Application of organic framework material in adsorption, storage and delivery of electronic special gas

Abstract

The invention discloses application of a vinyl-linked covalent organic framework material in adsorption, storage and delivery of electronic special gas. The vinyl-linked covalent organic framework material is formed by reaction of raw materials including an organic monomer 1 and an organic monomer 2; the organic monomer 1 is selected from a six-membered heteroaromatic ring containing 2-4 methyl active units; the organic monomer 2 is selected from a compound which contains 2-4 aldehyde groups and the number of 5-6 membered rings is not more than 3; in the vinyl-linked covalent organic framework material, an organic monomer 1 and an organic monomer 2 are connected through a carbon-carbon double bond formed by reaction of a methyl active unit and an aldehyde group. According to the invention, the problems of low delivery capacity, insufficient quality of delivered gas and the like of the existing adsorbent for storing and delivering the electronic special gas in the field can be solved.

Description

Technical Field

[0001] The present invention relates to the field of gas storage technology, and in particular to the application of a class of vinyl-linked covalent organic framework materials in the adsorption, storage and delivery of electronic specialty gases. Background Art

[0002] Electronic special gases are widely used in ion implantation, etching, vapor deposition, doping and other processes, and are the blood of integrated circuit manufacturing. In the ion implantation process, electronic special gases need to have high reactivity, resulting in most electronic special gases used in integrated circuits being corrosive, toxic, and reactive gases, such as phosphine, arsine, boron trifluoride, germanium tetrafluoride, etc., among which phosphine and arsine can be lethal at only ppm. Common high-pressure cylinder storage technology has a high risk of leakage, close to 0.74%, because the gas storage pressure is 13-130bar, which is far higher than atmospheric pressure. In contrast, the storage pressure of adsorption storage technology is lower than 1.0bar, and the leakage risk is lower than 0.0000074%, and it is listed as a safe storage technology for toxic gases. Therefore, the development of advanced adsorption storage technology is the key to achieving safe and efficient use of electronic special gases.

[0003] The core of adsorption storage technology lies in the development of advanced adsorbent materials. Metal Organic Frameworks (MOFs) have been widely studied and applied in the field of gas adsorption storage because of their high specific surface area, uniform pore size distribution, and finely regulated structure. For example, the patent specification with publication number CN117887086A provides the application of halogen-functionalized metal organic framework materials in the storage and delivery of fluorine-containing electronic special gases, wherein the halogen-functionalized metal organic framework materials include metal ions or clusters, and organic ligands, and the metal ions or clusters and / or organic ligands carry halogen groups, and the halogen groups are groups containing at least one element of fluorine, chlorine, bromine, and iodine. For another example, the patent specification with publication number CN110665329A discloses a method for delivering a gas for ion implantation, the method comprising: storing a gas selected from arsine, phosphine, diborane and boron trifluoride in a metal organic framework MOF, the metal organic framework comprising a coordination product of a metal ion and at least a bidentate organic ligand, the MOF being characterized in that it has a gas density between 1000 m 2 / g and 14500m 2 / g weight surface area, between and However, metal-organic frameworks often lead to structural instability and metal ion precipitation in highly reactive and corrosive gases, thus affecting the quality of electronic gases.

[0004] In contrast, covalent organic frameworks (COFs) have high specific surface area, uniform pore size distribution and highly adjustable structure, and neither the neutral framework nor the anionic framework of pure organic units contains metal cations. Therefore, COFs, as adsorption, storage and delivery materials for electronic gases, can simultaneously have high adsorption, storage, delivery capacity and electronic gas quality. Summary of the invention

[0005] The present invention provides a class of vinyl-linked covalent organic framework materials (COFs) for use in the adsorption, storage and delivery of electronic special gases. Vinyl-linked COFs have high stability, high specific surface area and pore volume, provide high adsorption, storage and accommodation space for electronic gases, and adjustable pore environment, as well as selectively introduced negatively charged anionic groups, which can weaken the adsorption of electronic special gases on the surface of the adsorbent, facilitate the desorption of electronic special gases, thereby improving the delivery capacity and efficiency, and COFs will not introduce metal impurities, and the quality of electronic special gases delivered by adsorption, storage and delivery is high. The present invention can solve the problems of low delivery capacity and insufficient delivery gas quality in existing adsorbents for electronic special gas storage and delivery in the field.

