Preparation method and application of Zn (II)-MOF material containing triphenylamine and thiazole [5, 4-d] thiazole groups

Abstract

The invention discloses a preparation method and application of a Zn (II)-MOF material containing triphenylamine and thiazole [5, 4-d] thiazole perssam.The preparation method comprises the steps that N, N, N ', N'-tetrakis (4-carboxyphenyl)-1, 4-phenylenediamine, 2, 5-bis (pyridine-4-yl) thiazolo [5, 4-d] thiazole and zinc nitrate hexahydrate are dissolved in a mixed solution of N, N '-dimethylformamide and deionized water, concentrated nitric acid is added through a pipette, stirring is carried out, and the Zn (II)-MOF material containing the triphenylamine and the thiazole [5, 4-d] thiazole perssam.The Zn (II)-MOF material containing the triphenylamine and the thiazole [5, 4-d] thiazole perssam.The Zn (II)-MOF material containing the triphenylamine is obtained. Sealing, and performing ultrasonic treatment for 30 minutes in an ultrasonic cleaner to fully and uniformly mix; and transferring the obtained solution into a stainless steel high-pressure reaction kettle, heating at 110-115 DEG C, cooling to room temperature, and generating orange acicular crystal substances on the container wall and the container bottom, thereby obtaining the Zn (II)-MOF material simultaneously containing triphenylamine and thiazole [5, 4-d] thiazole groups. The method has the advantages of low requirements on synthesis equipment, simplicity and convenience in operation, low cost, high product purity and good crystallization, and the yield can reach 73%; the main body structure is good in stability; the prepared product as a catalyst has the characteristics of high conversion rate and high stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of Zn(II)-MOF catalyst materials, and particularly relates to a preparation method and application of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups. Background Art

[0002] The rapid development of industrialization and the large consumption of fossil fuels have directly led to an increase in the concentration of CO2 in the atmosphere, which is considered to be the main cause of various extreme climate events in recent years. Developing efficient carbon dioxide capture and conversion technologies is a very meaningful research work. Among them, the cycloaddition of CO2 with epoxides is an effective way to convert CO2 into high-value-added chemicals. Therefore, it is particularly important to develop efficient catalysts that can catalyze this reaction under mild conditions.

[0003] Comparative Document: Preparation method of a conjugated microporous polymer (TZCPS) linked by thiazolo[5,4-d]thiazole (TzTz) disclosed in "Design, Synthesis and Carbon Dioxide Cycloaddition Catalysis of Thiazolo[5,4-d]thiazole Porous Organic Polymers" [Doctoral Dissertation of Jilin University, Meng Xianyu]: Dissolve 1,4-benzenedicarboxaldehyde (27 mg, 0.20 mmol) and dithioacetamide (24 mg, 0.20 mmol) in N,N-dimethylformamide (5 mL). After dissolution, transfer the reaction mixture to a stainless steel autoclave with a polytetrafluoroethylene liner and react at 120 °C for 3 days. After the reaction is completed and cooled to room temperature, filter with suction and wash with deionized water and ethanol. The obtained crude product is subjected to Soxhlet extraction with methanol, acetone and tetrahydrofuran for 24 hours respectively, and then dried under vacuum at 80 °C for 24 hours to obtain a brown-red powder TZCP-1 (40 mg, 90.2% yield). The preparations of TZCP-2, 3, and 4 use 1,3,5-benzenetricarboxaldehyde (22 mg, 0.13 mmol), 1,3,5-tris(4-formylphenyl)benzene (52 mg, 0.13 mmol) and 1,2,4,5-tetrakis(4-formylphenyl)benzene (49.5 mg, 0.1 mmol) as monomers in sequence, and the other synthesis methods and treatment methods are the same as those of TZCP-1. The obtained products are insoluble yellow powder TZCP-2 (34 mg, 85.6% yield), orange powder TZCP-3 (59 mg, 84.5% yield) and yellow powder TZCP-4 (54 mg, 78.8% yield) respectively; In this comparative document, TZCPS with catalytic activity for the catalytic CO2 cycloaddition reaction was synthesized. The reaction was carried out at 1 MPa CO2 and 100 °C for 24 h, demonstrating that TZCPs have good potential as catalysts for the CO2 cycloaddition reaction. Among them, Ix@TZCPs prepared by the organic iodine modification method have better catalytic activity for the CO2 cycloaddition reaction. However, the synthesis steps of the above two materials are complex, requiring many operating devices and having high requirements for the synthesis equipment. Moreover, the catalytic reaction needs to be carried out under the conditions of 1 MPa CO2 and 100 °C.

