Multi-aperture two-dimensional covalent organic framework material based on carbon-carbon double bond connection as well as preparation method and application of multi-aperture two-dimensional covalent organic framework material

Abstract

The invention provides a multi-aperture two-dimensional covalent organic framework material based on carbon-carbon double bond connection as well as a preparation method and application of the multi-aperture two-dimensional covalent organic framework material. The preparation method comprises the following steps: (1) under a protective atmosphere, putting 6, 6 '-dimethyl-3, 3'-bipyridazine, a multi-aldehyde aromatic monomer and benzoic anhydride into an ampoule bottle, the multi-aldehyde aromatic monomer being selected from a tri-aldehyde aromatic monomer or a tetra-aldehyde aromatic monomer; and (2) quickly freezing the ampoule bottle in the step (1) in a 77K liquid nitrogen bath, carrying out unfreezing circulation degassing through three freezing pumps, carrying out heating reaction at 150-250 DEG C for 72-120 hours, cooling to room temperature, and carrying out post-treatment to obtain the multi-aperture two-dimensional covalent organic framework material based on carbon-carbon double bond connection. The two-dimensional COFs obtained by performing a Navenger condensation reaction on an active methyl monomer and a multi-aldehyde aromatic monomer has relatively high crystallinity, specific surface area and stability, uniform two-dimensional layered morphology and a relatively wide absorption spectrum range, and the topological structure of the COFs comprises a uniform pore diameter and three different pore diameters.

Description

Technical Field

[0001] The present invention relates to the technical field of organic framework materials, and in particular to a two-dimensional covalent organic framework material with various pore sizes connected by carbon-carbon double bonds, and a preparation method and application thereof. Background Art

[0002] Covalent organic frameworks (COFs) are a new type of porous material, which is formed by light elements connected by covalent bonds in two or three-dimensional space, and has a long-range ordered structure and regular pore structure. In 2005, Yaghi's research group first reported a two-dimensional COF based on borate ester bonds. Due to the rich design of organic monomers, the orderliness and regularity of crystal materials and the diversity of covalent bond forms, COFs have the advantages of low density, high specific surface area, easy modification and functionalization. Therefore, the current COFs materials have excellent application prospects in the fields of gas storage and separation, heterogeneous catalysis, energy storage materials, optoelectronics, sensing and drug delivery.

[0003] The dynamic covalent bonds that have been developed for COF synthesis mainly include borate bonds, imine bonds, acylhydrazone bonds, imide bonds, etc. These chemical bonds have good reversibility, but there are still major problems in terms of stability, conjugation and semiconductor activity.

[0004] In 2016, Zhang's group reported a cyano-substituted carbon-carbon double bond bridged sp 2 Carbon-conjugated COFs, a class of materials with ultrahigh stability and all-carbon skeletons, as well as effective π electron delocalization. Recently, the formation of unsubstituted carbon-carbon double bonds through the Knoevenagel condensation reaction has provided a sustainable and reliable method for expanding the COFs system. Nevertheless, the reversibility of the carbon-carbon double bond formation reaction is poor, and the types of monomers currently available for synthesis are limited, which limits the further development of COFs materials.

[0005] Due to the large number of monomers available for Knoevenegal condensation polymerization, the geometric, electronic and topological structures of COFs connected by carbon-carbon double bonds are extremely feasible. In addition to excellent stability, several recently reported COFs with unsubstituted double bonds also show some novel characteristics. For example, Yaghi's group reported a vinyl-bridged COF that can load strong boron-based Lewis acids to catalyze Diels-Alder reactions; Thomas et al. discovered the photocyclization reaction of vinyl bonds between adjacent layers of vinyl-bridged COFs; Perepichka et al. found that the synthesized polymers have high quantum yields (up to 50%), and through the modification of monomers, it was proved that the photophysical properties of this type of COFs can be precisely adjusted. A difficulty in the rapid development of this type of COF is the poor reversibility of carbon-carbon double bond formation reactions (such as Knoevenegal condensation).

