Preparation method and application of carbon-based photocatalytic bactericide carrier

Abstract

This invention discloses a method for preparing and applying a carbon-based supported photocatalytic bactericide. The method includes the following steps: A) pulverizing carbon material to 4000-6000 mesh to obtain a carbon-based material; B) mixing organic photovoltaic material with chloroform in the following weight ratio: 0.01-0.02g organic photovoltaic material : 10-15ml chloroform to obtain a mixed solution; the organic photovoltaic material is a binary organic photocatalytic material PTQ10:ITIC-Th or PTQ10:PC71BM prepared using a molecular regulation strategy; C) uniformly coating the mixed solution from step B onto the carbon-based material from step A, with the weight ratio of the mixed solution to the carbon-based material being 1:5000-10000, and drying to obtain the carbon-based supported photocatalytic bactericide. The carbon-based supported photocatalytic bactericide obtained by this invention can remove more than 99% of Escherichia coli and Staphylococcus aureus, effectively solving the problem of food storage in enclosed spaces and extending the shelf life of food. It also has the characteristics of low cost, environmental friendliness, and reusability, and has good application prospects.

Description

Technical Field

[0001] This invention belongs to the field of photocatalysis technology, specifically a method for preparing and applying a carbon-based supported photocatalytic bactericide. Background Technology

[0002] With improved living standards, people have become accustomed to using refrigerators to store food, extending its shelf life through the low-temperature environment they provide. However, due to the high humidity and diverse range of foods stored in refrigerators—including vegetables, meats, fruits, and frozen drinks, both cooked and raw—food is prone to spoilage and microbial growth when left out for extended periods. Furthermore, the inherent odors of the food itself and cross-contamination between different foods can create unpleasant odors inside the refrigerator, causing both sensory discomfort and health risks. Therefore, finding and developing a safe, energy-efficient, effective, economical, and environmentally friendly sterilization method to extend food shelf life in enclosed spaces like refrigerators is crucial for sustainable development and holds significant importance. Summary of the Invention

[0003] The technical problem to be solved by the present invention is to provide a method for preparing and applying a carbon-based supported photocatalytic bactericide, which has excellent bactericidal ability, environmental protection characteristics and non-invasiveness.

[0004] The present invention solves the above-mentioned technical problems by means of the following technical solution:

[0005] The present invention discloses a method for preparing a carbon-based supported photocatalytic bactericide, comprising the following steps:

[0006] A. Crush carbon materials to 4000-6000 mesh to obtain carbon-based materials;

[0007] B. Mix the organic photovoltaic material with chloroform in the following weight ratio: 0.01-0.02g organic photovoltaic material: 10-15ml chloroform to obtain a mixed solution; the organic photovoltaic material is a binary organic photocatalytic material PTQ10:ITIC-Th or PTQ10:PC71BM prepared by a molecular regulation strategy.

[0008] C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000 to 10000. After drying, a carbon-based supported photocatalytic bactericide is obtained.

[0009] In step A, the carbon material is placed in a blender and pulverized for 30-50 seconds.

[0010] In step B, when mixing the organic photovoltaic material with chloroform, the stirring speed is 500 r / min and the stirring time is 15 min.

[0011] In step B, the organic photovoltaic material PTQ10:PC71BM is made by mixing PTQ10 and PC71BM in a weight ratio of 1:1, and the organic photovoltaic material PTQ10:ITIC-Th is made by mixing PTQ10 and ITIC-Th in a weight ratio of 1:1.

[0012] In step C, drying refers to drying in a constant temperature drying oven at 60°C for 24 hours.

[0013] The carbon-based photocatalytic bactericide obtained by the method of this invention can be used for the sterilization of harmful microorganisms. The operation method is as follows: the carbon-based photocatalytic bactericide is placed in a solution containing harmful microorganism Escherichia coli (E. coli) or a solution containing harmful microorganism Staphylococcus aureus (S. aureus). A xenon lamp is used as the light source, supplemented with a filter. After the dark adsorption reaches equilibrium, the light irradiation is started. Samples are taken every 15 minutes, and the concentration of surviving bacteria is determined by plate counting method. The killing rate is calculated until the sterilization purpose is achieved.

[0014] The xenon lamp has a power of 500W and a wavelength range of 420–760nm.

[0015] The concentration of both bacterial solutions was 10. 8 The dosage of the carbon-based supported photocatalytic bactericide is 1.0 to 5.0 mg of bactericide per 1 mL of bacterial solution.

