Preparation method of spherical porous structure two-dimensional covalent organic framework material

文档序号：845325 发布日期：2021-03-16 浏览：9次中文

阅读说明：本技术 一种球形多孔结构的二维共价有机骨架材料的制备方法 (Preparation method of spherical porous structure two-dimensional covalent organic framework material ) 是由何仰清王雪婷杨谦姚秉华于 2020-11-02 设计创作，主要内容包括：本发明公开了一种球形多孔结构的二维共价有机骨架材料的制备方法,以1,10-菲啰啉-2,9-二甲醛和2,4,6-三(4-氨基苯基)-1,3,5-三嗪为原料制备有机骨架材料COFs,再采用铱配合物LX1对有机骨架材料COFs进行修饰,得到具有球形多孔结构的二维共价有机骨架材料。本发明制备方法利用溶剂热法成功合成了有机骨架材料COFs,反应条件温和,合成工艺简单易于实现；以含铱的过渡金属配合物LX1对有机骨架材料COFs进行了功能修饰,可以增强其对可将光的吸收能力和电子传输能力及其COFs材料的稳定性；得到的球形多孔结构的COFs材料,该材料具有较高可见光催化制氢性能。(The invention discloses a preparation method of a spherical porous two-dimensional covalent organic framework material, which comprises the steps of preparing organic framework material COFs by using 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as raw materials, and modifying the organic framework material COFs by adopting iridium complex LX1 to obtain the spherical porous two-dimensional covalent organic framework material. The preparation method successfully synthesizes organic framework materials COFs by using a solvothermal method, has mild reaction conditions, and is simple and easy to realize; the iridium-containing transition metal complex LX1 is used for carrying out functional modification on organic framework material COFs, so that the absorption capacity and the electron transmission capacity of the iridium-containing transition metal complex to light and the stability of the COFs material can be enhanced; the obtained COFs material with the spherical porous structure has higher hydrogen production performance under the catalysis of visible light.)

1. A preparation method of a spherical porous two-dimensional covalent organic framework material is characterized in that 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine are used as raw materials to prepare an organic framework material COFs, and an iridium complex LX1 is adopted to modify the organic framework material COFs to obtain the spherical porous two-dimensional covalent organic framework material.

2. The method for preparing the two-dimensional covalent organic framework material with the spherical porous structure according to claim 1, wherein the method for preparing the organic framework material COFs specifically comprises the following steps: adding 1, 10-phenanthroline-2, 9-dicarbaldehyde, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, mesitylene, 1, 4-dioxane and glacial acetic acid into a pressure pipe, carrying out nitrogen degassing treatment for three times, reacting for 3 days at 100-120 ℃, and washing with tetrahydrofuran after the reaction is finished to obtain the organic framework materials COFs.

3. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure according to claim 2, wherein the mass ratio of 1, 10-phenanthroline-2, 9-dicarbaldehyde to 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 1: 1-2.

4. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure according to claim 2, wherein the mass-to-volume ratio of 1, 10-phenanthroline-2, 9-dicarbaldehyde to glacial acetic acid is 420-460 mg/mL, and the molar mass of the glacial acetic acid is 3 g/mol.

5. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure according to claim 2, wherein the volume ratio of mesitylene, 1, 4-dioxane and glacial acetic acid is 12.75-25.5: 2.25-4.5: 1.

6. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure according to claim 1, wherein the iridium complex LX1 is adopted to modify the COFs of the organic framework material, and specifically comprises the following steps:

adding organic framework materials COFs, anhydrous sodium carbonate and ethylene glycol monoethyl ether into an iridium complex LX1, heating and refluxing for 24h at 90-110 ℃ under the condition of nitrogen, then carrying out vacuum filtration, washing with water and drying to obtain the two-dimensional covalent organic framework material with the spherical porous structure.

7. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure, according to claim 6, is characterized in that the mass ratio of the iridium complex LX1 to the organic framework material COFs to the anhydrous sodium carbonate is 1: 4.5-9: 10.6-21.2, and the mass-volume ratio of the organic framework material COFs to the ethylene glycol monoethyl ether is 10-15 mg/mL.

