Non-penetrating covalent organic frameworks, methods of making and use thereof

Abstract

The application relates to the technical field of preparation of covalent organic framework materials, and discloses a non-penetrating covalent organic framework and a preparation method and application thereof. The covalent organic framework contains a structural unit shown in formula (I), and the structural unit shown in formula (I) is obtained by condensation reaction of a compound with a structure shown in formula (I-1) and a compound with a structure shown in formula (I-2). The non-penetrating covalent organic framework provided by the application has high crystallinity, permanent porosity, high specific surface area and good thermal stability, and due to the non-penetrating topological property, the non-penetrating covalent organic framework has excellent CO2 adsorption capacity.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of preparation of covalent organic framework materials, in particular, to a non-penetrating covalent organic framework and a preparation method and application thereof. BACKGROUND

[0002] Carbon dioxide (CO2) is an important greenhouse gas, and the environmental problems such as climate anomalies, glacier melting and sea level rise caused by excessive CO2 emission are becoming increasingly serious. Therefore, it is crucial to find suitable CO2 adsorption and storage materials.

[0003] At present, a variety of potential materials have been found in scientific research, such as zeolite, polymer (POPs), porous silicon (PS), metal organic framework (MOFs) and covalent organic framework (COFs) and the like. Among them, COFs are a very potential new material for CO2 adsorption and storage. It is a porous crystalline material composed of B, C, N, O and other elements connected by reversible covalent bonds. Due to its relatively clear structure, low density, high theoretical surface area and good stability, it has attracted widespread attention.

[0004] Therefore, it is urgent to develop a new porous material with high CO2 adsorption. SUMMARY

[0005] The purpose of the present application is to provide a new organic framework material with high crystallinity, permanent porosity, high specific surface area and good thermal stability, and excellent CO2 adsorption capacity.

[0006] In order to achieve the above purpose, the first aspect of the present application provides a non-penetrating covalent organic framework, which contains a structural unit shown in formula (I),

[0007]

[0008] The second aspect of the present application provides a non-penetrating covalent organic framework, which contains a structural unit shown in formula (I),

[0009]

[0010] The covalent organic framework belongs to tetragonal system, I-4 space group, and the cell parameters are respectively: α = 90.00°, β = 90.00°, γ = 90.00°.

[0011] The third aspect of the present application provides a method for preparing a non-penetrating covalent organic framework, which contains a structural unit shown in formula (I), and the method comprises:

[0012] The compound shown in formula (I-1) is condensed with the compound shown in formula (I-2) in the presence of solvent I and catalyst I to obtain a structural unit shown in formula (I),

[0013]

[0014] The fourth aspect of the present application provides a non-penetrating covalent organic framework prepared by the method described in the third aspect.

[0015] The fifth aspect of the present application provides an application of the non-penetrating covalent organic framework described in the first aspect, the second aspect or the fourth aspect in adsorbing CO2.

[0016] Compared with the prior art, the present application has at least the following advantages:

[0017] (1) The present application first synthesizes a non-penetrating dia-type topological three-dimensional covalent organic framework based on tetraphenyl adamantane;

[0018] (2) The present application proposes a completely new route for synthesizing 1,3,5,7-tetra(4-aminophenyl)adamantane based on 1,3,5,7-tetra(4-nitrophenyl)tetraphenyladamantane;

[0019] (3) The non-penetrating covalent organic framework provided by the present application has high crystallinity, permanent porosity, high specific surface area and good thermal stability, and due to its non-penetrating topological property, it has excellent CO2 adsorption capacity;

[0020] (4) The method for preparing the non-penetrating covalent organic framework provided by the present application has the characteristics of easy availability of synthetic raw materials, mild synthesis conditions, simple operation, less by-products and easy mass production. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 is the X-ray powder diffraction pattern of CNPC-300-1 in Example 1 provided by the present application;

[0022] Figure 2 is the Fourier infrared spectrum of CNPC-300-1 and TFPA, TAPA in Example 1 provided by the present application;

[0023] Figure 3 is the thermogravimetric analysis diagram of CNPC-300-1 in Example 1 provided by the present application;

[0024] Figure 4 is the adsorption isotherm curve of N2 at 77K of CNPC-300-1 in Example 1 provided by the present application and the pore size diagram of CNPC-300-1.