[0006] Application of vinyl-linked covalent organic framework materials in electronic specialty gas adsorption storage and delivery, wherein the vinyl-linked covalent organic framework materials are formed by reacting raw materials including organic monomer 1 and organic monomer 2;

[0007] The organic monomer 1 is selected from a six-membered heteroaromatic ring containing 2-4 methyl active units;

[0008] The organic monomer 2 is selected from compounds containing 2-4 aldehyde groups and the number of 5-6-membered rings does not exceed 3;

[0009] In the vinyl-linked covalent organic framework material, the organic monomer 1 and the organic monomer 2 are connected via a carbon-carbon double bond formed by the reaction of a methyl active unit and an aldehyde group.

[0010] The organic monomer 1 can be selected from one or more of 2,6-dimethylpyrazine, 2,5-dimethylpyrimidine, 3,6-dimethylpyridazine, 2,4,6-trimethylpyridine, 2,4,6-trimethyltriazine, and 2,3,5,6-tetramethylpyrazine.

[0011] The organic monomer 2 can be selected from one or more of terephthalaldehyde, 2,5-dimethoxy-1,4-terephthalaldehyde, 1,3,5-triphenylene trimesicaldehyde, 2,4,6-trihydroxy-1,3,5-benzene trimesicaldehyde, 1,4-di(4-formylphenyl)benzene, and 4,4'-biphenyl dicarboxaldehyde.

[0012] As an example, the organic monomer 1 is 2,4,6-trimethyltriazine, and the organic monomer 2 is terephthalaldehyde.

[0013] As an example, the organic monomer 1 is 2,4,6-trimethylpyridine, and the organic monomer 2 is terephthalaldehyde.

[0014] As an example, the organic monomer 1 is 2,6-dimethylpyrazine, and the organic monomer 2 is trimesic acid.

[0015] The vinyl-linked covalent organic framework material of the present invention can be prepared by referring to the prior art. Furthermore, the preparation process of the vinyl-linked covalent organic framework material can be free of metal.

[0016] In some embodiments, the specific surface area of ​​the vinyl-linked covalent organic framework material is 100-2000 m 2 g -1 , for example 650m 2 g -1 、1600m 2 g -1 etc., pore volume is 0.1-2.0cm 3 g -1 , for example 0.4cm 3 g -1 、0.8cm 3 g -1 etc., with a pore size of 0.5-2.5 nm.

[0017] In some embodiments, the vinyl-linked covalent organic framework material does not contain metal ions, so no additional metal impurities are introduced during the adsorption, storage, and delivery of the electronic special gas, thereby ensuring the cleanliness of the released electronic special gas.

[0018] The electronic special gas may include one or more of boron trifluoride, germanium tetrafluoride, arsenic pentafluoride, sulfur hexafluoride, nitrogen trifluoride, silicon tetrafluoride, fluoroalkanes, arsine, and phosphine.

[0019] In some embodiments, at 21° C. and 650 Torr, the adsorption storage capacity of the vinyl-linked covalent organic framework material for electronic special gases is 0.1-2.0 g cm -3 , for example 0.15 g cm -3 , 0.3 g cm -3 , 0.35 g cm -3 , 0.45gcm -3 etc., the delivery capacity under 650-5 Torr conditions is greater than or equal to 50% of the adsorption storage capacity, for example, greater than or equal to 55% of the adsorption storage capacity, greater than or equal to 78% of the adsorption storage capacity, greater than or equal to 87% of the adsorption storage capacity, etc.

[0020] The shape of the vinyl-linked covalent organic framework material can be one or more combinations of foam, granular, spherical, strip, block, cylindrical, cubic, disc, and pentagram. The shape of the vinyl-linked covalent organic framework material can be self-formed during synthesis or post-processed. The molding density of the vinyl-linked covalent organic framework material can be 0.3-2.0 g / cm -3 .

[0023] In some embodiments, the vinyl-linked covalent organic framework has an adsorption storage capacity of at least 0.34 g cm for the electronic specialty gas arsine at 21° C. and 650 torr. -3 , the delivery capacity under 650-5 torr conditions is greater than or equal to 80% of the adsorption storage capacity; the organic monomer 1 can be selected from one or more of 2,4,6-trimethyltriazine, 2,4,6-trimethylpyridine, and 2,6-dimethylpyrazine; the organic monomer 2 can be selected from one or more of terephthalaldehyde and 1,3,5-benzenetricarboxaldehyde.

