Fluorine-containing acylhydrazone-based covalent organic framework material, and preparation method and application thereof

Abstract

The present application relates to a kind of fluorine-containing acylhydrazone-based covalent organic framework material and its preparation method and application, a kind of fluorine-containing acylhydrazone-based covalent organic framework material is synthesized by Schiff base reaction, and it is used for photocatalytic preparation hydrogen peroxide.The fluorine-containing acylhydrazone-based covalent organic framework material of the present application has nanoscale porous fiber structure, and has good crystallinity and chemical stability, and shows excellent catalytic performance and cyclic stability in photocatalytic preparation hydrogen peroxide reaction, has potential application value in the field of environmental protection and energy conversion.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic materials, and in particular relates to a fluorine-containing acylhydrazone covalent organic framework material, a preparation method and an application thereof. Background Art

[0002] Hydrogen peroxide (H2O2), an important inorganic chemical product, is a slightly blue, transparent liquid at room temperature. It possesses strong oxidizing, bleaching, and bactericidal properties. Because its decomposition products are solely water and oxygen, leaving no harmful residues, it is widely used in textile printing and dyeing, papermaking, environmental protection, medicine, and the electronics industry. Currently, the anthraquinone method is the traditional H2O2 production process. This process uses alkyl anthraquinone as a carrier, heavy aromatic hydrocarbons, and trioctyl phosphate as a solvent. In the presence of a catalyst, the catalyst reacts with hydrogen to produce anthrahydroquinone. Subsequently, oxidation and extraction steps produce a high-concentration H2O2 product. This production process consumes large amounts of organic solvents and catalysts, resulting in high costs and potential safety and environmental risks. In contrast, photocatalytic H2O2 production, which meets the needs of environmental protection and low energy consumption, has become a research hotspot. Based on the advantages of photocatalytic H2O2 production, future research should focus on the development of non-precious metal-based catalysts with high activity, high stability and wide spectral response. By regulating the microstructure and surface properties of the catalysts, their adsorption and activation capabilities for water and oxygen can be enhanced to achieve efficient and green production of H2O2 and promote the large-scale application of photocatalytic technology in the field of H2O2 preparation.

[0003] Covalent organic frameworks (COFs) are a class of crystalline porous polymers composed of organic monomers linked by covalent bonds, exhibiting a highly ordered porous structure. Due to their structural advantages, such as tunable pore structure, high specific surface area, good stability, and ease of functionalization, acylhydrazone-based COFs have shown great potential in catalysis, adsorption, separation, sensing, and energy storage. Furthermore, the acylhydrazone groups impart electronic conjugation to the frameworks, enabling them to effectively absorb visible light, broadening the photoresponse range and improving solar energy utilization efficiency. This conjugated structure also facilitates the separation of photogenerated electron-hole pairs, suppressing the exciton recombination rate, improving carrier mobility, and thus enhancing photocatalytic activity. Therefore, acylhydrazone-based COFs have significant application potential in the photocatalytic production of H₂O₂. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to address the deficiencies in the catalysts for H2O2 production in the prior art, and to provide a fluorine-containing acylhydrazone covalent organic framework material and its preparation method and application, so as to achieve efficient, green and low-cost production of H2O2.

[0005] The present invention provides a fluorine-containing acylhydrazone covalent organic framework material, the general structural formula of the fluorine-containing acylhydrazone covalent organic framework material is:

[0006] or ; wherein, X is independently selected from one of hydroxyl, fluorine, chlorine, bromine, iodine; Y is independently selected from carbon or nitrogen atom; R 1 , R 2 , R 3 are independently selected from one of H, alkyl, alkoxy.

[0007] The application also provides a preparation method of the fluorine-containing acylhydrazone-based covalent organic framework material, comprising the following steps:

[0008] The fluorine-containing acylhydrazone-based covalent organic framework material is obtained by Schiff base reaction of the aromatic aldehyde monomer compound and the terephthalic dihydrazide monomer compound.

[0009] Preferably, the structural general formula of the aromatic aldehyde monomer compound is as follows:

[0010] ; wherein, X is independently selected from one of hydroxyl, fluorine, chlorine, bromine, iodine; Y is independently selected from carbon or nitrogen atom. Preferably, X is a fluorine atom, and Y is a carbon atom.