[0006] In addition, most of the COFs developed so far have a single pore size and low structural complexity. Although COFs with multiple pore sizes have been designed and manufactured, heteroporous COFs, that is, COFs containing multiple pore sizes in one network, have greater application potential due to their structural complexity and diversity, as well as the characteristics of easy functional modification. Summary of the invention

[0007] 1. Technical issues to be solved

[0008] In view of the deficiencies in the prior art, the present invention provides a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, and a preparation method and application thereof, which solves the problems raised in the above-mentioned background technology.

[0009] (II) Technical solution

[0010] To achieve the above objectives, the present invention is implemented through the following technical solutions:

[0011] According to a first aspect of the present invention, a method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds is provided, comprising the following steps:

[0012] (1) Under a protective atmosphere, placing 6,6'-dimethyl-3,3'-pyridazine, a polyaldehyde aromatic monomer and benzoic anhydride in an ampoule, wherein the polyaldehyde aromatic monomer is selected from a trialdehyde aromatic monomer or a tetraaldehyde aromatic monomer;

[0013] (2) The ampoule described in step (1) is rapidly frozen in a liquid nitrogen bath at 77K, degassed by three freeze pump-thaw cycles, and then heated at 150-250°C for 72-120h, cooled to room temperature, and post-treated to obtain the two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds.

[0014] 6,6'-Dimethyl-3,3'-bipyridazine is a pyridazine unit with two single atoms embedded in the ortho position. It has strong electron-deficient characteristics and rich properties. The electron-deficient nitrogen atom in pyridazine can enhance the acidity of hydrogen and initiate the formation of carbon-carbon double bonds through Knoevenegal condensation. The pyridazine unit with a "cis-azo" part has moderate Lewis basicity, which is related to its fixed "cis configuration" and the cooperative interaction of two adjacent single atoms. The pyridazine unit fully exposes two lone pairs of electrons, allowing the connection or selective capture of some metal cations in coordination chemistry. The present invention utilizes 6,6'-dimethyl-3,3'-pyridazine as a core monomer, activates the methyl group to form an active methylene carbon anion under the catalytic action of benzoic anhydride, forms an unsubstituted carbon-carbon double bond through a nucleophilic reaction, and synthesizes two-dimensional COFs of various pore sizes connected by carbon-carbon double bonds under vacuum heating conditions. The prepared two-dimensional COFs material is a two-dimensional layered structure with high crystallinity, excellent nanoscale pore structure, good thermal stability, a wide absorption spectrum range, and a high specific surface area.

[0015] Preferably, in step (1), when the polyaldehyde aromatic monomer is selected from a trialdehyde aromatic monomer, the molar ratio of the 6,6'-dimethyl-3,3'-pyridazine, the trialdehyde aromatic monomer and benzoic anhydride is 3:2:6;

[0016] When the polyaldehyde aromatic monomer is selected from tetraaldehyde aromatic monomers, the molar ratio of the 6,6'-dimethyl-3,3'-bipyridazine, tetraaldehyde aromatic monomer and benzoic anhydride is 2:1:4.

[0017] Preferably, in step (1), the trialdehyde aromatic monomer is selected from at least one of trimesicaldehyde, 1,3,5-tri(p-formylphenyl)benzene or [1,1'-biphenyl]-3,4',5-tricarbaldehyde;

[0018] The tetraaldehyde aromatic monomer is selected from at least one of 3'-(3,5-diformylphenyl)-[1,1'-biphenyl]-3,5-dicarbaldehyde or [1,1':4',1"-terphenyl]-3,3",5,5"-tetracarbaldehyde.

[0019] Preferably, in step (2), the post-treatment comprises: soaking the reaction product in methanol and 1M sodium hydroxide aqueous solution for 72 hours, collecting the filter residue by vacuum filtration, then eluting with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in sequence, Soxhlet extraction, and drying.