[0025] Figure 5 is the adsorption isotherm plot of CNPC-300-1 in Example 1 provided by the present application at 273 K, 0-1.0 bar for CO2;

[0026] Figure 6 is the schematic diagram of the crystal structure of CNPC-300-1 in Example 1 provided by the present application. DETAILED DESCRIPTION

[0027] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are provided as approximate descriptions of the ranges and are understood to be open-ended. Each range is a continuum of values between the upper and lower limits thereof and includes each and every value and sub-range therein. Any numerical value, however, can only be approximate. For example, a weight amount can be approximated to the nearest tenth of a gram, or the nearest whole number of a unit. Numerical ranges include all values from and including the lower and the upper values, in increments of one unit. In

[0028] It should be noted that the present application relates to the wavy line in the structural formula indicating the connecting position.

[0029] As described previously, the first aspect of the present application provides a non-penetrated covalent organic framework (hereinafter referred to as CNPC-300), which contains structural units represented by formula (I),

[0030]

[0031] Preferably, the structural units represented by formula (I) are obtained by condensation reaction of a compound represented by the structure of formula (I-1) and a compound represented by the structure of formula (I-2),

[0032]

[0033] As described previously, the second aspect of the present application provides a non-penetrated covalent organic framework, which contains structural units represented by formula (I),

[0034]

[0035] The covalent organic framework belongs to tetragonal system, I-4 space group, and the cell parameters are as follows: α = 90.00°, β = 90.00°, γ = 90.00°.

[0036] The present application does not have any particular limitation on the preparation method of the non-penetrating covalent organic framework, and those skilled in the art can select a synthetic route to prepare it according to the structural formula and known methods in the field of organic synthesis. However, in order to obtain higher yield and purity, according to a preferred embodiment, the third aspect of the present application provides a method for preparing a non-penetrating covalent organic framework containing a structural unit represented by formula (I), which comprises:

[0037] In the presence of solvent I and catalyst I, the compound represented by formula (I-1) (hereinafter referred to as TFPA) is condensed with the compound represented by formula (I-2) (hereinafter referred to as TAPA) to obtain a structural unit represented by formula (I),

[0038]

[0039] Preferably, the solvent I is selected from at least one of mesitylene, 1,4-dioxane, 1-butanol, o-dichlorobenzene, dimethylacetamide, ethanol, benzyl alcohol, toluene, and water.

[0040] More preferably, the solvent I is selected from at least one of mesitylene and 1,4-dioxane.

[0041] Further preferably, the solvent I is a combination of mesitylene and 1,4-dioxane, and the volume ratio of the mesitylene to the 1,4-dioxane is 1:0.1-9.0.

[0042] Particularly preferably, the solvent I is a combination of mesitylene and 1,4-dioxane, and the volume ratio of the mesitylene to the 1,4-dioxane is 1:0.1-7.0.

[0043] The inventors of the present application found that the covalent organic framework obtained when the volume ratio of the mesitylene to the 1,4-dioxane is 1:1.0-3.0 has higher crystallinity.

[0044] Preferably, the catalyst I is selected from at least one of acetic acid, trifluoroacetic acid, and p-toluenesulfonic acid. More preferably, the catalyst I is acetic acid. The inventors of the present application found that the covalent organic framework obtained in this preferred case has higher crystallinity.

[0045] It should be noted that the catalyst I in the present application can be an aqueous solution of the corresponding substance, and the amount involved is based on the entire solution system.

[0046] According to a preferred embodiment, the concentration of the aqueous acetic acid solution is 3-9 moL / L.

[0047] Preferably, the molar ratio of the compound of the structure shown in formula (I-1) to the compound of the structure shown in formula (I-2) is 1:0.8-1.5.

[0048] According to a preferred embodiment, the amount of the solvent I is 0.5-5.0 mL, and the amount of the catalyst I is 0.05-0.50 mL, based on the total amount of the compound of the structure shown in formula (I-1) and the compound of the structure shown in formula (I-2) being 0.1 mmol.

[0049] According to another preferred embodiment, the conditions of the condensation reaction at least meet the following requirements: the temperature is 120-140℃, and the time is 72-168 h.