[0024] In some embodiments, the vinyl-linked covalent organic framework has an adsorption storage capacity of at least 0.15 g cm for the electron-specific gas phosphine at 21° C. and 650 Torr. -3 , the delivery capacity under 650-5 torr conditions is greater than or equal to 80% of the adsorption storage capacity; the organic monomer 1 can be selected from one or more of 2,4,6-trimethyltriazine, 2,4,6-trimethylpyridine, and 2,6-dimethylpyrazine; the organic monomer 2 can be selected from one or more of terephthalaldehyde and 1,3,5-benzenetricarboxaldehyde.

[0025] The vinyl-linked covalent organic framework material may include one or more of a neutral framework and an ionic framework, wherein the pores of the ionic framework have free anions. That is, in some embodiments, the pores of the vinyl-linked covalent organic framework material have free anions. Further, the anions may be halogen anions (including Cl - 、F - Br - etc.), BF4 - PF6 - 、SiF6 2- 、SO4 2- The ionic framework can be formed by treating the heteroaromatic ring of the vinyl-linked covalent organic framework material, for example, bromide ions can be introduced into the raw material of the vinyl-linked covalent organic framework material by adding ethyl bromide, and further optionally, the introduced bromide ions can be replaced with BF4 by anion exchange. - PF6 -、SiF6 2- 、SO4 2- wait.

[0026] The application of the vinyl-linked covalent organic framework material in the adsorption, storage and delivery of electronic special gases can bring the electronic special gases into contact with the vinyl-linked covalent organic framework material, and achieve the adsorption, storage and delivery of the electronic special gases under the drive of adsorption and desorption pressure.

[0027] The present invention also provides a gas storage container, wherein the gas storage container contains one or more of the vinyl-linked covalent organic framework materials for adsorption, storage and delivery of electronic special gases.

[0028] The gas storage container can be connected to a gas filling mechanism and a gas releasing and delivering mechanism to respectively carry out processes such as filling, storing, releasing, and delivering the electronic special gas.

[0029] The gas storage container adsorbs, stores and delivers the electronic special gas, and the gas release and delivery mechanism can desorb and release the electronic special gas from the gas storage container and transport it to fluid utilization equipment, including but not limited to fluid utilization equipment for manufacturing semiconductor devices, photovoltaic solar panels, etc.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1) The vinyl-linked covalent organic framework material proposed in the present invention has ultra-high thermal stability, highly adjustable pore size and pore environment, and can realize customization of adsorbent materials based on different types of electronic special gases, such as fluorine-containing electronic special gases. The vinyl-linked covalent organic framework material can be customized by introducing negatively charged ions BF4 - PF6 - 、SiF6 2- etc., weakening the interaction between the framework and the fluorine-containing electronic special gas, thereby increasing the deliverable capacity of the electronic special gas.

[0032] 2) The vinyl-linked covalent organic framework material described in the present invention has a high specific surface area and pore volume, and has a high electronic special gas adsorption and storage space. At the same time, there is no metal catalysis in the synthesis of the vinyl-linked covalent organic framework material, and no metal impurities are introduced into the material. The quality of the electronic special gas adsorbed, stored and delivered is higher.

[0033] 3) The vinyl-linked covalent organic framework material of the present invention is easy to self-form during synthesis or post-processing, and the material has a highly adjustable stacking density and a high electron gas adsorption storage and deliverable capacity per unit volume. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1This is a schematic structural diagram of a vinyl-linked covalent organic framework material 1 synthesized by a solvent-free melt method in Example 1;

[0035] Figure 2 77K N2 adsorption isotherm diagram of vinyl-linked covalent organic framework material 1 synthesized by solvent-free melting method in Example 1;

[0036] Figure 3 This is a thermogravimetric curve of the vinyl-linked covalent organic framework material 1 synthesized by the solvent-free melting method in Example 1;

[0037] Figure 4 The adsorption-desorption isotherm diagram of germanium tetrafluoride at 294K for the vinyl-linked covalent organic framework material 1 synthesized by the solvent-free melting method in Example 1;

