, monomers and their application in sodium-ion batteries have not been reported. Summary of the invention

[0005] The first purpose of the present invention is to overcome the shortcomings of the existing synthesis technology and provide a 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer.

[0006] The second object of the present invention is to provide a method for synthesizing 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomers.

[0007] The third object of the present invention is to provide a tricyclic quinazoline-based two-dimensional conductive metal-organic framework material based on amino coordination.

[0008] The fourth object of the present invention is to provide a method for synthesizing tricyclic quinazoline-based two-dimensional conductive metal-organic framework materials based on amino coordination.

[0009] The fifth object of the present invention is to provide the application of the above-mentioned amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material as a gas adsorbent.

[0010] The sixth object of the present invention is to provide the application of the above-mentioned amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material as an electrode material for sodium ion batteries.

[0011] The technical solution of the present invention is summarized as follows:

[0012] 2,3,7,8,12,13-Hexamidotricyclic quinazoline hydrochloride monomer is represented by formula VI:

[0013]

[0014] The synthesis method of the above-mentioned 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer comprises the following steps:

[0015] (1) 5-bromo-2-nitrobenzaldehyde VII and concentrated sulfuric acid are mixed, and then N-bromosuccinimide is added, and the mixture is stirred at room temperature. After the reaction is completed, the reaction liquid is poured into ice water for mixing, filtered, and subjected to column chromatography to obtain 4,5-dibromo-2-nitrobenzaldehyde II in the form of a white powder;

[0016] (2) 4,5-dibromo-2-nitrobenzaldehyde II, methanol and ethyl acetate are mixed, stannous chloride dihydrate is added, stirred, and reacted at room temperature. After the reaction is completed, the mixture is neutralized with saturated sodium bicarbonate, filtered, and the filtrate is extracted with ethyl acetate and subjected to column chromatography to obtain 5,6-dibromobenz[c]isoxazole III in the form of a white powder;

[0017] (3) 5,6-dibromobenz[c]isoxazole III, ammonium acetate and sulfolane are mixed, glacial acetic acid is added under nitrogen protection, the mixture is stirred, and refluxed. After the reaction is completed, the mixture is filtered and the filter cake is washed with ethanol to obtain a brown-green powder 2,3,7,8,12,13-hexabromotricyclic quinazoline IV;

[0018] (4) Tri(dibenzylideneacetone)dipalladium, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine and toluene are mixed and reacted under nitrogen protection; after the reaction, the compound represented by formula IV, sodium tert-butoxide and benzophenone imine are added under nitrogen protection. After the reaction, the mixture is filtered with diatomaceous earth, washed with dichloromethane, and the filtrate is concentrated. Petroleum ether is added to precipitate solids, filtered, and subjected to column chromatography to obtain an orange-yellow powder N,N',N",N"',N"",N""'-(4b 1 ,5,10,15-tetraazanaphtho[1,2,3-gh]tetraphenyl-2,3,7,8,12,13-hexayl)hexa(1,1-diphenylmethaneimine), as shown in Formula V;

[0019] (5) dissolving the compound represented by formula V in tetrahydrofuran, adding 2M hydrochloric acid aqueous solution, stirring at room temperature, filtering after the reaction, washing the filter cake with tetrahydrofuran, and obtaining brown-yellow powder of 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer VI;

[0020] The reaction formula is as follows:

[0021]

[0022] The amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material, referred to as M3(TCQ)2, has a structural formula as shown in Formula I:

[0023]

[0024] Wherein M is Ni, Zn, Co or Cu.

[0025] The synthesis method of the above-mentioned amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material comprises the following steps:

[0026] The 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer VI is dispersed in an organic solvent to obtain a dispersion; the dispersion and the divalent metal ion M 2+ The aqueous solutions are mixed, and an alkali aqueous solution is added to react to obtain a tricyclic quinazoline-based two-dimensional conductive metal organic framework material I based on amino coordination. The reaction formula is as follows:

[0027]

[0028] Wherein M is Ni, Zn, Co or Cu.

[0029] The base is preferably aqueous ammonia, triethylamine or sodium acetate.

