Preparation method of carbon-based loaded organic photovoltaic material photocatalyst for removing grape downy mildew and botrytis cinerea

Abstract

The invention discloses a preparation method of a photocatalyst for removing downy mildew and botrytis cinerea of a carbon-based loaded organic photovoltaic material. The method comprises the following operation steps: A, cleaning coconut shells, and drying until the coconut shells are completely dried; b, crushing the completely dried coconut shells with a crusher, and sieving with a 200-mesh sieve to obtain coconut shell powder; c, drying the coconut shell powder, and performing high-temperature pyrolysis treatment on the dried coconut shell powder in a tubular furnace to obtain modified carbon-based material coconut shell carbon particles; d, mixing an organic photovoltaic material and chloroform according to the following weight ratio: 0.01-0.02 g of the organic photovoltaic material and 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; and E, uniformly coating modified carbon-based material coconut shell carbon particles with the organic photocatalyst mixed solution obtained in the step D, and drying at 60 DEG C for 24 hours to obtain the coconut shell carbon-based loaded organic photocatalyst. And F, adding the coconut shell carbon-based loaded organic photocatalyst obtained in the step E into a reinforcing agent polyethylene glycol solution, uniformly mixing for 0.5 h, and drying at 60 DEG C for 12 h to obtain the carbon-based loaded organic photovoltaic material photocatalyst for removing grape downy mildew and botrytis cinerea. The photocatalyst obtained by the method can efficiently and quickly remove the plasmopara viticola and the botrytis cinerea at the same time, can be repeatedly utilized, solves the problems of a photocatalyst loading process and cyclic utilization, and provides a real green, environment-friendly and pollution-free treatment method for removing the plasmopara viticola and the botrytis cinerea.

Description

Technical Field

[0001] The invention relates to the technical field of functional material preparation, in particular to a method for preparing a carbon-based organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold. Background Art

[0002] Table grapes typically suffer high postharvest losses and their shelf life is limited due to their high sensitivity to conditions during postharvest handling, storage, transportation and marketing. Fungal decay is a significant factor leading to huge economic losses in the table grape marketing chain, with estimated losses accounting for approximately 10-40% of the total grape production value. The safe and effective management of downy mildew and gray mold in grapes is a major challenge, as they are the pathogens responsible for downy mildew and gray mold in grapes, both of which are major diseases that damage grapes.

[0003] Sulfur dioxide fumigation has long been widely used to preserve grapes during storage. However, improper use of sulfur dioxide may cause fruit bleaching and browning. Some grape preservation technologies have emerged, but most of the treatment methods involve synthetic fungicides, which are harmful to human health and the environment. Therefore, it is urgent to develop a green and environmentally friendly photocatalyst preparation method that has simple use conditions and can simultaneously remove grape downy mildew and gray mold. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing a carbon-based organic photovoltaic material-loaded photocatalyst for removing grape downy mildew and gray mold. The photocatalyst obtained by the method can achieve efficient removal of grape downy mildew and gray mold at the same time and can be reused, providing a truly green, environmentally friendly and pollution-free treatment method for the removal of grape downy mildew and gray mold.

[0005] The present invention solves the above technical problems with the following technical solutions:

[0006] The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using a carbon-based organic photovoltaic material according to the present invention comprises the following steps:

[0007] A. Clean the coconut shell and dry it until it is completely dry;

[0008] B. Crushing the completely dried coconut shell with a pulverizer and passing it through a 200 mesh sieve to obtain coconut shell powder;

[0009] C. The coconut shell powder was dried at 100° C. for 24 h and then placed in a tube furnace for high temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles;

[0010] D. Mixing an organic photovoltaic material and chloroform in the following weight ratio: 0.01-0.02 g of organic photovoltaic material and 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is PTQ10:Y6, PTQ10:IEICO-4F or PTQ10:ITIC-Th;

[0011] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain a coconut shell carbon-based supported organic photocatalyst;

[0012] F. Add the coconut shell carbon-based organic photocatalyst of step E to the enhancer polyethylene glycol solution, add 5 mL of polyethylene glycol solution to every 5 g of organic photocatalyst, mix evenly for 0.5 h, and then dry at 60° C. for 12 h to obtain the carbon-based organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold.

[0013] In step A of the present invention, the drying treatment refers to placing the coconut shell in a forced air drying oven at a temperature of 70° C. and drying it for 48 hours.

[0014] In step B of the present invention, the coconut shell is crushed for 3 to 5 minutes.

