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CN-122011312-A - Ionic sodium sulfonate-based covalent organic framework material and preparation method and application thereof

CN122011312ACN 122011312 ACN122011312 ACN 122011312ACN-122011312-A

Abstract

The application discloses an ionic sodium sulfonate-based covalent organic framework material and a preparation method and application thereof, wherein the method comprises the following steps of S1, placing an aqueous solution of a surfactant in a reaction container, adding 4,4 '-diaminostilbene-2, 2' -sulfonic acid while stirring, S2, slowly dropwise adding 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde into the aqueous solution of the step S1 for heating reaction, precipitating solids after the reaction is finished, centrifuging to obtain a precipitate of a crude product, S3, washing and drying the precipitate obtained in the step S2, S4, placing the dried product in a sodium hydroxide solution for modification, and centrifuging, and S5, washing and drying the precipitate obtained in the step S4 to obtain the product. The ionic sodium sulfonate-based covalent organic framework material realizes the efficient adsorption of potassium ions.

Inventors

  • ZHU LINA
  • ZHOU YIXIAN
  • ZHAO YUJIE
  • KONG DEMING
  • JIANG HONGXIN
  • ZHANG CHUANGCHUANG
  • WANG ZHANPENG

Assignees

  • 天津大学

Dates

Publication Date
20260512
Application Date
20260206

Claims (10)

  1. 1. The preparation method of the ionic sodium sulfonate-based covalent organic framework is characterized by comprising the following steps of: s1, placing an aqueous solution of a surfactant in a reaction container, and adding 4,4 '-diaminostilbene-2, 2' -sulfonic acid while stirring; s2, dissolving 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in a solvent, slowly dripping the solution into the water solution in the step S1 for heating reaction, precipitating solid after the reaction is finished, and centrifuging to obtain a precipitate of a crude product; s3, washing and drying the precipitate obtained in the step S2; s4, putting the dried product into sodium hydroxide solution for modification, and then centrifuging; and S5, washing and drying the precipitate obtained in the step S4 to obtain the nano-porous material.
  2. 2. The method for preparing an ionic sodium sulfonate-based covalent organic framework according to claim 1, wherein the surfactant in the step S1 is cetyl pyridine bromide, and the concentration of the aqueous solution of cetyl pyridine bromide is 0.8-1.2 mg/mL, preferably 1mg/mL.
  3. 3. The method for preparing an ionic sodium sulfonate-based covalent organic framework according to claim 1, wherein the molar ratio of 4,4 '-diaminostilbene-2, 2' -sulfonic acid to 2,4, 6-trihydroxybenzene-1, 3, 5-trioxymethylene is 3:2.
  4. 4. The preparation method of the ionic sodium sulfonate-based covalent organic framework according to claim 2, wherein the solvent in the step S2 is one of o-dichlorobenzene, methylene dichloride and n-butanol, the reaction temperature is the azeotropic point of the system, the reaction time is 120-240 min, preferably, the solvent in the step S2 is n-butanol, the reaction temperature is the azeotropic point of the system, the reaction time is 120min, and ethanol is used for precipitating solids after the reaction is finished.
  5. 5. The method for preparing an ionic sodium sulfonate-based covalent organic framework according to claim 4, wherein the volume ratio of n-butanol to cetyl pyridinium bromide aqueous solution is 1 (3-5), preferably 1 (3.5-4).
  6. 6. The method for preparing an ionic sodium sulfonate-based covalent organic framework according to claim 1, wherein the concentration of sodium hydroxide solution in step S4 is 0.1M, and the stirring time is 6-12 hours, preferably 12 hours.
  7. 7. The method for preparing an ionic sodium sulfonate-based covalent organic framework according to claim 1, wherein, In the step S1, the stirring speed is 400-600 r/min, preferably 500r/min; And/or the dropping speed in the step S2 is 0.4-0.6 mL/min, preferably 0.5mL/min; And/or, in the step S3, the precipitate is centrifugally washed three times by tetrahydrofuran, centrifugally washed three times by methanol, and then dried for 4-6 hours at 45-80 ℃ to obtain COF-SO 3 H; And/or, in the step S5, the precipitate is centrifugally washed for 3-5 times by distilled water until the supernatant is neutral, and then frozen in a refrigerator at-20 ℃ for 12 hours, and dried in a freeze dryer at-40 to-60 ℃ for 24 hours, SO as to obtain the COF-SO 3 Na.
  8. 8. An ionic sodium sulfonate-based covalent organic framework prepared by a process comprising any one of claims 1-7.
  9. 9. The use of the ionic sodium sulfonate-based covalent organic framework of claim 8 for removing potassium ions by adsorption in a body of water.
  10. 10. The use according to claim 9, wherein, The pH=5-6 is regulated, the feeding concentration of the ionic sodium sulfonate-based covalent organic framework material is 1-3mg/mL, the temperature is 20-25 ℃ and the adsorption time is 10min, and more preferably, the pH=6 is regulated, the feeding concentration of the ionic sodium sulfonate-based covalent organic framework material is 2mg/mL, the temperature is 25 ℃ and the adsorption time is 10min; And/or the ionic sodium sulfonate-based covalent organic framework material is used repeatedly for removing potassium ions for 2-8 times; And/or, after the ionic sodium sulfonate-based covalent organic framework material adsorbs potassium ions, immersing the ionic sodium sulfonate-based covalent organic framework material in a NaNO 3 solution of 0.1M for 6 hours, and then repeatedly washing with deionized water until the solution becomes neutral, so as to realize the regeneration of the adsorbent.

