A novel three-dimensional covalent-organic framework ligand, preparation method and application thereof

Abstract

The present application relates to the technical field of covalent organic framework ligand precursor synthesis, in particular to a novel three-dimensional covalent-organic framework ligand, a preparation method and application thereof, the novel three-dimensional covalent-organic framework ligand of the present application is a brand-new six-connection space node three-dimensional covalent-organic framework ligand, the rotation angle between benzene rings is adjusted by a steric hindering group, so that the originally planar connection node is twisted into a space node of triangular prism configuration, the problem of few three-dimensional COFs space nodes, especially few high reaction site space nodes, in the background art is solved, the COF of the present application is a brand-new three-dimensional covalent-organic framework 3D-TMTAPB-COF, the pore size of the COF is 0.84 nm, the specific surface area is 939 m 2 g ‑1 The COF has good crystallinity, and the three-dimensional COF is a novel Class IIIa 6-fold interlocking acs topology structure.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of covalent organic framework ligand precursor synthesis, and particularly to a novel three-dimensional covalent-organic framework ligand, a preparation method and application thereof. BACKGROUND

[0002] Covalent organic framework is a new type of crystalline organic porous material, mainly composed of light elements such as C, H, O and N, and has a periodic pore structure. According to the dimension difference of COF precursor small molecules, COF can be divided into two-dimensional layered structure (2D COF) and three-dimensional network extension structure (3D COF). Compared with two-dimensional COF, three-dimensional COF has many unique properties, such as hierarchical and isolated channels, larger specific surface area, etc. These characteristics make three-dimensional COF have great potential application value in gas storage and separation, catalysis, energy storage, sensing, etc.

[0003] However, the synthesis of three-dimensional covalent organic framework ligands is very difficult, especially the synthesis of connecting nodes with high reaction sites (>4), which greatly limits the further development of three-dimensional COFs. However, three-dimensional COFs with high connecting nodes have more possibilities in theory, and may form three-dimensional COFs with larger specific surface area and lower density, laying a foundation for the application of three-dimensional COFs. SUMMARY

[0004] One of the purposes of the present application is to provide a novel three-dimensional covalent-organic framework ligand, which is a brand new six-connected spatial node three-dimensional covalent-organic framework ligand. The connecting node is adjusted by a steric hindering group to adjust the rotation angle between benzene rings. Thus, the originally planar connecting node is twisted into a three-prism spatial node. The problem of few spatial nodes of three-dimensional COFs, especially few spatial nodes with high reaction sites, is solved.

[0005] The second purpose of the present application is to provide a preparation method of a novel three-dimensional covalent-organic framework ligand, which is simple and easy to adjust.

[0006] The third purpose of the present application is to provide an application of a novel three-dimensional covalent-organic framework ligand.

[0007] The scheme adopted by one of the purposes of the present application is: a novel three-dimensional covalent-organic framework ligand, the molecular structure formula of which is:

[0008]

[0009] In the formula, R is methyl or ethyl.

[0010] The scheme adopted by the second object of the present application is: a preparation method of the novel three-dimensional covalent-organic framework ligand, the synthesis route is as follows:

[0011]

[0012] comprising the following steps:

[0013] (1) Compound 1 is dissolved in a solvent, then liquid bromine is slowly added at a certain temperature, after the addition is completed, the reaction is carried out at room temperature for a certain time, then the reaction is quenched, and the excess bromine is removed, the solution is filtered to obtain a white solid, which is washed and dried to obtain the product compound 2;

[0014] (2) Compound 2 is dissolved in a solvent, then hydrochloric acid and sodium nitrite are added, and the reaction is carried out at a certain temperature until the reaction is complete, then phosphorous acid is added and the reaction is carried out at room temperature until the reaction is complete, then the obtained system is filtered, washed and dried to obtain a brown product compound 3;

[0015] (3) The mixed system of compound 3, p-aminobenzoic acid pinacol ester and a catalyst is added to a solvent under an inert atmosphere, and the reaction is carried out at a certain temperature until the reaction is complete, then the obtained mixed system is extracted to remove the liquid, and the product is purified to obtain a gray-white solid, which is the novel three-dimensional covalent-organic framework ligand compound 4, namely TMTAPB or TETAPB.