[0011] Preferably, the structural general formula of the terephthalic dihydrazide monomer compound is as follows:

[0012] ; wherein, R 1 , R 2 are independently selected from one of H, alkyl, alkoxy. Preferably, R 1 , R 2 are both methoxy.

[0013] More preferably, the aromatic aldehyde monomer compound and the terephthalic dihydrazide monomer compound are 1,3,5-tris(3-fluoro-4-formylphenyl)benzene and 2,5-dimethoxyterephthalic dihydrazide, respectively.

[0014] Further, the Schiff base reaction system further comprises a solvent and an acid catalyst; the solvent is 1,4-dioxane and mesitylene, and the acid catalyst is an acetic acid solution. Preferably, the volume ratio of the 1,4-dioxane, the mesitylene and the acetic acid solution is 5:5:1.

[0015] Further, the molar ratio of the 1,3,5-tris(3-fluoro-4-formylphenyl)benzene to the 2,5-dimethoxyterephthalic dihydrazide is 1:1.5.

[0016] Further, the Schiff base reaction temperature is 100-150 o C, and the reaction time is 48-72 h.

[0017] The present invention also provides a method for preparing a fluorine-containing acylhydrazone covalent organic framework material, comprising the following steps:

[0018] The fluorine-containing acylhydrazone covalent organic framework material is obtained by reacting a s-tribenzoylhydrazide monomer compound with a dihalogenated terephthalaldehyde monomer compound through a Schiff base reaction.

[0019] Preferably, the general structural formula of the s-tribenzoylhydrazide monomer compound is as follows:

[0020] ; Wherein, Y is a carbon or nitrogen atom; R 1 、R 2 、R 3 is one of H, alkyl, and alkoxy. Preferably, Y is a carbon atom, R 1 、R 2 、R 3 All are methoxy groups.

[0021] Preferably, the general structural formula of the dihalogenated terephthalaldehyde monomer compound is as follows:

[0022] wherein X is independently selected from one of a hydroxyl group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferably, X is a fluorine atom.

[0023] Preferably, the s-triphenylhydrazide monomer compound and the dihalogenated terephthalaldehyde monomer compound are 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide and 2,5-difluoroterephthalaldehyde, respectively.

[0024] Furthermore, the Schiff base reaction system further includes a solvent and an acid catalyst; the solvent is N,N-dimethylacetamide and 1,3,5-trimethylbenzene, and the acid catalyst is an acetic acid solution. Preferably, the volume ratio of the N,N-dimethylacetamide, 1,3,5-trimethylbenzene, and acetic acid solution is 8:2:1.

[0025] Furthermore, the molar ratio of the 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide to the 2,5-difluoroterephthalaldehyde monomer compound is 1:1.5.

[0026] Furthermore, the Schiff base reaction temperature is 100-150 o C, reaction time is 48-72 h.

[0027] Further, the preparation method of the 5'-(4-(hydrazinecarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide comprises the following steps:

[0028] The dimethyl 3,3''-dimethoxy-5'-(3-methoxy-4-(methoxycarbonyl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylate, hydrazine hydrate, ethanol and toluene are mixed, and then the reaction is stirred under reflux conditions to obtain the 5'-(4-(hydrazinecarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide.

[0029] Further, the molar ratio of the dimethyl 3,3''-dimethoxy-5'-(3-methoxy-4-(methoxycarbonyl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylate and the hydrazine hydrate is 1:6.

[0030] Further, the temperature of the stirring reaction is 60-100 o C, and the time is 12-48 h.

[0031] The application further provides an application of a fluorine-containing acylhydrazone-based covalent organic framework material in photocatalytic preparation of hydrogen peroxide.

[0032] Advantages

[0033] (1) The fluorine-containing acylhydrazone-based covalent organic framework material is synthesized by adopting a Schiff base reaction, the material has a nanoscale porous fiber structure, has good crystallinity and chemical stability, exhibits excellent catalytic performance and cycle stability in the photocatalytic preparation of hydrogen peroxide, and has potential application value in the fields of environmental protection and energy conversion.

