Preparation method of coconut shell carbon-based loaded organic photovoltaic material decarbamazepine photocatalyst

Abstract

The invention discloses a preparation method of a coconut shell carbon-based loaded organic photovoltaic material decarbamazepine photocatalyst. The method comprises the following 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 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 a reinforcing agent polyethylene glycol solution into the organic photocatalyst mixed solution in the step E, uniformly mixing for 0.5 h, and drying at 60 DEG C for 12 h to obtain the coconut shell carbon-based loaded organic photovoltaic material carbamazepine photocatalyst. The photocatalyst obtained by the method disclosed by the invention can be used for efficiently and quickly removing carbamazepine and can be repeatedly utilized, the problems of a photocatalyst loading process and cyclic utilization are solved, and a real green, environment-friendly and pollution-free treatment method is provided for removing carbamazepine.

Description

Technical Field

[0001] The invention relates to the technical field of functional material preparation, in particular to a method for preparing a photocatalyst for removing carbamazepine from a coconut shell carbon-based loaded organic photovoltaic material. Background Art

[0002] Carbamazepine is a psychotropic drug that is widely used with more than 1,000 tons per year. Its half-life in water is 82 days and has been found in surface water, groundwater, and drinking water at concentrations of 3.09 μg / L, 610 ng / L, and 30 ng / L, respectively. Studies have shown that this micropollutant has cytotoxic, endocrine disrupting effects, and teratogenicity, threatening aquatic life and human health. Therefore, there is an urgent need to develop an effective technology to eliminate the adverse effects of carbamazepine residues on ecosystems and human health.

[0003] Among the many environmental pollution control technologies for carbamazepine treatment, the biodegradation method has a poor treatment effect on carbamazepine, the adsorption method only transfers carbamazepine and there is a risk of secondary pollution, and the chemical oxidation method has a better treatment effect on carbamazepine and will not cause secondary pollution. Advanced oxidation is a new and efficient PPCPs treatment technology, which mainly relies on the hydroxyl radicals (·OH) with strong oxidizing ability produced under different reaction conditions to completely oxidize large molecular refractory PPCPs into harmless inorganic substances (CO2 and H2O), thereby achieving effective removal of PPCPs in water. However, the reaction conditions of the persulfate activation method in the chemical oxidation method are relatively harsh, and the ozone preparation cost of the ozone method is relatively high. Therefore, it is urgent to develop a green, environmentally friendly, simple to use, reusable, and efficient photocatalyst preparation method for removing carbamazepine. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for preparing a photocatalyst for removing carbamazepine using a coconut shell carbon-based loaded organic photovoltaic material. The photocatalyst obtained by the method can achieve efficient removal of carbamazepine and can be reused, thus providing a truly green, environmentally friendly and pollution-free treatment method for the removal of carbamazepine.

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

[0006] The method for preparing a photocatalyst for removing carbamazepine by using a coconut shell carbon-based organic photovoltaic material 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. Dry the coconut shell powder at 100° C. for 12 h and then place it in a tubular furnace for high-temperature pyrolysis 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: 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is PM6:Y6, PM6:ITCPTC or PM6:Y6:ITCPTC;

[0011] 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 coconut shell carbon-based supported organic photocatalyst;

[0012] F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, mix evenly for 0.5h, and then dry at 60°C for 12h to obtain a coconut shell carbon-based loaded organic photovoltaic material photocatalyst for removing carbamazepine.

[0013] In step A of the present invention, the operation of the drying treatment is to place the coconut shell in a forced air drying oven at a temperature of 70° C. and dry 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 high-temperature pyrolysis of the coconut shell powder in a tubular furnace 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 later use.

[0016] In step E of the present invention, the organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:5000 to 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 organic photovoltaic materials PM6:Y6 and PM6:ITCPTC are mixed at a weight ratio of 1:1, and the PM6:Y6:ITCPTC is mixed at a weight ratio of 1:1:1.

[0019] In step D of the present invention, when the organic photovoltaic material is mixed with chloroform, the mixture is stirred and dissolved at 80° C. for 1 hour.

[0020] 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 carbamazepine by the modified carbon-based material, with a very good removal effect, a removal rate of up to 99%, and can be reused.

[0022] (2) Compared with inorganic catalysts, the photocatalyst obtained by the method of the present invention has unique advantages in wastewater purification, such as rapid and effective exciton dissociation, adjustable energy level, wide absorption spectrum and excellent chemical stability, so that it can generate a large number of hydroxyl radicals and holes with strong oxidizing properties in water, which can completely and quickly oxidize and remove carbamazepine.

[0023] (3) 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, and large specific surface area. The organic photovoltaic material loaded on the matrix material is reusable and degradable, achieving true green friendliness and no pollution to the environment, which is in line with the development concept of "renewable energy technology" of the national low-carbon, environmentally friendly and green key research and development plan. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a stability test chart of carbamazepine degradation by photocatalyst obtained in Example 1 of the present invention. 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 carbamazepine by using a coconut shell 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°C for 48 hours to make the coconut shell completely dry;

[0029] 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;

[0030] C. Dry the coconut shell powder at 100°C for 12 hours and then put it into a tube furnace for high-temperature pyrolysis to obtain the modified carbon-based material coconut shell carbon particles. During the operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate for 15

[0031] min, and then heated to 400 °C at a rate of 5 °C / min under nitrogen protection for 20 min.