8. The method for preparing the two-dimensional covalent organic framework material with the spherical porous structure according to any one of claims 1, 6 or 7, wherein the method for preparing the iridium complex LX1 comprises the following steps:

adding 2-bromo-5- (trifluoromethyl) pyridine, 4- (trifluoromethyl) phenylboronic acid, anhydrous potassium carbonate, palladium acetate and an ethanol aqueous solution into a round-bottom flask, heating and refluxing for 40min at 80 ℃, then adding brine, extracting for 4 times by using ethyl acetate, and evaporating to dryness by using a rotary evaporator to obtain 5- (trifluoromethyl) -2- (4- (trifluoromethyl) phenyl) pyridine, namely ligand L1;

adding iridium trichloride trihydrate and ethylene glycol monoethyl ether aqueous solution into a ligand L1, heating and refluxing for 24h at 90-110 ℃ under the protection of nitrogen, then carrying out vacuum filtration, and washing with water to obtain an iridium complex LX 1.

9. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure, which is characterized in that the molar ratio of 2-bromo-5- (trifluoromethyl) pyridine to 4- (trifluoromethyl) phenylboronic acid to anhydrous potassium carbonate to palladium acetate is 1:1.2:2: 0.02-0.05.

10. The preparation method of the two-dimensional covalent organic framework material with the spherical porous structure, which is characterized in that the molar ratio of the ligand L1 to the iridium trichloride trihydrate is 2.5-4: 1, and the molar volume ratio of the ligand L1 to the ethylene glycol monoethyl ether aqueous solution is 0.0625-0.100 mmol/mL.

Technical Field

The invention belongs to the field of photocatalytic materials, and particularly relates to a preparation method of a two-dimensional covalent organic framework material with a spherical porous structure.

Background

With the decreasing petroleum fuel reserves in nature, the search for new, clean and sustainable alternative new energy sources is a major scientific problem that human beings are urgently required to solve at present. The conversion of solar energy into storable "solar fuels" such as hydrogen energy through artificial photosynthesis is one of the most feasible and sustainable solutions to this challenge. Therefore, research and development of efficient photocatalytic systems for generating hydrogen energy by photo-induced water decomposition has attracted much interest to scientists in the field of energy research. The Covalent Organic Frameworks (COFs) are similar to semiconductor nitrogen carbide and are composed of light elements, so that the Covalent Organic Frameworks are heterogeneous photocatalysts which are cheap and easily available in raw materials, diversified and controllable in synthesized structure and wide in application prospect. Due to the pi electrons in the conjugated plane and the axial charge transmission performance, the COFs material has high carrier mobility, potential high-efficiency light-capturing performance and electron transmission capability. Therefore, in recent years, COFs have become one of the hot research spots in the field of photocatalytic water splitting hydrogen production. However, the synthesis of an efficient photocatalytic COFs tends to be somewhat challenging due to the limited photostability of the catalyst, low crystallinity, and slow multi-electron diffusion-controlled proton reduction process.

Disclosure of Invention

The invention aims to provide a preparation method of a spherical porous two-dimensional covalent organic framework material, and the prepared framework material has stronger visible light response performance and photocatalytic hydrogen production capacity.

In order to solve the technical problem, the invention discloses a preparation method of a two-dimensional covalent organic framework material with a spherical porous structure, which comprises the steps of preparing organic framework material COFs by using 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as raw materials, and modifying the organic framework material COFs by adopting an iridium complex LX1 to obtain the two-dimensional covalent organic framework material with the spherical porous structure.

Further, the preparation method of the organic framework material COFs specifically comprises the following steps: adding 1, 10-phenanthroline-2, 9-dicarbaldehyde, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, mesitylene, 1, 4-dioxane and glacial acetic acid into a pressure pipe, carrying out nitrogen degassing treatment for three times, reacting for 3 days at 100-120 ℃, and washing with tetrahydrofuran after the reaction is finished to obtain the organic framework materials COFs.

Further, the mass ratio of the 1, 10-phenanthroline-2, 9-dicarbaldehyde to the 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine is 1: 1-2.

Further, the mass-volume ratio of the 1, 10-phenanthroline-2, 9-dicarbaldehyde to the glacial acetic acid is 420-460 mg/mL, and the molar mass of the glacial acetic acid is 3 g/mol.

Further, the volume ratio of the mesitylene, the 1, 4-dioxane and the glacial acetic acid is 12.75-25.5: 2.25-4.5: 1.

Further, the iridium complex LX1 is adopted to modify organic framework material COFs, and specifically, the method comprises the following steps:

Furthermore, the mass ratio of the iridium complex LX1 to the organic framework material COFs to the anhydrous sodium carbonate is 1: 4.5-9: 10.6-21.2, and the mass-volume ratio of the organic framework material COFs to the ethylene glycol monoethyl ether is 10-15 mg/mL.

