Search

CN-121991323-A - Preparation method of porous aromatic framework material containing thiophene ring and adsorption application of sulfur dioxide and sulfur hexafluoride

CN121991323ACN 121991323 ACN121991323 ACN 121991323ACN-121991323-A

Abstract

The invention discloses a preparation method of a porous aromatic skeleton material containing thiophene rings and adsorption application of sulfur dioxide and sulfur hexafluoride, and belongs to the technical field of porous organic material polymers. According to the invention, the porous organic polymer IMU-PAF-S with high BET specific surface area is synthesized for the first time, and the S site of the thiophene ring in the material can effectively improve the adsorption capacity of SF 6 and SO 2 . The obtained material has good thermal and chemical stability, and the adsorption capacity of SF 6 and SO 2 reaches 79.1 cm 3 g ‑1 and 333 cm 3 g ‑1 under normal temperature and normal pressure (25 ℃ and 1 bar), and the adsorption capacity of the two gases creates the highest record in the reported porous organic material. The porous aromatic framework material containing the thiophene ring provides a new idea for efficiently adsorbing SF 6 and SO 2 .

Inventors

  • LIU XIONGLI
  • YAN XU
  • DONG ALIDEERTU
  • WANG XIAOYU
  • LIU MINGXUAN
  • DU YIXIAN
  • GU XIAOJUAN
  • WANG FEIYAN

Assignees

  • 内蒙古大学

Dates

Publication Date
20260508
Application Date
20260318

Claims (10)

  1. 1. The preparation method of the porous aromatic framework material containing the thiophene ring is characterized by comprising the following steps: 1) Under the protection of nitrogen, adding a thiophene ring-containing compound, 2-bipyridine, a catalyst and an organic solvent into a reaction container, and uniformly mixing to perform a reaction; 2) After the reaction is finished, hydrochloric acid is added into the reaction container, stirring is continued for 12 hours, after the stirring is finished, a reaction system is filtered, the obtained solid is leached by adopting low-boiling-point organic solvents such as tetrahydrofuran and the like, soxhlet extraction is carried out, and then the treated solid is placed into an oven for drying, so that residual solvents are removed, and a target solid product is obtained; In the step 1), the thiophene ring-containing compound is 2,5,8, 11-tetrabromo-cycloocta [1,2-b:4,3-b ':5,6-b ':8,7-b ' ] tetrathiophene, and the thiophene ring-containing compound has the following structure: 。
  2. 2. The preparation method of the porous aromatic framework material containing the thiophene ring according to claim 1, wherein the molar ratio of the thiophene ring-containing compound to 2-2 bipyridine in the step 1) is 1 (1-10).
  3. 3. The method for preparing a porous aromatic skeleton material containing thiophene rings according to claim 1, wherein the organic solvent in step 1) includes, but is not limited to, 1, 5-cyclooctadiene, ultra-dry tetrahydrofuran, and ultra-dry N, N-dimethylformamide.
  4. 4. The preparation method of the porous aromatic framework material containing the thiophene ring, which is characterized in that in the step 1), the thiophene ring-containing compound, 1, 5-cyclooctadiene, ultra-dry tetrahydrofuran and ultra-dry N, N-dimethylformamide are respectively and independently added, wherein the mass ratio of (1-10) to (300-500) to (200-500) is 1.
  5. 5. The method for preparing a porous aromatic skeleton material containing thiophene rings according to claim 1, wherein the catalyst in step 1) is bis (1, 5-cyclooctadiene) nickel.
  6. 6. The method for preparing a porous aromatic skeleton material containing thiophene rings according to claim 1, wherein the molar ratio of the thiophene ring-containing compound to bis (1, 5-cyclooctadiene) nickel in the step 1) is 1 (1-10).
  7. 7. The method for preparing the porous aromatic skeleton material containing the thiophene ring according to claim 1, wherein the reaction vessel in the step 1) comprises, but is not limited to, a glass bottle, a round bottom flask or a pressure-resistant bottle, and the mixing mode comprises, but is not limited to, stirring and ultrasonic treatment.
  8. 8. The method for preparing the porous aromatic skeleton material containing the thiophene ring according to claim 1, wherein the reaction temperature in the step 1) is 20-150 ℃ and the reaction time is 6-96 h.
  9. 9. The preparation method of the porous aromatic framework material containing the thiophene ring, which is disclosed in claim 1, is characterized in that in the step 2), the concentration of hydrochloric acid is 1-12M, the stirring mode comprises but is not limited to magnetic stirring, the reaction system is filtered after the stirring is completed, the obtained solid is leached by adopting low-boiling-point organic solvents such as tetrahydrofuran, the volume ratio of the solvent to the solid is 1:1, and the solid powder obtained through suction filtration is dried by a baking oven at 80-150 ℃ to 12 h.
  10. 10. Use of a porous aromatic framework material containing thiophene rings obtained by the method according to any one of claims 1-9, characterized in that the adsorption for SF 6 and SO 2 reaches 79.1 cm 3 g -1 and 333cm 3 g -1 at a temperature of 25 ℃ and a pressure of 1 bar at the adsorption of SF 6 and SO 2 .