[0034] (2) The fluorine-containing acylhydrazone-based covalent organic framework material has very excellent photocatalytic H2O2 production performance under pure oxygen conditions and is conducive to recycling of the catalyst under sunlight driving. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The H NMR spectrum of the 5'-(4-(hydrazinecarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide (HMDTD) synthesized in Example 1 is as follows. 1 H NMR spectrum.

[0036] Figure 2The present invention is a schematic diagram of the synthesis route of the fluorine-containing acylhydrazone covalent organic framework material; the monomers involved include 1,3,5-tris(3-fluoro-4-formylphenyl)benzene (TDDY), 2,5-dimethoxyterephthalic acid dihydrazide (BADD), 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide (HMDTD) and 2,5-difluoroterephthalaldehyde (BDHD); the fluorine-containing acylhydrazone covalent organic framework materials involved include the fluorine-containing acylhydrazone DHU-COF-TB material synthesized in Example 2 and the fluorine-containing acylhydrazone DHU-COF-HB material synthesized in Example 4; (a) is the synthesis route of the fluorine-containing acylhydrazone DHU-COF-TB material; (b) is the synthesis route of the fluorine-containing acylhydrazone DHU-COF-HB material.

[0037] Figure 3 4. The Fourier transform infrared spectra of the fluorine-containing acylhydrazone DHU-COF-TB material and TDDY and BADD synthesized in Example 2.

[0038] Figure 4 4. The Fourier transform infrared spectra of the fluorine-containing acylhydrazone DHU-COF-HB material, HMDTD and BDHD synthesized in Example 4.

[0039] Figure 5 This is the powder X-ray diffraction spectrum of the fluorine-containing acylhydrazone DHU-COF-TB material synthesized in Example 2.

[0040] Figure 6 This is the powder X-ray diffraction spectrum of the fluorine-containing acylhydrazone DHU-COF-HB material synthesized in Example 4.

[0041] Figure 7 This is the solid-state NMR carbon spectrum of the fluorine-containing acylhydrazone DHU-COF-TB material synthesized in Example 2.

[0042] Figure 8 This is the solid-state carbon nuclear magnetic resonance spectrum of the fluorine-containing acylhydrazone DHU-COF-HB material synthesized in Example 4.

[0043] Figure 9 : The nitrogen adsorption-desorption curve and BET specific surface area of ​​the fluorine-containing acylhydrazone DHU-COF-TB material synthesized in Example 2.

[0044] Figure 10 : The nitrogen adsorption-desorption curve and BET specific surface area of ​​the fluorine-containing acylhydrazone DHU-COF-HB material synthesized in Example 4.

[0045] Figure 11Scanning electron microscope images of the fluorine-containing acylhydrazone-based covalent organic framework materials synthesized in the examples; wherein (a) is Example 2; (b) is Example 4.

[0046] Figure 12 Water contact angle test images of the fluorine-containing acylhydrazone-based covalent organic framework materials synthesized in the examples; wherein (a) is Example 2; (b) is Example 4.

[0047] Figure 13 Thermogravimetric analysis curve of the fluorine-containing acylhydrazone-based DHU-COF-TB material synthesized in Example 2.

[0048] Figure 14 Thermogravimetric analysis curve of the fluorine-containing acylhydrazone-based DHU-COF-HB material synthesized in Example 4.

[0049] Figure 15 Photocatalytic H2O2 production concentration curve of the fluorine-containing acylhydrazone-based DHU-COF-TB material synthesized in Example 2.

[0050] Figure 16 Photocatalytic H2O2 production concentration curve of the fluorine-containing acylhydrazone-based DHU-COF-HB material synthesized in Example 4.

[0051] Figure 17 Bar contrast chart of the photocatalytic H2O2 production rate of the fluorine-containing acylhydrazone-based DHU-COF-TB material synthesized in Example 2 and the fluorine-containing acylhydrazone-based DHU-COF-HB material synthesized in Example 4 in different gas atmospheres.

[0052] Figure 18 Structural general formula schematic diagram of the fluorine-containing acylhydrazone-based covalent organic framework material of the present application. DETAILED DESCRIPTION

[0053] The application will be further described with reference to the following examples. It should be understood that these examples are intended to illustrate the application and are not intended to limit the scope of the application. Furthermore, since modifications to the application will occur to those skilled in the art, it is intended to cover any and all such modifications as fall within the scope of the appended claims.