Further, the preparation method of the iridium complex LX1 specifically comprises the following steps:

Further, the molar ratio of 2-bromo-5- (trifluoromethyl) pyridine to 4- (trifluoromethyl) phenylboronic acid to anhydrous potassium carbonate to palladium acetate is 1:1.2:2: 0.02-0.05; the molar volume ratio of the 4- (trifluoromethyl) phenylboronic acid to the ethanol aqueous solution is 0.1 mmol/mL.

Furthermore, the molar ratio of the ligand L1 to the iridium trichloride trihydrate is 2.5-4: 1, and the molar volume ratio of the ligand L1 to the ethylene glycol monoethyl ether aqueous solution is 0.0625-0.100 mmol/mL.

Compared with the prior art, the invention can obtain the following technical effects:

1) the preparation method successfully synthesizes organic framework materials COFs by using a solvothermal method, has mild reaction conditions, and is simple and easy to realize;

2) according to the preparation method, the iridium-containing transition metal complex LX1 is used for functionally modifying the COFs (organic frameworks), so that the light absorption capacity and the electron transmission capacity of the iridium-containing transition metal complex can be enhanced, and the stability of the COFs can be enhanced;

3) the COFs material with the spherical porous structure prepared by the preparation method has higher hydrogen production performance under catalysis of visible light;

4) the method provides reference for preparing other COFs materials.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:

FIG. 1 is an infrared spectrum of COFs prepared in example 1;

FIG. 2 is a solid nuclear magnetic spectrum of the COFs material prepared in example 1;

fig. 3 is a ultraviolet-visible diffuse reflection diagram of two consecutive COFs materials modified by 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TTA) which are raw materials used in the present invention;

FIG. 4 is a diagram of forbidden bandwidths of the COFs and Ir-COFs materials prepared in example 1, wherein a is the COFs and b is the Ir-COFs;

FIG. 5 is a scanning electron microscope image of the COFs and Ir-COFs materials prepared in example 1, wherein a is the COFs and b is the Ir-COFs;

FIG. 6 is a graph of the photocatalytic hydrogen production performance of the COFs and Ir-COFs materials prepared in example 1.

Detailed Description

The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.

The invention discloses a preparation method of a spherical porous structure two-dimensional covalent organic framework material, which specifically comprises the following steps:

step 1, preparing organic framework materials COFs by using 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine as raw materials,

the method specifically comprises the following steps: adding 1, 10-phenanthroline-2, 9-dicarbaldehyde, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, mesitylene, 1, 4-dioxane and glacial acetic acid into a pressure pipe, carrying out nitrogen degassing treatment for three times, reacting for 3 days at 100-120 ℃, and washing with tetrahydrofuran after the reaction is finished to obtain the organic framework materials COFs.

Wherein the mass ratio of the 1, 10-phenanthroline-2, 9-dicarbaldehyde to the 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine is 1: 1-2.

The mass-volume ratio of the 1, 10-phenanthroline-2, 9-dicarbaldehyde to the glacial acetic acid is 420-460 mg/mL, and the molar mass of the glacial acetic acid is 3 g/mol.

Wherein the volume ratio of the mesitylene, the 1, 4-dioxane and the glacial acetic acid is 12.75-25.5: 2.25-4.5: 1.

The specific synthetic route is as follows:

step 2, modifying organic framework materials COFs by adopting iridium complexes LX1 to obtain two-dimensional covalent organic framework materials with spherical porous structures

Step 2.1, preparing an iridium complex LX1, specifically:

Wherein the molar ratio of 2-bromo-5- (trifluoromethyl) pyridine to 4- (trifluoromethyl) phenylboronic acid to anhydrous potassium carbonate to palladium acetate is 1:1.2:2: 0.02-0.05; the molar volume ratio of the 4- (trifluoromethyl) phenylboronic acid to the ethanol aqueous solution is 0.1 mmol/mL.

Wherein the molar ratio of the ligand L1 to the iridium trichloride trihydrate is 2.5-4: 1, and the molar volume ratio of the ligand L1 to the ethylene glycol monoethyl ether aqueous solution is 0.0625-0.100 mmol/mL.

Step 2.2, modifying organic framework material COFs by adopting an iridium complex LX1, which specifically comprises the following steps:

The mass ratio of the iridium complex LX1 to the organic framework material COFs to the anhydrous sodium carbonate is 1: 4.5-9: 10.6-21.2, and the mass volume ratio of the organic framework material COFs to the ethylene glycol monoethyl ether is 10-15 mg/mL.