[0020] Preferably, the extracting solution of the Soxhlet extraction comprises acetone and methanol, and the Soxhlet extraction time is 48h;

[0021] The drying temperature is 60° C., and the drying time is 12 h.

[0022] According to a second aspect of the present invention, there is provided a two-dimensional covalent organic framework material of various pore sizes based on carbon-carbon double bonds obtained according to the above-mentioned preparation method, wherein the two-dimensional covalent organic framework material of various pore sizes based on carbon-carbon double bonds is an orthorhombic crystal system, and the lattice is stacked in an AA mode along the vertical direction.

[0023] Preferably, the topological configuration of the two-dimensional covalent organic framework material with multiple pore sizes connected by carbon-carbon double bonds is selected from at least one of hexagonal, tetragonal or multi-pore.

[0024] Preferably, the specific surface area of ​​the two-dimensional covalent organic framework material with various pore sizes connected by carbon-carbon double bonds is 300 m 2 g -1 ~800m 2 g -1 .

[0025] Preferably, the visible light absorption band edge wavelength of the two-dimensional covalent organic framework material with various pore sizes connected by carbon-carbon double bonds is ≥450nm.

[0026] According to a third aspect of the present invention, there is provided a two-dimensional covalent organic framework material of various pore sizes based on carbon-carbon double bonds obtained according to the above preparation method for use in the field of photocatalytic hydrogen production, photocatalytic production of hydrogen peroxide or ion detection.

[0027] (III) Beneficial effects

[0028] The present invention provides a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, and a preparation method and application thereof. It has the following beneficial effects:

[0029] (1) This scheme provides a method for preparing a two-dimensional covalent organic framework material with various pore sizes connected by carbon-carbon double bonds. 6,6'-dimethyl-3,3'-pyridazine is used as the core monomer. Under the catalysis of benzoic anhydride, the methyl group is activated to form an active methylene carbon anion, and an unsubstituted carbon-carbon double bond is formed through a nucleophilic reaction. Under vacuum heating conditions, two-dimensional COFs with various pore sizes connected by carbon-carbon double bonds are synthesized, filling the gap in the field of COFs material synthesis using 6,6'-dimethyl-3,3'-pyridazine.

[0030] (2) This scheme provides a method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds. By reacting 6,6'-dimethyl-3,3'-pyridazine and a polyaldehyde aromatic monomer, hexagonal and quadrilateral topological structures are obtained. It is even possible to prepare heteroporous COFs structures with three pore sizes at the same time, which increases the structural complexity and diversity, making heteroporous COFs easier to carry out functional modification, and can have better applications in the fields of photocatalytic hydrogen production, photocatalytic production of hydrogen peroxide or ion detection.

[0031] (3) This scheme provides a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, which has high crystallinity, uniform two-dimensional layered morphology, high specific surface area, wide absorption spectrum range and good thermal stability. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 X-ray diffraction patterns of two-dimensional covalent organic framework materials with various pore sizes connected by carbon-carbon double bonds prepared in Examples 1 to 3 of the present invention;

[0033] Figure 2 Scanning electron microscope images of two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds prepared in Examples 1 to 3 of the present invention;

[0034] Figure 3 Transmission electron micrographs of two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds prepared in Examples 1 to 3 of the present invention;

[0035] Figure 4 The nitrogen adsorption-desorption isotherm spectra of two-dimensional covalent organic framework materials with various pore sizes connected by carbon-carbon double bonds prepared in Examples 1 to 3 of the present invention;

[0036] Figure 5 The UV-visible absorption spectra of two-dimensional covalent organic framework materials with various pore sizes connected by carbon-carbon double bonds prepared in Examples 1 to 3 of the present invention;

[0037] Figure 6 Thermogravimetric analysis spectra of two-dimensional covalent organic framework materials with various pore sizes connected by carbon-carbon double bonds prepared in Examples 1 to 3 of the present invention under a nitrogen atmosphere;

[0038] Figure 7 X-ray diffraction patterns of two-dimensional covalent organic framework materials of various pore sizes based on carbon-carbon double bonds prepared in Examples 4 and 5 of the present invention. DETAILED DESCRIPTION

[0039] In order to better illustrate the content of the present invention, a detailed description is given below in conjunction with specific embodiments.

