Preparation method of photocatalyst for removing fluorine-containing pollutants from modified carbon-based loaded organic photovoltaic material

Abstract

The invention discloses a preparation method of a photocatalyst for removing fluorine-containing pollutants from a modified carbon-based loaded organic photovoltaic material. The method comprises the following steps: A, mixing a crushed carbon material with deionized water; b, placing the mixed solution in an ice bath environment, and then adding concentrated acid / amino-rich materials; c, putting the mixed solution into a polytetrafluoroethylene reaction kettle, and heating for 24 hours; d, filtering, washing and drying the mixed solution to obtain a modified carbon-based material; e, mixing an organic photovoltaic material and chloroform according to a certain weight ratio to obtain an organic photocatalyst mixed solution; and F, uniformly coating the modified carbon-based material with the organic photocatalyst mixed solution, and drying at 60 DEG C for 24 hours to obtain the photocatalyst. The photocatalyst obtained by the method disclosed by the invention can be used for efficiently and quickly removing the fluorine-containing pollutants, and can be repeatedly used, so that a real green, environment-friendly and pollution-free treatment method is provided for removing the fluorine-containing pollutants.

Description

Technical Field

[0001] The present invention relates to the technical field of functional material preparation, and specifically to a preparation method of a photocatalyst for removing fluorine-containing pollutants by a modified carbon-based supported organic photovoltaic material. Background Art

[0002] Fluorine-containing pollutants (including perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.) are a kind of perfluorinated compounds synthesized artificially and are widely used in fields such as semiconductors, chemical engineering, and food packaging. Due to the multi-field and large-scale application of fluorine-containing pollutants, the presence of fluorine-containing pollutants has been detected in key river basins and drinking water in many countries around the world. The incidence of skeletal fluorosis, cancer, infertility, etc. among residents is getting higher and higher, which is highly related to the excessive intake of organic fluorides. The chemical structure of fluorine-containing pollutants is extremely stable and is not easily degraded under the action of high temperature, strong light, biological enzymes, etc., and is considered a permanent chemical. The global pollution control of fluorine-containing pollutants is extremely urgent.

[0003] Currently, the methods for degrading fluorine-containing pollutants in wastewater mainly include electrochemical method, membrane separation method, microbial method, and adsorption method. These methods all have some technical problems: the electrochemical method has too high energy consumption, high loss of electrode materials, and high treatment cost during the degradation process; the membrane separation method has low efficiency, high cost, and the membrane is easily contaminated; the microbial method has a long action time and is easily affected by factors such as temperature, nutrient components, and ion concentration; the adsorption photocatalysis method is considered the most direct and effective technology for treating fluorine-containing pollutants, but the commonly used adsorbents for the adsorption method, such as iron-based composite materials, bentonite, and modified TiO 2 There are the following technical problems to be overcome: (1) Iron-based composite materials and bentonite are easily corroded in an acidic environment, and their fluorine-containing pollutant adsorption efficiency is proportional to the input amount. A large amount of input will cause secondary pollution and is not easy to recycle; (2) Modified TiO 2 Belongs to an inorganic photocatalyst. Compared with organic catalysts, it has a narrow absorption spectrum, a wide band gap, slow exciton generation and separation efficiency, and is easily agglomerated in water, resulting in low fluorine-containing pollutant adsorption efficiency. Moreover, using an excessive amount will be accompanied by secondary pollution and is not easy to recycle.

[0004] Therefore, there is an urgent need to develop a preparation method of a photocatalyst that can effectively remove fluorine-containing pollutants and is recyclable and environmentally friendly. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a preparation method of a photocatalyst for removing fluorine-containing pollutants by a modified carbon-based supported organic photovoltaic material. The photocatalyst obtained by this method can achieve the efficient removal of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and is recyclable, providing a truly green, environmentally friendly, and pollution-free treatment method for the removal of fluorine-containing pollutants.

[0006] The present invention solves the above technical problems with the following technical solutions:

[0007] A preparation method of a photocatalyst for removing fluorine-containing pollutants from a modified carbon-based supported organic photovoltaic material according to the present invention includes the following operating steps:

[0008] A. Crush carbon materials to 6000-8000 mesh to obtain carbon powder;

[0009] B. Mix the carbon powder in step A with deionized water according to the following weight ratio to obtain a mixed solution A: 10 g of carbon powder and 100 ml of deionized water;

[0010] C. Place the mixed solution A in an ice bath environment, and then dropwise add concentrated acid / amino-rich material. After mechanical stirring evenly, obtain a mixed solution B; the addition amount of the concentrated acid / amino-rich material is 8-15% of the weight of the mixed solution A, and the concentrated acid / amino-rich material is concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid or polyethyleneimine;