[0050] It should be noted that the method for preparing the compound of the structure shown in formula (I-1) and the compound of the structure shown in formula (I-2) is not particularly limited in the present application, and those skilled in the art can select according to the technical means known in the art. However, in order to obtain a covalent organic framework with higher crystallinity and better thermal stability, a preferred embodiment is exemplarily provided in the following of the present application, and those skilled in the art should not be construed as a limitation of the present application.

[0051] According to a preferred embodiment, the method further comprises preparing the compound of the structure shown in formula (I-1) by using a method comprising the following steps:

[0052] The first contact reaction is carried out between 1,3,5,7-tetraphenyladamantane and 1,1-dichloromethyl ether in the presence of a solvent II and a catalyst II under a protective atmosphere.

[0053] Preferably, the solvent II is selected from at least one of dichloromethane, chloroform, and toluene.

[0054] Preferably, the catalyst II is selected from at least one of titanium tetrachloride, phosphorus trichloride, and iron trichloride.

[0055] Preferably, the molar ratio of the 1,3,5,7-tetraphenyladamantane to the 1,1-dichloromethyl ether is 1:4-20.

[0056] Preferably, the amount of the solvent II is 100-900 mL, and the amount of the catalyst II is 10-100 mL, based on the total amount of the 1,1-dichloromethyl ether and the 1,3,5,7-tetraphenyladamantane being 0.1 mol.

[0057] Preferably, the conditions of the first contact reaction at least meet the following requirements: the reaction is carried out under stirring, the stirring speed is 1000-6000 rpm, the temperature is -30℃ to 30℃, and the time is 0.5-3 h.

[0058] According to another preferred embodiment, the method further comprises preparing the compound with the structure shown in formula (I-2) by using a method comprising the following steps:

[0059] contacting 1,3,5,7-tetra(4-nitrophenyl)tetraphenyladamantane with hydrogen gas in the presence of solvent III and catalyst III for a second time.

[0060] Preferably, the solvent III is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, ethanol.

[0061] Preferably, the catalyst III is selected from at least one of palladium on carbon, Raney nickel. Exemplarily, the palladium on carbon can be 5wt% palladium on carbon, 10wt% palladium on carbon.

[0062] It should be noted that the amount of hydrogen gas used in the present application is such that the second contact reaction can maintain a certain pressure, and a preferred embodiment is exemplarily provided in the following of the present application, and those skilled in the art should not be construed as a limitation of the present application.

[0063] Preferably, the amount of solvent III is 100-1000mL, and the amount of catalyst III is 0.01-1.00g, based on 1mmol of 1,3,5,7-tetra(4-nitrophenyl)tetraphenyladamantane.

[0064] Preferably, the second contact reaction is carried out under stirring at a speed of 1000-6000rpm, at a temperature of 20-40℃, for a time of 0.2-48h, and at a pressure of 0.5-2.0MPa.

[0065] The preparation method of the present application can further comprise various post-treatment methods commonly used in the art, such as filtration, washing, purification, drying, etc. The present application does not have special limitations on the post-treatment steps. For example, the present application can first wash the mixture obtained after the contact reaction, filter, and dry the filter residue.

[0066] As described above, the third aspect of the present application provides a non-penetrating covalent organic framework prepared by the method of the foregoing second aspect.

[0067] As described above, the fourth aspect of the present application provides the use of the non-penetrating covalent organic framework of the foregoing first aspect or the foregoing third aspect in adsorbing CO2.

[0068] It should be noted that, in the absence of special instructions, room temperature in the present application means 25±2℃.

[0069] The present application will be described in detail below by way of examples.

[0070] In the following examples, the raw materials used are commercially available unless otherwise specified.

[0071] Preparation Example 1: Preparation of a compound having a structure shown in formula (I-1)

[0072] A mixture of 1,3,5,7-tetraphenyladamantane (8.6 mmol) and dichloromethane (150 mL) was stirred at a speed of 2000 rpm under nitrogen protection and cooled to -10°C in a salt-ice bath. Then TiCl4(19.0 mL) was slowly added, and stirring was continued for 30 min. Finally, 1,1-dichloromethyl ether (137.9 mmol) was added, stirring was continued for 30 min, the temperature was raised to room temperature, and stirring was continued overnight to obtain mixture I.

