阅读说明：本技术 一种含咔唑结构单元的多孔芳香骨架材料及其制备方法和应用 (Porous aromatic skeleton material containing carbazole structural unit and preparation method and application thereof ) 是由 夏立新 张红翠 闫卓君 布乃顺 邵慧敏 杨东奇 许彦梅 郑桂月 于 2019-09-18 设计创作，主要内容包括：本发明属于化学新材料技术领域,具体涉及一种含咔唑结构单元的多孔芳香骨架材料,包括如下步骤：在氮气条件下,将含有溴基的咔唑类有机化合物与1,3,5-三乙炔基苯置于反应容器中,加入催化剂、有机溶剂80℃反应3天；待反应结束后,冷却到室温,分别用N,N’-二甲基甲酰胺、四氢呋喃、丙酮、二氯甲烷和甲醇多次洗涤,得到粗产品；再用四氢呋喃、二氯甲烷和甲醇对粗产品进行索氏提取；在90℃真空干燥10小时,得到多孔芳香骨架材料LNUs。本发明采用廉价的单体,反应条件温和,可以在一个反应器皿中一步完成。合成方法具有广泛的适用性。本发明得到的含咔唑结构单元的多孔芳香骨架材料可用于核废料中放射性碘的捕获,具有很好的应用前景。(The invention belongs to the technical field of new chemical materials, and particularly relates to a porous aromatic skeleton material containing a carbazole structural unit, which comprises the following steps: under the condition of nitrogen, putting carbazole organic compounds containing bromo and 1,3, 5-triethynyl benzene into a reaction vessel, adding a catalyst and an organic solvent, and reacting for 3 days at 80 ℃; after the reaction is finished, cooling to room temperature, and respectively washing with N, N' -dimethylformamide, tetrahydrofuran, acetone, dichloromethane and methanol for multiple times to obtain a crude product; then carrying out Soxhlet extraction on the crude product by using tetrahydrofuran, dichloromethane and methanol; vacuum drying at 90 deg.C for 10 hr to obtain porous aromatic skeleton material LNUs. The invention adopts cheap monomers, has mild reaction conditions and can be completed in one reaction vessel in one step. The synthesis method has wide applicability. The porous aromatic skeleton material containing the carbazole structural unit can be used for capturing radioactive iodine in nuclear waste, and has a good application prospect.)

1. A porous aromatic skeleton material containing carbazole structural units is characterized in that carbazole organic monomers with different structures and 1,3, 5-triethylalkynyl benzene are used as building elements, and Sonogashira-Hagihara coupling reaction is utilized to obtain the porous aromatic skeleton material LNUs containing carbazole structural units under the catalysis of tetrakis (triphenylphosphine) palladium and cuprous iodide.

2. The porous aromatic scaffold material containing carbazole structural units according to claim 1, having the following structural formula:

3. the method for preparing a porous aromatic skeleton material containing carbazole structural units according to claim 2, comprising the steps of: under the condition of nitrogen, putting carbazole organic compounds containing bromo and 1,3, 5-triethynyl benzene into a reaction vessel, adding a catalyst and an organic solvent, and reacting for 3 days at 80 ℃; after the reaction is finished, cooling to room temperature, and respectively washing with N, N' -dimethylformamide, tetrahydrofuran, acetone, dichloromethane and methanol for multiple times to obtain a crude product; then carrying out Soxhlet extraction on the crude product by using tetrahydrofuran, dichloromethane and methanol; vacuum drying at 90 deg.C for 10 hr to obtain porous aromatic skeleton material LNUs.

4. The method for preparing a porous aromatic skeleton material containing carbazole structural units according to claim 3, wherein the organic carbazole compound containing bromo is 3, 6-dibromo-9-phenylcarbazole, 2, 7-dibromocarbazole or 3, 6-dibromocarbazole.

5. The method for preparing a porous aromatic skeleton material containing carbazole structural units according to claim 3, wherein the molar ratio of carbazole organic compounds containing bromo groups is: 1,3, 5-triethynylbenzene ═ 3: 2.