[0038] Figure 5 This is an adsorption-desorption isotherm diagram of boron trifluoride for the vinyl-linked covalent organic framework material 1 synthesized by the solvent-free melting method in Example 1 at 294K;

[0039] Figure 6 The adsorption-desorption isotherm diagram of arsine at 294K for the vinyl-linked covalent organic framework material 1 synthesized by the solvent-free melting method in Example 1;

[0040] Figure 7 This is the adsorption-desorption isotherm diagram of phosphine for the vinyl-linked covalent organic framework material 1 synthesized by the solvent-free melting method in Example 1 at 294K. DETAILED DESCRIPTION

[0041] The present invention will be further described below in conjunction with the accompanying drawings and specific examples. It should be understood that these examples are only intended to illustrate the present invention and are not intended to limit the scope of the present invention. The operating methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturer.

[0042] Example 1

[0043] Synthesis of vinyl-linked covalent organic framework materials 1.

[0044] Solvent synthesis: Weigh 2,4,6-trimethyltriazine (TMTA, 554.2 mg, 4.5 mmol), terephthalaldehyde (TPA, 905.4 mg, 6.75 mmol) and potassium hydroxide (757.4 mg, 13.5 mmol) and add 100 mL of a 3 / 7 v / v 1,2-dichlorobenzene / n-butanol mixed solution (350 mL Schlenk tube). After the solid is completely dissolved, the reaction mixture is heated at 120 ° C for 3 days to form a yellow precipitate that is separated by filtration and washed with methanol for 24 hours by Soxhlet extraction. The light yellow powder product is vacuum dried at 120 ° C for 12 hours to obtain a vinyl-linked covalent organic framework material 1 with a yield of about 80%, which can be used as an adsorbent.

[0045] Solvent-free melting method: 2,4,6-trimethyltriazine (554.2 mg, 4.5 mmol), terephthalaldehyde (905.4 mg, 6.75 mmol) and benzoic anhydride (1145.3 mg, 5.07 mmol) were carefully loaded into a thick-walled glass tube resistant to high temperature and pressure. After evacuating the tube until the pressure inside reached 0.15 mmHg, it was removed from the vacuum line and the glass tube was sealed by flame to isolate the air. The sealed glass tube was placed in a 200 ° C oven for 5 days. After the reaction, a yellow powder solid was obtained. After soaking it in N, N-dimethylformamide (DMF) and CH3OH, Soxhlet extraction was carried out in tetrahydrofuran solvent for 48 hours to obtain a yellow complete block of vinyl-linked covalent organic framework material 1 with a yield of about 94%, which can be used as an adsorbent.

[0046] Example 1 Structural diagram of the adsorbent, 77K N2 adsorption isotherm, and thermogravimetric curve are shown in Figures 1 and 1 Figure 1 , Figure 2 , Figure 3 As shown in FIG. 1 , and the adsorption-desorption isotherms of germanium tetrafluoride, boron trifluoride, arsine, and phosphine of the adsorbent of Example 1 at 294K are shown in FIG. Figure 4-Figure 7 The BET specific surface area of ​​the adsorbent in Example 1 is 1165 m 2 / g. Thermogravimetric curves show that it has excellent thermal stability, with a decomposition temperature as high as 800K. Figure 4 , Figure 5 In the adsorption isotherms of the adsorbent material synthesized by the solvent-free method in Example 1, the adsorption-desorption hysteresis loops are relatively small for the strongly polar BF3 and GeF4, indicating its excellent release and delivery ability. Figure 6 , Figure 7 In the figure, the adsorption-desorption isotherms of AsH3 and PH3 basically coincide, which also shows the excellent electron gas release and delivery ability of the material.

[0047] Example 2

[0048] Weigh 2,4,6-trimethylpyridine (2mmol, 240mg), terephthalaldehyde (3mmol, 402mg) and benzoic anhydride (2.25mmol, 509mg) and carefully put them into a thick-walled glass tube resistant to high temperature and pressure. After evacuating the tube until the pressure inside reaches 0.15mmHg, remove it from the vacuum line and seal the glass tube with a flame to isolate it from the air. Place the sealed glass tube in a 200℃ oven for reaction for 5 days. After the reaction, a solid powder of yellow powder is obtained. After soaking it in DMF and CH3OH, Soxhlet extraction is carried out in tetrahydrofuran solvent for 48 hours to obtain a yellow complete block, which can be used as an adsorbent with a yield of about 89%. Example 2 The specific surface area of ​​the adsorbent is 1532m 2 g -1 , the adsorption storage capacity of AsH3 is 0.41 g cm -3 , the deliverable capacity of AsH3 is 87.8% of the storage capacity.