[0016] The carbon-based photocatalytic bactericide obtained by the method of the present invention can be used for sterilization in a closed space. The operation is as follows: the carbon-based photocatalytic bactericide is placed in a transparent porous film package and sealed, and then placed in a closed space. The amount of the carbon-based photocatalytic bactericide is 1-5 mg of bactericide per 1L volume.

[0017] The enclosed space is a refrigerator.

[0018] The photocatalytic technology employed in this invention is an ideal energy utilization technology. The photocatalytic oxidation process also consumes oxygen and produces carbon dioxide. In the confined space of a storage room, this can reduce a small amount of oxygen and increase a certain amount of carbon dioxide, which is beneficial for inhibiting the respiration of fruits and vegetables. Furthermore, the residual bacteria in the gas, under the action of light, cause the cross-linking and rupture of nucleic acids and proteins, killing the biological activity of nucleic acids and leading to bacterial death. This further kills bacteria in the storage environment, achieving the purpose of antibacterial preservation, and has potential application prospects.

[0019] The method of the present invention has the following beneficial effects:

[0020] (1) The carbon-based photocatalytic bactericide obtained by the method of the present invention can remove more than 99% of Escherichia coli and Staphylococcus aureus, and can be reused.

[0021] (2) The carbon-based photocatalytic bactericide obtained by the method of the present invention generates electron-hole pairs when irradiated by light based on its own photocatalytic performance. These pairs react with water and oxygen in the air to generate hydroxyl radicals and superoxide radicals, which attack bacteria and outer cells, penetrate the cell membrane of bacteria and destroy the cell membrane structure, thereby completely killing bacteria. This process can achieve the purpose of highly efficient inactivation of bacteria without the aid of any external chemical substances. It has excellent bactericidal ability, environmental protection characteristics and non-invasiveness.

[0022] (3) The carbon-based photocatalytic bactericide obtained by the method of this invention has excellent antibacterial properties and can be applied in sealed food storage spaces such as refrigerators. Moreover, the preparation method is simple, low-cost, and environmentally friendly, and can be industrialized, thus having great promotional value.

[0023] (4) The matrix material used in the method of the present invention is a natural carbon-based material, which has many excellent properties such as being green, having high porosity, and having a large specific surface area. It is also reusable and biodegradable, achieving true green friendliness and environmental pollution-free. Detailed Implementation

[0024] The technical solution of the present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way.

[0025] Example 1

[0026] The present invention relates to the preparation and application of a carbon-based supported photocatalytic bactericide, comprising the following steps:

[0027] A. Put 10g of carbon material into a high-speed blender and crush it for 30 seconds to obtain 4000 mesh carbon-based material.

[0028] B. Mix the organic photovoltaic material with chloroform in the following weight ratio: organic photovoltaic material PTQ10: PC71BM 0.01g: chloroform 10ml to obtain a mixed solution; the organic photovoltaic material is composed of PTQ10 and PC71BM mixed in a weight ratio of 1:1. When mixing the organic photovoltaic material with chloroform, use a magnetic stirrer to stir at a speed of 500r / min for 15min.

[0029] C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000. The mixture is dried in a constant temperature drying oven at 60°C for 24 hours to obtain a carbon-based supported photocatalytic bactericide.

[0030] D. Divide the carbon-based photocatalytic bactericide obtained in step C into two portions, A and B. Place portion A in a solution containing the harmful microorganism *Escherichia coli* (E. coli), and portion B in a solution containing the harmful microorganism *Staphylococcus aureus* (S. aureus). Place each portion in a reactor, using a 500W xenon lamp as the light source, supplemented with a filter. Irradiation begins after dark-state adsorption reaches equilibrium, lasting 0–60 minutes. Samples are taken every 15 minutes, and the concentration of surviving bacteria is determined using the plate count method to calculate the sterilization rate. The wavelength range of the xenon lamp is 420–760 nm; the concentration of both bacterial solutions is 10. 8 The dosage of the carbon-based supported photocatalytic bactericide is 1.0 mg of bactericide per 1 mL of bacterial solution.

[0031] The antibacterial effect of this embodiment is as follows: As can be seen from Table 1, after 60 minutes of light exposure, the sterilization rate of the two bacteria reached 99%, demonstrating an antibacterial effect.

