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CN-121988400-A - ZIF-8-Fe/P-g-C3N4Graphite-like carbon gel microsphere and preparation method and application thereof

CN121988400ACN 121988400 ACN121988400 ACN 121988400ACN-121988400-A

Abstract

The invention discloses ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres and a preparation method and application thereof, and relates to the technical field of environmental and food pollutant treatment. The invention firstly carries out high-temperature calcination treatment on the graphite-like carbon, ZIF-8-Fe, urea and hydrogen phosphate after acid treatment to prepare the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon composite material with high specific surface area, multistage pore structure and rich adsorption sites, and then carries out crosslinking reaction on sodium alginate and calcium ions to prepare the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microsphere. The prepared ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microsphere not only can utilize the porous structure and abundant active sites to enrich PAT, but also can carry out photocatalytic degradation on the PAT under ultraviolet excitation, has good treatment effect on the PAT, and is easy to separate and recycle and good in stability.

Inventors

  • Zheng Meie
  • Shao yujia
  • MA FEI
  • GUO MENGRU
  • LIU SIYU
  • LIU PEIPEI
  • CHENG YING

Assignees

  • 湖北工程学院

Dates

Publication Date
20260508
Application Date
20260316

Claims (10)

  1. 1. The preparation method of the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microsphere is characterized by comprising the following steps of: S1, mixing sugarcane leaf powder and ferric salt, heating and carbonizing to obtain graphite-like carbon, mixing the graphite-like carbon with acid liquor, and sequentially performing water washing and drying treatment to obtain graphite-like carbon powder after acid treatment; s2, mixing ZIF-8-Fe powder, urea, hydrogen phosphate and the graphite-like carbon powder subjected to acid treatment, performing high-temperature calcination treatment, and sequentially washing and drying the high-temperature calcination product to obtain a ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon composite material; S3, mixing the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon composite material with an aqueous solution of sodium alginate to obtain a colloidal solution, dropwise adding the colloidal solution into the aqueous solution containing calcium ions to cause the calcium ions and the sodium alginate to undergo a crosslinking reaction, and standing in a dark place to obtain the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microsphere.
  2. 2. The method for preparing the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres according to claim 1, wherein in step S1: The ferric salt comprises at least one of ferric citrate, ferric chloride, ferric nitrate and ferric sulfate, and/or, The mass ratio of the sugarcane top powder to the ferric salt is 2 (1-5), and/or, The temperature of the heating carbonization is 600-800 ℃, the time of the heating carbonization is 1-3 h, and/or, The acid solution is sulfuric acid solution with the mass fraction of 95%, the mass-volume ratio of the graphite-like carbon to the acid solution is 1g (15-30) mL, the mixing temperature of the graphite-like carbon and the acid solution is 60-80 ℃, and the mixing time of the graphite-like carbon and the acid solution is 8-12 h.
  3. 3. The method for preparing ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres as set forth in claim 1, wherein in step S2, the step of preparing ZIF-8-Fe powder comprises the steps of: zinc acetate, ferric sulfate and 1, 2-dimethyl imidazole are respectively mixed with methanol to correspondingly form a first solution, a second solution and a third solution, the first solution, the second solution and the third solution are mixed and subjected to precipitation reaction, solid matters are obtained through separation, and ZIF-8-Fe powder is obtained through cleaning, drying and grinding of the solid matters.
  4. 4. The process for preparing a ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microsphere as defined in claim 3, wherein the mass-volume ratio of zinc acetate to methanol is (0.5-1) g (100-150) mL, the mass-volume ratio of iron sulfate to methanol is 1g (20-25) mL, the mass-volume ratio of 1, 2-dimethylimidazole to methanol is 1g (10-15) mL, the volume ratio of the first solution, the second solution and the third solution is 2 (1-2): (1-2), and/or, The precipitation reaction is carried out at room temperature, and the time of the precipitation reaction is 5-7 h.
  5. 5. The method for preparing the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres according to claim 1, wherein in step S2: The mass ratio of the urea to the hydrogen phosphate to the ZIF-8-Fe powder to the graphite-like carbon powder after the acid treatment is 100:10 (1-3) (1-13), and/or, The temperature of the high-temperature calcination treatment is 500-700 ℃, and the time of the high-temperature calcination treatment is 2-4 hours.
  6. 6. The method for preparing the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres according to claim 1, wherein in step S3: The light-shielding standing time is 5-12 hours, and/or, The mass concentration of sodium alginate in the sodium alginate aqueous solution is 20g/L, the mass concentration of calcium salt in the calcium ion-containing aqueous solution is 50g/L, the mass-volume ratio of the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon composite material to the sodium alginate aqueous solution is 1g (80-100) mL, and the volume ratio of the sodium alginate aqueous solution to the calcium ion-containing aqueous solution is 1 (2-5).
  7. 7. The method for preparing the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres according to claim 1, wherein the particle size of the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres is 1-4 mm.
  8. 8. ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres, characterized in that the ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres are prepared by the preparation method of any one of claims 1 to 7.
  9. 9. Use of ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres as defined in claim 8 for removal of patulin.
  10. 10. Use of ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres as claimed in claim 9 for removal of patulin, comprising the steps of: ZIF-8-Fe/P-g-C 3 N 4 /graphite-like carbon gel microspheres and a solution containing patulin are mixed and subjected to patulin removal under ultraviolet light.