[0049] Example 3

[0050] Weigh 2,6-dimethylpyrazine (6mmol, 649μL), trimesic acid (4mmol, 648mg) and benzoic anhydride (12mmol, 2714mg) and carefully put them into a thick-walled glass tube resistant to high temperature and pressure. After evacuating the tube until the pressure inside reaches 0.15mmHg, remove it from the vacuum line and seal the glass tube with a flame to isolate it from the air. Place the sealed glass tube in a 200℃ oven for reaction for 5 days. After the reaction, a yellow powder solid is obtained. After soaking it in DMF and CH3OH, Soxhlet extraction is carried out in tetrahydrofuran solvent for 48h to obtain a yellow cylindrical complete block, which can be used as an adsorbent with a yield of about 90%. Example 3 The specific surface area of ​​the adsorbent is 811m 2 g -1 , the adsorption storage capacity of AsH3 is 0.34 g cm -3 The adsorption storage capacity of PH3 is 0.158 g cm -3 , the deliverable capacity of PH3 was 88.6% of its adsorption storage capacity.

[0051] Example 4

[0052] Synthesis of anionic COFs: Weigh 2,6-dimethylpyrazine (6mmol, 649μL), trimesic acid (4mmol, 648mg), benzoic anhydride (12mmol, 2714mg) and ethyl bromide (12mmol, 960μL) and carefully put them into a thick-walled glass tube resistant to high temperature and pressure. After evacuating the tube until the pressure inside reaches 0.15mmHg, remove it from the vacuum line and seal the glass tube with a flame to isolate it from the air. Put the sealed glass tube into a 200℃ oven for reaction for 5 days. After the reaction, a yellow powder solid is obtained. After soaking it in DMF and CH3OH, Soxhlet extraction is carried out in tetrahydrofuran solvent for 48h to obtain a yellow cylindrical complete block, which can be used as an adsorbent with a yield of about 85%. Example 4 The specific surface area of ​​the adsorbent is 735m 2 g -1 , pore volume 0.58cm 3 g -1 The adsorption storage capacity of GeF4 is 0.57 g cm -3 , the deliverable capacity of GeF4 is 0.35 g cm -3 ; The adsorption storage capacity of BF3 is 0.57 g cm -3 The deliverable capacity of BF3 is 0.41 g cm -3 .

[0053] Example 5

[0054] Synthesis of anionic COFs: Weigh 2,6-dimethylpyrazine (6mmol, 649μL), trimesic acid (4mmol, 648mg), benzoic anhydride (12mmol, 2714mg) and ethyl bromide (12mmol, 960μL) and carefully put them into a thick-walled glass tube resistant to high temperature and pressure. After evacuating the tube until the pressure inside reaches 0.15mmHg, remove it from the vacuum line and seal the glass tube with a flame to isolate it from the air. Put the sealed glass tube into a 200℃ oven for 5 days. After the reaction, a yellow powder solid is obtained. After soaking it in DMF and CH3OH, Soxhlet extraction is carried out in tetrahydrofuran solvent for 48h to obtain a yellow cylindrical complete block with a yield of about 85%. Then, ion exchange is carried out using (NH4)2SiF6 (1mol / L) solution. After multiple washings with methanol, SiF6-rich pores are obtained. 2- Anionic COFs can be used as adsorbents. Example 5 The specific surface area of ​​the adsorbent is 682 m 2 g -1 , pore volume 0.49cm 3 g -1 , the adsorption storage capacity of GeF4 is 0.48 g cm -3, the deliverable capacity of GeF4 is 0.31 g cm -3 ; The adsorption storage capacity of BF3 is 0.36 g cm -3 , the deliverable capacity of BF3 is 55.6% of its adsorption storage capacity.

[0055] Table 1 shows the structural properties, adsorption storage capacity and delivery capacity of the adsorbents of Examples 1-5. Example 1 is an adsorbent synthesized by a solvent-free melting method. In Table 1, the electronic special gas adsorption storage condition is 650 torr, and the delivery release condition is 294K, 650-5 torr.