[0032] Table 1. Sterilization rate of Example 1

[0033]

[0034] Example 2

[0035] The present invention relates to the preparation and application of a carbon-based supported photocatalytic bactericide, comprising the following steps:

[0036] A. Put 10g of carbon material into a high-speed blender and crush it for 40 seconds to obtain 6000 mesh carbon-based material.

[0037] B. Mix the organic photovoltaic material with chloroform in the following weight ratio: PTQ10 organic photovoltaic material: 0.02g ITIC-Th: 10ml chloroform to obtain a mixed solution; the organic photovoltaic material is composed of PTQ10 and ITIC-Th mixed in a weight ratio of 1:1. When mixing the organic photovoltaic material with chloroform, use a magnetic stirrer to stir at a speed of 500r / min for 15min.

[0038] C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000. The mixture is dried in a constant temperature drying oven at 60°C for 24 hours to obtain a carbon-based supported photocatalytic bactericide.

[0039] D. Divide the carbon-based photocatalytic bactericide obtained in step C into two portions, A and B. Place portion A in a solution containing the harmful microorganism *Escherichia coli* (E. coli), and portion B in a solution containing the harmful microorganism *Staphylococcus aureus* (S. aureus). Place each portion in a reactor, using a 500W xenon lamp as the light source, supplemented with a filter. Irradiation begins after dark-state adsorption reaches equilibrium, lasting 0–60 minutes. Samples are taken every 15 minutes, and the concentration of surviving bacteria is determined using the plate count method to calculate the sterilization rate. The wavelength range of the xenon lamp is 420–760 nm; the concentration of both bacterial solutions is 10. 8 The dosage of the carbon-based supported photocatalytic bactericide is 5.0 mg of bactericide per 1 mL of bacterial solution.

[0040] The antibacterial effect of this embodiment is as follows: As can be seen from Table 2, after 20 minutes of light exposure, the sterilization rate of the two bacteria reached 99%, demonstrating an antibacterial effect.

[0041] Table 2. Sterilization rate of Example 2

[0042]

[0043] Example 3

[0044] The present invention relates to the preparation and application of a carbon-based supported photocatalytic bactericide, comprising the following steps:

[0045] A. Put 10g of carbon material into a high-speed blender and crush it for 30 seconds to obtain 5000 mesh carbon-based material.

[0046] B. Mix the organic photovoltaic material with chloroform in the following weight ratios: Mix 0.01g of organic photovoltaic material PTQ10:PC71BM with 15ml of chloroform to obtain mixed solution A. The organic photovoltaic material is composed of PTQ10 and PC71BM mixed in a 1:1 weight ratio. Mix 0.01g of organic photovoltaic material PTQ10:ITIC-Th with 15ml of chloroform to obtain mixed solution B. The organic photovoltaic material is composed of PTQ10 and ITIC-Th mixed in a 1:1 weight ratio. When mixing the organic photovoltaic material with chloroform, use a magnetic stirrer to stir at a speed of 500 rpm for 15 minutes.

[0047] C. The mixed solutions A and B from step B are uniformly coated onto the carbon-based material from step A, with the weight ratio of the mixed solutions to the carbon-based material being 1:10000. The mixtures are then dried in a constant temperature drying oven at 60°C for 24 hours to obtain Group A carbon-based supported photocatalytic bactericide and Group B carbon-based supported photocatalytic bactericide.

[0048] D. Divide the carbon-based photocatalytic bactericide obtained in step C into two portions, A and B. Place portion A in a solution containing the harmful microorganism *Escherichia coli* (E. coli), and portion B in a solution containing the harmful microorganism *Staphylococcus aureus* (S. aureus), and place them separately in reactors. Divide the carbon-based photocatalytic bactericide obtained in step C into two portions, A and B. Place portion A in a solution containing the harmful microorganism *Escherichia coli* (E. coli), and portion B in a solution containing the harmful microorganism *Staphylococcus aureus* (S. aureus), and place them separately in reactors. Use a 500W xenon lamp as the light source, supplemented with a filter. Irradiation begins after dark-state adsorption reaches equilibrium, and is performed for 0–60 minutes. Samples are taken every 15 minutes, and the concentration of surviving bacteria is determined using the plate count method to calculate the sterilization rate. The wavelength range of the xenon lamp is 420–760 nm; the concentration of both bacterial solutions is 10. 8 The dosage of the carbon-based supported photocatalytic bactericide is 3.0 mg of bactericide per 1 mL of bacterial solution.