The synthesis schematic formula of the iridium complex LX1 and the structure modification process of the Ir-COFs material are as follows:

according to the preparation method of the two-dimensional covalent organic framework material with the spherical porous structure, the covalent organic framework material is successfully synthesized by a solvothermal method and is subjected to functional modification, so that the novel covalent organic framework material is successfully obtained, the purification method is simple, and the synthesized Ir-COFs has a good photocatalytic hydrogen production effect under the irradiation of visible light.

The preparation method successfully synthesizes organic framework materials COFs by using a solvothermal method, has mild reaction conditions, and is simple and easy to realize; according to the preparation method, the iridium-containing transition metal complex LX1 is used for functionally modifying the COFs (organic frameworks), so that the light absorption capacity and the electron transmission capacity of the iridium-containing transition metal complex can be enhanced, and the stability of the COFs can be enhanced; the COFs material with the spherical porous structure prepared by the preparation method has higher hydrogen production performance under catalysis of visible light; the method provides reference basis for preparing other COFs materials.

Example 1

Step 1: preparation of organic framework material COFs

Step 1.1: weighing 92mg of 1, 10-phenanthroline-2, 9-diformaldehyde and 92mg of 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine (TTA));

step 1.2: putting the raw materials weighed in the step 1.1 into a pressure pipe, and adding 5.1mL of mesitylene, 0.9mL of 1, 4-dioxane and 0.2mL of 3g/mol glacial acetic acid;

step 1.3: degassing the pressure pipe filled with the raw materials and the solvent in the step 1.2 by using nitrogen for three times, and ensuring that the reaction is carried out under the anhydrous and oxygen-free conditions;

step 1.4: reacting the pressure tube of step 1.3 at a temperature of 120 ℃ for three days;

step 1.5: and (3) washing the product after the reaction in the step (1.4) by using tetrahydrofuran to obtain the two-dimensional COFs material with the spherical porous structure, namely the organic framework material COFs. The infrared spectrum and the solid nuclear magnetic diagram are shown in figure 1 and figure 2.

Step 2: iridium complex LX1 is adopted to modify organic framework material COFs

Step 2.1: weighing 1mmoL of 2-bromo-5- (trifluoromethyl) pyridine, 1.2 mmoL of 4- (trifluoromethyl) phenylboronic acid, 2mmoL of anhydrous potassium carbonate, 0.02mmoL of palladium acetate and 12mL of ethanol aqueous solution (the volume ratio of ethanol to water is 3:1) and adding the mixture into a round-bottom flask;

step 2.2: heating and refluxing the round-bottom flask obtained in the step 2.1 at 80 ℃ for 40 min;

step 2.3: adding brine into the product obtained in the step 2.2, extracting the product with ethyl acetate for four times, and evaporating the product by using a rotary evaporator to dryness to obtain a white solid 5- (trifluoromethyl) -2- (4- (trifluoromethyl) phenyl) pyridine, namely a ligand L1;

step 2.4: weighing 10.5 mmoL of the ligand synthesized in the step 2.3, adding 0.2mmoL of iridium trichloride trihydrate and 8mL of ethylene glycol monoethyl ether aqueous solution (the volume ratio of ethanol to water is 3:1), and heating and refluxing for 24h at 110 ℃ under the protection of nitrogen;

step 2.5: carrying out vacuum filtration on the product obtained in the step 2.4, washing with water, and drying to obtain a yellow solid, namely the iridium complex LX 1;

step 2.6; weighing 110 mg of the iridium complex LX in the step 2.5, and adding 90mg of the organic framework materials COFs in the step 1, 212mg of anhydrous sodium carbonate and 6mL of ethylene glycol monoethyl ether, and heating and refluxing for 24h at 110 ℃ under the condition of nitrogen;

step 2.7: and (3) carrying out vacuum filtration on the product obtained in the step (2.6), washing with water, and drying to obtain the iridium complex LX1 modified Ir-COFs material, namely the two-dimensional covalent organic framework material Ir-COFs with the spherical porous structure. The scanning electron microscope is shown in FIG. 3.