[0040] Example 1

[0041] A method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, comprising the following steps:

[0042] In a glove box with argon atmosphere, 111.7 mg of 6,6'-dimethyl-3,3'-bipyridazine (Db), 64.9 mg of mesitylene (Bt) and 271.5 mg of benzoic anhydride were added to a round-bottom ampoule; the ampoule was then quickly frozen in a liquid nitrogen bath at 77K, degassed after three freeze-pump-thaw cycles, and sealed under vacuum and transferred to a constant temperature oven, heated to 200°C for reaction for 120 h; after the reaction, the ampoule was naturally cooled to room temperature, the reaction product was taken out, and immersed in methanol and 1M sodium hydroxide aqueous solution for 72 h respectively, the filter residue was collected by vacuum filtration, and washed with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in turn, and extracted with a mixed solution of acetone and methanol for 48 h, and the solid product was collected and dried in vacuum at 60°C for 12 h to obtain a yellow solid, recorded as DbBt-COF.

[0043] Example 2

[0044] A method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, comprising the following steps:

[0045] In an argon atmosphere glove box, 111.7 mg of 6,6'-dimethyl-3,3'-bipyridazine (Db), 156.2 mg of 1,3,5-tri(p-formylphenyl)benzene (Tb) and 271.5 mg of benzoic anhydride were added to a round-bottomed ampoule; the ampoule was then rapidly frozen in a liquid nitrogen bath at 77 K, degassed after three freeze-pump-thaw cycles, and then sealed under vacuum and transferred to a constant temperature oven, heated to 200 °C for reaction. After the reaction, the ampoule was naturally cooled to room temperature, the reaction product was taken out, and immersed in methanol and 1M sodium hydroxide aqueous solution for 72 hours respectively, the filter residue was collected by vacuum filtration, and washed with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in turn, and extracted with a mixed solution of acetone and methanol for 48 hours, the solid product was collected and dried in vacuum at 60°C for 12 hours to obtain a yellow solid, recorded as DbTb-COF.

[0046] Example 3

[0047] A method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, comprising the following steps:

[0048] In an argon atmosphere glove box, 111.7 mg of 6,6'-dimethyl-3,3'-bipyridazine (Db), 102.7 mg of 3'-(3,5-diformylphenyl)-[1,1'-biphenyl]-3,5-dicarbaldehyde (Dd) and 271.5 mg of benzoic anhydride were added to a round-bottomed ampoule; the ampoule was then rapidly frozen in a liquid nitrogen bath at 77 K, degassed after three freeze-pump-thaw cycles, and sealed under vacuum before being transferred to a constant temperature oven. The reaction was heated to 200°C for 120 hours. After the reaction, the ampoule was naturally cooled to room temperature, the reaction product was taken out, and immersed in methanol and 1M sodium hydroxide aqueous solution for 72 hours respectively. The residue was collected by vacuum filtration, and washed with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in turn, and extracted with a mixed solution of acetone and methanol for 48 hours. The solid product was collected and dried in vacuo at 60°C for 12 hours to obtain a yellow solid, which was recorded as DbDd-COF.

[0049] The preparation formulas of the above Examples 1 to 3 and the structural formulas of DbBt-COF, DbTb-COF and DbDd-COF are as follows:

[0050]

[0051] The performance of the two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds prepared in Examples 1 to 3 was tested respectively. Figures 1 to 6 shown.

[0052] according to Figure 1 It can be seen that the DbBt-COF prepared in Example 1, the DbTb-COF prepared in Example 2, and the DbDd-COF prepared in Example 3 are all consistent with the results of theoretical simulation, indicating that the prepared two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds belong to the orthorhombic crystal system, have a high crystalline structure, and the lattices are stacked in an AA mode along the vertical direction. The resulting one-dimensional channels have abundant strong hydrogen bond acceptance sites, which are generated by decorative cis-azo units with two pairs of fully exposed lone pairs of electrons.