[0030] The organic solvent is preferably N,N-dimethylformamide, but other organic solvents may also be used.

[0031] The above-mentioned amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material is used as a gas adsorbent.

[0032] The gas is preferably carbon dioxide.

[0033] Application of amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework materials as electrode materials for sodium-ion batteries.

[0034] Advantages of the present invention:

[0035] The amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal organic framework material of the present invention has a simple synthesis step, mild reaction conditions, good crystallinity, gas adsorption performance and excellent sodium ion battery cycle stability. The amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal organic framework material obtained by the present invention is used as a positive electrode material for a sodium ion battery, the electrolyte solution is a 1.0M NaPF6 diethylene glycol dimethyl ether solution, the voltage range is 1.0 to 3.6V, and the scan rate is 1Ag -1 It exhibits excellent cycling stability and Coulombic efficiency under the conditions of .

[0036] 2,3,7,8,12,13-Hexamidotricyclicquinazoline hydrochloride monomer can be used for the synthesis of amino-coordinated tricyclicquinazoline-based two-dimensional conductive metal-organic framework materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 This is the H NMR spectrum of the 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer synthesized in Example 1.

[0038] Figure 2 This is a high-resolution mass spectrum of the 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer prepared in Example 1.

[0039] Figure 3 This is the X-ray powder diffraction pattern of Ni3(TCQ)2 prepared in Example 2.

[0040] Figure 4 This is the infrared spectrum of Ni3(TCQ)2 prepared in Example 2. By comparing with monomer (VI), the amino peak in Ni3(TCQ)2 obviously disappears, proving the successful coordination of the framework material.

[0041] Figure 5 This is a carbon dioxide adsorption-desorption diagram of Ni3(TCQ)2 prepared in Example 2.

[0042] Figure 6The sodium ion battery performance of Ni3(TCQ)2 prepared in Example 2, the electrolyte solution is 1.0M NaPF6 diethylene glycol dimethyl ether solution, the voltage range is 1.0~3.6V, and the scan rate is 1A g -1 . DETAILED DESCRIPTION

[0043] The present invention will be further described below in conjunction with specific embodiments and accompanying drawings.

[0044] Example 1

[0045] The synthesis method of 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer comprises the following steps:

[0046] (1) 17.4 mmol of 5-bromo-2-nitrobenzaldehyde (VII) and 60 mL of 98% concentrated sulfuric acid were mixed, and then 43.9 mmol of N-bromosuccinimide was added. The mixture was stirred at room temperature for 24 hours. After the reaction was completed, the reaction liquid was poured into ice water, mixed, filtered, and subjected to column chromatography to obtain 4,5-dibromo-2-nitrobenzaldehyde (II) in the form of a white powder;

[0047] (2) 6.5 mmol of 4,5-dibromo-2-nitrobenzaldehyde (II) was mixed with 30 mL of methanol and 30 mL of ethyl acetate, and 19.5 mmol of stannous chloride dihydrate was added, stirred, and reacted at room temperature. After the reaction was completed, it was neutralized with saturated sodium bicarbonate, filtered, and the filtrate was extracted with ethyl acetate and subjected to column chromatography to obtain 5,6-dibromobenz[c]isoxazole (III) in the form of a white powder;

[0048] (3) 2.2 mmol of 5,6-dibromobenz[c]isoxazole (III), 14.0 mmol of ammonium acetate and 20 mL of sulfolane were mixed, 10 mL of glacial acetic acid was added under nitrogen protection, the mixture was stirred, and heated under reflux for 16 hours. After the reaction was completed, the mixture was filtered and the filter cake was washed with ethanol to obtain a brown-green powder 2,3,7,8,12,13-hexabromotricyclic quinazoline (IV);

[0049] (4) 0.3 mmol of tris(dibenzylideneacetone)dipalladium, 0.8 mmol of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine and 100 mL of toluene were mixed and reacted under nitrogen protection; after the reaction, 1.9 mmol of the compound represented by formula (IV), 56.9 mmol of sodium tert-butoxide and 16.4 mmol of benzophenone imine were added under nitrogen protection. After the reaction, the mixture was filtered with diatomaceous earth and washed with dichloromethane. The filtrate was concentrated and petroleum ether was added to precipitate solids. The solids were filtered and subjected to column chromatography to obtain an orange powder N,N',N",N"',N"",N""'-(4b 1,5,10,15-tetraazanaphthylidene[1,2,3-gh]tetraphenyl-2,3,7,8,12,13-hexayl)hexa(1,1-diphenylmethaneimine), as shown in formula (V);

