Benzobithiazolyl three-dimensional COF catalyst, preparation method thereof and application of benzobithiazolyl three-dimensional COF catalyst in photocatalytic production of H2O2
By synthesizing benzobisthiazolyl three-dimensional COF catalyst in normal pressure and air atmosphere, and using water and air to efficiently produce H2O2 under photocatalytic conditions, the high temperature and high pressure and environmental pollution problems of COF synthesis methods in the prior art, as well as the high energy consumption and environmental pollution problems of traditional H2O2 production methods are solved.
Patent Information
- Application Number
- CN202510250284.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-04
- Publication Date
- 2025-06-03
AI Technical Summary
The existing COF synthesis methods have problems such as high temperature and high pressure conditions, the use of a large number of organic solvents, high cost and environmental pollution. The traditional H2O2 production methods have problems such as high energy consumption, flammable and explosive raw materials and environmental pollution.
The benzobisthiazolyl three-dimensional COF catalyst is synthesized by condensation of sulfur-containing nitrogen-containing heterocyclic compounds with aldehyde derivatives and spontaneous oxidative dehydrogenation driven by aromaticization, and H2O2 is produced using water and air under photocatalytic conditions.
It realizes efficient synthesis of catalysts in normal pressure and air atmosphere, reduces cost and environmental pollution, improves H2O2 production efficiency, and the catalyst has excellent catalytic activity.
Smart Images
Figure CN120082037A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of catalyst preparation, and specifically relates to a benzobisthiazole-based three-dimensional COF catalyst, a preparation method thereof, and an application thereof in photocatalytic hydrogen 2 O 2 production. Background Art
[0002] COF is a porous crystalline polymer formed by the dynamic covalent polymerization of organic building blocks, having structural diversity, periodic conjugated structures, and semiconductor properties. Due to its advantages of low density, excellent stability, and high porosity, it shows great application potential in catalysis. The introduction of thiazole groups can endow COF with continuous π conjugation, a rigid skeleton, and strong stability, and thus has excellent photocatalytic potential. In addition, one-dimensional / two-dimensional / three-dimensional COF (1D / 2D / 3D COF) with different structures has a significant impact on the production of photocatalytic hydrogen 2 O 2 . 1D COF may have limitations in terms of light absorption and accessibility of active sites; 2D COF may undergo structural deformation during the photocatalytic process, resulting in damage or even amorphization of the stacked arrays, thereby affecting its photocatalytic performance. In contrast, 3D COF constructed by covalently connecting organic building blocks presents a 3D extended network, and the π planes of 3D COF mostly do not overlap, which helps to maintain the inherent properties of the precursors and uniformly distribute specific functional groups in the three-dimensional space. The good pore structure of the 3D scaffold has a positive effect on the mass transfer and exposure of active sites, making it an ideal candidate for photocatalytic hydrogen 2 O 2 production.
[0003] There are some significant drawbacks in current COF synthesis methods, which affect the preparation efficiency, cost-effectiveness, and practical applications of COF materials. 1) High-temperature and high-pressure conditions are required, and high-boiling organic solvents are used, increasing the safety risks and operation complexity of experiments; 2) A large amount of organic solvents is required, increasing the cost and environmental burden; 3) Some methods require specific reaction devices, increasing the experimental complexity and experimental cost.
[0004] H 2 O 2 is an important industrial raw material and renewable energy source. The traditional anthraquinone oxidation method has disadvantages such as high energy consumption, flammable and explosive raw materials, environmental pollution, high cost, and complex by-product treatment. In contrast, using solar-driven oxygen reduction reaction (ORR) and water oxidation reaction (WOR) to produce hydrogen 2 O 2 is a promising alternative method, which consumes only oxygen (or air) and water as raw materials and can meet the growing demand for green and sustainable energy development. Currently, for hydrogen2 O 2 The preparation process of the produced catalyst mainly uses precious metals and carbon-based materials, which have problems of high cost, low catalytic efficiency and environmental pollution. Summary of the Invention
[0005] Aiming at the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a benzobisthiazole-based three-dimensional COF catalyst, its preparation method and its application in photocatalytic production of H 2 O 2 In this invention, through the aldimine condensation of sulfur- and nitrogen-containing heterocyclic compounds and aromatic aldehyde derivatives, and under the drive of aromatization, it spontaneously oxidizes and dehydrogenates in air to synthesize a benzobisthiazole-based three-dimensional COF (BBTz-3DCOF) catalyst, which can efficiently utilize water and air to produce H 2 O 2 .