[0004] Meanwhile, metal-organic frameworks (MOFs), as a new type of crystalline porous material, have the characteristics of clear and diverse structures, precisely controllable channels, and high-density active sites, and have unique advantages in the above fields. However, relatively few active sites, low porosity, monotonous pore environment, and generally poor stability limit the practical applications of MOFs. For example, the catalytic CO2 cycloaddition reaction is usually carried out under high pressure and / or high temperature conditions. Therefore, it is very necessary to develop MOF catalysts with good stability, low cost, and high catalytic activity.

[0005] Introducing photoactive motifs into MOFs is very interesting because they have the potential for electron transfer and radical generation under light irradiation, which can endow MOFs with additional properties such as photomagnetism, photocatalytic properties, and light-controlled guest adsorption. Triphenylamine, as a photo-responsive organic dye with high stability, anti-fatigue properties, and photochromic performance, is widely used in the synthesis of photoactive materials such as organic semiconductors, dye-sensitized solar cells, and MOFs. The tetradentate carboxylic acid ligand N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine has two triphenylamine motifs, rotatable C-C single bonds, and electron-donating properties. The four carboxylic acid groups of this ligand are severely non-coplanar, and the geometric conformation can be adjusted according to different reaction conditions. Therefore, it has obvious advantages over rigid ligands in constructing MOFs with new structures. However, the number of MOFs constructed using N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine is still limited at present. The main reason is that the solubility of this large-size ligand is very low, making crystallization quite difficult. The thiazolo[5,4-d]thiazole moiety has a large π-conjugated heterocycle and thus has good optical and electrical properties. When the ligands containing thiazolo[5,4-d]thiazole groups are arranged in parallel within the framework, there is spatial valence charge transfer in the coplanar part, which can effectively promote the conversion of light energy into chemical energy.

[0006] The following defects exist in the prior art: First, there are disadvantages such as high requirements for synthesis equipment, complex operation, and poor stability, which limit the practical application of the catalyst; Second, some catalysts have disadvantages such as poor stability, low catalytic activity, and the need to provide additional reaction conditions, which result in poor practicality of the catalyst in the actual catalytic CO2 cycloaddition reaction; Third, the MOF constructed using N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine has a good catalytic effect on the reaction, but the solubility of this large-sized ligand is very low, making crystallization quite difficult and increasing the synthesis difficulty.

[0007] Therefore, this paper provides a preparation method and application of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups. Summary of the Invention

[0008] To solve the above technical problems, the present invention discloses a preparation method and application of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, which has low requirements for synthesis equipment, is simple and convenient to operate, has low cost, high product purity, good crystallization, and the yield can reach 73%; the main structure has good stability, and the framework will not collapse after activation, or when soaked in common solvents (such as CH3OH, CH3CN, CH2CI2, DMF, cyclohexane, etc.) for 20 days, or when heated to within 200°C; the prepared product has the characteristics of high conversion rate and high stability as a catalyst, and particularly has extremely high catalytic activity for the cycloaddition reaction of carbon dioxide and various epoxy substrates under visible light irradiation.

[0009] To achieve the above technical effects, the present invention provides a preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, including the following steps: S1. Dissolve N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and zinc nitrate hexahydrate in a mixed solution of N,N'-dimethylformamide and deionized water, add concentrated nitric acid with a pipette, seal it, and place it in an ultrasonic cleaner for ultrasonic treatment for 30 minutes to make it fully mixed and uniform; S2. Transfer the solution obtained in step S1 to a polytetrafluoroethylene and stainless steel high-pressure reaction kettle, heat it at 110~115°C, and then cool it to room temperature. Orange-red needle-like crystalline substances appear on the container wall and the bottom of the container, which is the Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups.

[0010] Preferably, the molar ratio of N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and zinc nitrate hexahydrate is 1:2:2.

[0011] Preferably, the volume ratio of N,N'-dimethylformamide, deionized water, and concentrated nitric acid is 50:10:1.

[0012] Preferably, the heating time is 24 - 36 h, and the cooling rate is 5 - 10 °C / min.