Description

Preparation method of porous aromatic framework material containing thiophene ring and adsorption application of sulfur dioxide and sulfur hexafluoride Technical Field The invention belongs to the technical field of porous organic material polymers, and particularly relates to a preparation method of a porous aromatic skeleton material containing thiophene rings and application of sulfur dioxide and sulfur hexafluoride adsorption. Background Sulfur hexafluoride (SF 6) is an important base material in the fields of semiconductor manufacturing, integrated circuit processing, electrical equipment, etc., as a typical electron specialty gas. SF 6 has excellent chemical stability, electrical insulation property, electronegativity and other characteristics, and is widely applied to plasma etching and cleaning in the manufacturing process of electronic devices and insulating and arc extinguishing media in high-voltage electrical equipment. SF 6, a strong greenhouse gas, has a global warming potential of approximately 23900 times that of carbon dioxide (CO 2) and can have serious adverse environmental effects if leaked or discharged during the production, use and recovery of SF 6. Therefore, developing a stable adsorption material suitable for efficient capture and recovery of SF 6 is of great importance for reducing the environmental risk thereof. In addition, another sulfur-containing gas, sulfur dioxide (SO 2), is one of the major components in flue gas pollutants, widely derived from industrial processes such as fossil fuel combustion, industrial exhaust emissions, and metal smelting. SO 2 is easy to cause environmental problems such as acid rain, haze and the like in the discharge process, and has adverse effects on human health, for example, the occurrence risk of diseases of respiratory system and cardiovascular system is increased. Therefore, developing stable adsorption materials suitable for high-efficiency capture and recovery of SO 2 is of great significance in reducing SO 2 emissions, reducing environmental risks and improving environmental friendliness of industrial processes. In the prior industry, methods of recycling, purifying, decomposing and the like are mainly adopted for treating sulfur hexafluoride (SF 6). The recovery, purification and cryogenic separation process has the advantages of complex equipment, high energy consumption, limited treatment efficiency on SF 6, high operation cost of a plasma decomposition technology, and difficulty in realizing recycling mainly by harmless treatment. The removal and control of SO 2 in existing industrial processes is mainly dependent on chemical adsorption or chemical absorption techniques, and pollutant removal is usually achieved by chemical reaction of an alkaline adsorbent with SO 2. Although the method has higher removal efficiency, most of the adsorption processes are irreversible reactions, the adsorbent is difficult to realize effective regeneration after the reaction, and the adsorbent is generally required to be replaced integrally or subjected to complex treatment, so that the method is unfavorable for recycling of resources and long-term stable operation. The porous organic framework material has the structural characteristics of high specific surface area, large porosity, adjustable pore size distribution and the like, can provide sufficient adsorption sites for gas molecules, and is beneficial to improving the adsorption capacity of the unit-mass material. Meanwhile, the framework structure of the material can be regulated and controlled through molecular design, so that the selective adsorption of specific gas is realized. Disclosure of Invention Aiming at the defects of the prior art, the invention aims to provide a porous aromatic framework material with high adsorption capacity to SF 6 and SO 2. According to the invention, the porous organic polymer IMU-PAF-S with high BET specific surface area (IMU= Inner Mongolia University) is synthesized for the first time, and the S site of the thiophene ring in the material can effectively improve the adsorption capacity of SF 6 and SO 2. The obtained material has good thermal and chemical stability, and the adsorption capacity of SF 6 and SO 2 reaches 79.1 cm 3g-1 and 333 cm 3g-1 under normal temperature and normal pressure (25 ℃ and 1 bar), and the adsorption capacity of the two gases creates the highest record in the reported porous organic material. The invention aims at realizing the following technical scheme that the sulfur-containing porous organic polymer material has the following chemical structure: A preparation method of a porous aromatic framework material containing thiophene rings comprises the following steps: 1) Under the protection of nitrogen, adding a thiophene ring-containing compound, 2-bipyridine, a catalyst and an organic solvent into a reaction container, and uniformly mixing to perform a reaction; 2) After the reaction is finished, hydrochloric acid is added into the re