[0054] Source of raw materials: 3,3''-dimethoxy-5'-(3-methoxy-4-(methoxycarbonyl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dimethyl ester (Jilin Zhongke Science and Technology Co., Ltd.), hydrazine hydrate (85wt%, Sinopharm Chemical Reagent Co., Ltd.), toluene (Shanghai Titan Technology Co., Ltd.), 1,3,5-tris(3-fluoro-4-formylphenyl)benzene (Jilin Zhongke Science and Technology Co., Ltd.), 2,5-dimethoxyterephthalic acid hydrazide (Jilin Zhongke Science and Technology Co., Ltd.), and 2,5-difluoroterephthalaldehyde (Jilin Zhongke Science and Technology Co., Ltd.).

[0055] Example 1

[0056] Dimethyl 3,3''-dimethoxy-5'-(3-methoxy-4-(methoxycarbonyl)phenyl)-[1,1':3',1''-terphenyl]-4,4''-dicarboxylate (1.0 g, 1.75 mmol), hydrazine hydrate (15.0 mL, 10.5 mmol), ethanol (10.0 mL), and toluene (10.0 mL) were added sequentially into a 100 mL round-bottom flask at 85°C. o C and refluxed for 24 h, then cooled to room temperature. The white precipitate was filtered, washed with ethanol, and o C and dried under reduced pressure for 12 h to give 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide (0.79 g, 1.54 mmol) as a white powder with a yield of 79%.

[0057] The NMR spectrum of 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide obtained in this example is as follows Figure 1 shown.

[0058] Example 2

[0059] 1,3,5-Tris(3-fluoro-4-formylphenyl)benzene (15.0 mg, 0.034 mmol), 2,5-dimethoxyterephthaloylhydrazide (13.0 mg, 0.051 mmol), 1,4-dioxane (0.5 mL), 1,3,5-trimethylbenzene (0.5 mL) and acetic acid solution (6 mol / L, 0.1 mL) were added to an ampoule (2.0 mL) in sequence and ultrasonically dispersed for 5 min. Vacuum and backfill with nitrogen three times, seal the ampoule under vacuum, and place it at 120 oThe reaction was continued in a constant temperature oven at 4°C for 72 h. After completion of the reaction, the mixture was cooled to room temperature and filtered through a fritted funnel. The obtained product was washed sequentially with tetrahydrofuran and n-hexane and then dried under vacuum for 12 h to obtain DHU-COF-TB material (46.2 mg) as a slightly yellow powder with a yield of 88.3%.

[0060] The schematic diagram of the synthesis route of the fluorine-containing acylhydrazone DHU-COF-TB material obtained in this example is as follows: Figure 2 As shown in a, the Fourier transform infrared spectrum is as follows Figure 3 The powder X-ray diffraction spectrum is shown as Figure 5 As shown, the solid state carbon NMR spectrum is as follows Figure 7 As shown, the nitrogen adsorption and desorption curves are as follows Figure 9 As shown in the scanning electron microscope image Figure 11 As shown in a, the water contact angle test diagram is as follows Figure 12 As shown in a, the thermogravimetric analysis curve is as follows Figure 13 The above results show that the prepared DHU-COF-TB material has a crystalline skeleton, regularly arranged pores, a large specific surface area, good thermal stability, a fibrous microstructure and good hydrophilicity.

[0061] Example 3

[0062] The application of fluorine-containing acylhydrazone-based DHU-COF-TB materials in the field of photocatalytic H2O2 production specifically includes the following steps:

[0063] The photocatalytic production of H2O2 was carried out in a sealed glass bottle. 7.5 mg of DHU-COF-TB synthesized in Example 2 was used as the catalyst, 15.0 mL of a mixture of water and ethanol (v / v = 9:1) was used as the reaction system solution, and the light intensity was 1.35 kW / m 2 The solar simulator is used as the irradiation light source to keep the temperature of the space where the sealed glass bottle is located at 25 o C. Before the start of the catalytic reaction, oxygen was introduced into the reactor for 30 minutes to remove other gases such as carbon dioxide. During the reaction, samples were taken every ten minutes for one hour, and the liquid product was detected by colorimetry using an ultraviolet spectrophotometer to detect the concentration of related liquid products.

