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CN-122006681-A - Metal organic framework carbon nano tube composite material enriched with triazole bactericide, and preparation method and application thereof

CN122006681ACN 122006681 ACN122006681 ACN 122006681ACN-122006681-A

Abstract

The invention discloses a metal organic frame carbon nano tube composite material for enriching triazole bactericides, a preparation method and application thereof, belonging to the technical field of pesticide detection, the invention prepares a material of which the surface of Fe 3 O 4 @CNT is coated with Co-MOF-74, the triazole fungicide is used for solid phase extraction, so that the problem of matrix interference is effectively solved, and the triazole fungicide can be enriched by 10 times after being treated by a magnetic solid phase extraction method, so that the sensitivity, precision and accuracy of detection are effectively improved.

Inventors

  • WU JINGNA
  • YANG XIUJUAN
  • LI JINCHAO
  • LUO JINGWEN
  • WEI LUYANG
  • SHI PENGTAO
  • ZHANG LIJUAN
  • ZHANG YU
  • DENG YOUZHAN

Assignees

  • 广西壮族自治区亚热带作物研究所（广西亚热带农产品加工研究所）

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. The preparation method of the triazole fungicide-enriched metal organic framework carbon nanotube composite material is characterized by comprising the following steps of: dissolving ferric salt, anhydrous sodium acetate and polyethylene glycol in ethylene glycol, and magnetically stirring after ultrasonic treatment; adding carboxylated carbon nanotubes in the magnetic stirring process, and carrying out a first solvothermal reaction on the obtained uniform mixture; Naturally cooling to room temperature after the first solvothermal reaction is finished, and washing and drying to obtain Fe 3 O 4 @CNT; Dispersing the Fe 3 O 4 @CNT, the soluble cobalt salt and the ferrous salt in N, N-dimethylformamide, and performing ultrasonic treatment at room temperature to form a uniform suspension; Adding 2, 5-dihydroxyterephthalic acid, absolute ethyl alcohol and water into the uniform suspension under the condition of continuous ultrasonic stirring, continuing ultrasonic until the mixture is completely mixed, and carrying out a second solvothermal reaction on the obtained mixture; and after the second solvothermal reaction is finished, naturally cooling to room temperature, washing and drying to obtain the metal organic framework carbon nano tube composite material enriched with the triazole bactericide.
  2. 2. The method for preparing the triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 1, wherein the mass ratio of the ferric salt to the anhydrous sodium acetate to the polyethylene glycol is (1.2-1.4) to (3.5-4.0) to 1.0.
  3. 3. The method for preparing a triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 1, wherein the mass ratio of the polyethylene glycol to the carboxylated carbon nanotubes is 1.0:0.3.
  4. 4. The method for preparing a triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 1, wherein the temperature of the first solvothermal reaction is 180-200 ℃ and the time is 8-12h.
  5. 5. The method for preparing the triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 1, wherein the mass ratio of Fe 3 O 4 @CNT to soluble cobalt salt to ferrous salt is 15:66.5:22.17.
  6. 6. The method for preparing a triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 1, wherein the mass ratio of Fe 3 O 4 @CNT to 2, 5-dihydroxyterephthalic acid is 1:1.
  7. 7. The method for preparing a triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 1, wherein the temperature of the second solvothermal reaction is 110-130 ℃ and the time is 22-26h.
  8. 8. A metal organic framework carbon nanotube composite material enriched with triazole bactericides, which is characterized in that the composite material is prepared by the preparation method according to any one of claims 1 to 7.
  9. 9. The use of the triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 8 in magnetic solid phase extraction of triazole fungicides.
  10. 10. The use of the triazole fungicide-enriched metal organic framework carbon nanotube composite material according to claim 8 for detecting triazole fungicide in fruit and vegetable juice.