[0056] Table 1

[0057]

[0058] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. Application of vinyl-linked covalent organic framework materials in electronic specialty gas adsorption, storage and delivery, characterized in that: The vinyl-linked covalent organic framework material is formed by reacting raw materials including organic monomer 1 and organic monomer 2; The organic monomer 1 is selected from a six-membered heteroaromatic ring containing 2-4 methyl active units; The organic monomer 2 is selected from compounds containing 2-4 aldehyde groups and the number of 5-6-membered rings does not exceed 3; In the vinyl-linked covalent organic framework material, the organic monomer 1 and the organic monomer 2 are connected via a carbon-carbon double bond formed by the reaction of a methyl active unit and an aldehyde group.

2. The use according to claim 1, characterized in that: The organic monomer 1 is selected from one or more of 2,6-dimethylpyrazine, 2,5-dimethylpyrimidine, 3,6-dimethylpyridazine, 2,4,6-trimethylpyridine, 2,4,6-trimethyltriazine, and 2,3,5,6-tetramethylpyrazine; The organic monomer 2 is selected from one or more of terephthalaldehyde, 2,5-dimethoxy-1,4-terephthalaldehyde, 1,3,5-triphenylene carboxaldehyde, 2,4,6-trihydroxy-1,3,5-benzene trimoxaldehyde, 1,4-di(4-formylphenyl)benzene, and 4,4'-biphenyl dicarboxaldehyde.

3. The use according to claim 1, characterized in that: The specific surface area of ​​the vinyl-linked covalent organic framework material is 100-2000 m 2 g -1 , pore volume is 0.1-2.0cm 3 g -1 , pore size is 0.5-2.5nm.

4. The use according to claim 1, characterized in that: The vinyl-linked covalent organic framework material does not contain metal ions.

5. The use according to claim 1, characterized in that: The electronic special gas includes one or more of boron trifluoride, germanium tetrafluoride, arsenic pentafluoride, sulfur hexafluoride, nitrogen trifluoride, silicon tetrafluoride, fluoroalkanes, arsine, and phosphine.

6. The use according to claim 1, characterized in that: The adsorption storage capacity of the vinyl-linked covalent organic framework material for electronic special gases is 0.1-2.0 g cm at 21 °C and 650 torr. -3 , the deliverable capacity under 650-5 Torr conditions is greater than or equal to 50% of the adsorption storage capacity.

7. The use according to claim 1, characterized in that: The shape of the vinyl-linked covalent organic framework material is one or more combinations of foam, granular, spherical, strip, block, cylindrical, cubic, disc, and pentagram; The molding density of the vinyl-linked covalent organic framework material is 0.3-2.0 g cm -3 .

8. The use according to claim 1, characterized in that: The vinyl-linked covalent organic framework material has an adsorption storage capacity of at least 0.34 g cm for the electronic specialty gas arsine at 21° C. and 650 torr. -3 , the deliverable capacity under 650-5 Torr conditions is greater than or equal to 80% of the adsorption storage capacity; The organic monomer 1 is selected from one or more of 2,4,6-trimethyltriazine, 2,4,6-trimethylpyridine and 2,6-dimethylpyrazine; The organic monomer 2 is selected from one or more of terephthalaldehyde and 1,3,5-trimethylbenzenecarboxaldehyde.

9. The use according to claim 1, characterized in that: The vinyl-linked covalent organic framework material has an adsorption storage capacity of at least 0.15 g cm for the electronic specialty gas phosphine at 21° C. and 650 torr. -3 , the deliverable capacity under 650-5 Torr conditions is greater than or equal to 80% of the adsorption storage capacity; The organic monomer 1 is selected from one or more of 2,4,6-trimethyltriazine, 2,4,6-trimethylpyridine and 2,6-dimethylpyrazine; The organic monomer 2 is selected from one or more of terephthalaldehyde and 1,3,5-trimethylbenzenecarboxaldehyde.

10. The use according to any one of claims 1 to 9, characterized in that: The pores of the vinyl-linked covalent organic framework material have free anions, which are halogen anions, BF4 - PF6 - 、SiF6 2- 、SO4 2- At least one of .

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