[0050] (5) 0.1 mmol of the compound represented by formula (V) was dissolved in 18 mL of tetrahydrofuran, and 21 mL of 2M hydrochloric acid aqueous solution was added and stirred at room temperature. After the reaction was completed, the mixture was filtered and the filter cake was washed with tetrahydrofuran. The H NMR spectrum showed Figure 1 and high resolution mass spectra are shown in Figure 2 The obtained brown-yellow powder is proved to be 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer (VI); see Figure 1 and Figure 2 .

[0051] The reaction formula is as follows:

[0052]

[0053] The H NMR spectrum of 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer is shown in Figure 1 .

[0054] The high-resolution mass spectrum of 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer is shown in Figure 2 .

[0055] Example 2

[0056] The synthesis method of a tricyclic quinazoline-based two-dimensional conductive metal organic framework material based on amino coordination comprises the following steps:

[0057] 0.028 mmol of 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer (VI) was dispersed in 7.2 mL of N,N-dimethylformamide (the organic solvent may also be N,N-dimethylacetamide or methanol), and ultrasonicated for 5 minutes to obtain a dispersion; the dispersion was mixed with 0.042 mmol of an aqueous solution of nickel acetate tetrahydrate (3.6 mL), and a 2.0 M aqueous sodium acetate solution (ammonia or triethylamine aqueous solution may also be used), and ultrasonicated for 5 minutes. The mixture was reacted at 85° C. for 72 hours, cooled to room temperature, filtered, washed with N,N-dimethylformamide, water and acetone, respectively, and dried to obtain a black powder. The X-ray powder diffraction pattern was shown in FIG. Figure 3 And infrared spectrum see Figure 4 , it was proved that a tricyclic quinazoline-based two-dimensional conductive metal-organic framework material based on amino coordination was obtained, abbreviated as Ni3(TCQ)2. By comparing with the monomer (VI), the amino peak in Ni3(TCQ)2 obviously disappeared, proving the successful coordination of the framework material.

[0058] The reaction formula is as follows:

[0059]

[0060] Zinc acetate dihydrate, cobalt acetate tetrahydrate and copper nitrate trihydrate were used to replace the nickel acetate tetrahydrate of this embodiment, respectively, and the other conditions were the same as this embodiment, to obtain different amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework materials: Co3(TCQ)2, Zn3(TCQ)2, Cu3(TCQ)2, all of which were black powders.

[0061] Example 3

[0062] The application of Ni3(TCQ)2 as a carbon dioxide adsorbent comprises the following steps:

[0063] 15 mg Ni3(TCQ)2 was placed in a test tube, sealed, evacuated, and heated at 85°C for 8 hours. After the sample was fully dried, the test tube was placed at 273K and a carbon dioxide gas flow was introduced. The relative pressure range of the test was 0-0.03 (test pressure relative to standard atmospheric pressure). The adsorption amount of carbon dioxide was calculated to be 49.2 cm based on the measured gas adsorption-desorption curve. 3 g -1 .See Figure 5 .

[0064] Example 4

[0065] The application of Ni3(TCQ)2 as a sodium ion battery electrode material includes the following steps:

[0066] Ni3(TCQ)2, acetylene black and PVDF were mixed uniformly in a mass ratio of 4:5:1 to obtain a mixture, 70% of the mass of the mixture was added to the mixture, and N-methylpyrrolidone was mixed to prepare a slurry, which was evenly coated on an aluminum foil, dried, and cut into electrode sheets. The measured voltage range was 1.0-3.6 V, the electrolyte solution was 1.0 M NaPF6 in diethylene glycol dimethyl ether, and the scanning rate was 1 A g -1 After 1000 cycles, the charge and discharge capacity of the battery can be maintained at 88 mAh g -1 The Coulombic efficiency is kept at nearly 100%. This shows that Ni3(TCQ)2 has excellent cycle stability as an electrode material for sodium ion batteries. Figure 6 .