[0013] A Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the above preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups is characterized in that N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine and 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole are used as organic linkers. Each Zn(II) center coordinates with three N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine and two 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole. Zn1 and Zn2 in the unit cell are connected by the carboxyl groups of the N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine ligand to form a [Zn2(COO)2] secondary building unit. These secondary building units are connected by N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine to form a two-dimensional layer, and adjacent layers are further connected by a linear 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole ligand to form a typical three-dimensional column-layered porous framework.

[0014] Preferably, the three-dimensional column-layered porous framework has a quadrilateral open channel with dimensions of 17.23 Å × 14.84 Å.

[0015] Preferably, in the three-dimensional column-layered porous framework, the completely deprotonated N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine in the framework coordinates with six Zn(II). All its benzene rings are non-coplanar. With the plane where the four carboxylic acid carbon atoms are located as a reference, the angles between the four benzene rings and the central benzene ring are 27.13°, 42.01°, 40.30°, and 31.32° respectively.

[0016] Preferably, in the three-dimensional columnar-layered porous framework, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole connecting the [Zn2(COO)2] secondary building blocks are arranged in parallel, and the π…π stacking distance between coplanar heterocyclic pairs is 3.893 Å.

[0017] Application of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups based on the above in the cycloaddition reaction of carbon dioxide and epoxides, characterized in that: the structural formula of the epoxy substrate and the catalytic reaction equation are: ; Among them, R is CH3, Cl, CH2=CH-, CH3-CH2-CH2- or Ph-O-CH2-.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention has low requirements for synthesis equipment, is simple and convenient to operate, has low cost, high product purity, good crystallization, and the yield can reach 73%; (2) The main structure of the product of the present invention has good stability, and the framework will not collapse after activation or soaking in common solvents (such as CH3OH, CH3CN, CH2CI2, DMF, cyclohexane, etc.) for 20 days, or heating to within 200 °C; (3) The product prepared by the present invention has the characteristics of high conversion rate and high stability as a catalyst, and especially has extremely high catalytic activity for the cycloaddition reaction of carbon dioxide and various epoxy substrates under visible light irradiation, and has an attractive application prospect. Description of the Drawings

[0019] Figure 1 is the basic structural unit diagram of a Zn(II)-MOF single crystal containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method provided by the present invention; Figure 2 shows the coordination mode and configuration of the ligand N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine ligand in the Zn(II)-MOF single crystal framework containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method provided by the present invention; Figure 3 is the structural diagram of the coplanar dimer pair of 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole in the Zn(II)-MOF single crystal framework containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method provided by the present invention; Figure 4Three-dimensional structure diagram of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method provided by the present invention after removing guest solvent molecules; Figure 5 PXRD patterns before and after activation and simulated PXRD patterns of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups obtained in the examples of the present invention; Figure 6 PXRD patterns of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups obtained in the examples of the present invention after being soaked in different solvents for 20 days; Figure 7 Thermogravimetric analysis diagrams of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method provided by the present invention before and after activation; Figure 8 PXRD patterns before and after five cycles of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups obtained in the examples of the present invention for catalytic carbon dioxide cycloaddition reaction; Figure 9 Catalytic yield diagram of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups obtained in the examples of the present invention for cyclic catalytic carbon dioxide cycloaddition reaction; Detailed implementation manners

[0020] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making creative efforts fall within the protection scope of the present invention.

[0021] In this embodiment, the following problems exist in the prior art: The inventors found the following defects in the prior art: First, there are disadvantages such as high requirements for synthesis equipment, complex operations, and poor stability, which limit the practical application of the catalyst; Second, some catalysts have disadvantages such as poor stability, low catalytic activity, and the need to provide additional reaction conditions, which result in poor practicality of the catalyst in the actual catalytic CO2 cycloaddition reaction; Third, the MOF constructed using N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine has a good catalytic effect on the reaction, but the solubility of this large-size ligand is very low, making crystallization quite difficult and increasing the synthesis difficulty; Therefore, as Figures 1 to 9 shown, the present invention provides a preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, including the following steps: S1. Dissolve N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and zinc nitrate hexahydrate in a mixed solution of N,N'-dimethylformamide and deionized water. Add concentrated nitric acid with a pipette, seal it, and place it in an ultrasonic cleaner for ultrasonic treatment for 30 minutes to make it fully and uniformly mixed. S2. Transfer the solution obtained in step S1 to a polytetrafluoroethylene and stainless steel autoclave, heat it at 110 - 115 °C, and then cool it to room temperature. Orange-red needle-like crystalline substances appear on the container wall and the bottom of the container, which is the Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups.