[0015] In step C of the present invention, the operation of the tubular furnace for high-temperature pyrolysis treatment is as follows: putting the coconut shell powder into the tubular furnace, closing the furnace plug, evacuating for 15 minutes, passing nitrogen for 20 minutes, heating to 200° C. at a heating rate of 5° C. / min under nitrogen protection, then heating to 700° C. at a heating rate of 10° C. / min, keeping for 3 hours, cooling to room temperature, and bagging for standby use.

[0016] In step E of the present invention, the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:5000-10000.

[0017] In step F of the present invention, the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: 5% to 20% polyethylene glycol and 80% to 95% ultrapure water.

[0018] In step D of the present invention, the PTQ10:Y6, PTQ10:IEICO-4F and PTQ10:ITIC-Th are mixed in a weight ratio of 1:1.

[0019] In step D of the present invention, when preparing the organic photocatalyst mixed solution, the organic photovoltaic material and chloroform are mixed and then stirred and dissolved at 80° C. for 1 hour.

[0020] The method of the present invention has the following beneficial effects:

[0021] (1) The photocatalyst obtained by the method of the present invention can achieve the removal of grape downy mildew and gray mold by modified carbon-based materials, with a very good removal effect, a removal rate of 99.9%, and can be reused.

[0022] (2) The method of the present invention is based on its own photocatalytic properties. When irradiated with light, electron-hole pairs are generated, which react with water and oxygen in the air to generate hydroxyl radicals and superoxide radicals, which attack bacteria and outer cells, penetrate the bacterial cell membrane and destroy the cell membrane structure, thereby completely killing the bacteria. This process does not require the use of any foreign chemical substances and can achieve the purpose of highly efficient inactivation of bacteria. It has excellent bactericidal ability, environmental protection characteristics and non-invasiveness.

[0023] (3) The photocatalyst of the present invention has excellent antibacterial properties and can be used in the fields of fruits and vegetables, food processing, food packaging, etc. that are in direct contact with humans. In addition, the preparation method is simple, low-cost, and environmentally friendly, and can be industrialized and produced, which has great promotion value.

[0024] (4) The matrix material used in the present invention is a natural product carbon-based material with many excellent properties such as hydrophilicity, greenness, high porosity, large specific surface area, etc., and the organic photovoltaic material loaded on the matrix material is reusable and degradable, achieving true green friendliness and environmental pollution-free. DETAILED DESCRIPTION

[0025] The technical solution of the present invention is further described below in conjunction with specific embodiments, but the present invention is not limited thereto.

[0026] Example 1

[0027] The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using a carbon-based organic photovoltaic material is carried out according to the following steps:

[0028] A. Wash the coconut shell with ultrapure water and put it into a blast drying oven at 70℃ for 48 hours to make the coconut shell completely

[0029] Completely dry;

[0030] B. Grind the completely dried coconut shell with a grinder for 3 to 5 minutes and then pass it through a 200-mesh sieve to obtain coconut shell powder;

[0031] C. Dry the coconut shell powder at 100°C for 24 hours and then put it into a tubular furnace for high-temperature pyrolysis treatment to obtain modified carbon-based coconut shell carbon particles; during operation, put the coconut shell powder into the tubular furnace, close the furnace plug, evacuate for 15 minutes, pass nitrogen for 20 minutes, and then heat it to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heat it to 700°C at a heating rate of 10°C / min, keep it for 3 hours, and then cool it to

[0032] Room temperature, bag and set aside;

[0033] D. Mixing 0.015 g of the organic photovoltaic material PTQ10:Y6 with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PTQ10:Y6 is obtained by mixing PTQ10 and Y6 in a weight ratio of 1:1;

[0034] During the preparation, the organic photovoltaic material was mixed with chloroform and then dissolved by stirring at 80°C for 1 h;

[0035] E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain the modified carbon-based supported organic photocatalyst, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500; F. 5g of the modified carbon-based supported organic photocatalyst in step E is added with 5ml of the enhancer polyethylene glycol solution and evenly mixed for 0.5h, and then dried at 60° C. for 12h to obtain the carbon-based supported organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold of the present invention, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: 15% polyethylene glycol and 85% deionized water.

[0036] The photocatalyst (3 mg / mL) prepared in this example was used to treat grape downy mildew (1×10 7 CFU / mL) and Botrytis cinerea (1×10 7 CFU / mL) degradation, and the removal rate was 99.9% within 60 minutes, which had an antibacterial effect, as shown in Table 1.