[0032] 200℃, then heated to 700℃ at a heating rate of 10℃ / min, kept for 3h, cooled to room temperature, and packed in bags for later use;

[0033] D. Mixing 0.015 g of an organic photovoltaic material PM6:Y6 with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PM6:Y6 is obtained by mixing PM6 and Y6 at a weight ratio of 1:1; during preparation, the organic photovoltaic material and chloroform are mixed and then stirred and dissolved at 80° C. for 1 hour;

[0034] 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 organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:7500;

[0035] F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, and the mixture is uniformly mixed for 0.5h and then dried at 60°C for 12h to obtain a coconut shell carbon-based organic photovoltaic material-supported photocatalyst for removing carbamazepine, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: polyethylene glycol 20%,

[0036] Deionized water 80%.

[0037] The coconut shell carbon-based organic photovoltaic material-loaded photocatalyst for removing carbamazepine prepared in this example was used to treat wastewater containing carbamazepine, and the removal rate was 99.2% after 20 minutes of degradation.

[0038] Figure 1 The purpose is to evaluate the potential of the catalyst in practical applications through cyclic tests. In the recycling experiment, the system was subjected to twenty-five consecutive photocatalytic tests under the same experimental conditions. Even after 25 cycles, the photocatalytic degradation efficiency of CBZ at a concentration of 10 mg / L was still as high as 95.36%, indicating that the sample has good stability and excellent reaction activity in this multiphase photocatalytic oxidation process.

[0039] Example 2

[0040] The method for preparing a photocatalyst for removing carbamazepine by using a coconut shell carbon-based organic photovoltaic material 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 12h and then put it into a tube furnace for high temperature pyrolysis to obtain the modified carbon-based material coconut shell carbon particles. During the operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate for 15

[0045] min, and then heated to 400 °C at a rate of 5 °C / min under nitrogen protection for 20 min.

[0046] 200℃, then heated to 700℃ at a heating rate of 10℃ / min, kept for 3h and cooled to room temperature.

[0047] Bag and set aside;

[0048] D. Mixing 0.015 g of an organic photovoltaic material PM6:ITCPTC with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PM6:ITCPTC is obtained by mixing PM6 and ITCPTC 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;

[0049] 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 organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:7500;

[0050] F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, and the mixture is uniformly mixed for 0.5h and then dried at 60°C for 12h to obtain a coconut shell carbon-based organic photovoltaic material-supported photocatalyst for removing carbamazepine, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: polyethylene glycol 5%,

[0051] Deionized water 95%.

[0052] The coconut shell carbon-based organic photovoltaic material-loaded photocatalyst for removing carbamazepine prepared in this example was used to treat wastewater containing carbamazepine, and the removal rate was 99.3% after degradation for 20 minutes.

[0053] Example 3

[0054] The method for preparing a photocatalyst for removing carbamazepine by using a coconut shell carbon-based organic photovoltaic material is carried out according to the following steps:

[0055] 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

[0056] Completely dry;

[0057] 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;

[0058] C. Dry the coconut shell powder at 100°C for 12 hours and then put it into a tube furnace for high-temperature pyrolysis to obtain the modified carbon-based material coconut shell carbon particles. During the operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate for 15

[0059] min, and then heated to 400 °C at a rate of 5 °C / min under nitrogen protection for 20 min.

[0060] 200℃, then heated to 700℃ at a heating rate of 10℃ / min, kept for 3h and cooled to room temperature.

[0061] Bag and set aside;

[0062] D. Mix 0.015 g of organic photovoltaic material PM6:Y6:ITCPTC with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PM6:Y6:ITCPTC is composed of PM6, Y6 and ITCPTC in a weight ratio of

[0063] 1:1:1 mixture; during preparation, the organic photovoltaic material is mixed with chloroform and then stirred and dissolved at 80°C

[0064] 1h;

[0065] 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 organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:7500;

[0066] F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, and the mixture is uniformly mixed for 0.5h and then dried at 60°C for 12h to obtain a coconut shell carbon-based organic photovoltaic material-supported photocatalyst for removing carbamazepine, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: polyethylene glycol 10%,

[0067] Deionized water 90%.

[0068] The coconut shell carbon-based organic photovoltaic material-loaded photocatalyst for removing carbamazepine prepared in this example was used to treat wastewater containing carbamazepine, and the removal rate was 99.4% after 20 minutes of degradation.

[0069] Example 4

[0070] The method for preparing a photocatalyst for removing carbamazepine by using a coconut shell carbon-based organic photovoltaic material is carried out according to the following steps:

[0071] 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

[0072] 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 12 hours and then put it into a tube furnace for high-temperature pyrolysis to obtain the modified carbon-based material coconut shell carbon particles. During the operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate for 15

[0075] min, and then heated to 400 °C at a rate of 5 °C / min under nitrogen protection for 20 min.