[0022] Furthermore, the molar ratio of N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and zinc nitrate hexahydrate is 1:2:2. Furthermore, the volume ratio of N,N'-dimethylformamide, deionized water, and concentrated nitric acid is 50:10:1. Furthermore, the heating time is 24 - 36 h, and the cooling rate is 5 - 10 °C / min. Among them, 1 mmol of zinc nitrate hexahydrate, 1 mmol of 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and 0.5 mmol of N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine were added to a mixed solution containing 2.5 mL of N,N'-dimethylformamide, 0.5 mL of deionized water, and 50 μL of concentrated nitric acid. After sealing, it was placed in an ultrasonic cleaner and sonicated for 30 minutes to make it fully mixed evenly. Then it was transferred to a 25 mL autoclave, heated to 115 °C and kept at a constant temperature for 24 h, and cooled to room temperature at a rate of 10 °C / h. Orange-red needle-like crystalline substances appeared on the container wall and the bottom of the container. The solution was poured out, and the orange-red needle-like crystalline substances were gently taken out with a spatula and dried at room temperature in an air atmosphere. It was the Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups, and the yield was 73% (calculated based on N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine). The main peaks of infrared test (KBr, cm-1): 3422(s), 3047(m), 2942(w), 1656(s), 1610(m), 1592(s), 1529(s), 1497(s), 1411(s), 1389(m), 1318(m), 1232(s), 1177(m), 1096(m), 1028(m), 1009 (m), 912(w), 855(m), 784(m), 705(m), 644 (m), 552(w). The Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups can scale up the synthesis (g scale) of all raw materials and solvents in the same proportion under the same reaction conditions. This method has low requirements for synthesis equipment, is simple and convenient to operate, has low cost, high product purity, good crystallization, and the yield can reach 73%.

[0023] Based on the above preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, the present invention provides a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, which is characterized in that: N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-benzenediamine and 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole are used as organic linkers, and each Zn(II) center coordinates with three N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-benzenediamine and two 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole. Zn1 and Zn2 in the unit cell are connected by the carboxyl groups of the N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-benzenediamine ligand to form a [Zn2(COO)2] secondary building unit. These secondary building units are connected by N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-benzenediamine to form a two-dimensional layer, and adjacent layers are further connected by a linear 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole ligand to form a typical three-dimensional column-layered porous framework.

[0024] Furthermore, the three-dimensional column-layered porous framework has a quadrilateral open channel with a size of 17.23 Å × 14.84 Å; Furthermore, in N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-benzenediamine and 2,5-bis(pyridin-4-yl)thiazolo[5,4-d], the completely deprotonated N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-benzenediamine in the framework coordinates with six Zn(II), and all its benzene rings are non-coplanar. With the plane where the four carboxylic acid carbon atoms are located as a reference, the angles between the four benzene rings and the central benzene ring are 27.13°, 42.01°, 40.30°, and 31.32° respectively; Furthermore, in the three-dimensional column-layered porous framework, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole connecting the [Zn2(COO)2] secondary building modules are arranged in parallel, and the π…π stacking distance between coplanar heterocyclic pairs is 3.893 Å; Among them, a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups based on the above is applied to the cycloaddition reaction of carbon dioxide and epoxide according to the following steps, which specifically include the following steps: S1. Add the activated Zn(II)-MOF and the cocatalyst TBAB into a round-bottom flask. Seal the bottle mouth with a butyl rubber stopper, purge the reaction system with CO2 gas, and then add the corresponding epoxy substrate; S2. Fix a balloon filled with carbon dioxide at the end of the needle passing through the rubber stopper. Heat the reaction mixture to the desired temperature while slowly stirring with a magnetic stir bar; S3. After the reaction is completed, recover the catalyst Zn(II)-MOF by centrifugation, and identify the product using proton nuclear magnetic resonance and carbon nuclear magnetic resonance; S4. Under the optimal reaction parameters, use 3-chloro-1,2-epoxypropane, 3,4-epoxy-1-butene, propyl epoxypropane, and 2-(phenoxymethyl)oxirane as substrates respectively to test the general applicability evaluation data of Zn(II)-MOF in the CO2 cycloaddition reaction; S5. In the experiment of visible light-promoted catalytic cycloaddition reaction, use epoxypropane as the representative substrate, and all reactant dosages and reaction conditions adopt the optimal reaction parameters screened in the previous experiment.