[0037] Table 1 Sterilization rate of Example 1

[0038]

[0039] Example 2

[0040] The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using a carbon-based organic photovoltaic material according to the present invention is carried out according to the following steps:

[0041] A. Wash the coconut shell with ultrapure water and put it into a blast drying oven at 70℃ for 48 hours to make the coconut shell completely

[0042] Completely dry;

[0043] B. Grind the completely dried coconut shell with a grinder for 3 to 5 minutes and then pass it through a 200-mesh sieve to obtain coconut shell powder;

[0044] C. Dry the coconut shell powder at 100℃ for 24h and then put it into a tube furnace for high temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles; during operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate the

[0045] After heating for 15 min, nitrogen was passed through for 20 min, and then heated to 200 °C at a heating rate of 5 °C / min under nitrogen protection, and then heated to 700 °C at a heating rate of 10 °C / min, maintained for 3 h, and then cooled to

[0046] Room temperature, bag and set aside;

[0047] D. Mix 0.015 g of the organic photovoltaic material PTQ10:IEICO-4F with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PTQ10:IEICO-4F is obtained by mixing PTQ10 and IEICO-4F in a weight ratio of 1:1. During the preparation, the organic photovoltaic material and chloroform are mixed and then stirred at 80°C to dissolve.

[0048] Solution 1h;

[0049] E. The organic photocatalyst mixed solution obtained in step D is uniformly coated on the modified carbon-based coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain a modified carbon-based supported organic photocatalyst, wherein

[0050] The weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500; F. Add 5 ml of the enhancer polyethylene glycol to 5 g of the modified carbon-based organic photocatalyst loaded in step E.

[0051] The solution was uniformly mixed for 0.5 h and then dried at 60° C. for 12 h to obtain the carbon-based organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold of the present invention, wherein the polyethylene glycol solution was prepared by mixing the following raw materials in weight percentage: 10% polyethylene glycol and 90% deionized water.

[0052] The photocatalyst (3 mg / mL) prepared in this example was used to treat grape downy mildew (1×10 7 CFU / mL) and Botrytis cinerea (1×10 7 CFU / mL) degradation, and the removal rate was 99.9% within 60 minutes, which had an antibacterial effect, as shown in Table 2.

[0053] Table 2 Sterilization rate of Example 2

[0054]

[0055] Example 3

[0056] The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using a carbon-based organic photovoltaic material is carried out according to the following steps:

[0057] A. Wash the coconut shell with ultrapure water and put it into a blast drying oven at 70℃ for 48 hours to make the coconut shell completely

[0058] Completely dry;

[0059] B. Grind the completely dried coconut shell with a grinder for 3 to 5 minutes and then pass it through a 200-mesh sieve to obtain coconut shell powder;

[0060] C. Dry the coconut shell powder at 100°C for 24 hours and then put it into a tube furnace for high-temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles; during operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate the

[0061] After heating for 15 min, nitrogen was passed through for 20 min, and then heated to 200 °C at a heating rate of 5 °C / min under nitrogen protection, and then heated to 700 °C at a heating rate of 10 °C / min, maintained for 3 h, and then cooled to

[0062] Room temperature, bag and set aside;

[0063] D. Mix 0.015 g of organic photovoltaic material PTQ10:ITIC-Th with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PTQ10:ITIC-Th is composed of PTQ10 and ITIC-Th in a weight ratio of 1:1.

[0064] During preparation, the organic photovoltaic material is mixed with chloroform and then stirred and dissolved at 80°C for 1h; E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles.

[0065] The modified carbon-based organic photocatalyst was obtained after drying at 60°C for 24 hours.

[0066] The weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500; F. Add 5g of the modified carbon-based organic photocatalyst loaded in step E to 5ml of the enhancer polyethylene glycol solution and mix evenly for 0.5h, and then dry at 60°C for 12h to obtain the carbon-based organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold of the present invention, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: 5% polyethylene glycol and 95% deionized water.

[0067] The photocatalyst (3 mg / mL) prepared in this example was used to treat grape downy mildew (1×10 7 CFU / mL) and Botrytis cinerea (1×10 7 CFU / mL) degradation, and the removal rate was 99.9% within 60 minutes, which had an antibacterial effect, as shown in Table 3.