[0016] Preferably, in the step (1), the solvent is acetic acid, liquid bromine is added at 1-4℃, and the reaction is carried out for 2-4 hours, then the reaction is quenched by using excess sodium bisulfite or sodium thiosulfate.

[0017] Preferably, in the step (2), the solvent is a mixed solution of acetic acid and water in a volume ratio of 2:1, and the reaction temperature is-5 to 5℃.

[0018] Preferably, in the step (2), the molar ratio of compound 2, hydrochloric acid, sodium nitrite and phosphorous acid is 1:7-10.5:5.5-8.25:130-195.

[0019] Preferably, in the step (3), the catalyst is a palladium salt catalyst and a carbonate catalyst; preferably, the palladium salt catalyst is at least one of tetrakis(triphenylphosphine)palladium, palladium acetate and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, and the carbonate catalyst is at least one of cesium carbonate and potassium carbonate; more preferably, the molar ratio of compound 3, p-aminobenzoic acid pinacol ester, palladium salt catalyst and carbonate catalyst is 1:6.5-8:0.05-0.6:5-6.

[0020] Preferably, in the step (3), the solvent is a mixed solution of water, 1,4-dioxane or dimethylformamide in a volume ratio of 1:5-1, the reaction temperature is 90-120 DEG C, and the obtained mixed system is extracted with any one of dichloromethane, chloroform, tetrahydrofuran or ethyl acetate.

[0021] The application achieves the third object by adopting the following scheme: an application of the novel three-dimensional covalent-organic framework ligand, and a three-dimensional covalent organic framework COF material prepared by using the novel three-dimensional covalent-organic framework ligand.

[0022] Preferably, the three-dimensional covalent organic framework 3D-TMTAPB-COF is prepared by reacting the compound TMTAPB with p-phthalaldehyde.

[0023] Preferably, the molecular structure of the three-dimensional covalent organic framework 3D-TMTAPB-COF is The three-dimensional covalent organic framework is a Class IIIa 6-fold interlocking acs topology structure.

[0024] The application has the following advantages and beneficial effects:

[0025] The novel three-dimensional covalent-organic framework ligand of the application is a brand-new six-connection space node three-dimensional covalent-organic framework ligand, and the connection node is used to adjust the rotation angle between benzene rings by steric hindering groups, so that the originally planar connection node is twisted into a space node of a triangular prism configuration, thereby solving the problem of few three-dimensional COFs space nodes and especially few high reaction site space nodes in the background art.

[0026] The preparation method of the application has simple synthesis method, easy adjustment and high product yield.

[0027] The COF of the application is a brand-new three-dimensional covalent organic framework 3D-TMTAPB-COF, the pore size of the COF is 0.84 nm, the specific surface area is 939 m 2 g -1 The COF has good crystallinity, and the three-dimensional COF is a novel Class IIIa 6-fold interlocking acs topology structure. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 The nuclear magnetic resonance H spectrum of compound 2 is shown in the following figure: 1 The nuclear magnetic resonance H spectrum of compound 2 is shown in the following figure:

[0029] Figure 2 The nuclear magnetic resonance H spectrum of compound 2 is shown in the following figure: 13 The nuclear magnetic resonance H spectrum of compound 2 is shown in the following figure:

[0030] Figure 3 The nuclear magnetic resonance H spectrum of compound 2 is shown in the following figure: 1 The nuclear magnetic resonance H spectrum of compound 2 is shown in the following figure:

[0031] Figure 4 NMR for compound 3 13 H spectrum;