[0073] After the reaction was completed, mixture I was poured into 300 mL of ice water, 1 mol / L hydrochloric acid (200 mL) was added, stirring was continued for 30 min, the aqueous phase was washed twice with dichloromethane, the organic phase was sequentially washed with 1 mol / L HCl, deionized water, saturated NaHCO3solution, and saturated brine, and the organic phases were combined. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The residue was subjected to column chromatography and purification, and recrystallized from 1,4-dioxane to obtain white 1,3,5,7-tetra(4-formylphenyl)adamantane (TFPA) crystals at a yield of 53%. The yield was calculated based on the amount of 1,3,5,7-tetraphenyladamantane used.

[0074] Preparation Example 2: Preparation of a compound having a structure shown in formula (I-2)

[0075] A mixture of 1,3,5,7-tetra(4-nitrophenyl)adamantane (0.645 mmol), palladium / carbon (10 wt%, 0.2 g), tetrahydrofuran (80 mL), and N,N-dimethylformamide (10 mL) was stirred at a speed of 3300 rpm under 1.0 MPa hydrogen at room temperature. After 48 h of reaction, mixture II was obtained. Mixture II was added to water, filtered, and the residue was dried in a high-vacuum drying oven at 100°C for 8 h to obtain 1,3,5,7-tetra(4-aminophenyl)adamantane at a yield of 90%. The yield was calculated based on the amount of 1,3,5,7-tetra(4-nitrophenyl)adamantane used.

[0076] Example 1: Preparation of a non-penetrating covalent organic framework

[0077] After 1,3,5,7-tetra(4-formylphenyl)adamantane (TFPA, 0.025 mmol) and 1,3,5,7-tetra(4-aminophenyl)adamantane (TAPA, 0.025 mmol) were ground uniformly in a mortar, they were added to a glass tube, then mesitylene (0.25 mL), 1,4-dioxane (0.75 mL), 9 mol / L acetic acid aqueous solution (0.1 mL) were slowly added, the glass tube was frozen in liquid nitrogen, vacuum sealed in a methane / oxygen flame. Finally, it was placed in a 125°C oven for 7 days. After the reaction was completed, the glass tube was opened with a glass cutter, and the product was washed with acetone and n-hexane five times, respectively, filtered, and the residue was dried in a vacuum drying oven at 65°C for 3 h to obtain the yellow target product (CNPC-300-1) with a yield of 77%. The yield was calculated based on the total amount of 1,3,5,7-tetra(4-formylphenyl)adamantane and 1,3,5,7-tetra(4-aminophenyl)adamantane.

[0078] Example 2

[0079] After 1,3,5,7-tetra(4-formylphenyl)adamantane (TFPA, 0.025 mmol) and 1,3,5,7-tetra(4-aminophenyl)adamantane (TAPA, 0.025 mmol) were ground uniformly in a mortar, they were added to a glass tube, then mesitylene (0.5 mL), 1,4-dioxane (0.5 mL), 6 mol / L acetic acid (0.1 mL) were slowly added, the glass tube was frozen in liquid nitrogen, vacuum sealed in a methane / oxygen flame. Finally, it was placed in a 140°C oven for 3 days. After the reaction was completed, the glass tube was opened with a glass cutter, and the product was washed with acetone and n-hexane five times, respectively, filtered, and the residue was dried in a vacuum drying oven at 65°C for 3 h to obtain the yellow target product (CNPC-300-2) with a yield of 61%. The yield was calculated based on the total amount of 1,3,5,7-tetra(4-formylphenyl)adamantane and 1,3,5,7-tetra(4-aminophenyl)adamantane.

[0080] Example 3

[0081] The preparation method of this example is similar to that of Example 1, except that:

[0082] The weight ratio of mesitylene to 1,4-dioxane was 1:9, and the total weight of the two was the same as that of Example 1, and the other conditions were the same as those of Example 1. The yellow target product (CNPC-300-3) was obtained with a yield of 42%. The yield was calculated based on the total amount of 1,3,5,7-tetra(4-formylphenyl)adamantane and 1,3,5,7-tetra(4-aminophenyl)adamantane.

[0083] Example 4

[0084] The preparation method in this embodiment is similar to that in Example 1, except that:

[0085] Equivalent molar amounts of acetic acid aqueous solution were replaced with trifluoroacetic acid aqueous solution of the same concentration (based on solute), and all other conditions were the same as in Example 1, yielding the yellow target product (CNPC-300-4) in 21% yield. The yield was calculated based on the sum of the amounts of 1,3,5,7-tetra(4-formylphenyl)adamantane and 1,3,5,7-tetra(4-aminophenyl)adamantane.

