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CN-120757788-B - Metal organic framework and preparation method and application thereof

CN120757788BCN 120757788 BCN120757788 BCN 120757788BCN-120757788-B

Abstract

The invention relates to the technical field of organic materials, in particular to a metal-organic framework, a preparation method and application thereof, wherein the metal-organic framework is CuBaTi MOFs, the metal-organic framework has a layered structure and a porous structure, cuBaTi MOFs is modified by a surfactant, and CuBaTi MOFs is compounded by mineral components. The metal organic framework can effectively inhibit bacteria and adsorb ethylene, and the prepared antibacterial film can not only realize fresh-keeping antibacterial effect of vegetables and fruits and delay maturation and spoilage of the vegetables and fruits, but also has good mechanical properties, and meanwhile, the preparation method of the metal organic framework is simple and convenient, low in cost, green and environment-friendly, and has wide application prospects.

Inventors

  • ZHANG WENNI

Assignees

  • 广州亿品鲜技术有限公司

Dates

Publication Date
20260505
Application Date
20250529

Claims (8)

  1. 1. A metal-organic framework is characterized in that the metal-organic framework is CuBaTi MOFs, The metal organic framework has a layered structure and a porous structure, and is a copper-barium-titanium three-dimensional framework; the CuBaTi MOFs is modified by hexadecyl trimethyl ammonium bromide, and the concentration of the hexadecyl trimethyl ammonium bromide is 0.01-0.05 mol/L; The CuBaTi MOFs is compounded by mineral components, wherein the mineral components are carboxylated nano mica and/or diatomite, and the mass ratio of the copper-barium-titanium three-dimensional frame to the mineral components is 1:1-5; the ligand of CuBaTi MOFs is trimesic acid; the metal-organic framework is prepared by a preparation method comprising the following steps: 1) Dissolving a copper source and a barium source in a solvent for first mixing, adding a titanium source for second mixing, adding a ligand for third mixing, and carrying out microwave solvothermal reaction to obtain a copper-barium-titanium three-dimensional frame; 2) Modifying the copper-barium-titanium three-dimensional framework by using a surfactant, and adding mineral components for ultrasonic compounding.
  2. 2. A method of preparing the metal-organic framework of claim 1, comprising: 1) Dissolving a copper source and a barium source in a solvent for first mixing, adding a titanium source for second mixing, adding a ligand for third mixing, and carrying out microwave solvothermal reaction to obtain a copper-barium-titanium three-dimensional frame; 2) Modifying the copper-barium-titanium three-dimensional framework by using a surfactant, and adding mineral components for ultrasonic compounding.
  3. 3. The production method according to claim 2, wherein in step 1), the copper source is selected from one or two or more of copper sulfate, copper nitrate, copper chloride and copper acetate; the barium source is selected from barium chloride and/or barium nitrate; The titanium source is selected from one or more of tetrabutyl titanate, titanium tetrachloride and isopropyl titanate; the solvent is an aqueous solution of N, N-dimethylformamide.
  4. 4. A method of preparing according to claim 3, wherein in step 1) the molar ratio of copper source, barium source, titanium source and ligand is 1:0.5-2:0.5-2:1-3, wherein the copper source is calculated as copper ion, the barium source is calculated as barium ion and the titanium source is calculated as titanium ion.
  5. 5. The method according to any one of claims 2 to 4, wherein in step 1), the first mixing conditions include a temperature of 15 to 30 ℃ and an ultrasonic power of 200 to 400W for 10 to 30min; The second mixing condition comprises temperature of 15-30deg.C, ultrasonic power of 200-400W for 10-30min; the third mixing condition comprises 15-30deg.C, stirring speed of 300-600rpm, and time of 10-30min; the conditions of the microwave solvothermal reaction comprise the microwave power of 200-500w, the temperature of 110-150 ℃ and the time of 20-60min.
  6. 6. The method according to claim 5, wherein in step 2), the mineral component is carboxylated nano mica and/or diatomaceous earth.
  7. 7. The method according to claim 6, wherein in the step 2), the modification conditions include a temperature of 40-80 ℃ and an ultrasonic power of 200-400W for 10-30min; The compounding conditions comprise the temperature of 15-30 ℃, the ultrasonic power of 200-400W and the time of 10-30min.
  8. 8. An antibacterial film comprising the metal-organic framework of claim 1 and a PE resin.