Description

ZIF-8-Fe/P-g-C 3N4/graphite-like carbon gel microsphere and preparation method and application thereof Technical Field The invention relates to the technical field of environmental and food pollutant treatment, in particular to a ZIF-8-Fe/P-g-C 3N4/graphite-like carbon gel microsphere, and a preparation method and application thereof. Background Patulin (PAT) is a toxic secondary metabolite produced by fungi such as aspergillus and penicillium during fruit and vegetable spoilage, and is widely found in mildewed fruits and vegetables and their products. PAT can be enriched in human body through food chain, and long-term intake can cause risks such as acute poisoning, digestive system injury, immunosuppression, etc. In order to ensure food safety, countries and regions such as European Union, the United states and China strictly limit the residual amount of PAT in foods, wherein the residual limit of PAT in foods such as fruit juice is set to 50 mug/L by organizations such as European Union. At present, the removal technology for PAT in foods and environments mainly comprises physical adsorption, chemical degradation and biological enzymolysis. The physical adsorption method is simple to operate, and porous materials are often adopted for adsorption removal, but the problems of limited adsorption capacity, poor selectivity and difficult material recovery are generally existed. Although the chemical degradation method such as ozone oxidation, hydrogen peroxide treatment and the like can realize PAT decomposition to a certain extent, the reaction conditions are severe, byproducts with unknown structures or higher toxicity are easy to generate, and secondary pollution risks exist. The biological enzymolysis method utilizes specific hydrolase or oxidoreductase to degrade PAT, has the advantages of mild reaction conditions and strong specificity, but the enzymolysis efficiency is easily restricted by environmental factors, and the enzyme preparation has high cost, insufficient stability and difficult recovery and reuse. Therefore, the existing PAT removal technology still has significant shortcomings in the aspects of removal efficiency, safety, reusability, environmental friendliness and the like, and development of a novel pollutant treatment material with high removal efficiency, easy separation and recovery and good stability is needed. Disclosure of Invention The invention mainly aims to provide ZIF-8-Fe/P-g-C 3N4/graphite-like carbon gel microspheres and a preparation method and application thereof, and aims to solve the problems of low removal efficiency, poor material stability and poor reusability of the conventional PAT removal technology. In order to achieve the above purpose, the invention provides a preparation method of ZIF-8-Fe/P-g-C 3N4/graphite-like carbon gel microspheres, which comprises the following steps: S1, mixing sugarcane leaf powder and ferric salt, heating and carbonizing to obtain graphite-like carbon, mixing the graphite-like carbon with acid liquor, and sequentially performing water washing and drying treatment to obtain graphite-like carbon powder after acid treatment; s2, mixing ZIF-8-Fe powder, urea, hydrogen phosphate and the graphite-like carbon powder subjected to acid treatment, performing high-temperature calcination treatment, and sequentially washing and drying the high-temperature calcination product to obtain a ZIF-8-Fe/P-g-C 3N4/graphite-like carbon composite material; S3, mixing the ZIF-8-Fe/P-g-C 3N4/graphite-like carbon composite material with an aqueous solution of sodium alginate to obtain a colloidal solution, dropwise adding the colloidal solution into the aqueous solution containing calcium ions to cause the calcium ions and the sodium alginate to undergo a crosslinking reaction, and standing in a dark place to obtain the ZIF-8-Fe/P-g-C 3N4/graphite-like carbon gel microsphere. In one embodiment, in step S1: The ferric salt comprises at least one of ferric citrate, ferric chloride, ferric nitrate and ferric sulfate, and/or, The mass ratio of the sugarcane top powder to the ferric salt is 2 (1-5), and/or, The temperature of the heating carbonization is 600-800 ℃, the time of the heating carbonization is 1-3 h, and/or, The acid solution is sulfuric acid solution with the mass fraction of 95%, the mass-volume ratio of the graphite-like carbon to the acid solution is 1g (15-30) mL, the mixing temperature of the graphite-like carbon and the acid solution is 60-80 ℃, and the mixing time of the graphite-like carbon and the acid solution is 8-12 h. In one embodiment, the ZIF-8-Fe powder is prepared according to the following steps: zinc acetate, ferric sulfate and 1, 2-dimethyl imidazole are respectively mixed with methanol to correspondingly form a first solution, a second solution and a third solution, the first solution, the second solution and the third solution are mixed and subjected to precipitation reaction, solid matters are obtained through separation, and ZIF-