[0032] Figure 5 NMR for compound TMTAPB 1 H spectrum;

[0033] Figure 6 NMR for compound TMTAPB 13 C spectrum;

[0034] Figure 7 NMR for compound 5 1 H spectrum;

[0035] Figure 8 NMR for compound 5 13 C spectrum;

[0036] Figure 9 NMR for compound 6 1 H spectrum;

[0037] Figure 10 NMR for compound 6 13 C spectrum;

[0038] Figure 11 NMR for compound TETAPB 1 H spectrum;

[0039] Figure 12 NMR for compound TETAPB 13 C spectrum;

[0040] Figure 13 Infrared spectrum of 3D-TMTAPB-COF;

[0041] Figure 14 NMR for 3D-TMTAPB-COF 13 C spectrum;

[0042] Figure 15 Scanning electron microscope image of 3D-TMTAPB-COF;

[0043] Figure 16 Nitrogen adsorption isotherm at 77K and pore size distribution of COF of 3D-TMTAPB-COF, wherein a is nitrogen adsorption isotherm at 77K, and b is pore size distribution of COF;

[0044] Figure 17 PXRD pattern of 3D-TMTAPB-COF, and single crystal photograph of 3D-TMTAPB-COF under microscope, wherein a is PXRD pattern of 3D-TMTAPB-COF, and b is single crystal photograph of 3D-TMTAPB-COF under microscope;

[0045] Figure 18 Schematic diagram of the structure of 3D-TMTAPB-COF;

[0046] Figure 19 Figure 2 is the adsorption amount of SF6 and N2 by 3D-TMTAPB-COF and the IAST selective adsorption curve of 3D-TMTAPB-COF. Figure a is the adsorption amount of SF6 and N2 by the COF under the conditions of 273K and 298K, and Figure b is the IAST selective adsorption curve of the COF at 298K. DETAILED DESCRIPTION

[0047] For a better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.

[0048] The specific synthetic route is as follows:

[0049] The synthesis process of TMTAPB (R is methyl) is as follows:

[0050]

[0051] (1) Compound 1 was placed in a round-bottom flask, acetic acid was added as a solvent, and then liquid bromine was slowly added dropwise in an ice bath. After the addition was completed, the reaction was allowed to proceed at room temperature for 2 hours, and then the reaction was quenched with an excess of sodium bisulfite, and the excess bromine was removed. The solution was filtered to obtain a white solid, which was washed with water, a small amount of ethanol, and dried under vacuum. The obtained white solid was product 2. Its molecular formula is:

[0052] (2) Compound 2 was placed in a round-bottom flask, acetic acid and water were added as solvents, and then hydrochloric acid and sodium nitrite were added. The mixture was reacted at 0°C for 40 minutes. Phosphorous acid was then added and the mixture was reacted at room temperature for 12 hours. The resulting liquid was filtered, washed with water, washed with ethanol, and vacuum dried to obtain a brown product 3. Its molecular formula is:

[0053] (3) Compound 3 was placed in a double-necked round-bottom flask, and p-aminophenylboronic acid pinacol ester, tetrakistriphenylphosphine palladium, and potassium carbonate were added. 1,4-dioxane and water were then added as solvents under a nitrogen atmosphere. The mixture was reacted at 100°C for 48 hours. The resulting solution was extracted with dichloromethane, and the solvent was dried to obtain a black solid. Column chromatography was used to purify the mixture to obtain an off-white solid, namely, compound TMTAPB, whose molecular formula is: The molar ratio of compound 3, p-aminophenylboronic acid pinacol ester, tetrakistriphenylphosphine palladium, and potassium carbonate is 1:6.5:0.05:5. The eluent is dichloromethane:methanol = 200:1.

[0054] The synthesis process of TETAPB (R is ethyl) is as follows:

[0055]

[0056] The synthesis conditions of TETAPB and TMTAPB are basically the same.