[0076] 200℃, then heated to 700℃ at a heating rate of 10℃ / min, kept for 3h and cooled to room temperature.

[0077] Bag and set aside;

[0078] D. Mix 0.01 g of organic photovoltaic material PM6:Y6:ITCPTC with 10 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PM6:Y6:ITCPTC is composed of PM6, Y6 and ITCPTC in a weight ratio of 1:1:1

[0079] During the preparation, the organic photovoltaic material is mixed with chloroform and then stirred and dissolved at 80° C. for 1 hour;

[0080] 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 modified carbon-based supported organic photocatalyst, wherein the organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:5000;

[0081] F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, and the mixture is uniformly mixed for 0.5h and then dried at 60°C for 12h to obtain a coconut shell carbon-based organic photovoltaic material-supported photocatalyst for removing carbamazepine, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: polyethylene glycol 20%,

[0082] Deionized water 80%.

[0083] The coconut shell carbon-based organic photovoltaic material-loaded photocatalyst for removing carbamazepine prepared in this example was used to treat wastewater containing carbamazepine, and the removal rate was 99.4% after 20 minutes of degradation.

[0084] Example 5

[0085] The method for preparing a photocatalyst for removing carbamazepine by using a coconut shell carbon-based organic photovoltaic material is carried out according to the following steps:

[0086] 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

[0087] Completely dry;

[0088] 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;

[0089] C. Dry the coconut shell powder at 100°C for 12 hours and then put it into a tube furnace for high-temperature pyrolysis to obtain the modified carbon-based material coconut shell carbon particles. During the operation, put the coconut shell powder into the tube furnace, close the furnace plug, and evacuate for 15

[0090] min, and then heated to 400 °C at a rate of 5 °C / min under nitrogen protection for 20 min.

[0091] 200℃, then heated to 700℃ at a heating rate of 10℃ / min, kept for 3h and cooled to room temperature.

[0092] Bag and set aside;

[0093] D. Mix 0.02 g of organic photovoltaic material PM6:Y6:ITCPTC with 20 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PM6:Y6:ITCPTC is composed of PM6, Y6 and ITCPTC in a weight ratio of 1:1:1

[0094] During the preparation, the organic photovoltaic material is mixed with chloroform and then stirred and dissolved at 80° C. for 1 hour;

[0095] 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 modified carbon-based supported organic photocatalyst, wherein the organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:10000;

[0096] F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, and the mixture is uniformly mixed for 0.5h and then dried at 60°C for 12h to obtain a coconut shell carbon-based organic photovoltaic material-supported photocatalyst for removing carbamazepine, wherein the polyethylene glycol solution is prepared by mixing the following raw materials in weight percentage: polyethylene glycol 10%,

[0097] Deionized water 90%.

[0098] The coconut shell carbon-based organic photovoltaic material-loaded photocatalyst for removing carbamazepine prepared in this example was used to treat wastewater containing carbamazepine, and the removal rate was 99.4% after degradation for 20 minutes.

Claims

1. A method for preparing a photocatalyst for removing carbamazepine by using coconut shell 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. Dry the coconut shell powder at 100° C. for 12 h and then place it in a tubular furnace for high-temperature pyrolysis 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: 10-20 ml of chloroform to obtain an organic photocatalyst mixed solution; the organic photovoltaic material is PM6:Y6, PM6:ITCPTC or PM6:Y6:ITCPTC; 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 coconut shell carbon-based supported organic photocatalyst; F. Add the organic photocatalyst mixed solution of step E to the enhancer polyethylene glycol solution, the weight ratio of the organic photocatalyst mixed solution to the enhancer polyethylene glycol solution is 1:0.5, mix evenly for 0.5h, and then dry at 60°C for 12h to obtain a coconut shell carbon-based loaded organic photovoltaic material photocatalyst for removing carbamazepine.

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

3. The method for preparing a photocatalyst for removing carbamazepine from coconut shell 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 carbamazepine by using coconut shell carbon-based organic photovoltaic materials according to claim 1, characterized in that: In step C, the operation of high-temperature pyrolysis of the coconut shell powder in a tubular furnace is as follows: placing the coconut shell powder in 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 carbamazepine by using coconut shell carbon-based organic photovoltaic materials according to claim 1, characterized in that: In step E, the organic photocatalyst mixed solution and the modified carbon-based material coconut shell carbon particles are prepared in a weight ratio of 1:5000 to 10000.

6. The method for preparing a photocatalyst for removing carbamazepine by using coconut shell carbon-based organic photovoltaic materials according to claim 1, 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 carbamazepine by using coconut shell carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step D, the organic photovoltaic materials PM6:Y6 and PM6:ITCPTC are mixed at a weight ratio of 1:1, and the PM6:Y6:ITCPTC is mixed at a weight ratio of 1:1:

1.

8. The method for preparing a photocatalyst for removing carbamazepine by using coconut shell carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step D, the organic photovoltaic material is mixed with chloroform and dissolved by stirring at 80° C. for 1 hour.

Images