[0053] according to Figure 2 and Figure 3 As shown, the two-dimensional covalent organic framework materials of various pore sizes based on carbon-carbon double bonds prepared in Examples 1 to 3 all have a uniform two-dimensional layered morphology.

[0054] according to Figure 4 It can be seen that the specific surface area of ​​DbBt-COF prepared in Example 1 is 644 m 2 g -1 The specific surface area of ​​DbTb-COF prepared in Example 2 is 302 m 2 g-1 The specific surface area of ​​DbDd-COF prepared in Example 3 is 788 m 2 g -1 , all have a high specific surface area.

[0055] according to Figure 5 It can be seen that the visible light absorption band edge wavelengths of the two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds prepared in Examples 1 to 3 are all above 450 nm.

[0056] according to Figure 6 It can be seen that the residual mass of DbBt-COF prepared in Example 1 under a nitrogen atmosphere at 800°C is 60.2%, the residual mass of DbTb-COF prepared in Example 2 under a nitrogen atmosphere at 800°C is 74.0%, and the residual mass of DbDd-COF prepared in Example 3 under a nitrogen atmosphere at 800°C is 66.0%, indicating that the two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds prepared in the present invention have good thermal stability.

[0057] Example 4

[0058] A method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, comprising the following steps:

[0059] In an argon atmosphere glove box, 111.7 mg of 6,6'-dimethyl-3,3'-bipyridazine (Db), 95.3 mg of [1,1'-biphenyl]-3,4',5-tricarbaldehyde (Tp) and 271.5 mg of benzoic anhydride were added to a round-bottomed ampoule; the ampoule was then rapidly frozen in a liquid nitrogen bath at 77 K, degassed after three freeze-pump-thaw cycles, and sealed under vacuum before being transferred to a constant temperature oven and heated to 200 °C. The reaction was carried out for 120 hours. After the reaction was completed, the ampoule was naturally cooled to room temperature, the reaction product was taken out, and immersed in methanol and 1M sodium hydroxide aqueous solution for 72 hours respectively. The residue was collected by vacuum filtration, and washed with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in turn, and extracted with a mixed solution of acetone and methanol for 48 hours. The solid product was collected and dried in vacuo at 60°C for 12 hours to obtain a yellow solid, which was recorded as DbTp-COF.

[0060] Example 5

[0061] A method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, comprising the following steps:

[0062] In an argon atmosphere glove box, 111.7 mg of 6,6'-dimethyl-3,3'-bipyridazine (Db), 102.7 mg of [1,1':4',1"-terphenyl]-3,3",5,5"-tetracarboxaldehyde (Ta) and 271.5 mg of benzoic anhydride were added to a round-bottomed ampoule; the ampoule was then rapidly frozen in a liquid nitrogen bath at 77 K, degassed after three freeze-pump-thaw cycles, and then sealed under vacuum and transferred to a constant temperature oven. Heat to 200°C and react for 120 hours. After the reaction, cool the ampoule naturally to room temperature, take out the reaction product, soak it in methanol and 1M sodium hydroxide aqueous solution for 72 hours respectively, collect the filter residue by vacuum filtration, and rinse with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in turn, and extract with a mixed solution of acetone and methanol for 48 hours, collect the solid product and dry it in vacuum at 60°C for 12 hours to obtain a yellow solid, recorded as DbTa-COF.

[0063] The preparation formulas of the above-mentioned Examples 4 and 5 and the structural formulas of DbTp-COF and DbTa-COF are as follows:

[0064]

[0065] By performing X-ray diffraction on the two-dimensional covalent organic framework materials with various pore sizes based on carbon-carbon double bonds prepared in Example 4 and Example 5, as shown in FIG. Figure 7 As shown, both the DbTp-COF prepared in Example 4 and the DbTa-COF prepared in Example 5 have good crystallinity.

