Synthetic method of organic molecular cage porous material

Abstract

The invention discloses a synthesis method of an organic molecular cage porous material, which comprises the following steps: S1, adding triphenylphosphine trialdehyde and 1, 3, 5, 7-tetra (4-benzylamino)-adamantane into a glass reaction tube according to a molar ratio of 4: 3, then adding 1, 4-dioxane, adding acetic acid in an ultrasonic state, circularly freezing and extracting for three times, sealing the glass reaction tube with flame, and carrying out suction filtration, washing and drying to obtain an organic molecular cage porous material; standing and reacting at 115-125 DEG C for 3-4 days, filtering to remove small molecular impurities, and drying in vacuum to obtain an intermediate; s2, dissolving the intermediate in chloroform, adding a mixed solution of sodium borohydride and methanol at the temperature of 0 DEG C, stirring for reaction, and purifying after reaction to obtain the organic molecular cage porous material. The invention provides a synthesis method of an organic molecular cage porous material. The finally obtained organic molecular cage porous material with a molecular cage structure can be used as a carrier of a noble metal catalyst.

Description

Technical Field

[0001] The invention relates to the technical field of nanomaterials, and in particular to a method for synthesizing an organic molecular cage porous material. Background Art

[0002] Porous materials are a type of material with a two-dimensional or three-dimensional network structure. The development of porous materials has gone through the process from traditional inorganic porous materials (such as zeolites) to inorganic-organic hybrid materials MOFs, and then to the organic porous materials that have emerged in the past decade. Organic porous materials include: covalent organic framework materials COFs, organic porous polymers POPs and organic porous molecular cages POCs. They have the advantages of large specific surface area, stable physical and chemical properties, a wide range of monomer selection, and strong designability. Therefore, organic porous materials can be used in gas adsorption and separation, environment, energy, medicine, biology, catalysis and other fields.

[0003] Unlike organic porous materials with continuous skeletons, porous crystalline materials composed of discrete organic molecules are relatively rare. Porous organic cages need to rely on weak intermolecular interactions (π-π, CH···π, van der Waals forces, etc.) to form crystalline materials to maintain porosity. The specific surface area of ​​these materials is not inferior to many traditional porous materials.

[0004] In addition to forming porous materials through self-stacking, organic molecular cages can also be used as monomers to synthesize porous materials. In recent years, people have found that organic molecular cages with "pre-porous" structures can form cage-based porous materials with continuous skeletons through coordination bonds, covalent bonds and hydrogen bonds. Such materials have been widely used in host-guest chemistry, catalysis, adsorption and separation.

[0005] The invention provides a method for synthesizing an organic molecular cage porous material. The synthesized material has a stable porous structure and can be used as an excellent carrier of a noble metal catalyst. Summary of the invention

[0006] In view of the above technical problems, the present invention provides a method for synthesizing an organic molecular cage porous material.

[0007] Technical solution: A method for synthesizing an organic molecular cage porous material comprises the following steps: S1: Triphenylphosphine trialdehyde and 1,3,5,7-tetrakis(4-benzylamino)-adamantane were added into a glass reaction tube at a molar ratio of 4:3, and then 1,4-dioxane was added. Acetic acid was added under ultrasonic conditions, and the reaction was performed three times by freezing extraction. The glass reaction tube was sealed with a flame, and the reaction was allowed to stand at 115-125°C for 3-4 days. After filtering, small molecular impurities were removed, and the intermediate was obtained by vacuum drying. S2: dissolving the intermediate in chloroform, adding a mixed solution of sodium borohydride and methanol at 0°C, stirring for reaction, and purifying after the reaction to obtain the organic molecular cage porous material.

[0008] Furthermore, the structural formula of the triphenylphosphine trialdehyde is as follows: .

[0009] Furthermore, the structural formula of the 1,3,5,7-tetrakis(4-benzylamino)-adamantane is as follows: .

[0010] Furthermore, the molar concentration of triphenylphosphine trialdehyde in 1,4-dioxane is 0.05-0.5 mol / L.

[0011] Furthermore, the molar ratio of triphenylphosphine trialdehyde to acetic acid is 1:1-1.5.

[0012] Furthermore, the solid obtained by filtration is washed multiple times with DMF, and then stripped with THF for 10-20 hours, and then dried.

[0013] Furthermore, the drying temperature is 60-80°C.

[0014] Furthermore, the molar ratio of the sodium borohydride to triphenylphosphine trialdehyde is 10-30:1.

[0015] Beneficial effects: The present invention provides a method for synthesizing an organic molecular cage porous material, wherein the aldehyde group on triphenylphosphine trialdehyde and the amine group of 1,3,5,7-tetrakis(4-benzylamino)-adamantane are dehydrated to construct an imine bond, and finally an organic molecular cage porous material with a molecular cage structure is obtained. The structure has a relatively large number of rigid phenyl groups and a rigid support structure of adamantane, and the structure is stable, and can be used as a carrier of a noble metal catalyst. DETAILED DESCRIPTION

[0016] The present invention is described in detail below.