[0006] To solve the above technical problems, the present invention adopts the following technical solutions:
[0007] A preparation method of a benzobisthiazole-based three-dimensional COF catalyst, comprising the following steps:
[0008] Ultrasonically mix 2,5-diamino-1,4-benzenedithiol dihydrochloride and N,N-dimethylformamide to obtain a mixed solution.
[0009] Add tetrakis(4-formylphenyl)methane and glacial acetic acid to the mixed solution, mix well and react in an oil bath. Glacial acetic acid undergoes a protonation reaction with the lone pair electrons on the amino group in 2,5-diamino-1,4-benzenedithiol dihydrochloride, and tetrakis(4-formylphenyl)methane undergoes a Schiff base reaction with 2,5-diamino-1,4-benzenedithiol dihydrochloride. The amino group and the aldehyde group condense to form an imine bond, and then under the drive of aromatization, it spontaneously oxidizes and dehydrogenates in air. After the reaction ends and cools to room temperature, wash and dry to obtain a benzobisthiazole-based three-dimensional COF catalyst.
[0010] The present invention synthesizes a benzobisthiazole-based three-dimensional COF catalyst through the aldimine condensation of sulfur- and nitrogen-containing heterocyclic compounds and aromatic aldehyde derivatives and spontaneous oxidation and dehydrogenation under the drive of aromatization, which can efficiently utilize water and air to produce H 2 O 2 , and solves the problems of high cost, low catalytic efficiency and environmental pollution existing in the prior art which mainly uses precious metals and carbon-based materials.
[0011] In a preferred embodiment of the present invention, the molar ratio of tetrakis(4-formylphenyl)methane to 2,5-diamino-1,4-benzenedithiol dihydrochloride is 1:2 to 2.2.
[0012] In a preferred embodiment of the present invention, the dosage ratio of tetra(4-formylphenyl)methane to glacial acetic acid is 5 mmol: 0.4 mL to 0.8 mL.
[0013] In a preferred embodiment of the present invention, the dosage ratio of 2,5-diamino-1,4-benzenedithiol dihydrochloride to N,N-dimethylformamide is 10 mmol: 20 mL to 40 mL.
[0014] In a preferred embodiment of the present invention, the oil bath reaction temperature is 135 °C to 145 °C, and the oil bath reaction time is 48 h to 72 h.
[0015] In a preferred embodiment of the present invention, the drying method is freeze-drying treatment, and the freeze-drying treatment temperature is -60 °C. The freeze-drying treatment can increase the specific surface area and pore size of the catalyst and better maintain the porous structure.
[0016] Another object of the present invention is to provide a benzobisthiazole-based three-dimensional COF catalyst prepared by the preparation method described in any one of the above.
[0017] The third object of the present invention is to provide an application of the benzobisthiazole-based three-dimensional COF catalyst described above in photocatalytic production of H 2 O 2 2.
[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0019] 1. In the present invention, 2,5-diamino-1,4-benzenedithiol dihydrochloride and N,N-dimethylformamide are ultrasonically mixed to obtain a mixed solution; tetra(4-formylphenyl)methane and glacial acetic acid are added to the mixed solution, and after mixing, an oil bath reaction is carried out. Glacial acetic acid undergoes a protonation reaction with the lone pair electrons on the amino group in 2,5-diamino-1,4-benzenedithiol dihydrochloride, and tetra(4-formylphenyl)methane and 2,5-diamino-1,4-benzenedithiol dihydrochloride undergo a Schiff base reaction. The amino group and the aldehyde group condense to form an imine bond, and under the drive of aromatization, it spontaneously oxidizes and dehydrogenates in the air. After the reaction is completed and cooled to room temperature, it is washed and dried to obtain a benzobisthiazole-based three-dimensional COF catalyst. The synthesis route is as follows. The present invention synthesizes a benzobisthiazole-based three-dimensional COF catalyst by the aldehyde-imine condensation of a sulfur- and nitrogen-containing heterocyclic compound and an aromatic aldehyde derivative, and spontaneously oxidizes and dehydrogenates under the drive of aromatization. Under photocatalytic conditions, it can efficiently utilize water and air to produce H 2 O 2 2, solving the problems in the prior art that mainly use precious metals and carbon-based materials, which have high costs, low catalytic efficiency, and environmental pollution.
[0020] Synthesis route:
[0021]
[0022] 2. The catalyst synthesis of the present invention can be completed under normal pressure and in an air atmosphere, with less solvent used, less safety hazard, and low cost. Without a sacrificial agent, excellent production of H 2 O 2 effect can be achieved in pure water and an air atmosphere. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 Transmission electron microscope images of the benzobisthiazole-based three-dimensional COF catalyst prepared by the present invention at different magnifications.