[0086] Test Example 1: X-ray Powder Diffraction Spectroscopy Characterization

[0087] The CNPC-300-1 sample from Example 1 was analyzed by PXRD using a Malvern Panaco Intelligent Empyrean X-ray powder diffractometer. The X-ray powder diffractometer's angle range was 2°–40°. Specific results can be found in [the table below]. Figure 1 .

[0088] Test Example 2: Characterization of Infrared Spectroscopic Properties

[0089] CNPC-300-1, TFPA, and TAPA from Example 1 were respectively mixed with potassium bromide, ground, and pressed into thin sheets. Measurements were then performed using an IRSpirit FTIR spectrometer with a wavelength range of 400-4000 cm⁻¹. -1 For details, please see Figure 2 .

[0090] Test Example 3: Characterization of Thermal Stability

[0091] The CNPC-300-1 sample from Example 1 was subjected to thermogravimetric analysis (TGA). Specifically, under N2 protection, a Shimadzu DTG-60 thermogravimetric analyzer was used to scan the sample, increasing the temperature from 25°C to 800°C at a rate of 10°C / min. The TG curve was obtained, and the results are shown below. Figure 3 .

[0092] Test Example 4: Characterization of Adsorption Properties

[0093] The CNPC-300-1 prepared in Example 1 was subjected to... The ASAP 2060 surface area analyzer (manufactured by McMurray) was used to determine the specific surface area and carbon dioxide adsorption capacity of the samples. Specific results are shown below. Figure 4 and Figure 5 .

[0094] Test Example 5: Characterization of Theoretical Crystal Structure

[0095] The theoretical crystal structure of CNPC-300-1 from Example 1 was obtained by combining PXRD data and adsorption data with MaterialStudio software simulation. The specific results are shown in Table 1.

[0096] The products of Examples 2-4 were subjected to the same tests as those in Test Examples 1-5 above, and the test results are shown in Table 2.

[0097] Table 1

[0098]

[0099]

[0100] Table 2

[0101] Properties Example 1 Example 2 Example 3 Example 4 <![CDATA[Saturation adsorption capacity of N2 (cm 3 g -1 )]]> 600 525 413 243 BET specific surface area (m 2 g -1 )]]> 1827.5 1503.2 1100.0 563.7 273CO2uptake at 273K / 1 bar (cm3 / g 3 g -1 )]]> 231 210 131 84

[0102] The X-ray powder diffraction patterns of CNPC-300-1, CNPC-300-2, CNPC-300-3, and CNPC-300-4 provided by the present invention are similar. For example, the present invention provides the X-ray powder diffraction pattern of CNPC-300-1.

[0103] Depend on Figure 1 It can be seen that the PXRD curve of CNPC-300-1 in Example 1 is basically consistent with the simulated PXRD curve, indicating that the present invention has successfully synthesized the aforementioned three-dimensional covalent organic framework with non-penetrating dia-type topology.

[0104] The Fourier transform infrared spectra of CNPC-300-1, CNPC-300-2, CNPC-300-3, and CNPC-300-4 provided by this invention are similar. For example, this invention provides the Fourier transform infrared spectrum of CNPC-300-1.

[0105] Depend on Figure 2 It can be seen that TFAP is 1697cm tall. -1 The -CHO absorption peak and TAPA are at 3300-3100 cm⁻¹ -1 -NH at the location 2 The absorption peak disappeared, while CNPC-300-1 reached 1623 cm⁻¹. -1 The appearance of the infrared absorption peak of -C=N proves that an imine bond has been formed.

[0106] The thermogravimetric analysis (TGA) diagrams of CNPC-300-1, CNPC-300-2, CNPC-300-3, and CNPC-300-4 provided by this invention are similar. For example, this invention provides the TGA diagram of CNPC-300-1.

[0107] Depend on Figure 3 It can be seen that the slight weight loss of CNPC-300-1 before 400℃ is due to the evaporation of solvent and a small amount of water. Significant weight loss only begins to appear at around 400℃, indicating that CNPC-300-1 can withstand high temperatures of 400℃ and has good thermal stability.