[0025] Meanwhile, in the experiment of visible light-promoted catalytic cycloaddition reaction, use epoxypropane as the representative substrate, and all reactant dosages and reaction conditions adopt the optimal reaction parameters screened in the previous experiment. However, the difference is that a 300 W xenon lamp should be placed 10 cm away from the reaction system, and the reaction is carried out completely under the irradiation of the xenon lamp. After each catalytic reaction, centrifuge to recover the catalyst Zn(II)-MOF, wash it with methanol multiple times, air dry it at room temperature, and use it for the next catalytic reaction. In the recyclability study, fresh co-catalyst TBAB is added in each test.

[0026] The following application examples were obtained by conducting experiments according to the above operation steps: Application Example 1: Add 130 mg of activated Zn(II)-MOF and 13 mg of TBAB into a 25 ml round-bottom flask. Seal the flask with a butyl rubber stopper, purge it with CO2 for 15 minutes, and then add the epoxy substrate 1,2-epoxypropane (20 mmol). Fix a balloon filled with carbon dioxide at the end of the needle passing through the rubber stopper. At room temperature, slowly stir with a magnetic stirrer (the rotation speed is maintained at 200 revolutions per minute). Place the reaction system in a fume hood at room temperature without light. After 18 hours of reaction, recover the catalyst Zn(II)-MOF by centrifugation, wash it with methanol 3 - 5 times, 10 mL each time, air dry it at room temperature, and use it for the next catalytic reaction. The product is extracted three times with ethyl acetate (20 mL × 3), and then column chromatography separation is carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 1a ( ), with a yield of 99%.

[0027] 130 mg of the activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 mL round-bottom flask. The flask was sealed with a butyl rubber stopper and purged with CO2 for 15 minutes, and then the epoxy substrate 1,2-epoxypropane (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). A 300 W xenon lamp was placed 10 cm away from the reaction system, and the reaction was carried out completely under the irradiation of the xenon lamp. After reacting for 4 hours, the Zn(II)-MOF used as the catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 1a ( ), with a yield of 99%. The nuclear magnetic resonance spectroscopic data of product 1a: 1 1H NMR (400 MHz, CDCl3) δ 5.17 (1H, m), 4.64 (2H, d), 4.32(2H,d), 1.42(3H, s) ppm; 13 13C NMR (100 MHz, CDCl3) δ 155.5, 74.7, 71.5, 71.5, 19.2 ppm.

[0028] Application Example 2: 130 mg of the activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 mL round-bottom flask. The flask was sealed with a butyl rubber stopper and purged with CO2 for 15 minutes, and then the epoxy substrate 3-chloro-1,2-epoxypropane (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). The reaction system was placed in a fume hood at room temperature without light for the reaction. After reacting for 18 hours, the Zn(II)-MOF used as the catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 2a ( ), with a yield of 99%.

[0029] 130 mg of activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper, purged with CO2 for 15 minutes, and then the epoxy substrate 3-chloro-1,2-epoxypropane (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). A 300 W xenon lamp was placed 10 cm away from the reaction system, and the reaction was carried out entirely under the irradiation of the xenon lamp. After 4 hours of reaction, the Zn(II)-MOF used as a catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 2a ( ), with a yield of 99%. The nuclear magnetic resonance spectral data of product 2a: 1 1H NMR (400 MHz, CDCl3) δ 5.02 (1H, m), 4.63 (2H, m), 3.78(2H, m) ppm; 13 13C NMR (100 MHz, CDCl3) δ 154.7, 78.8, 67.6, 43.1 ppm.

[0030] Application Example 3: 130 mg of activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper, purged with CO2 for 15 minutes, and then the epoxy substrate 3,4-epoxy-1-butene (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). The reaction system was placed in a fume hood at room temperature without light for the reaction. After 18 hours of reaction, the Zn(II)-MOF used as a catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 3a ( ), with a yield of 99%.

