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CN-122011378-A - Preparation method and application of bowl-shaped polyaniline microsphere

CN122011378ACN 122011378 ACN122011378 ACN 122011378ACN-122011378-A

Abstract

The invention relates to a preparation method and application of bowl-shaped polyaniline microsphere, which are used for synthesizing polyaniline microsphere with regular bowl-shaped morphology by precisely controlling key parameters such as oxidation degree of aniline monomer, size of a template, dosage of a polymerization initiator and the like. The bowl-shaped polyaniline microsphere is formed by self-assembly of polyaniline molecules, and the inside of the bowl-shaped polyaniline microsphere is provided with a continuous and uniformly distributed nanoscale pore structure. The unique bowl mouth and bowl bottom dimensions in the bowl-shaped microsphere structure enable the microsphere to simultaneously have the characteristics of concave in a cavity, micron hollow hemispheric shape, nano-scale bowl wall thickness, high surface area-volume ratio and high porosity, are beneficial to providing more active sites, and can be used for super capacitor electrodes, gas sensor electrodes and electromagnetic shielding materials.

Inventors

  • LIU XUANYONG
  • ZHANG MIN
  • SUN TINGTING
  • CAO YUANMING

Assignees

  • 东华大学

Dates

Publication Date
20260512
Application Date
20251230

Claims (10)

  1. 1. A preparation method of bowl-shaped polyaniline microsphere comprises the following steps: (1) Adding the sulfonated polystyrene microspheres into deionized water, and uniformly mixing to obtain a component A; (2) Adding the oxidized aniline into doping acid, and uniformly mixing to obtain a component B; (3) Adding the component B into the component A, and mechanically stirring in an ice-water bath to uniformly mix to obtain a component C; (4) Continuously stirring the component C at low temperature, adding an initiator to initiate reaction, and then centrifuging, washing and drying to obtain polyaniline@polystyrene composite microspheres; (5) And (3) dissolving the polyaniline@polystyrene composite microspheres in a template removing solvent, mixing and stirring, and then washing and drying to obtain bowl-shaped polyaniline microspheres.
  2. 2. The preparation method of the sulfonated polystyrene microspheres in the step (1) according to claim 1, wherein the sulfonated polystyrene microspheres in the step (1) are prepared by adding 30-80 mL of concentrated sulfuric acid into 2.0 g polystyrene microspheres, mixing uniformly, heating and stirring at 50-70 ℃ for 3-7 hours.
  3. 3. The method according to claim 1, wherein the aniline is oxidized in the step (2) by ultrasonic treatment or heating and stirring, specifically, the aniline solution is oxidized to a tan color by ultrasonic treatment for more than 0.5 hours or heating and stirring at 40 ℃ for more than 0.5 hours.
  4. 4. The preparation method of claim 1, wherein the doping acid in the step (2) comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, camphorsulfonic acid, dodecylbenzenesulfonic acid, salicylic acid or sulfosalicylic acid, the concentration of the doping acid is 0.2-2.0 mol-L -1 , and the molar ratio of the doping acid to aniline is 2-10:1.
  5. 5. The method according to claim 1, wherein the volume ratio of component B to component a in step (3) is 10:1.
  6. 6. The method according to claim 1, wherein the initiator in the step (4) comprises at least one of ammonium persulfate, potassium persulfate, hydrogen peroxide, and ferrous salt.
  7. 7. The preparation method of claim 1, wherein the molar ratio of aniline to initiator in the step (4) is 1:2-3:1, the time of the initiation reaction is 12-36 hours, and the temperature is 0-10 ℃.
  8. 8. The preparation method of claim 1, wherein the template removing solvent in the step (5) is N, N-dimethylformamide, and the stirring time is 2-5 hours, and the temperature is 10-25 ℃.
  9. 9. A bowl-shaped polyaniline microsphere prepared according to the preparation method of claim 1.
  10. 10. Use of the bowl-shaped polyaniline microsphere according to claim 9 in the fields of supercapacitor electrodes, gas sensor electrodes and electromagnetic shielding materials.