[0017] Embodiment 1: A method for synthesizing an organic molecular cage porous material comprises the following steps: S1: Add triphenylphosphine trialdehyde (500 mg, 1.44 mmol) and 1,3,5,7-tetrakis(4-benzylamino)-adamantane (542 mg, 1.08 mmol) into a glass reaction tube, then add 3 mL of 1,4-dioxane, add 100 μL of acetic acid under ultrasonication, cycle freeze extraction three times, flame seal the glass reaction tube, and react at 120°C for 3 days. The filtered solid is washed with DMF for several times, and then extracted with THF for 10-20 hours. After the extraction, it is dried at 70°C to obtain an intermediate; S2: The intermediate was dissolved in 10 mL of chloroform, and a mixed solution of 1.3 g of sodium borohydride and methanol (20 mL) was added at 0°C, and the mixture was stirred for reaction. After the reaction, the mixture was extracted with DCM, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and purified by column chromatography to obtain the organic molecular cage porous material.

[0018] The structural formula of triphenylphosphine trialdehyde is as follows: ; The structural formula of 1,3,5,7-tetrakis(4-benzylamino)-adamantane is as follows: .

[0019] Embodiment 2: 100 mg of the organic molecular cage porous material prepared in Example 1 was dispersed in 10 mL of methanol, and 0.05 mol of K2PdCl4 or K2PtCl4 or HAuCl4 was added. The mixture was stirred at room temperature for 24 h, and then 2 mL of NaBH4 in MeOH (2 M) was added dropwise for reduction. The mixture was stirred for 2 h, and washed by centrifugation with MeOH and H2O. The lower solid was collected and dried in vacuo at 65 °C for 12 h to obtain a noble metal-loaded supported catalyst with yields of 95%, 83% and 90%, respectively. The contents of Pd, Pt and Au determined by ICP were 2.7 wt%, 3.3 wt% and 4.8 wt%, respectively.

[0020] Embodiment 3: Weigh 100 mg of the organic molecular cage porous material prepared in Example 1 and 10 mg of PdCl2 into a reaction bottle, add 50 mL of acetonitrile under nitrogen atmosphere, stir at 80 °C for 12 h, collect the lower layer of solid by centrifugation, extract with acetone for 12 h, and dry in vacuo at 65 °C to obtain a solid with a yield of 96.1%. The Pd content in the material determined by ICP was 3.8 wt%.

[0021] Although the present invention has been disclosed as above in terms of preferred embodiments, they are not intended to limit the present invention. Anyone skilled in the art can make various changes or modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection defined by the claims of this application.

Claims

1. A method for synthesizing an organic molecular cage porous material, characterized in that: The following steps are involved: S1: Triphenylphosphine trialdehyde and 1,3,5,7-tetrakis(4-benzylamino)-adamantane were added into a glass reaction tube at a molar ratio of 4:3, and then 1,4-dioxane was added. Acetic acid was added under ultrasonic conditions, and the reaction was performed three times by freezing extraction. The glass reaction tube was sealed with a flame, and the reaction was allowed to stand at 115-125°C for 3-4 days. After filtering, small molecular impurities were removed, and the intermediate was obtained by vacuum drying. S2: dissolving the intermediate in chloroform, adding a mixed solution of sodium borohydride and methanol at 0°C, stirring for reaction, and purifying after the reaction to obtain the organic molecular cage porous material.

2. The method for synthesizing an organic molecular cage porous material according to claim 1, characterized in that: The structural formula of the triphenylphosphine trialdehyde is as follows: ； The structural formula of the 1,3,5,7-tetrakis(4-benzylamino)-adamantane is as follows: 。 3. The method for synthesizing an organic molecular cage porous material according to claim 2, characterized in that: The molar concentration of the triphenylphosphine trialdehyde in 1,4-dioxane is 0.05-0.5 mol / L.

4. The method for synthesizing an organic molecular cage porous material according to claim 3, characterized in that: The molar ratio of triphenylphosphine trialdehyde to acetic acid is 1:1-1.

5.

5. The method for synthesizing an organic molecular cage porous material according to claim 3 or 4, characterized in that: The solid obtained by filtration is washed with DMF for multiple times, and then stripped with THF for 10-20 hours, and then dried.

6. The method for synthesizing an organic molecular cage porous material according to claim 5, characterized in that: The drying temperature is 60-80°C.

7. The method for synthesizing an organic molecular cage porous material according to claim 6, characterized in that: The molar ratio of the sodium borohydride to triphenylphosphine trialdehyde is 10-30:1.

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