[0024] Figure 2 Photocatalytic hydrogen production rate diagram of the benzobisthiazole-based three-dimensional COF catalyst prepared by the present invention. 2 O 2 Rate diagram.
[0025] Figure 3 13C CP MAS diagram of the benzobisthiazole-based three-dimensional COF catalyst prepared by the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS
[0026] The following combines the embodiments of the present invention, and uses preferred embodiments and accompanying drawings for detailed description. The technical solutions in the embodiments of the present invention are clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.
[0027] It should be noted that all the professional terms used in the present invention are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention. Unless otherwise specifically stated, all kinds of raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be obtained through market purchase or prepared by existing methods.
[0028] Example 1
[0029] A preparation method of a benzobisthiazole-based three-dimensional COF catalyst, comprising the following steps:
[0030] The synthesis process is as follows:
[0031]
[0032] (1) Add 0.2452 g, 10 mmol of 2,5-diamino-1,4-benzenedithiol dihydrochloride and 30 mL of N,N-dimethylformamide to a three-necked flask and mix well by ultrasonic to obtain a mixed solution.
[0033] (2) Then, 0.2162 g (5 mmol) of tetrakis(4-formylphenyl)methane and 0.5 mL of glacial acetic acid were added to the mixed solution. After mixing evenly, the reaction was carried out in an oil bath at 140 °C for 72 h. Bubbling was carried out throughout the process using an air pump. After the reaction ended and cooled to room temperature, it was washed 4 times with deionized water, and then the sample was freeze-dried at -60 °C to obtain a benzobisthiazole-based three-dimensional COF catalyst, denoted as BBTz-3DCOF. The 13C CP MAS diagram of the benzobisthiazole-based three-dimensional COF catalyst is as shown in Figure 3 shown.
[0034] Example 2
[0035] A preparation method of a benzobisthiazole-based three-dimensional COF catalyst includes the following steps:
[0036] The synthesis process is as follows:
[0037]
[0038] (1) 10.5 mmol of 2,5-diamino-1,4-benzenedithiol dihydrochloride and 20 mL of N,N-dimethylformamide were added to a three-necked flask and mixed evenly by ultrasonic to obtain a mixed solution.
[0039] (2) Then, 0.2162 g (5 mmol) of tetrakis(4-formylphenyl)methane and 0.4 mL of glacial acetic acid were added to the mixed solution. After mixing evenly, the reaction was carried out in an oil bath at 135 °C for 48 h. Bubbling was carried out throughout the process using an air pump. After the reaction ended and cooled to room temperature, it was washed 4 times with deionized water, and then the sample was freeze-dried at -60 °C to obtain a benzobisthiazole-based three-dimensional COF catalyst.
[0040] Example 3
[0041] A preparation method of a benzobisthiazole-based three-dimensional COF catalyst includes the following steps:
[0042] The synthesis process is as follows:
[0043]
[0044] (1) 11 mmol of 2,5-diamino-1,4-benzenedithiol dihydrochloride and 40 mL of N,N-dimethylformamide were added to a three-necked flask and mixed evenly by ultrasonic to obtain a mixed solution.
[0045] (2) Then, 0.2162 g (5 mmol) of tetrakis(4-formylphenyl)methane and 0.8 mL of glacial acetic acid were added to the mixed solution. After mixing evenly, the reaction was carried out in an oil bath at 148 °C for 60 h. Bubbling was carried out throughout the process using an air pump. After the reaction ended and cooled to room temperature, it was washed 4 times with deionized water, and then the sample was freeze-dried at -60 °C to obtain a benzobisthiazole-based three-dimensional COF catalyst.
[0046] Figure 1 This is the transmission electron microscope image of the benzobisthiazole-based three-dimensional COF catalyst prepared in the present invention at different magnifications. It can be seen from the figure that the lattice spacing of the catalyst is not obvious, indicating that the crystallinity of the catalyst is poor.
[0047] Figure 2 This is the photocatalytic H 2 O 2 production rate graph of the benzobisthiazole-based three-dimensional COF catalyst prepared in the present invention. It can be seen that the photocatalytic production rate of H 2 O 2 of the benzobisthiazole-based three-dimensional COF catalyst prepared in the present invention is 6930.29 μmol g -1 h -1 . This indicates that the BBTz-3DCOF catalyst has strong catalytic activity in the photocatalytic reaction system. The 3D structure may provide more active sites or be more conducive to the absorption and transmission of light, thus improving the catalytic efficiency.