[0057] Example 1

[0058] Synthesis of compound 2

[0059] Compound 1 (1.4 g, 3.6 mmol) and 25 ml of acetic acid were added to a 250 ml double-necked round-bottom flask and stirred at 0°C. Using a dropping funnel, 9 ml of liquid bromine (9 ml, 17.5 mmol) was slowly added dropwise to the solution. The reaction was allowed to proceed at room temperature for 2 hours. The reaction was then quenched with an excess of sodium bisulfite and the excess Br2 was removed. After the solution turned from orange to white, it was filtered to obtain an off-white solid. This was washed with copious amounts of water and a small amount of ethanol, and then dried under vacuum to yield compound 3.

[0060] 1 H NMR (400MHz, DMSO-d6, ppm): δ = 7.25 (s, 6H), 5.36 (s, 6H), 1.72 (s, 9H).

[0061] 13 C NMR (100MHz, DMSO-d6) δ = 141.9, 137.4, 134.2, 132.8, 131.9, 108.3, 20.0.

[0062] Synthesis of compound 3

[0063] To a 250ml round-bottom flask, add 3.5g of compound 2 (3.5g, 4mmol), 20ml of glacial acetic acid, 10ml of water, and 5ml of concentrated hydrochloric acid and stir at 0°C. Then, dissolve 1.5g of sodium nitrite in 5ml of water and slowly add it dropwise to the reaction solution. Let it react for 40 minutes. Then, add 35ml of hypophosphorous acid and let it react at room temperature for 10 hours. Filter to obtain a brown solid, which is the product.

[0064] 1 H NMR (400MHz, CDCl3, ppm): δ=7.67 (t, J=4Hz, 3H), 7.28 (d, J=4Hz, 6H), 1.72 (s, 9H).

[0065] 13 C NMR (100MHz, CDCl3) δ = 144.9, 137.5, 133.5, 132.7, 131.0, 123.3, 19.5.

[0066] Synthesis of compound TMTAPB

[0067] To a 100ml round-bottom flask, add 500mg of compound 3 (500mg, 0.61mmol), p-aminophenylboronic acid pinacol ester (820mg, 6.1mmol), bistriphenylphosphinoferrocenedichloropalladium (80mg, 0.11mmol), and potassium carbonate (1g, 7.2mmol). Under nitrogen, add 25ml of 1,4-dioxane and 25ml of water, and react at 90°C for 48 hours. The solvent was evaporated, and the resulting solid was purified by column chromatography (silica gel column, eluent: dichloromethane:methanol = 200:1) to obtain an off-white solid as the product.

[0068] 1 H NMR (400MHz, DMSO-d6, ppm): δ = 7.62 (s, 3H), 7.48 (d, J = 8Hz, 12H), 7.23 (s, 6H), 6.65 (d, J = 8Hz, 12H), 5.23 (s, 12H), 1.84 (s, 9H).

[0069] 13 C NMR (100MHz, DMSO-d6) δ = 148.4, 142.5, 141.5, 139.7, 132.2, 127.6, 127.5, 123.6, 120.8, 114.2, 19.5.

[0070] Example 2

[0071] Synthesis of compound 5

[0072] Compound 4 (1.6 g, 3.6 mmol) and 25 ml of acetic acid were added to a 250 ml double-necked round-bottom flask and stirred at 0°C. Using a dropping funnel, 9 ml of liquid bromine (9 ml, 17.5 mmol) was slowly added dropwise to the solution. The reaction was allowed to proceed at room temperature for 2 hours. The reaction was then quenched with an excess of sodium bisulfite and the excess Br2 was removed. After the solution turned from orange to white, it was filtered to obtain an off-white solid. This was washed with copious amounts of water and a small amount of ethanol, and then dried under vacuum to yield compound 5.

[0073] 1 H NMR (400MHz, DMSO-d6, ppm): δ = 7.29 (s, 6H), 4.57 (s, 6H), 2.12 (q, 6H), 0.71 (t, 9H).