Fig. 1 is an infrared spectrum of the COFs materials prepared in example 1 and 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TTA), which are used as raw materials. As can be seen from FIG. 1, the COFs of the organic framework material is 1620cm^-1A stretching vibration peak appears, from which the formation of carbon-nitrogen double bonds (C ═ N) can be determined, i.e. it is stated that the imine bond skeleton of the material has been formed during synthesis. Further, as can be seen from FIG. 1, the peak of stretching vibration of aldehyde group (-CHO) of 1, 10-phenanthroline-2, 9-dicarbaldehyde as a synthetic raw material was 1700cm^-12,4, 6-tris (4-aminophenyl) -1,3, 5-trisAmino (-NH) groups of oxazines (TTA)₂) Has a characteristic peak of 3341cm^-1. However, according to the infrared spectrogram of the sample, characteristic peaks of aldehyde groups and amino groups disappear in the COFs material, and the fact that the two reaction monomers are subjected to dehydration condensation to form the COFs material with a macromolecular polymerization structure is proved.

FIG. 2 is a solid nuclear magnetic spectrum of the COFs1 material prepared in example 1. It can be observed from fig. 2 that a single peak appears at 169ppm, which is attributable to the characteristic peak of carbon-nitrogen double bonds (C ═ N), and it can be further confirmed that the material synthesized in example 1 is indeed formed by imine bonds. While peaks at 152, 118,135,128 and 143ppm are the carbon atoms of the phenanthroline and benzene ring regions. Meanwhile, a characteristic peak belonging to aldehyde groups at 190ppm was not observed, indicating that aldehyde groups had disappeared in the synthesis of the material by solvothermal method, further demonstrating the successful synthesis of the COFs.

Fig. 3 is a uv-visible diffuse reflectance chart of the raw materials 1, 10-phenanthroline-2, 9-dicarbaldehyde and 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TTA) used in example 1, which modify two consecutive COFs materials. As can be seen from fig. 3, the two COFs materials obtained have significantly improved absorption capacity for visible light compared to the respective monomers. After the iridium complex LX1 is structurally modified, the response performance of the iridium complex LX1 to visible light is obviously improved. The forbidden band widths of the two are respectively 2.13eV and 1.81eV (see FIG. 4). Compared with COFs before structure modification, the Ir-COFs after the iridium complex LX1 structure modification has a narrower forbidden band width, so that the utilization rate of light is higher, and the Ir-COFs can show stronger photocatalytic hydrogen production performance under visible light.

FIG. 5 is a scanning electron microscope image of the COFs and Ir-COFs materials prepared in example 1. As can be seen from fig. 5, the COFs materials synthesized by solvothermal method are spherical porous materials, but have agglomeration phenomenon. In addition, compared with COFs, the Ir-COFs obtained by modifying the iridium complex LX1 structure is dispersed more uniformly, so that the Ir-COFs has larger specific surface and active sites, and the photocatalytic performance of the Ir-COFs is improved.

FIG. 6 is a graph of the photocatalytic hydrogen production performance of the COFs and Ir-COFs materials prepared in example 1. As can be seen from FIG. 6, the two obtained COFs materials have higher photocatalytic hydrogen production capacity under the irradiation of visible light, but the hydrogen production performance of the Ir-COFs material is stronger than that of the COFs, and the result is probably the comprehensive result of the Ir-COFs material which has higher absorption performance on the visible light and uniform particle dispersion and simultaneously takes the iridium complex LX1 as a co-catalyst.

Example 2

Step 1: preparation of organic framework material COFs

Step 1.1: weighing 92mg of 1, 10-phenanthroline-2, 9-diformaldehyde and 184mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TTA));

step 1.2: putting the raw materials weighed in the step 1.1 into a 25mL pressure pipe, and adding 4.2mL mesitylene, 0.84mL 1, 4-dioxane and 0.21mL glacial acetic acid of 3 g/mol;

step 1.4: reacting the pressure tube of step 1.3 at a temperature of 100 ℃ for three days;

Step 2: iridium complex LX1 is adopted to modify organic framework material COFs

Step 2.1: weighing 1mmoL of 2-bromo-5- (trifluoromethyl) pyridine, 1.2 mmoL of 4- (trifluoromethyl) phenylboronic acid, 2mmoL of anhydrous potassium carbonate, 0.03mmoL of palladium acetate and 12mL of ethanol aqueous solution (the volume ratio of ethanol to water is 3:1) and adding the mixture into a round-bottom flask;

step 2.2: heating and refluxing the round-bottom flask obtained in the step 2.1 at 80 ℃ for 40 min;

step 2.4: weighing 10.6 mmoL of the ligand L synthesized in the step 2.3, adding 0.2mmoL of iridium trichloride trihydrate and 6mL of ethylene glycol monoethyl ether aqueous solution (the volume ratio of ethanol to water is 3:1), and heating and refluxing for 24h at 100 ℃ under the protection of nitrogen;

step 2.5: carrying out vacuum filtration on the product obtained in the step 2.4, washing with water, and drying to obtain a yellow solid, namely the iridium complex LX 1;

step 2.6; weighing 110 mg of the iridium complex LX in the step 2.5, and adding 60mg of the organic framework materials COFs in the step 1, 180mg of anhydrous sodium carbonate and 5mL of ethylene glycol monoethyl ether, and heating and refluxing for 24h at 100 ℃ under the condition of nitrogen;