[0048] By comparing with the relevant research on the photocatalytic production of H 2 O 2 of the latest COF catalyst in 2025, it is further proved that the BBTz-3DCOF prepared in the present invention has excellent catalytic effects, as shown in Table 1.
[0049] Table 1 Performance comparison results of the catalyst prepared in the present invention and the existing catalyst for photocatalytic production of H 2 O 2
[0050]
[0051] In summary, in the present invention, 2,5-diamino-1,4-benzenedithiol dihydrochloride and N,N-dimethylformamide are ultrasonically mixed to obtain a mixed solution; tetra(4-formylphenyl)methane and glacial acetic acid are added to the mixed solution, and after mixing evenly, an oil bath reaction is carried out. The glacial acetic acid undergoes a protonation reaction with the lone pair electrons on the amino group in 2,5-diamino-1,4-benzenedithiol dihydrochloride, and tetra(4-formylphenyl)methane undergoes a Schiff base reaction with 2,5-diamino-1,4-benzenedithiol dihydrochloride. The amino group and the aldehyde group condense to form an imine bond, and under the drive of aromatization, spontaneous oxidative dehydrogenation occurs. After the reaction ends and is cooled to room temperature, and after washing and drying, a benzobisthiazolyl three-dimensional COF catalyst is obtained. The present invention synthesizes a benzobisthiazolyl three-dimensional COF catalyst by the aldehyde imine condensation of a sulfur- and nitrogen-containing heterocyclic compound and an aromatic aldehyde derivative, and spontaneous oxidative dehydrogenation under the drive of aromatization, and can efficiently utilize water and air to produce H 2 O 2 under photocatalytic conditions, solving the problems in the prior art that mainly use noble metals and carbon-based materials, which have high costs, low catalytic efficiency and environmental pollution.
[0052] It should be noted that when the present invention involves a numerical range, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the adopted step methods are the same as those in the examples, in order to prevent repetition, the present invention describes preferred examples. Although the preferred embodiments of the present invention have been described, those skilled in the art can make additional changes and modifications to these embodiments once they know the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present invention.
[0053] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.
Claims
1. A method for preparing a benzobisthiazolyl three-dimensional COF catalyst, characterized in that: The following steps are involved: Ultrasonic mixing of 2,5-diamino-1,4-benzenedithiol dihydrochloride and N,N-dimethylformamide to obtain a mixed solution; Tetrakis(4-formylphenyl)methane and glacial acetic acid are added to the mixed solution, and the mixture is mixed and then reacted in an oil bath. The glacial acetic acid and the lone pair of electrons on the amino group in 2,5-diamino-1,4-benzenedithiol dihydrochloride undergo a protonation reaction, and tetrakis(4-formylphenyl)methane and 2,5-diamino-1,4-benzenedithiol dihydrochloride undergo a Schiff base reaction, and the amino group and the aldehyde group condense to form an imine bond. Then, the mixture is spontaneously oxidized and dehydrogenated in the air under the driving force of aromatization. After the reaction is completed, the mixture is cooled to room temperature, washed and dried, and a benzobisthiazolyl three-dimensional COF catalyst is obtained.
2. The method for preparing a benzobisthiazolyl three-dimensional COF catalyst according to claim 1, characterized in that: The molar ratio of tetrakis(4-formylphenyl)methane to 2,5-diamino-1,4-benzenedithiol dihydrochloride is 1:2 to 2.
2.
3. The method for preparing a benzobisthiazolyl three-dimensional COF catalyst according to claim 1, characterized in that: The usage ratio of tetrakis(4-formylphenyl)methane to glacial acetic acid is 5mmol:0.4mL~0.8mL.
4. The method for preparing a benzobisthiazolyl three-dimensional COF catalyst according to claim 1, characterized in that: The usage ratio of 2,5-diamino-1,4-benzenedithiol dihydrochloride and N,N-dimethylformamide is 10mmol:20mL~40mL.
5. The method for preparing a benzobisthiazolyl three-dimensional COF catalyst according to claim 1, characterized in that: The oil bath reaction temperature is 135°C to 145°C, and the oil bath reaction time is 48h to 72h.
6. The method for preparing a benzobisthiazolyl three-dimensional COF catalyst according to claim 1, characterized in that: The drying method is freeze-drying.
7. A benzobisthiazolyl three-dimensional COF catalyst, characterized in that: The compound is prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the benzobisthiazolyl three-dimensional COF catalyst according to claim 7 in photocatalytic production of H2O2.