[0031] 130 mg of activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper and purged with CO2 for 15 minutes, then the epoxy substrate 3,4-epoxy-1-butene (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). A 300 W xenon lamp was placed 10 cm away from the reaction system, and the reaction was carried out completely under the irradiation of the xenon lamp. After 4 hours of reaction, the Zn(II)-MOF used as a catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 3a ( ), with a yield of 99%. The nuclear magnetic resonance spectroscopic data of product 3a: 1 H NMR (400 MHz, CDCl3) δ 4.95 (1H, m), 4.58 (2H, d),1.76(2H, m), 1.42(2H, m), 0.93(3H, t) ppm; 13 C NMR (100 MHz, CDCl3) δ 155.1,78.9, 68.8, 34.4, 18.2, 13.9 ppm.

[0032] Application Example 4: 130 mg of activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper and purged with CO2 for 15 minutes, then the epoxy substrate propyl epoxypropane (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). The reaction system was placed in a fume hood at room temperature without light for the reaction. After 18 hours of reaction, the Zn(II)-MOF used as a catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 4a ( ), with a yield of 99%.

[0033] 130 mg of activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper, purged with CO2 for 15 minutes, and then the epoxy substrate propyl glycidyl ether (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, the mixture was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). A 300 W xenon lamp was placed 10 cm away from the reaction system, and the reaction was carried out entirely under the irradiation of the xenon lamp. After 4 hours of reaction, the Zn(II)-MOF used as the catalyst was recovered by centrifugation, washed 3 - 5 times with methanol, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 4a ( ), with a yield of 98%. The nuclear magnetic resonance spectroscopic data of product 4a: 1 H NMR (400 MHz, CDCl3) δ 5.93 (1H, m), 5.47 (2H, d), 5.37(1H,m), 4.55(2H, d), ppm; 13 C NMR (100 MHz, CDCl3) δ 154.9, 134.5, 118.2, 77.1,69.1 ppm.

[0034] Application Example 5: 130 mg of activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper, purged with CO2 for 15 minutes, and then the epoxy substrate 2-(phenoxymethyl)oxirane (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, the mixture was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). The reaction system was placed in a fume hood at room temperature without light. After 18 hours of reaction, the Zn(II)-MOF used as the catalyst was recovered by centrifugation, washed 3 - 5 times with methanol, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL × 3), and then column chromatography was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 5a ( ), with a yield of 96%.

[0035] 130 mg of the activated Zn(II)-MOF and 13 mg of TBAB were added to a 25 ml round-bottom flask. The flask was sealed with a butyl rubber stopper, purged with CO2 for 15 minutes, and then the epoxy substrate 2-(phenoxymethyl)oxirane (20 mmol) was added. A balloon filled with carbon dioxide was fixed at the end of the needle passing through the rubber stopper. At room temperature, it was slowly stirred with a magnetic stirrer (the rotation speed was maintained at 200 revolutions per minute). A 300 W xenon lamp was placed 10 cm away from the reaction system, and the reaction was carried out completely under the irradiation of the xenon lamp. After 4 hours of reaction, the Zn(II)-MOF used as a catalyst was recovered by centrifugation, washed with methanol 3 - 5 times, 10 mL each time, air-dried at room temperature, and used for the next catalytic reaction. The product was extracted three times with ethyl acetate (20 mL×3), and then column chromatography separation was carried out using an eluent with a volume ratio of n-hexane:ethyl acetate of 4:1 to obtain product 5a ( ), with a yield of 94%. The nuclear magnetic resonance spectroscopic data of product 5a: 1 H NMR (400 MHz, CDCl3) δ 7.29 (2H, m), 6.98 (1H, m), 6.93(2H, t), 4.95(1H, m), 4.55(2H, m), 4.68(2H, m), ppm; 13 C NMR (100 MHz, CDCl3) δ 157.8, 154.5, 129.6, 121.6, 114.7, 75.7, 68.2, 67.5 ppm.

[0036] After that, the stability of a Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups prepared was tested: The prepared Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups was soaked in different solvents for 20 days, and then X-ray powder diffraction characterization was carried out. As Figure 6 shown, by comparing the characteristic peaks of its theoretical simulation, it can be seen that the characteristic peaks of the PXRD pattern of the soaked sample did not change. This indicates that the material has good chemical stability. Figure 7 The thermogravimetric analysis diagrams of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method provided by the present invention before and after activation are shown. It can be seen that the material remains intact before being heated to 200 °C and has good thermal stability. After the prepared Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups was subjected to five catalytic cycloaddition reaction cycles, X-ray powder diffraction characterization was carried out, and the results are as Figure 8As shown, after five cycles of use, the structure of the prepared Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups remains unchanged.