[0074] 13C NMR (100MHz, DMSO-d6) δ = 141.4, 140.5, 136.6, 133.0, 132.3, 108.3, 24.7, 15.3.

[0075] Synthesis of compound 6

[0076] To a 250ml round-bottom flask, add 3.5g of compound 5 (3.6g, 4.0mmol), 20ml of glacial acetic acid, 10ml of water, and 5ml of concentrated hydrochloric acid and stir at 0°C. Then, dissolve 1.5g of sodium nitrite in 5ml of water and slowly add it dropwise to the reaction solution. Let it react for 40 minutes. Then, add 35ml of hypophosphorous acid and let it react at room temperature for 10 hours. Filter to obtain a brown solid, which is the product.

[0077] 1 H NMR (400MHz, CDCl3, ppm): δ = 7.68 (t, J = 4Hz, 3H), 7.37 (d, J = 4Hz, 6H), 2.07 (d, 6H), 0.69 (t, 9H).

[0078] 13 C NMR (100MHz, CDCl3) δ = 143.8, 140.3, 136.7, 132.7, 131.7, 122.6, 24.6, 15.0.

[0079] Synthesis of compound TETAPB

[0080] To a 100ml round-bottom flask was added 500mg of compound 6 (527mg, 0.61mmol), p-aminophenylboronic acid pinacol ester (820mg, 6.1mmol), bistriphenylphosphinoferrocenedichloropalladium (80mg, 0.11mmol), and potassium carbonate (1g, 7.2mmol). Under nitrogen, 25ml of 1,4-dioxane and 25ml of water were added and reacted at 90°C for 48 hours. The solvent was evaporated, and the resulting solid was purified by column chromatography (silica gel column, eluent: dichloromethane:methanol = 200:1) to obtain an off-white solid as the product.

[0081] 1 H NMR (400MHz, DMSO-d6, ppm): δ = 7.63 (s, 3H), 7.46 (d, J = 8Hz, 12H), 7.30 (s, 6H), 6.64 (d, J = 8Hz, 12H), 5.75 (s, 12H), 2.22 (d, 6H), 0.77 (t, 9).

[0082] 13C NMR (100 MHz, DMSO-d6) δ = 53.6, 146.4, 145.9, 144.4, 144.1, 132.8, 132.6, 129.6, 126.2, 119.4, 60.1, 21.0.

[0083] Example 3

[0084] The synthesis process of 3D-TMTAPB-COF is as follows:

[0085]

[0086] TMTAPB (17.9 mg, 0.06 mmol) and p-xylylene aldehyde (8.0 mg, 0.06 mmol) were dissolved in a mixed solution of 0.8 mL of o-dichlorobenzene and 0.2 mL of chlorobenzene, then 0.1 mL of acetic acid with a concentration of 11 M was added to the above solution, and finally it was placed in a 120 °C oven for reaction for 72 hours to obtain a yellow powder; the yellow powder was suction filtered, and the COF powder was washed with a Soxhlet extractor filled with tetrahydrofuran and dichloromethane, respectively. Finally, the COF powder was vacuum dried to obtain sample 3D-TMTAPB-COF.

[0087] Figure 13 The infrared spectrum of 3D-TMTAPB-COF is shown, and from the figure it can be seen that a new peak is generated at 1625 cm -1 in the infrared spectrum (FTIR), indicating the generation of an imine bond.

[0088] Figure 14 The nuclear magnetic resonance C spectrum of 3D-TMTAPB-COF is shown, and the peak at 157.7 in the nuclear magnetic resonance carbon spectrum further indicates the generation of an imine bond. 13

[0089] Figure 15 The scanning electron microscope image of 3D-TMTAPB-COF is shown, and from the figure it can be seen that the COF has a shuttle-like morphology with a size of about 15 um.

