CN-121975077-A - Pyrazinyl nitrogen-rich hydrophobic porous organic cage material, and preparation method and application thereof

Abstract

The invention discloses a pyrazinyl nitrogen-rich hydrophobic porous organic cage material, and a preparation method and application thereof, and belongs to the technical field of porous organic cage materials. The invention uses resorcinol calix [4] arene, pyrazine-2, 5-diamine, organic solvent and the like to react to obtain the pyrazinyl nitrogen-rich hydrophobic porous organic cage material. The nitrogen-rich pyrazine ring is introduced into the material to enhance the adsorption capacity to SF 6 , and the isobutyl is introduced to endow the material with stronger hydrophobicity, so that the material keeps stable structure and unchanged adsorption performance under high humidity. The obtained material has good water and chemical stability, the SF 6 adsorption capacity under the conditions of normal temperature and normal pressure of 25 o C and 1 bar is up to 53.6 cm 3 g ‑1 ,SF 6 , and the nitrogen (N 2 ) adsorption capacity ratio reaches 20.02 recorded by the wound record, and the adsorption capacity ratio reaches the highest value in all the porous organic cage materials reported at present. The pyrazinyl nitrogen-rich hydrophobic porous organic cage material provides a new idea for efficient adsorption separation of SF 6 .

Inventors

• LIU XIONGLI
• LIU MINGXUAN
• DONG ALIDEERTU
• Guo Ajie
• WANG FEIYAN
• GU XIAOJUAN
• WANG XIAOYU
• DU YIXIAN

Assignees

• 内蒙古大学

Dates

Publication Date

20260505

Application Date

20260129

Claims (9)

1. 1. A pyrazinyl nitrogen-rich hydrophobic porous organic cage material is characterized in that the porous organic cage material is named IMUPOC-DA and has the following structural formula 。
2. 2. The method for preparing the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 1, wherein two organic ligands of hydrophobic organic ligand resorcinol calix [4] arene and nitrogen-rich organic ligand pyrazine-2, 5 diamine are dissolved in a solvent, and brownish red powder is prepared through solvothermal reaction, wherein the reaction path is as follows 。
3. 3. The method for preparing the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 2, wherein the molar ratio of the hydrophobic organic ligand resorcinol calix [4] arene to the nitrogen-rich organic ligand pyrazine-2, 5 diamine is 1:2.
4. 4. The method for preparing the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 2, wherein the reaction temperature is 65-120 o ℃ and the reaction time is 1-60 h.
5. 5. The method for preparing the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 2, wherein the organic solvent comprises but is not limited to chloroform, o-xylene and m-xylene.
6. 6. The method for preparing the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 2, wherein the mixing mode includes but is not limited to one of stirring and ultrasound.
7. 7. The method for preparing the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to any one of claims 2 to 6, further comprising the steps of cooling the reaction to room temperature, filtering, washing the product with methanol, and drying in an oven to remove residual solvent to obtain a solid porous organic cage material product.
8. 8. The use of the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 1, wherein the pyrazinyl nitrogen-rich hydrophobic porous organic cage material is used for SF 6 adsorption.
9. 9. The use of the pyrazinyl nitrogen-rich hydrophobic porous organic cage material according to claim 8, wherein the SF 6 adsorption capacity is up to 53.6 cm 3 g -1 ,SF 6 and the N 2 adsorption capacity ratio is up to 20.02 at normal temperature and pressure 25 o C, 1 bar.

Description

Pyrazinyl nitrogen-rich hydrophobic porous organic cage material, and preparation method and application thereof Technical Field The invention belongs to the technical field of porous organic cage materials, and particularly relates to a pyrazinyl nitrogen-rich hydrophobic porous organic cage material, a preparation method thereof and application of the material in adsorption separation of sulfur hexafluoride. Background Sulfur hexafluoride (SF 6) is widely used in critical industrial fields such as very large scale integrated circuit manufacturing and high voltage power transmission and distribution equipment due to its excellent electrical insulation and arc extinguishing properties. However, SF 6 is also a powerful greenhouse gas, its global warming potential is 23900 times that of carbon dioxide, and it is stable in the atmosphere for about 3200 years. With the increasing strictness of global 'two carbon' targets and environmental regulations, the reduction of SF 6 and the efficient recycling become an urgent global environmental challenge. Therefore, the development of the efficient and sustainable SF 6 separation and recovery technology has important practical significance. At present, the treatment modes of waste gas containing SF 6 in the industry are mainly divided into two types, namely an incineration degradation method, in which SF 6 is decomposed through high-temperature calcination, but toxic and harmful byproducts such as hydrofluoric acid are generated in the process, secondary environmental pollution is easily caused, and a mixed gas substitution technology, in which SF 6 is mixed with gases such as N 2 and carbon dioxide (CO 2) to reduce the dosage of SF 6, but the dilution strategy can only reduce the emission increment and can not fundamentally solve the pollution problem of SF 6. In contrast, the adsorption separation technology based on the porous material has the core advantages of high selectivity and low energy consumption, becomes a high-efficiency green gas purification separation method, and has very attractive application potential in the field of mixed gas separation such as SF 6/N2. Porous organic materials such as Metal Organic Frameworks (MOFs), porous Organic Cages (POCs) and the like have the advantages of high specific surface area, abundant active sites, adjustable framework structures, easily functionalized pore channels and the like, and are widely applied to the fields of gas storage and separation, catalysis, water treatment and the like. However, in the separation process of SF 6/N2 mixed gas, a large amount of moisture is usually present in the pretreatment stage, but most MOFs materials are easy to collapse in structure under a high humidity environment, and cannot realize the unification of adsorption capacity and water stability. Therefore, whether SF 6 can be efficiently adsorbed in a high humidity environment remains an urgent problem to be solved. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a method for efficiently adsorbing SF 6 under the condition of industrial application. The invention provides a nitrogen-rich POC material constructed by taking a nitrogen-rich ligand pyrazine-2, 5-diamine as a structural element for the first time for SF 6 adsorption separation under the industrial application condition. The nitrogen-rich pyrazine ring is introduced into the material to enhance the adsorption capacity to SF 6, and the isobutyl is introduced to endow the material with stronger hydrophobicity, so that the material has stable structure under high humidity and the adsorption capacity is not reduced. The obtained material has good water and chemical stability, the SF 6 adsorption capacity at normal temperature and normal pressure (25 o C,1 bar) is up to 53.6 cm 3 g-1,SF6, and the N 2 adsorption capacity ratio reaches 20.02 recorded by the creation, and the adsorption capacity ratio is the highest value in all the porous organic cage materials reported at present. In addition, after 5 consecutive adsorption cycles, no decay of the adsorption capacity of the material occurred. In conclusion, the novel nitrogen-rich POCs material is beneficial to solving the problems of poor adsorption capacity, poor water and chemical stability, high energy consumption, poor cycle performance and the like of the conventional SF 6 adsorption material. In order to achieve the above object, the present invention provides the following technical solutions: a pyrazinyl nitrogen-rich hydrophobic porous organic cage material is characterized in that the porous organic cage material is named IMUPOC-DA and has the following structural formula 。 The invention also provides a preparation method of the pyrazinyl nitrogen-rich hydrophobic porous organic cage material, which comprises the steps of dissolving two organic ligands of hydrophobic organic ligand resorcinol calix [4] arene and nitrogen-rich organic ligand pyrazine-2, 5 diamine in a