Description

Metal organic framework and preparation method and application thereof Technical Field The invention relates to the technical field of organic materials, in particular to a metal-organic framework, a preparation method and application thereof. Background Conventional food preservative films are usually made of polymeric materials such as Polyethylene (PE), polyvinyl chloride (PVC) or polyvinylidene chloride (PVDC), and the like, and are mainly used for delaying food spoilage by physical barriers (such as oxygen and water vapor isolation). However, the material can only passively prevent the pollution of external microorganisms, and cannot inhibit the growth of microorganisms such as bacteria, mold and the like existing on the surface of food, so that the fresh-keeping effect is limited, and the material is especially suitable for high-moisture and high-nutrition food (such as meat, fruits and vegetables, dairy products and the like). With the increasing demands for food safety and extended shelf life, the simple physical barrier has failed to meet the requirements. Foods are susceptible to microbial contamination during processing, transportation and storage, leading to spoilage and even the initiation of food-borne diseases. Therefore, the development of preservative films with active antibacterial function becomes a research hot spot, and aims to inhibit or kill pathogenic bacteria (such as escherichia coli, staphylococcus aureus, salmonella and the like) and spoilage microorganisms on the surface of food, so that the shelf life of the food is prolonged. The core of the antibacterial film is to introduce antibacterial components into the traditional polymer base material, so that the antibacterial film has continuous or slow-release antibacterial performance. The main technical routes at present comprise a, natural antibacterial agents such as chitosan (with broad-spectrum antibacterial property), plant essential oil (such as cinnamaldehyde and thymol), lysozyme and the like, which are concerned by safety and degradability, b, inorganic antibacterial agents such as nano silver (Ag), nano zinc oxide (ZnO) and nano titanium dioxide (TiO 2), which destroy microbial structures through metal ion release or photocatalysis, c, organic synthetic antibacterial agents such as quaternary ammonium salts and potassium sorbate and the like, which interfere the functions of microbial cell membranes through charge, and d, a composite antibacterial system, which combines various antibacterial agents or carriers (such as cyclodextrin and nanocellulose) to improve synergistic effect and slow release performance. Although the antibacterial film has wide prospect, the technical realization still needs to solve the problems that the antibacterial performance depends on metal coatings such as silver, zinc and the like, and the problems of high cost, heavy metal migration risk, narrow antibacterial spectrum and the like exist. In addition, the traditional film can not effectively adsorb ethylene gas released by fruits and vegetables, so that the ripening speed is increased and the shelf life is shortened. Therefore, it is necessary to develop a new antibacterial film. Disclosure of Invention The invention aims to solve the problems of insufficient antibacterial performance and weak ethylene regulation and control capability of the traditional fruit and vegetable package, thereby providing a metal organic framework, a preparation method and application thereof, wherein the metal organic framework can effectively inhibit bacteria and adsorb ethylene, and the prepared antibacterial film can not only realize fresh-keeping antibacterial effect of vegetables and fruits and delay maturation and spoilage of the vegetables and fruits, but also has good mechanical properties, and meanwhile, the preparation method of the metal organic framework is simple and convenient, has low cost, is green and environment-friendly, and has wide application prospect. In order to achieve the above object, in a first aspect, the present invention provides a metal-organic framework, wherein the metal-organic framework is CuBaTi MOFs, The metal-organic framework has a layered structure and a porous structure; the CuBaTi MOFs is modified by a surfactant; the CuBaTi MOFs is compounded via mineral components. Preferably, the surfactant is cetyltrimethylammonium bromide. Preferably, the mineral component is carboxylated nano mica and/or diatomaceous earth. In a second aspect, the present invention provides a method for preparing the metal-organic framework according to the first aspect, the method comprising: 1) Dissolving a copper source and a barium source in a solvent for first mixing, adding a titanium source for second mixing, adding a ligand for third mixing, and carrying out microwave solvothermal reaction to obtain a copper-barium-titanium three-dimensional frame; 2) Modifying the copper-barium-titanium three-dimensional framework by using a surfactant,