[0090] Figure 16 a The nitrogen adsorption isotherm graph of 3D-TMTAPB-COF at 77 K is shown, and b is the pore size distribution graph of the COF, from which it can be seen that the specific surface area of the COF is 939 m 2 g -1 , and the pore size is 0.84 nm.

[0091] Figure 17 ​a PXRD patterns of 3D-TMTAPB-COF, A represents the experimental XRD pattern, B represents the refined XRD pattern, C represents the difference of XRD between the experimental and refined patterns, D represents the Bragg positions of the crystal structure, b three-dimensional reciprocal lattice of 3D-TMTAPB-COF and the single crystal photograph under microscope. It can be seen from it that the reflection condition shows that the possible space group is P6 / mcc and P6cc. According to the standard of I / σ>1, the resolution is limited to It is worth noting that Class IIIa interpenetration is observed in 3D-TMTAPB-COF, indicating the existence of translation vector (Zt=3) and symmetry operation (Zn=2). Finally, the Rietveld refinement gives the lattice parameters α=β=90°, γ=120°, wherein Rwp=8.05% and Rp=5.85%.

[0092] Figure 18 a) is the molecular model of the single-layer framework of the COF (left), and the simplified acs topology structure of the COF (right), b) A1, A2, A3 and A4, A5, A6 respectively carry two directions of triple interpenetration structure, and finally the six-fold interpenetration structure of the COF. c) the channel structure of the COF in the c-axis direction and its simplified schematic diagram.

[0093] Figure 19 a) in the curve A, the SF6adsorption isotherm of the COF at 273K, curve B represents the SF6adsorption isotherm of the COF at 298K, curve C represents the nitrogen adsorption isotherm of the COF at 273K, and curve D represents the nitrogen adsorption isotherm of the COF at 298K. b) is the IAST selective adsorption curve of the COF. It can be seen from the figure that the adsorption amount of TMTAPB at 273K and 298K, 1 bar is 82.14 cm 3 / g and 67.71 cm 3 / g, which is much larger than the adsorption amount of nitrogen under the same conditions. The IAST separation selectivity value of the COF for SF6 / N2(10 / 90) is 437 calculated by ideal solution adsorption theory, which shows potential application value for separating SF6 in air.

[0094] Table 1 is the unit cell parameters and atomic coordinates of 3D-TMTAPB-COF obtained by Rietveld refinement

[0095]

[0096]

[0097]

[0098] Sulfur hexafluoride (SF6) is a man-made gas with very high electrical insulation and arc extinguishing properties, and has a very wide role in the electrical industry. However, SF6 is also a very serious greenhouse gas, and is one of the six greenhouse gases specified in the Kyoto Protocol. Its greenhouse effect is 25,000 times that of carbon dioxide, and is the strongest of the six. Therefore, efficient separation of SF6 in air has important significance for environmental protection. Because the COF has through-pore channels, a suitable pore size, and a high specific surface area, we believe that the COF has potential value in SF6 / N2 adsorption separation applications. We next tested the SF6 and N2 adsorption performance of the COF. The results showed that the COF has a high SF6 adsorption capacity, and the adsorption capacity for SF6 at 273 K and 298 K was 82.14 cm 3 / g and 67.71 cm 3 / g, respectively. At the same time, the COF has very small N2 adsorption capacity at 273 K and 298 K. Under the conditions of 298 K and 1 bar, we calculated the IAST separation selectivity value of the COF for SF6 / N2 (10 / 90) according to the ideal solution adsorption theory, and the value was 437. The results show that the IAST separation selectivity value of the COF is higher than that of most of the reported crystalline porous materials, and has potential application value in SF6 / N2 separation.

[0099] The above is the preferred embodiment of the present application, of course, cannot be limited to the scope of the present invention, should be noted that for those skilled in the art, without departing from the principles of the present invention, can make a number of improvements and changes, these improvements and changes are also considered to be within the scope of the present invention.