[0037] Application of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups prepared by the preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups as described above in the cycloaddition reaction of carbon dioxide and epoxides, characterized in that: the structural formula of the epoxy substrate and the catalytic reaction equation are as follows: ; wherein, R is CH3, Cl, CH2=CH-, CH3-CH2-CH2- or Ph-O-CH2-.

[0038] In summary, compared with the prior art, the beneficial effects of the present invention are as follows: (1) The present invention has low requirements for synthesis equipment, is simple and convenient to operate, has low cost, high product purity, good crystallization, and the yield can reach 73%; (2) The main structure of the product of the present invention has good stability. Before and after activation, or soaked in common solvents (such as CH3OH, CH3CN, CH2CI2, DMF, cyclohexane, etc.) for 20 days, or heated to within 200°C, the framework will not collapse; (3) The product prepared by the present invention has the characteristics of high conversion rate and high stability as a catalyst, especially has extremely high catalytic activity in the cycloaddition reaction of carbon dioxide and various epoxy substrates under visible light irradiation, and has an attractive application prospect.

[0039] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprising", "including" or any other variant thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device.

[0040] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. Preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, characterized in that: It includes the following steps: S1. Dissolve N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and zinc nitrate hexahydrate in a mixed solution of N,N'-dimethylformamide and deionized water. Add concentrated nitric acid with a pipette, seal it, and place it in an ultrasonic cleaner for ultrasonic treatment for 30 minutes to mix them evenly. S2. Transfer the solution obtained in step S1 to a polytetrafluoroethylene and stainless steel high-pressure reactor, heat it at 110 - 115 °C, and then cool it to room temperature. Orange-red needle-like crystalline substances appear on the container wall and the bottom of the container, which is the Zn(II)-MOF material containing both triphenylamine and thiazolo[5,4-d]thiazole groups.

2. The preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to claim 1, characterized in that: The molar ratio of N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole, and zinc nitrate hexahydrate is 1:2:

2.

3. The preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to claim 1, characterized in that: The volume ratio of N,N'-dimethylformamide, deionized water, and concentrated nitric acid is 50:10:

1.

4. The preparation method of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to claim 1, characterized in that: The heating time is 24 - 36 h, and the cooling rate is 5 - 10 °C / min.

5. A Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups, which is prepared by the preparation method of the Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to any one of claims 1 to 4, is characterized in that: N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine and 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole are used as organic linkers. Each Zn(II) center coordinates with three N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine and two 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole. Zn1 and Zn2 in the unit cell are connected by the carboxyl groups of the N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine ligand to form a [Zn2(COO)2] secondary building unit. These secondary building units are connected by N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine to form a two-dimensional layer, and adjacent layers are further connected by a linear 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole ligand to form a typical three-dimensional column-layered porous framework.

6. The Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to claim 5, characterized in that: The three-dimensional column-layered porous framework has a quadrilateral open channel with dimensions of 17.23 Å × 14.84 Å, and the inner wall of the channel is densely distributed with unsaturated Zn(II) sites, triphenylamine, and thiazolo[5,4-d]thiazole groups.

7. A Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to claim 5, characterized in that: In the three-dimensional column-layered porous framework, N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine and 2,5-bis(pyridin-4-yl)thiazolo[5,4-d] are completely deprotonated in the framework. The N,N,N',N'-tetrakis(4-carboxyphenyl)-1,4-phenylenediamine coordinates with six Zn(II). All its benzene rings are non-coplanar. Taking the plane where the four carboxylic acid carbon atoms are located as a reference, the angles between the four benzene rings and the central benzene ring are 27.13°, 42.01°, 40.30°, and 31.32° respectively.

8. The Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups according to claim 5, characterized in that: In the described three-dimensional columnar-layered porous framework, 2,5-bis(pyridin-4-yl)thiazolo[5,4-d]thiazole that connects the [Zn2(COO)2] secondary building blocks is arranged in parallel, and the π…π stacking distance between coplanar heterocyclic pairs is 3.893 Å.

9. Use of a Zn(II)-MOF material containing triphenylamine and thiazolo[5,4-d]thiazole groups in the catalytic cycloaddition reaction of carbon dioxide and epoxides, characterized in that: The structural formula of the described epoxy substrate and the catalytic reaction equation are as follows: ； Among them, R is CH3, Cl, CH2=CH-, CH3-CH2-CH2-, or Ph-O-CH2-.

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