[0064] The concentration curve of H2O2 produced by photocatalysis is as follows Figure 15 As shown in Figure 2, the average yield of H2O2 was 2458.2 μmol g -1 h -1 .

[0065] Example 4

[0066] 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3''-dimethoxy-[1,1':3',1''-terphenyl]-4,4''-dicarboxylic acid dihydrazide (15.0 mg, 0.026 mmol) obtained in Example 1, 2,5-difluoroterephthalaldehyde (6.7 mg, 0.039 mmol), N,N-dimethylacetamide (0.8 mL), 1,3,5-trimethylbenzene (0.2 mL) and acetic acid solution (9 mol / L, 0.1 mL) were added to an ampoule (2.0 mL) and ultrasonically dispersed for 5 min. Vacuum and backfill with nitrogen three times, seal the ampoule under vacuum, and place it at 120 o The reaction was continued in a constant temperature oven at 4°C for 72 h. After the reaction was completed, the mixture was cooled to room temperature and filtered through a fritted funnel. The obtained product was then vacuum dried in tetrahydrofuran and then n-hexane for 12 h to obtain a yellow powder of DHU-COF-HB (34.8 mg) with a yield of 85.6%.

[0067] The schematic diagram of the synthesis route of the fluorine-containing acylhydrazone DHU-COF-HB material obtained in this example is as follows: Figure 2 As shown in b, the Fourier transform infrared spectrum is as follows Figure 4 The powder X-ray diffraction spectrum is shown as Figure 6 As shown, the solid state carbon NMR spectrum is as follows Figure 8 As shown, the nitrogen adsorption and desorption curves are as follows Figure 10 As shown in the scanning electron microscope image Figure 11 As shown in b, the water contact angle test diagram is as follows Figure 12 As shown in b, the thermogravimetric analysis curve is as follows Figure 14 The above results show that the prepared DHU-COF-HB material has a crystalline skeleton, regularly arranged pores, a large specific surface area, good thermal stability, a spherical microstructure and good hydrophilicity.

[0068] Example 5

[0069] The application of the fluorine-containing acylhydrazone-based DHU-COF-HB material in photocatalytic H2O2 production specifically includes the following steps:

[0070] The photocatalytic production of H2O2 was carried out in a sealed glass bottle. 7.5 mg of DHU-COF-HB synthesized in Example 4 was used as the catalyst, 15.0 mL of a mixture of water and ethanol (v / v = 9:1) was used as the reaction system solution, and the light intensity was 1.35 kW / m 2 The solar simulator is used as the irradiation light source to keep the temperature of the space where the sealed glass bottle is located at 25 o C. Before the catalytic reaction begins, oxygen is introduced into the reactor The reaction was continued for 30 min to remove carbon dioxide and other gases. During the reaction, samples were taken every ten minutes for one hour, and the concentration of liquid-phase related products was detected by colorimetric method using UV-visible absorption spectroscopy.

[0071] The concentration curve of H2O2 produced by photocatalysis is as follows Figure 16 As shown in Figure 2, the average yield of H2O2 was 911.7 μmol g -1 h -1 .

[0072] Example 6

[0073] 7.5 mg of the fluorinated acylhydrazone covalent organic framework materials synthesized in Examples 2 and 4 were used as catalysts, 15.0 mL of a mixture of water and ethanol (v / v = 9:1) was used as the reaction system solution, and a light intensity of 1.35 kW / m 2 The solar simulator is used as the irradiation light source, and the temperature of the space where the sealed glass bottle is located is kept at 25 o C. Before the start of the catalytic reaction, oxygen was introduced into the reactor for 30 minutes. During the reaction, samples were taken every ten minutes for one hour. The liquid product was developed by colorimetry and the concentration of liquid-phase related products was detected using UV-visible absorption spectroscopy to obtain the photocatalytic H2O2 production rate in an oxygen environment.

[0074] 7.5 mg of the fluorinated acylhydrazone covalent organic framework materials synthesized in Examples 2 and 4 were used as catalysts, 15.0 mL of a mixture of water and ethanol (v / v = 9:1) was used as the reaction system solution, and a light intensity of 1.35 kW / m 2 The solar simulator is used as the irradiation light source, and the temperature of the space where the sealed glass bottle is located is kept at 25 o C. Before the start of the catalytic reaction, air was introduced into the reactor for 30 minutes. During the reaction, samples were taken every ten minutes for one hour. The liquid product was developed by colorimetry and the concentration of liquid-phase related products was detected using UV-visible absorption spectroscopy to obtain the photocatalytic H2O2 production rate in an air environment.