Description

Ionic sodium sulfonate-based covalent organic framework material and preparation method and application thereof Technical Field The invention belongs to the technical field of water treatment and environmental protection, and particularly relates to an ionic sodium sulfonate-based covalent organic framework material, a preparation method thereof and application thereof in effectively capturing and removing potassium ions in water. Background In the field of water treatment and environmental protection, the control of metal ion contamination has been a challenging problem. The metal ions can enter the human body through the food chain, and long-term accumulation can cause various health problems including damage to the nervous system, kidney diseases, and the like. In addition, the metal ions can also react with other chemical substances in the water to generate toxic compounds, so that the water pollution is further aggravated. Therefore, developing an effective metal ion removal technique is critical to ensure water quality safety and human health. Potassium ions (k+) are one of the electrolytes necessary for the human body, but excessive intake also has an effect on health. In humans, hyperkalemia can lead to heart problems such as arrhythmias and even sudden cardiac arrest. Too much potassium ions in sewage and soil are also a serious hazard in terms of the environment. Excessive potassium ions are discharged into the water body, so that the imbalance of the aquatic ecosystem can be caused, the growth and the reproduction of aquatic organisms are influenced, and even the phenomenon of water bloom is caused. In the soil, excessive accumulation of potassium ions affects the soil structure, reduces the soil fertility, and further affects the growth and yield of crops. At present, the technology for removing potassium ions mainly comprises methods such as ion exchange, membrane separation, adsorption and the like. Although effective, the ion exchange process is costly and requires periodic resin replacement. Membrane separation technology has the problems of membrane pollution and high energy consumption. Covalent Organic Frameworks (COFs) are used as novel porous materials, and have uniform and adjustable pore diameters and large specific surface area due to the highly ordered porous structure, can be accurately designed and constructed by an organic synthesis method, realize functional diversification and show great potential in the aspect of removing metal ions. However, the synthesis of COFs materials generally requires high temperature and high pressure, consumes high energy, is not friendly to the environment, and does not conform to the concept of green chemistry. The synthesis conditions are strictly controlled and the overall time is long, which limits the mass production and application to a certain extent. Therefore, the novel synthetic green and efficient covalent organic framework material is developed and is used for efficiently removing potassium ions in water and soil, so that the quality of water and soil can be improved, the health of human beings can be ensured, and the environment protection and sustainable development can be promoted. Disclosure of Invention The present invention aims to solve one of the technical problems in the related art to a certain extent, and therefore, an object of the present invention is to provide an ionic sodium sulfonate-based covalent organic framework material. The invention further aims to provide a preparation method of the green and efficient ionic sodium sulfonate-based covalent organic framework material. It is a further object of the present invention to provide the use of an ionic sodium sulfonate-based covalent organic framework material to capture and/or remove potassium ions from a body of water. The invention adopts the technical scheme that: in a first aspect of the present invention, The embodiment of the invention provides a preparation method of an ionic sodium sulfonate-based covalent organic framework, which comprises the following steps: s1, placing an aqueous solution of a surfactant in a reaction container, and adding 4,4 '-diaminostilbene-2, 2' -sulfonic acid while stirring; s2, dissolving 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde in a solvent, slowly dripping the solution into the water solution in the step S1 for heating reaction, precipitating solid after the reaction is finished, and centrifuging to obtain a precipitate of a crude product; s3, washing and drying the precipitate obtained in the step S2; s4, putting the dried product into sodium hydroxide solution for modification, and then centrifuging; and S5, washing and drying the precipitate obtained in the step S4 to obtain the nano-porous material. In some embodiments, the surfactant of step S1 is cetyl pyridinium bromide, and the concentration of the aqueous solution of cetyl pyridinium bromide is 0.8-1.2 mg/mL, preferably 1mg/mL. In some embodiments, in step S1, the