[0067] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other modifications, simplifications or simple modifications that do not deviate from the design principles and construction strategies of the present invention are included in the protection scope of the present invention.

Claims

1. 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer, characterized in that As shown in formula (VI):

2. The method for synthesizing the 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer of claim 1, characterized in that The steps include: (1) 5-bromo-2-nitrobenzaldehyde (VII) and concentrated sulfuric acid are mixed, and then N-bromosuccinimide is added, and the mixture is stirred at room temperature. After the reaction is completed, the reaction liquid is poured into ice water for mixing, filtered, and subjected to column chromatography to obtain 4,5-dibromo-2-nitrobenzaldehyde (II) in the form of a white powder; (2) 4,5-dibromo-2-nitrobenzaldehyde (II) is mixed with methanol and ethyl acetate, and stannous chloride dihydrate is added, stirred, and reacted at room temperature. After the reaction is completed, the mixture is neutralized with saturated sodium bicarbonate, filtered, and the filtrate is extracted with ethyl acetate and subjected to column chromatography to obtain 5,6-dibromobenz[c]isoxazole (III) in the form of a white powder; (3) 5,6-dibromobenz[c]isoxazole (III), ammonium acetate and sulfolane are mixed, glacial acetic acid is added under nitrogen protection, stirred, refluxed and heated. After the reaction is completed, the filter is filtered and the filter cake is washed with ethanol to obtain a brown-green powder 2,3,7,8,12,13-hexabromotricyclic quinazoline (IV); (4) Tri(dibenzylideneacetone)dipalladium, 1,1'-binaphthyl-2,2'-bisdiphenylphosphine and toluene are mixed and reacted under nitrogen protection; after the reaction, the compound represented by formula (IV), sodium tert-butoxide and benzophenone imine are added under nitrogen protection. After the reaction, the mixture is filtered with diatomaceous earth, washed with dichloromethane, and the filtrate is concentrated. Petroleum ether is added to precipitate solids, filtered, and subjected to column chromatography to obtain an orange powder N,N',N",N"',N"",N""'-(4b 1 ,5,10,15-tetraazanaphthylidene[1,2,3-gh]tetraphenyl-2,3,7,8,12,13-hexayl)hexa(1,1-diphenylmethaneimine), as shown in formula (V); (5) dissolving the compound represented by formula (V) in tetrahydrofuran, adding 2M hydrochloric acid aqueous solution, stirring at room temperature, filtering after the reaction is completed, and washing the filter cake with tetrahydrofuran to obtain a brown-yellow powder of 2,3,7,8,12,13-hexamidotricyclic quinazoline hydrochloride monomer (VI); The reaction formula is as follows:

3. A tricyclic quinazoline-based two-dimensional conductive metal organic framework material based on amino coordination, referred to as M3(TCQ)2, is characterized by its structural formula as shown in formula (I): Wherein M is Ni, Zn, Co or Cu.

4. The method for synthesizing the amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal organic framework material according to claim 3, characterized in that The steps include: The 2,3,7,8,12,13-hexaaminotricyclic quinazoline hydrochloride monomer (VI) is dispersed in an organic solvent to obtain a dispersion; the dispersion and a divalent metal ion M 2+ The aqueous solutions are mixed, and an alkali aqueous solution is added to react to obtain a tricyclic quinazoline-based two-dimensional conductive metal organic framework material (I) based on amino coordination. The reaction formula is as follows: Wherein M is Ni, Zn, Co or Cu.

5. The synthesis method according to claim 4, characterized in that The base is aqueous ammonia, triethylamine or sodium acetate.

6. The synthesis method according to claim 4, characterized in that The organic solvent is N,N-dimethylformamide.

7. Use of the amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material of claim 3 as a gas adsorbent.

8. The use according to claim 7, characterized in that The gas is carbon dioxide.

9. Application of the amino-coordinated tricyclic quinazoline-based two-dimensional conductive metal-organic framework material of claim 3 as an electrode material for sodium ion batteries.

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