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CN-122006605-A - Nitro-containing covalent organic framework aerogel and application thereof in toxic aerosol treatment

CN122006605ACN 122006605 ACN122006605 ACN 122006605ACN-122006605-A

Abstract

The invention discloses a nitro-containing covalent organic framework aerogel and application thereof in toxic aerosol treatment, and belongs to the technical field of functional materials. The aerogel is completed by a three-step method, namely, firstly, 2-nitro-1, 4-phenylenediamine and di-tert-butyl dicarbonate react in tetrahydrofuran to prepare N 1 ,N 4 -bis-Boc-2-nitro-1, 4-phenylenediamine monomer, then, the nitro-containing covalent organic framework hydrogel is obtained through ultrasonic, deprotection and sealing reactions, finally, solvent replacement and freeze drying are carried out to obtain the target aerogel, and the technological parameters of each step are controlled. The aerogel has a hierarchical porous structure, the nitro modification endows the aerogel with high adsorption and degradation activity, the adsorption capacity of the aerogel for DMMP, CEES and mixed toxin agents is more than or equal to 300 mg.g ‑1 , the degradation efficiency for 12 hours is more than 90%, the environmental adaptability and the long-term stability are excellent, the aerosol can be efficiently treated under complex conditions, and the application prospect in the fields of safety protection and environmental treatment is wide.

Inventors

  • SUI ZHUYIN
  • ZHANG QUANQI
  • GUO TIANJIAO
  • SONG QIAN

Assignees

  • 烟台大学

Dates

Publication Date
20260512
Application Date
20260327

Claims (10)

  1. 1. The preparation method of the nitro covalent organic framework aerogel is characterized by comprising the following steps of: S1, reacting 2-nitro-1, 4-phenylenediamine with di-tert-butyl dicarbonate in tetrahydrofuran, and purifying to obtain N 1 ,N 4 -bis Boc-2-nitro-1, 4-phenylenediamine monomer; S2, mixing the trialdehyde phloroglucinol with the N 1 ,N 4 -di-Boc-2-nitro-1, 4-phenylenediamine monomer obtained in the S1, dissolving in dioxane and deionized water, dropwise adding trifluoroacetic acid to remove a BOC protecting group after ultrasonic dissolution, and performing sealing reaction to obtain hydrogel; s3, sequentially cleaning the hydrogel obtained in the step S2 by tetrahydrofuran and tert-butyl alcohol to replace a solvent, and freeze-drying to obtain the nitro-containing covalent organic framework aerogel.
  2. 2. The method for preparing the nitro-containing covalent organic framework aerogel according to claim 1, wherein in S1, the dosage ratio of the 2-nitro-1, 4-phenylenediamine, the di-tert-butyl dicarbonate and the tetrahydrofuran is 10mmol to 40mL to 100mL.
  3. 3. The method for preparing a nitro-group-containing covalent organic framework aerogel according to claim 1, wherein in S1, the end point of the reaction is monitored by thin layer chromatography; The purification process comprises rotary evaporation, dissolution, precipitation, suction filtration and vacuum drying, wherein the difference of the weight quality of the two times is less than or equal to 0.1mg.
  4. 4. The method for preparing a nitro-covalent organic framework aerogel according to claim 1, wherein in S2, the ratio of the amount of the substance of the trialdehyde phloroglucinol to the substance of the N 1 ,N 4 -bis Boc-2-nitro-1, 4-phenylenediamine monomer is 3:2; The dosage ratio of dioxane to deionized water is 3.4mL to 600 mu L.
  5. 5. The method for preparing a nitro-group-containing covalent organic framework aerogel according to claim 1, wherein in S2, the power of ultrasonic dissolution is 200W, and the frequency of ultrasonic dissolution is 40kHz; The sealing reaction condition is that the temperature is 120-160 ℃ and the time is 48-72h.
  6. 6. The method for preparing the nitro-containing covalent organic framework aerogel according to claim 1, wherein in S3, the specific operation steps of replacing the solvent are that tetrahydrofuran is used for cleaning for 4 times, the cleaning time is more than or equal to 12 hours, tert-butanol is used for cleaning for 3 times, and the cleaning time is more than or equal to 12 hours.
  7. 7. The preparation method of the nitro-containing covalent organic framework aerogel according to claim 1, wherein in the step S3, the specific operation steps of freeze drying are that the freeze drying is carried out for 24-36 h under the conditions of-50 to-40 ℃ and the vacuum degree of less than or equal to 10 Pa.
  8. 8. A nitro-containing covalent organic framework aerogel prepared by the method of any one of claims 1-7.
  9. 9. Use of the nitro-group-containing covalent organic framework aerogel according to claim 8 in toxic aerosol treatment.
  10. 10. The use according to claim 9, wherein the toxic agent aerosol is one or both of dimethyl methylphosphonate, 2-chloroethyl ethyl sulfide.