6. the method for preparing a porous aromatic skeleton material containing carbazole structural units according to claim 3, wherein the catalyst is a mixture of cuprous iodide and tetrakis (triphenylphosphine) palladium.

7. The method for preparing a porous aromatic skeleton material containing carbazole structural units according to claim 6, wherein the ratio of cuprous iodide: tetrakis (triphenylphosphine) palladium ═ 1: 3-5.

8. The method for preparing a porous aromatic skeleton material containing carbazole structural units according to claim 3, wherein the organic solvent is a mixture of anhydrous N, N' -dimethylformamide and anhydrous triethylamine.

9. Use of a porous aromatic skeleton material comprising carbazole structural units according to claim 1 as a solid adsorbent for capturing radioactive iodine.

10. Use according to claim 9, characterized in that the method is as follows: placing the porous aromatic skeleton material containing carbazole structural units as claimed in claim 1 and solid iodine or iodine solution in a closed system to adsorb iodine.

Technical Field

The invention belongs to the technical field of new chemical materials, and particularly relates to a porous aromatic skeleton material containing a carbazole structural unit, and a preparation method and application thereof.

Background

With the increasing demand of society for energy, the utilization of nuclear energy is also more and more emphasized in the daily life of human beings. A key issue today is how to safely and efficiently process nuclear waste generated from the nuclear fission of uranium fuel. Compared with solid radioactive wastes, the gaseous radioactive wastes have larger pollution area and stronger harm because of having great fluidity and being easy to move along with the airflow. Radioactive iodine has been a research hotspot for scientists because of its very long half-life (1.57 × 10)⁷Years) and can affect the human metabolic response and thus cause physical harm. Therefore, enrichment and storage of gaseous iodine in nuclear power plants has become the most important issue in radioactive waste gas treatment worldwide.

The solid phase adsorption method is the most commonly used method for enriching and storing radioactive gas iodine, and the currently adopted technology for capturing iodine vapor mainly uses zeolite molecular sieves and metal organic framework materials as iodine adsorbents. However, these solid adsorbents have their own drawbacks, such as lower adsorption capacity and poor thermochemical stability, which limit their further applications. Porous aromatic matrix materials are a recently developed class of highly crosslinked, nanoporous polymers. They have low framework density, continuous porosity and high thermochemical stability, so that the porous aromatic framework material has wide application prospects in the fields of gas adsorption, separation, heterogeneous catalysis and the like.

Carbazole is an important nitrogen-containing heterocyclic compound, is relatively stable to heat, acid and alkali, has a rigid main chain and a conjugated electron-rich system, is beneficial to forming a permanent porous material, and has a nitrogen-containing structure which can enhance the interaction between an adsorbate and an adsorbent, so that the adsorption capacity of the carbazole on guest molecules is improved. The invention adopts 1,3, 5-triethylalkynyl benzene and carbazole monomers with different structures as construction elements, prepares a porous aromatic skeleton material containing carbazole structural units through Sonogashira-Hagihara coupling reaction, and systematically characterizes the structure and the performance through analysis methods such as Fourier transform infrared spectroscopy, thermogravimetric analysis, powder X-ray diffraction, a scanning electron microscope, a transmission electron microscope and the like. The porous aromatic skeleton material has excellent thermochemical stability, simultaneously has a large number of carbazole structural units and rich acetylene bonds, and has a unique skeleton structure which is very favorable for increasing the interaction force between the material and iodine molecules, so that the porous aromatic skeleton material is used as a stable and high-capacity novel solid adsorbent for capturing radioactive iodine in nuclear waste.

Disclosure of Invention

The invention aims to provide a simple and feasible preparation method of a porous aromatic skeleton material containing a carbazole structural unit and application of the porous aromatic skeleton material to radioactive iodine capture.