[0108] The adsorption isotherm and pore size diagram of CNPC-300-1, CNPC-300-2, CNPC-300-3 and CNPC-300-4 provided by the present invention are similar. For example, the present invention provides an adsorption isotherm and pore size diagram of CNPC-300-1 for N2 at 77K. Figure 4 This is the adsorption isotherm curve of CNPC-300-1 at 77K for N2 provided in Example 1 of this invention, and the pore size diagram of CNPC-300-1.

[0109] Depend on Figure 4 It can be seen that the specific surface area of ​​CNPC-300-1 reaches 1827.5 m². 2 g -1 The pore size is micropores, mainly distributed at around 1.6 nm.

[0110] The adsorption isotherm curves of CO2 for CNPC-300-1, CNPC-300-2, CNPC-300-3, and CNPC-300-4 provided by this invention are similar. By way of example, this invention provides the adsorption isotherm curve of CO2 for CNPC-300-1.

[0111] Depend on Figure 5 It can be seen that CNPC-300-1 has good CO2 adsorption capacity, reaching 231 cm⁻² under conditions of 273 K and 1 bar. 3 / g -1 Compared to existing porous materials, it is already at an advanced level.

[0112] The crystal structures of CNPC-300-1, CNPC-300-2, CNPC-300-3, and CNPC-300-4 provided by this invention are very similar. For example, as shown in the figure... Figure 6 As shown, this invention provides a schematic diagram of the crystal structure of CNPC-300-1. (From...) Figure 6 It is known that CNPC-300-1 has a non-penetrating dia-type topology, which results in high porosity and excellent gas adsorption capacity due to its non-penetrating topological properties.

[0113] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including that each technical feature is combined in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A non-penetrating covalent organic framework, characterized in that, The covalent organic framework contains structural units of formula (I), Formula (I); The covalent organic framework belongs to tetragonal system, I-4 space group, and the cell parameters are respectively: ; The covalent organic framework is prepared by a method comprising the following steps: condensing a compound of formula (I-1) with a compound of formula (I-2) in the presence of solvent I and catalyst I to obtain structural units of formula (I), Formula (I-1), Formula (I-2); The solvent I is a combination of mesitylene and 1,4-dioxane, and the volume ratio of the mesitylene to the 1,4-dioxane is 1:1.0-3.

0. The catalyst I is acetic acid.

2. The non-intrusive covalent organic framework of claim 1, wherein, The molar ratio of the compound of formula (I-1) to the compound of formula (I-2) is 1:0.8-1.

5.

3. The non-intrusive covalent organic framework of claim 1 or 2, wherein, The condensation reaction is performed under the following conditions: temperature 120-140℃, time 72-168h.

4. The non-intrusive covalent organic framework of claim 1 or 2, wherein, The method further comprises preparing the compound of formula (I-1) by a method comprising the following steps: under a protective atmosphere, in the presence of solvent II and catalyst II, subjecting 1,3,5,7-tetraphenyladamantane to a first contact reaction with 1,1-dichloromethyl ether; the solvent II is selected from at least one of dichloromethane, chloroform, toluene; the catalyst II is selected from at least one of titanium tetrachloride, phosphorus trichloride, iron trichloride.

5. The non-penetrating covalent organic framework of claim 4, wherein, The molar ratio of the 1,3,5,7-tetraphenyladamantane to the 1,1-dichloromethyl ether is 1:4-20.

6. The non-penetrating covalent organic framework of claim 4, wherein, The first contact reaction is performed under the following conditions: stirring at a speed of 1000-6000rpm, temperature -30℃ to 30℃, time 0.5-3h.

7. The non-penetrating covalent organic framework of claim 4, wherein, The method further comprises preparing the compound of formula (I-2) by a method comprising the following steps: under a protective atmosphere, in the presence of solvent III and catalyst III, subjecting 1,3,5,7-tetra(4-nitrophenyl)adamantane to a second contact reaction with hydrogen; the solvent III is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, ethanol; the catalyst III is selected from at least one of palladium on carbon, Raney nickel.

8. The non-penetrating covalent organic framework of claim 7, wherein, The second contact reaction is performed under the following conditions: stirring at a speed of 1000-6000rpm, temperature 20-40℃, time 0.2-48h, pressure 0.5-2.0MPa.

9. Use of the non-penetrating covalent organic framework of any one of claims 1-8 for adsorbing CO2.

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