Description

Nitro-containing covalent organic framework aerogel and application thereof in toxic aerosol treatment Technical Field The invention belongs to the technical field of functional materials, and particularly relates to nitro-containing covalent organic framework aerogel and application thereof in toxic aerosol treatment. Background The toxic aerosol has the characteristics of high diffusion rate and wide hazard range, has strong toxicity to human health and ecological environment, and is an important prevention and control object in the fields of safety protection and environmental management. Dimethyl methylphosphonate (DMMP) as a nerve agent mimetic and 2-chloroethyl ethyl sulfide (CEES) as a sulfur mustard mimetic are two typical high-hazard agent mimetics, and how to achieve efficient treatment of both aerosols and synchronous adsorption and degradation has become a key technical problem to be solved urgently in the field. The graded porous functional material has high specific surface area, developed pore channel structure and excellent mass transfer efficiency, so that the graded porous functional material becomes an ideal candidate material for toxic aerosol treatment. Among them, covalent Organic Framework (COF) aerogel has been widely focused and studied in this field by virtue of outstanding advantages such as structural design, functional regulation, excellent physical and chemical stability, and the like. At present, the prior art has concentrated on conventional functional groups such as amino groups, carboxyl groups and the like in the functional modification research of covalent organic framework aerogel, and related research of introducing nitro groups into covalent organic framework aerogel and applying the covalent organic framework aerogel to DMMP and CEES aerosol treatment has not been reported yet. The nitro has the characteristic of strong electron withdrawing, can not only remarkably improve the adsorption performance of the material on polar toxicant simulants such as DMMP and CEES, but also can be used as an active site to effectively promote the degradation reaction of the polar toxicant simulants, and is expected to realize the efficient adsorption and the rapid degradation of DMMP and CEES aerosol if the nitro modification is combined with the mass transfer advantage of a hierarchical porous structure. In addition, the existing porous materials applied to DMMP and CEES treatment have the problems of insufficient adsorption capacity and low degradation efficiency, are poor in environmental adaptability, are easy to attenuate in the conditions of extreme humidity and air pressure, are poor in long-term stability, and are difficult to match with the requirements of actual application scenes. Therefore, the nitro-containing covalent organic framework aerogel with high adsorption capacity, high degradation efficiency, good environmental adaptability (capable of adapting to 10-90% humidity and 0.5-1.5 standard atmospheric pressure) and excellent long-term stability is developed, the controllable preparation of materials is realized through a solvent replacement-freeze drying process, and the nitro-containing covalent organic framework aerogel is applied to the treatment of DMMP and CEES aerosols, so that the nitro-containing covalent organic framework aerogel has important practical significance and practical application value. Disclosure of Invention Aiming at the technical problems, the invention provides a nitro-containing covalent organic framework aerogel and application thereof in toxic agent aerosol treatment. The aerogel is simple in preparation process and excellent in performance, and can be prepared by combining solvent replacement with a freeze-drying process, so that the problems of insufficient adsorption capacity, low degradation efficiency, poor extreme environmental adaptability and the like of the existing materials on DMMP and CEES can be effectively solved, and the actual application requirements can be met. In order to achieve the above purpose, the present invention provides the following technical solutions: The preparation method of the nitro covalent organic framework aerogel comprises the following steps: S1, reacting 2-nitro-1, 4-phenylenediamine with di-tert-butyl dicarbonate in tetrahydrofuran, and purifying to obtain N 1,N4 -bis Boc-2-nitro-1, 4-phenylenediamine monomer; S2, mixing the trialdehyde phloroglucinol with the N 1,N4 -di-Boc-2-nitro-1, 4-phenylenediamine monomer obtained in the S1, dissolving in dioxane and deionized water, dropwise adding trifluoroacetic acid to remove a BOC protecting group after ultrasonic dissolution, and performing sealing reaction to obtain hydrogel; s3, sequentially cleaning the hydrogel obtained in the step S2 by tetrahydrofuran and tert-butyl alcohol to replace a solvent, and freeze-drying to obtain the nitro-containing covalent organic framework aerogel. The invention gives the material excellent adsorption and degradati