In order to achieve the purpose, the invention adopts the technical scheme that: a porous aromatic skeleton material LNus containing carbazole structural units is obtained by taking carbazole organic monomers with different structures and 1,3, 5-triethylalkynyl benzene as building elements and utilizing a Sonogashira-Hagihara coupling reaction under the catalysis of tetrakis (triphenylphosphine) palladium and cuprous iodide.

The porous aromatic skeleton material containing the carbazole structural unit has the following structural formula:

the preparation method of the porous aromatic skeleton material containing the carbazole structural unit comprises the following steps: under the condition of nitrogen, putting carbazole organic compounds containing bromo and 1,3, 5-triethynyl benzene into a reaction vessel, adding a catalyst and an organic solvent, and reacting for 3 days at 80 ℃; after the reaction is finished, cooling to room temperature, and respectively washing with N, N' -dimethylformamide, tetrahydrofuran, acetone, dichloromethane and methanol for multiple times to obtain a crude product; then carrying out Soxhlet extraction on the crude product by using tetrahydrofuran, dichloromethane and methanol; vacuum drying at 90 deg.C for 10 hr to obtain porous aromatic skeleton material LNUs.

In the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the carbazole organic compound containing the bromo group is 3, 6-dibromo-9-phenylcarbazole, 2, 7-dibromocarbazole or 3, 6-dibromocarbazole.

According to the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the carbazole organic compound containing the bromo group is prepared by the following steps of: 1,3, 5-triethynylbenzene ═ 3: 2.

in the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the catalyst is a mixture of cuprous iodide and tetrakis (triphenylphosphine) palladium.

The preparation method of the porous aromatic skeleton material containing the carbazole structural unit comprises the following steps of (by mass ratio): tetrakis (triphenylphosphine) palladium ═ 1: 3-5.

In the preparation method of the porous aromatic skeleton material containing the carbazole structural unit, the organic solvent is a mixture of anhydrous N, N' -dimethylformamide and anhydrous triethylamine.

The application of the porous aromatic skeleton material containing the carbazole structural unit as a solid adsorbent in capturing radioactive iodine.

The application and the method are as follows: and (3) placing the porous aromatic skeleton material containing the carbazole structural unit and solid iodine or iodine solution in a closed system to adsorb iodine.

The invention has the beneficial effects that:

1. the invention adopts cheap monomers, has mild reaction conditions and can be completed in one reaction vessel in one step.

2. The synthesis method adopted by the invention has wide applicability.

3. The porous aromatic skeleton material containing the carbazole structural unit prepared by the invention can be used for capturing radioactive iodine in nuclear waste, and has a good application prospect.

Drawings

FIG. 1 a: the infrared spectrogram of the porous aromatic skeleton material LNU-12 synthesized by the method and the reaction monomer;

FIG. 1 b: the infrared spectrogram of the porous aromatic skeleton material LNU-13 synthesized by the method and the reaction monomer;

FIG. 1 c: the infrared spectrogram of the porous aromatic skeleton material LNU-14 synthesized by the method and the reaction monomer;

FIG. 2: the thermogravimetric curve of the porous aromatic skeleton material synthesized by the invention;

FIG. 3: powder X-ray diffraction patterns of the synthetic porous aromatic matrix materials of the present invention;

FIG. 4: scanning electron micrographs of the porous aromatic skeleton material synthesized by the invention;

wherein, a is LNU-12; LNU-13; LNU-14;

FIG. 5: a transmission electron microscope image of the porous aromatic skeleton material synthesized by the invention;

wherein, a is LNU-12; LNU-13; LNU-14;

FIG. 6: the iodine adsorption curve chart of the porous aromatic skeleton material synthesized by the invention;

FIG. 7: the adsorption process of the porous aromatic skeleton material synthesized by the invention in iodine normal hexane solution;

wherein, a is LNU-12; LNU-13; LNU-14;

FIG. 8: the thermogravimetric curve of the porous aromatic skeleton material synthesized by the invention after iodine adsorption;

FIG. 9: the iodine release diagram of the porous aromatic skeleton material synthesized by the invention after absorbing iodine;

Detailed Description