Description

Preparation method and application of bowl-shaped polyaniline microsphere Technical Field The invention belongs to the field of polymer materials, and particularly relates to a preparation method and application of bowl-shaped polyaniline microspheres. Background Polyaniline (PANI) is a typical conductive polymer material, and has the advantages of low cost and easy acquisition of raw materials, simple synthesis method, good environmental stability, easy doping and the like, thus having wide application prospect in various fields. However, the conventional polyaniline materials are mostly irregular particles or blocks, have relatively small specific surface areas and limited active sites, which limits the application effect in various fields to a certain extent. For example, in the super capacitor, the larger specific surface area and the proper pore structure are beneficial to improving the capacitance performance of the electrode material, and in the aspect of a gas sensor, the special microstructure can enhance the adsorption and desorption capacity of target gas, so that the sensitivity and the response speed of the sensor are improved. Conventional polyaniline materials cannot meet the application requirements. Therefore, the development of polyaniline materials having novel microstructures is one of the hot spots of current research. At present, although some reports about the preparation of polyaniline with a special morphology exist, the research on polyaniline with a bowl-shaped microsphere structure is relatively few. The bowl-shaped microsphere structure is beneficial to increasing the specific surface area, and the unique bowl-shaped inner cavity can provide more active sites and accommodating spaces, is beneficial to adsorption, storage and reaction of substances, and is expected to remarkably improve the performance of polyaniline in the application fields of electrodes, sensing, electromagnetic shielding and the like. Disclosure of Invention The invention aims to solve the technical problem of providing a preparation method and application of bowl-shaped polyaniline microspheres, so as to solve the problems of limited application effect due to limited active sites and relatively small specific surface area of the existing polyaniline structure. The invention provides a preparation method of bowl-shaped polyaniline microspheres, which comprises the following steps: (1) Adding the sulfonated polystyrene microspheres into deionized water, and uniformly mixing to obtain a component A; (2) Adding the oxidized aniline into doping acid, and uniformly mixing to obtain a component B; (3) Adding the component B into the component A, and mechanically stirring in an ice-water bath to uniformly mix to obtain a component C; (4) Continuously stirring the component C at low temperature, adding an initiator to initiate reaction, and then centrifuging, washing and drying to obtain polyaniline@polystyrene composite microspheres; (5) And (3) dissolving the polyaniline@polystyrene composite microspheres in a template removing solvent, mixing and stirring, and then washing and drying to obtain bowl-shaped polyaniline microspheres. Preferably, the sulfonated polystyrene microsphere in the step (1) is prepared by adding 30-80 mL of concentrated sulfuric acid into 2.0-g polystyrene microsphere, mixing uniformly, heating and stirring at 50-70 ℃ for 3-7 hours. Preferably, the step (2) oxidizes aniline by means of ultrasonic or heat agitation. Further, in the step (2), the aniline is oxidized specifically by ultrasonic treatment of the aniline solution for more than 0.5 hour or heating and stirring at 40 ℃ for more than 0.5 hour, and the solution is oxidized to be yellow brown. Preferably, the doping acid in the step (2) comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, camphorsulfonic acid, dodecylbenzene sulfonic acid, salicylic acid or sulfosalicylic acid, the concentration range of the doping acid is 0.2-2.0mol.L -1, and the molar ratio of the doping acid to aniline is 2-10:1. Preferably, the volume ratio of the component B to the component A in the step (3) is 10:1. Preferably, the initiator in the step (4) comprises at least one of ammonium persulfate, potassium persulfate, hydrogen peroxide and ferrous salt. Preferably, in the step (4), the molar ratio of the aniline to the initiator is 1:2-3:1. Preferably, the time for initiating the reaction in the step (4) is 12-36 hours, and the temperature is 0-10 ℃. Preferably, the template removing solvent in the step (5) is N, N-Dimethylformamide (DMF), the stirring time is 2-5 hours, and the temperature is 10-25 ℃. The invention provides the bowl-shaped polyaniline microsphere prepared by the preparation method, and the bowl-shaped polyaniline microsphere has the characteristics of concave cavities, micron hollow hemispheres, high surface area-volume ratio, high porosity and the like. The invention also provides application of the bowl-shaped polya