[0068] Table 3 Sterilization rate of Example 3

[0069]

[0070] Example 4

[0071] The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using a carbon-based organic photovoltaic material according to the present invention comprises the following steps:

[0072] A. Wash the coconut shell with ultrapure water and put it into a blast drying oven at 70°C for 48 hours to make the coconut shell completely dry;

[0073] B. Grind the completely dried coconut shell with a grinder for 3 to 5 minutes and then pass it through a 200-mesh sieve to obtain coconut shell powder;

[0074] C. Dry the coconut shell powder at 100°C for 24 hours and then put it into a tubular furnace for high-temperature pyrolysis treatment to obtain modified carbon-based coconut shell carbon particles; during operation, put the coconut shell powder into the tubular furnace, close the furnace plug, evacuate for 15 minutes, pass nitrogen for 20 minutes, and then heat it to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heat it to 700°C at a heating rate of 10°C / min, keep it for 3 hours, then cool it to room temperature, and bag it for later use;

[0075] D. Mixing 0.015 g of an organic photovoltaic material PTQ10:Y6 with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PTQ10:Y6 is obtained by mixing PTQ10 and Y6 at a weight ratio of 1:1; during preparation, the organic photovoltaic material and chloroform are mixed and stirred and dissolved at 80° C. for 1 hour;

[0076] E. The organic photocatalyst mixed solution obtained in step D is uniformly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain a modified carbon-based supported organic photocatalyst, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:7500;

[0077] F. Add 6 g of the modified carbon-based organic photocatalyst in step E to 5 ml of the enhancer polyethylene glycol solution and mix evenly for 0.5 h. Then dry at 60° C. for 12 h to obtain the carbon-based organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold of the present invention, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: 20% polyethylene glycol and 80% deionized water.

[0078] When used, the photocatalyst prepared in this example is placed in a transparent porous film package and sealed to prepare a preservative. The sealed photocatalyst is placed in a 20 cm square transparent box without a cover containing 20 grapes, and placed at 37°C for a period of time, and the appearance and other indicators of the grapes are observed. The amount of the photocatalyst used is 0.15 g. Under the same temperature conditions, the control group only placed 20 grapes in a 20 cm square transparent box without a cover.

[0079] The antibacterial effect of this embodiment is as follows: the grapes in the control group without the antibacterial catalyst of the present invention began to rot on the first day and were completely rotten on the second day. The grapes in the test group with the antibacterial catalyst of the present invention began to rot slightly on the fourth day and were completely rotten on the sixth day, which has excellent antibacterial effect.

Claims

1. A method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials, characterized in that: The method comprises the following steps: A. Clean the coconut shell and dry it until it is completely dry; B. Crushing the completely dried coconut shell with a pulverizer and passing it through a 200 mesh sieve to obtain coconut shell powder; C. Drying the coconut shell powder at 100° C. for 24 h and then placing it in a tubular furnace for high-temperature pyrolysis treatment to obtain modified carbon-based material coconut shell carbon particles; D. Mixing an organic photovoltaic material and chloroform in the following weight ratio: 0.01-0.02 g of organic photovoltaic material and 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is PTQ10:Y6, PTQ10:IEICO-4F or PTQ10:ITIC-Th; E. The organic photocatalyst mixed solution obtained in step D is evenly coated on the modified carbon-based material coconut shell carbon particles, and then dried at 60° C. for 24 hours to obtain a coconut shell carbon-based supported organic photocatalyst; F. Add the coconut shell carbon-based organic photocatalyst of step E to the enhancer polyethylene glycol solution, add 5 mL of polyethylene glycol solution to every 5 g of organic photocatalyst, mix evenly for 0.5 h, and then dry at 60° C. for 12 h to obtain the carbon-based organic photovoltaic material photocatalyst for removing grape downy mildew and gray mold.

2. The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials according to claim 1, characterized in that: In step A, the drying process refers to placing the coconut shell in a forced air drying oven at a temperature of 70° C. and drying it for 48 hours.

3. The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step B, the coconut shell is crushed for 3 to 5 minutes.

4. The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step C, the operation of the tubular furnace for high-temperature pyrolysis treatment is: putting the coconut shell powder into the tubular furnace, closing the furnace plug, evacuating for 15 minutes, passing nitrogen for 20 minutes, heating to 200°C at a heating rate of 5°C / min under nitrogen protection, and then heating to 700°C at a heating rate of 10°C / min, keeping for 3 hours, cooling to room temperature, and bagging for later use.

5. The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step E, the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material coconut shell carbon particles is 1:5000-10000.

6. The method for preparing a photocatalyst for removing grape downy mildew and gray mold according to claim 1 or the carbon-based organic photovoltaic material, characterized in that: In step F, the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: 5% to 20% polyethylene glycol and 80% to 95% ultrapure water.

7. The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step D, the PTQ10:Y6, PTQ10:IEICO-4F, and PTQ10:ITIC-Th are mixed in a weight ratio of 1:

1.

8. The method for preparing a photocatalyst for removing grape downy mildew and gray mold by using carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step D, when preparing the organic photocatalyst mixed solution, the organic photovoltaic material and chloroform are mixed and then stirred and dissolved at 80° C. for 1 hour.

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