Description

Metal organic framework carbon nano tube composite material enriched with triazole bactericide, and preparation method and application thereof Technical Field The invention belongs to the technical field of pesticide detection, and particularly relates to a metal organic framework carbon nano tube composite material for enriching triazole bactericides, and a preparation method and application thereof. Background In agricultural planting and postharvest storage and transportation systems, the application of the bactericide has irreplaceable effects. Triazole bactericides are taken as a second major class of bactericides worldwide, have a market ratio of about 21 percent, and are widely used in the whole process of fruit and vegetable production to prevent and control diseases before picking and rot in a storage period. However, its frequent use has led to the general detection of proto-drug and its active metabolite residues in fruit and vegetable tissues (peel and pulp), raising potential food safety concerns. Meanwhile, the bactericide is easy to accumulate in soil due to the characteristics of high environmental stability and slow degradation. In continuous cropping or rotation cropping systems, residues can migrate to successive cropping crops through soil adsorption, root absorption, decomposition of successive cropping residues and the like. Currently, standards such as GB 2763-2021 only set the Maximum Residual Limit (MRL) of a single triazole fungicide for the whole fruit/raw material, and beverage products only set limit standards of a small amount of fungicide pesticides for coffee beans, jasmine flowers, tea leaves and the like, and actual supervision usually refers to the MRL of the raw material fruit and combines dilution coefficients for conversion. In recent years, light processed products such as non-concentrated reduced (NFC) juice and cold pressing are rapidly rising, and the processes only take pulp to squeeze juice and discard peel residues, so that the residual concentration can be reduced further theoretically. Meanwhile, the European Union sets stricter limit requirements for infant fruit and vegetable juice. Therefore, there is a need to develop a sample pretreatment technology with high enrichment factor, high selectivity and repeated use, so as to accurately capture trace triazole residues in a complex sugar acid matrix, and provide a sensitive, efficient and green detection means for the quality safety and trade clearance of fruit and vegetable juice. Disclosure of Invention In order to solve the technical problems, the invention provides a metal organic framework carbon nano tube composite material for enriching triazole bactericides, and a preparation method and application thereof. In order to achieve the above purpose, the present invention provides the following technical solutions: the invention provides a preparation method of a metal organic framework carbon nano tube composite material enriched with triazole bactericides, which comprises the following steps: dissolving ferric salt, anhydrous sodium acetate and polyethylene glycol in ethylene glycol, and magnetically stirring after ultrasonic treatment; adding carboxylated carbon nanotubes in the magnetic stirring process, and carrying out a first solvothermal reaction on the obtained uniform mixture; Naturally cooling to room temperature after the first solvothermal reaction is finished, and washing and drying to obtain Fe 3O4 @CNT; Dispersing the Fe 3O4 @CNT, the soluble cobalt salt and the ferrous salt in N, N-dimethylformamide, and performing ultrasonic treatment at room temperature to form a uniform suspension; Adding 2, 5-dihydroxyterephthalic acid, absolute ethyl alcohol and water into the uniform suspension under the condition of continuous ultrasonic stirring, continuing ultrasonic until the mixture is completely mixed, and carrying out a second solvothermal reaction on the obtained mixture; and after the second solvothermal reaction is finished, naturally cooling to room temperature, washing and drying to obtain the metal organic framework carbon nano tube composite material enriched with the triazole bactericide. The invention provides a Fe 3O4 @CNT@Co-MOF composite material for enriching triazole bactericides and application thereof. The core of the invention is to construct a magnetic adsorption material with a core-shell structure, so as to realize efficient and selective enrichment and rapid separation, and the specific principle is as follows: 1. The material has the structural design that Fe 3O4 is used as a magnetic core, the material is endowed with the capability of rapid separation under an external magnetic field, CNT is used as an intermediate conductive carrier, the stability and the dispersibility of the material are enhanced, and Co-MOF-74 grown on the surface in situ forms a porous functional shell layer, so that rich coordination active sites and molecular size screening effect are provided, and