[0066] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds, characterized in that: The following steps are involved: (1) Under a protective atmosphere, placing 6,6'-dimethyl-3,3'-pyridazine, a polyaldehyde aromatic monomer and benzoic anhydride in an ampoule, wherein the polyaldehyde aromatic monomer is selected from a trialdehyde aromatic monomer or a tetraaldehyde aromatic monomer; (2) The ampoule described in step (1) is rapidly frozen in a liquid nitrogen bath at 77K, degassed by three freeze pump-thaw cycles, and then heated at 150-250°C for 72-120h, cooled to room temperature, and post-treated to obtain the two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds.

2. The method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds according to claim 1, characterized in that: In step (1), when the polyaldehyde aromatic monomer is selected from a trialdehyde aromatic monomer, the molar ratio of the 6,6'-dimethyl-3,3'-pyridazine, the trialdehyde aromatic monomer and benzoic anhydride is 3:2:6; When the polyaldehyde aromatic monomer is selected from tetraaldehyde aromatic monomers, the molar ratio of the 6,6'-dimethyl-3,3'-bipyridazine, tetraaldehyde aromatic monomer and benzoic anhydride is 2:1:

4.

3. The method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds according to claim 1, characterized in that: In step (1), the trialdehyde aromatic monomer is selected from at least one of trimesic acid aldehyde, 1,3,5-tri(p-formylphenyl)benzene or [1,1'-biphenyl]-3,4',5-tricarbaldehyde; The tetraaldehyde aromatic monomer is selected from at least one of 3'-(3,5-diformylphenyl)-[1,1'-biphenyl]-3,5-dicarbaldehyde or [1,1':4',1"-terphenyl]-3,3",5,5"-tetracarbaldehyde.

4. The method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds according to claim 1, characterized in that: In step (2), the post-treatment comprises: soaking the reaction product in methanol and 1M sodium hydroxide aqueous solution for 72 hours, collecting the residue by vacuum filtration, then eluting with methanol, dichloromethane, chloroform, acetone and tetrahydrofuran in sequence, Soxhlet extraction and drying.

5. The method for preparing a two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds according to claim 1, characterized in that: The extracting solution of the Soxhlet extraction includes acetone and methanol, and the time of the Soxhlet extraction is 48 hours; The drying temperature is 60° C., and the drying time is 12 h.

6. A two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds obtained by the preparation method according to any one of claims 1 to 5, characterized in that: The two-dimensional covalent organic framework material with various pore sizes connected based on carbon-carbon double bonds is an orthorhombic crystal system, and the lattice is stacked in an AA mode along the vertical direction.

7. A two-dimensional covalent organic framework material with multiple pore sizes based on carbon-carbon double bonds according to claim 6, characterized in that: The topological configuration of the two-dimensional covalent organic framework material with multiple pore sizes connected based on carbon-carbon double bonds is selected from at least one of hexagonal, tetragonal or multi-pore.

8. The two-dimensional covalent organic framework material of various pore sizes based on carbon-carbon double bonds according to claim 6, characterized in that: The specific surface area of ​​the two-dimensional covalent organic framework material with various pore sizes based on carbon-carbon double bonds is 300 m 2 g -1 ~800m 2 g -1 .

9. The two-dimensional covalent organic framework material of various pore sizes based on carbon-carbon double bonds according to claim 6, characterized in that: The visible light absorption band edge wavelength of the two-dimensional covalent organic framework material with various pore sizes connected based on carbon-carbon double bonds is ≥450nm.

10. An application of a two-dimensional covalent organic framework material with multiple pore sizes based on carbon-carbon double bonds obtained by the preparation method according to any one of claims 1 to 5 or a two-dimensional covalent organic framework material with multiple pore sizes based on carbon-carbon double bonds according to any one of claims 6 to 9 in the field of photocatalytic hydrogen production, photocatalytic production of hydrogen peroxide or ion detection.

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