Example 3

Step 1: preparation of organic framework material COFs

Step 1.1: weighing 92mg of 1, 10-phenanthroline-2, 9-diformaldehyde and 138mg of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine (TTA));

step 1.2: putting the raw materials weighed in the step 1.1 into a 25mL pressure pipe, and adding 3.3mL mesitylene, 0.66mL 1, 4-dioxane and 0.22mL glacial acetic acid of 3 g/mol;

step 1.4: reacting the pressure tube of step 1.3 at a temperature of 110 ℃ for three days;

Step 2: iridium complex LX1 is adopted to modify organic framework material COFs

Step 2.1: weighing 1mmoL of 2-bromo-5- (trifluoromethyl) pyridine, 1.2 mmoL of 4- (trifluoromethyl) phenylboronic acid, 2mmoL of anhydrous potassium carbonate, 0.04mmoL of palladium acetate and 12mL of ethanol aqueous solution (the volume ratio of ethanol to water is 3:1) and adding the mixture into a round-bottom flask;

step 2.2: heating and refluxing the round-bottom flask obtained in the step 2.1 at 80 ℃ for 40 min;

step 2.4: weighing 10.8 mmoL of the ligand synthesized in the step 2.3, adding 0.2mmoL of iridium trichloride trihydrate and 8.8mL of ethylene glycol monoethyl ether aqueous solution (the volume ratio of ethanol to water is 3:1), and heating and refluxing for 24h at 90 ℃ under the protection of nitrogen;

step 2.5: carrying out vacuum filtration on the product obtained in the step 2.4, washing with water, and drying to obtain a yellow solid, namely the iridium complex LX 1;

step 2.6; weighing 110 mg of the iridium complex LX in the step 2.5, adding 45mg of the organic framework material COFs in the step 1, 106mg of anhydrous sodium carbonate and 4.5mL of ethylene glycol monoethyl ether, and heating and refluxing for 24 hours at 90 ℃ under the condition of nitrogen;

Example 4

Step 1: preparation of organic framework material COFs

Step 1.1: weighing 92mg of 1, 10-phenanthroline-2, 9-diformaldehyde and 92mg of 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine (TTA));

step 1.2: putting the raw materials weighed in the step 1.1 into a 25mL pressure pipe, and adding 2.55mL mesitylene, 0.45mL 1, 4-dioxane and 0.2mL 3g/mol glacial acetic acid;

step 1.4: reacting the pressure tube of step 1.3 at a temperature of 120 ℃ for three days;

Step 2: iridium complex LX1 is adopted to modify organic framework material COFs

Step 2.1: weighing 1mmoL of 2-bromo-5- (trifluoromethyl) pyridine, 1.2 mmoL of 4- (trifluoromethyl) phenylboronic acid, 2mmoL of anhydrous potassium carbonate, 0.05mmoL of palladium acetate and 12mL of ethanol aqueous solution (the volume ratio of ethanol to water is 3:1) and adding the mixture into a round-bottom flask;

step 2.2: heating and refluxing the round-bottom flask obtained in the step 2.1 at 80 ℃ for 40 min;

step 2.4: weighing 10.7 mmoL of the ligand synthesized in the step 2.3, adding 0.2mmoL of iridium trichloride trihydrate and 10mL of ethylene glycol monoethyl ether aqueous solution (the volume ratio of ethanol to water is 3:1), and heating and refluxing for 24h at 105 ℃ under the protection of nitrogen;

step 2.5: carrying out vacuum filtration on the product obtained in the step 2.4, washing with water, and drying to obtain a yellow solid, namely the iridium complex LX 1;

step 2.6; weighing 110 mg of iridium complex LX in the step 2.5, and adding 80mg of organic framework materials COFs in the step 1, 120mg of anhydrous sodium carbonate and 5.7mL of ethylene glycol monoethyl ether, and heating and refluxing for 24h at 105 ℃ under the condition of nitrogen;

While the foregoing description shows and describes several preferred embodiments of the invention, it is to be understood, as noted above, that the invention is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.

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