Claims

1. A novel three-dimensional covalent-organic framework ligand, characterized by: Its molecular structure is: ， Wherein R is methyl or ethyl.

2. A method for preparing a novel three-dimensional covalent-organic framework ligand according to claim 1, characterized in that: The synthetic route is as follows: ， The following steps are involved: (1) Compound 1 is dissolved in a solvent, and then liquid bromine is slowly added dropwise at a certain temperature. After the addition is completed, the reaction is allowed to proceed at room temperature for a certain period of time. The reaction is then quenched and excess bromine is removed. The solution is filtered to obtain a white solid, which is then washed and dried. The obtained white solid is the product, Compound 2; (2) Compound 2 is dissolved in a solvent, and then hydrochloric acid and sodium nitrite are added and reacted at a certain temperature until the reaction is complete. Then phosphorous acid is added and reacted at room temperature until the reaction is complete. The resulting system is filtered, washed, and dried to obtain a brown product, Compound 3; (3) A solvent is added to a mixed system of compound 3, p-aminophenylboronic acid pinacol ester, and a catalyst under an inert atmosphere, and the reaction is completed at a certain temperature. The obtained mixed system is extracted and the liquid is removed. The product is purified to obtain an off-white solid, namely the novel three-dimensional covalent-organic framework ligand compound 4, namely TMTAPB or TETAPB.

3. The method for preparing the novel three-dimensional covalent-organic framework ligand according to claim 2, characterized in that: In the step (1), the solvent is acetic acid, and liquid bromine is added dropwise at 1-4°C. After reacting for 2-4 hours, an excess of sodium bisulfite or sodium thiosulfate is used to quench the reaction.

4. The method for preparing the novel three-dimensional covalent-organic framework ligand according to claim 2, characterized in that: In the step (2), the solvent is a mixed solution of acetic acid and water in a volume ratio of 2:1, and the reaction temperature is -5 to 5°C.

5. The method for preparing the novel three-dimensional covalent-organic framework ligand according to claim 2, characterized in that: In step (2), the molar ratio of compound 2, hydrochloric acid, sodium nitrite and phosphorous acid is 1: 7-10.5: 5.5-8.25: 130-195.

6. The method for preparing the novel three-dimensional covalent-organic framework ligand according to claim 2, wherein: In the step (3), the catalyst is a palladium salt catalyst and a carbonate catalyst; the palladium salt catalyst is at least one of tetrakistriphenylphosphine palladium, palladium acetate, and 1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, and the carbonate catalyst is at least one of cesium carbonate and potassium carbonate, and the molar ratio of the compound 3, p-aminophenylboronic acid pinacol ester, palladium salt catalyst, and carbonate catalyst is 1: 6.5-8: 0.05-0.6: 5-6.

7. The method for preparing a novel three-dimensional covalent-organic framework ligand according to claim 2, characterized in that: In the step (3), the solvent is a mixed solution of water, 1,4-dioxane or dimethylformamide in a volume ratio of 1:5-1, the reaction temperature is 90-120°C, and the obtained mixed system is extracted with any one of dichloromethane, chloroform, tetrahydrofuran and ethyl acetate.

8. Use of the novel three-dimensional covalent-organic framework ligand according to claim 1 or the novel three-dimensional covalent-organic framework ligand prepared by the preparation method according to any one of claims 2 to 7, characterized in that: The novel three-dimensional covalent-organic framework ligand is used to prepare a three-dimensional covalent organic framework COF material.

9. The use according to claim 8, characterized in that: The three-dimensional covalent organic framework 3D-TMTAPB-COF was prepared by reacting the compound TMTAPB with terephthalaldehyde. The molecular structure of the three-dimensional covalent organic framework 3D-TMTAPB-COF is: The three-dimensional covalent organic framework is a Class IIIa 6-fold interlocked acs topology structure.

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