[0049] The antibacterial effect of this embodiment is as follows: Under light irradiation, the bactericide using PTQ10:PC71BM can achieve a bactericidal rate of 99% against both bacteria after 15 minutes, and the bactericide using PTQ10:ITIC-Th can achieve a bactericidal rate of 99% against both bacteria after 20 minutes. Both have antibacterial effects, and the material using PTQ10:PC71BM is superior to PTQ10:ITIC-Th.

[0050] Example 4

[0051] The present invention relates to the preparation and application of a carbon-based supported photocatalytic bactericide, comprising the following steps:

[0052] A. Put 10g of carbon material into a high-speed blender and pulverize for 50 seconds to obtain 6000 mesh carbon-based material.

[0053] B. Mix the organic photovoltaic material with chloroform in the following weight ratio: organic photovoltaic material PTQ10: PC71BM 0.01g: chloroform 10ml to obtain a mixed solution; the organic photovoltaic material is composed of PTQ10 and PC71BM mixed in a weight ratio of 1:1. When mixing the organic photovoltaic material with chloroform, use a magnetic stirrer to stir at a speed of 500r / min for 15min.

[0054] C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000. The mixture is dried in a constant temperature drying oven at 60°C for 24 hours to obtain a carbon-based supported photocatalytic bactericide.

[0055] D. Divide the carbon-based photocatalytic bactericide obtained in step C into two portions, A and B. Place portion A in a solution containing the harmful microorganism *Escherichia coli* (E. coli), and portion B in a solution containing the harmful microorganism *Staphylococcus aureus* (S. aureus). Place each portion in a reactor, using a 500W xenon lamp as the light source, supplemented with a filter. Irradiation begins after dark-state adsorption reaches equilibrium, lasting 0–60 minutes. Samples are taken every 15 minutes, and the concentration of surviving bacteria is determined using the plate count method to calculate the sterilization rate. The wavelength range of the xenon lamp is 420–760 nm; the concentration of both bacterial solutions is 10. 8 The dosage of the carbon-based supported photocatalytic bactericide is 5.0 mg of bactericide per 1 mL of bacterial solution.

[0056] The antibacterial effect of this embodiment is as follows: As can be seen from Table 3, after 10 minutes of light exposure, the kill rate of the two bacteria reached 99%, which shows that it has an antibacterial effect.

[0057] Table 3. Sterilization rate of Example 4

[0058]

[0059] Example 5

[0060] This invention relates to the application of a carbon-based supported photocatalytic bactericide in refrigerator sterilization, comprising the following steps:

[0061] A. Put 10g of carbon material into a high-speed blender and crush it for 40 seconds to obtain 5000 mesh carbon-based material.

[0062] B. Mix the organic photovoltaic material with chloroform in the following weight ratio: organic photovoltaic material PTQ10: PC71BM 0.01g: chloroform 15ml to obtain a mixed solution; the organic photovoltaic material is composed of PTQ10 and PC71BM mixed in a weight ratio of 1:1. When mixing the organic photovoltaic material with chloroform, use a magnetic stirrer to stir at a speed of 500r / min for 15min.

[0063] C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000. The mixture is dried in a constant temperature drying oven at 60°C for 24 hours to obtain a carbon-based supported photocatalytic bactericide.

[0064] D. The carbon-based photocatalytic bactericide obtained in step C was placed in a transparent porous film package and sealed. The package was then placed near an LED light inside a 100L refrigerator. Petri dishes containing LB solid culture medium were placed in the refrigerator with the lid off for 30 minutes. Three parallel experiments were conducted. After 30 minutes, the petri dishes were placed in a constant temperature incubator for 24 hours, and the colony counts were recorded. Under the same conditions, the control group did not use the photocatalytic bactericide. The amount of the photocatalytic bactericide used was 0.1g.

[0065] The antibacterial effect of this embodiment is as follows: after 30 minutes of light irradiation, bacteria such as Escherichia coli were present on the culture dishes of the control group, while no bacteria were present on the culture dishes of the experimental group. The photocatalytic bactericide PTQ10:PC71BM has excellent bactericidal performance.

[0066] Example 6

[0067] This invention relates to the application of a carbon-based supported photocatalytic bactericide in refrigerator sterilization, comprising the following steps:

[0068] A. Put 10g of carbon material into a high-speed blender and crush it for 40 seconds to obtain 5000 mesh carbon-based material.