[0075] 7.5 mg of the fluorinated acylhydrazone covalent organic framework materials synthesized in Examples 2 and 4 were used as catalysts, 15.0 mL of a mixture of water and ethanol (v / v = 9:1) was used as the reaction system solution, and a light intensity of 1.35 kW / m 2 The solar simulator is used as the irradiation light source, and the temperature of the space where the sealed glass bottle is located is kept at 25 oC. Before the catalytic reaction began, argon was introduced into the reactor for 30 minutes to remove oxygen and other gases from the solution. During the reaction, samples were taken every ten minutes for one hour. The liquid product was developed using a colorimetric method, and the concentration of the liquid-phase related products was detected using UV-visible absorption spectroscopy to obtain the photocatalytic H2O2 production rate under an argon environment.

[0076] Comparison of H2O2 production rates of fluorinated acylhydrazone-containing covalent organic framework materials as catalysts in oxygen, air, and argon atmospheres Figure 17 As shown. Figure 17 It can be seen that the two synthesized fluorine-containing acylhydrazone covalent organic framework materials have the highest photocatalytic production rate of H2O2 in an oxygen atmosphere, proving that oxygen is the key raw material for the reaction and that the DHU-COF-TB material has better performance.

Claims

1. A fluorine-containing acylhydrazone covalent organic framework material, wherein the general structural formula of the fluorine-containing acylhydrazone covalent organic framework material is: in, X is a fluorine atom; Y is independently selected from a carbon or nitrogen atom; R 1 、R 2 、R 3 Each independently selected from one of H, alkyl and alkoxy.

2. A method for preparing the fluorine-containing acylhydrazone covalent organic framework material according to claim 1, comprising the following steps: The fluorine-containing acylhydrazone covalent organic framework material is obtained by reacting an aromatic aldehyde monomer compound with a terephthalic hydrazide monomer compound through a Schiff base reaction.

3. The preparation method according to claim 2, wherein: The general structural formula of the aromatic aldehyde monomer compound is shown below: Wherein, X is a fluorine atom; and Y is independently selected from a carbon or nitrogen atom.

4. The preparation method according to claim 2, wherein: The general structural formula of the terephthalic acid hydrazide monomer compound is shown below: Among them, R 1 、R 2 Each independently selected from one of H, alkyl and alkoxy.

5. A method for preparing the fluorine-containing acylhydrazone covalent organic framework material according to claim 1, comprising the following steps: The fluorine-containing acylhydrazone covalent organic framework material is obtained by reacting a s-tribenzoylhydrazide monomer compound with a dihalogenated terephthalaldehyde monomer compound through a Schiff base reaction.

6. The preparation method according to claim 5, characterized in that: The general structural formula of the s-tribenzoylhydrazide monomer compound is shown below: Wherein, Y is a carbon or nitrogen atom; R 1 、R 2 、R 3 It is one of H, alkyl and alkoxy.

7. The preparation method according to claim 5, characterized in that: The general structural formula of the dihalogenated terephthalaldehyde monomer compound is shown below: Wherein, X is a fluorine atom.

8. The preparation method according to claim 5, characterized in that: The s-triphenylhydrazide monomer compound is 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3"-dimethoxy-[1,1':3',1"-terphenyl]-4,4"-dicarboxylic acid dihydrazide.

9. The preparation method according to claim 8, characterized in that: The preparation method of the 5'-(4-(hydrazinocarbonyl)-3-methoxyphenyl)-3,3"-dimethoxy-[1,1':3',1"-terphenyl]-4,4"-dicarboxylic acid dihydrazide comprises: Mix dimethyl 3,3"-dimethoxy-5'-(3-methoxy-4-(methoxycarbonyl)phenyl)-[1,1':3',1"-terphenyl]-4,4"-dicarboxylate, hydrazine hydrate, ethanol and toluene, and then stir and react under reflux to obtain the product.

10. Use of the fluorine-containing acylhydrazone covalent organic framework material according to claim 1 in photocatalytic production of hydrogen peroxide.

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