[0069] B. Mix the organic photovoltaic material with chloroform in the following weight ratio: PTQ10 organic photovoltaic material: 0.01g ITIC-Th: 15ml chloroform to obtain a mixed solution; the organic photovoltaic material is composed of PTQ10 and ITIC-Th mixed in a weight ratio of 1:1. When mixing the organic photovoltaic material with chloroform, use a magnetic stirrer to stir at a speed of 500 rpm for 15 minutes.

[0070] C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000. The mixture is dried in a constant temperature drying oven at 60°C for 24 hours to obtain a carbon-based supported photocatalytic bactericide.

[0071] D. The carbon-based photocatalytic bactericide obtained in step C was placed in a transparent porous film package and sealed. The package was then placed near an LED light inside a 100L refrigerator. Petri dishes containing LB solid culture medium were placed in the refrigerator with the lid off for 30 minutes. Three parallel experiments were conducted. After 30 minutes, the petri dishes were placed in a constant temperature incubator for 24 hours, and the number of colonies on the petri dishes was counted. Under the same conditions, the control group did not use the photocatalytic bactericide. The amount of the photocatalytic bactericide used was 0.5g.

[0072] The antibacterial effect of this example is as follows: after 15 minutes of light exposure, bacteria such as Escherichia coli were present on the culture dishes of the control group, while no bacteria were present on the culture dishes of the experimental group. The photocatalytic bactericide PTQ10:ITIC-Th has excellent bactericidal performance.

Claims

1. A method for preparing a carbon-based supported photocatalytic bactericide, characterized in that, The following steps are included: A. Crush carbon materials to 4000-6000 mesh to obtain carbon-based materials; B. Mix the organic photovoltaic material with chloroform in the following weight ratio: 0.01-0.02g organic photovoltaic material: 10-15ml chloroform. Stirring is used during mixing at a speed of 500r / min for 15 minutes to obtain a mixed solution. The organic photovoltaic material is a binary organic photocatalytic material PTQ10:ITIC-Th or PTQ10:PC71BM prepared using a molecular regulation strategy. The organic photovoltaic material PTQ10:PC71BM is prepared by mixing PTQ10 and PC71BM in a weight ratio of 1:1, and the organic photovoltaic material PTQ10:ITIC-Th is prepared by mixing PTQ10 and ITIC-Th in a weight ratio of 1:

1. C. The mixed solution from step B is uniformly coated onto the carbon-based material from step A. The weight ratio of the mixed solution to the carbon-based material is 1:5000 to 10000. The mixture is dried in a constant temperature drying oven at 60°C for 24 hours. After drying, a carbon-based supported photocatalytic bactericide is obtained.

2. The preparation method of the carbon-based supported photocatalytic bactericide according to claim 1, characterized in that, In step A, the carbon material is placed in a blender and pulverized for 30-50 seconds.

3. The application of the carbon-based supported photocatalytic bactericide obtained by the preparation method according to claim 1 or 2, characterized in that, The carbon-based photocatalytic bactericide is used to sterilize harmful microorganisms. The operation method is as follows: The carbon-based photocatalytic bactericide is placed in a solution containing harmful microorganisms Escherichia coli or Staphylococcus aureus. A xenon lamp is used as the light source, supplemented with a filter. After the dark adsorption reaches equilibrium, the light is irradiated. Samples are taken every 15 minutes, and the concentration of surviving bacteria is determined by plate counting method. The kill rate is calculated until the sterilization purpose is achieved.

4. The application of the carbon-based supported photocatalytic bactericide according to claim 3, characterized in that, The xenon lamp has a power of 500W and a wavelength range of 420–760nm.

5. The application of the carbon-based supported photocatalytic bactericide according to claim 3, characterized in that, The concentration of both bacterial solutions was 10. 8 The dosage of the carbon-based supported photocatalytic bactericide is 1.0 to 5.0 mg of bactericide per 1 mL of bacterial solution.

6. The application of the carbon-based supported photocatalytic bactericide obtained by the preparation method according to claim 1 or 2, characterized in that, The carbon-based photocatalytic bactericide is used for sterilization in a closed space. The procedure is as follows: the carbon-based photocatalytic bactericide is placed in a transparent porous film package and sealed. The package is then placed in a closed space. The dosage of the carbon-based photocatalytic bactericide is 1-5 mg of bactericide per 1 L volume.

7. The application of the carbon-based supported photocatalytic bactericide according to claim 6, characterized in that, The enclosed space is a refrigerator.

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