[0011] D. Put the mixed solution B into a polytetrafluoroethylene reaction kettle and heat it in an oven for 24 h;

[0012] E. Filter, wash and dry the solution after the reaction in step D to obtain a modified carbon-based material;

[0013] F. Mix the organic photovoltaic material with chloroform according to the following weight ratio to obtain an organic photocatalyst mixed solution: 0.01-0.02 g of organic photovoltaic material: 10-20 ml of chloroform; the organic photovoltaic material is PTQ10:Y6, PTQ10:PY-IT, PTQ10:XS6, PTQ10:MeIC or PTQ10:Y6:PY-IT;

[0014] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material. The dosage ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:5000-10000 by weight. After drying at 60°C for 24 h, a photocatalyst for removing fluorine-containing pollutants from a modified carbon-based supported organic photovoltaic material is obtained.

[0015] In step A of the present invention, when crushing, the carbon materials are put into a planetary ball mill for crushing, and the crushing time of the carbon materials is 10-12 h.

[0016] In step C of the present invention, the water temperature of the ice bath environment is 2-10°C; the rate of the mechanical stirring is 500-800 r / min, and the stirring time is 30 min.

[0017] In step D of the present invention, the volume of the mixed solution B accounts for 1 / 3 of the reaction kettle; the temperature of the oven heating is 80°C.

[0018] In step E of the present invention, the filtration is carried out by using a filter paper with a pore size of 0.1 - 1 μm to collect the carbon-based material; the washing is carried out by rinsing the collected carbon-based material with deionized water 3 - 5 times; the drying is carried out in an oven at a temperature of 60 °C for 24 h.

[0019] In step F of the present invention, PTQ10:Y6, PTQ10:PY-IT, PTQ10:XS6, and PTQ10:MeIC are all mixed in a weight ratio of 1:1, and PTQ10:Y6:PY-IT is mixed in a weight ratio of 1:1:1.

[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 effectively remove fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.) by the modified carbon-based material, and the removal effect is very good, with a removal rate of up to 100%, and it 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 fast and effective exciton dissociation, adjustable energy levels, broad absorption spectra, and excellent chemical stability, which enable it to generate a large number of highly oxidizing hydroxyl radicals and holes in water, and can quickly and thoroughly oxidize and remove fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.).

[0023] (3) The matrix carbon material used in the present invention has many excellent properties such as hydrophilicity, greenness, high porosity, and large specific surface area. Moreover, the organic photovoltaic material loaded on the matrix material can be reused and degraded, achieving true green friendliness and no environmental pollution. Description of the Drawings

[0024] Figure 1 It is a stability test chart of the photocatalyst for degrading fluorine-containing pollutants obtained in Example 1 of the present invention. Detailed Embodiments

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

[0026] Example 1

[0027] The preparation method of the photocatalyst for removing fluorine-containing pollutants by the modified carbon-based supported organic photovoltaic material of the present invention is operated according to the following steps:

[0028] A. Put 10 g of carbon material into a wall breaker and crush it for 11 h to obtain carbon powder with a particle size of 7000 mesh;

[0029] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain a mixed solution A;

[0030] C. In an ice bath environment (water temperature is 6 °C), 12 g of concentrated sulfuric acid is added dropwise to the mixed solution A, and mechanically stirred at a rotation speed of 650 r / min for 30 min to obtain a mixed solution B;

[0031] D. Add the mixed solution B to 1 / 3 of the polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0032] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

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

[0034] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based material supported with organic photovoltaic material of the present invention, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0035] The photocatalyst for removing fluorine-containing pollutants of the modified carbon-based material supported with organic photovoltaic material prepared in this example is used for the degradation of fluorine-containing pollutants (perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and the removal rate is 100% after 40 minutes. See the removal effect and stability in Figure 1 as shown.

[0036] Example 2

[0037] The preparation method of the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based material supported with organic photovoltaic material of the present invention is operated according to the following steps:

[0038] A. Put 10 g of carbon material into a wall breaker and crush it for 11 h to obtain carbon powder with a mesh size of 7000;

[0039] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain a mixed solution A;

[0040] C. In an ice bath environment (water temperature is 6 °C), 12 g of concentrated sulfuric acid is added dropwise to the mixed solution A, and mechanically stirred at a rotation speed of 650 r / min for 30 min to obtain a mixed solution B;

[0041] D. Add the mixed solution B to 1 / 3 of the polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0042] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0043] F. Mix 0.015 g of the organic photovoltaic material PTQ10:Y6 with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:Y6 is obtained by mixing PTQ10 and Y6 in a weight ratio of 1:1;

[0044] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants from the modified carbon-based material supported organic photovoltaic material of the present invention, where the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0045] The photocatalyst for removing fluorine-containing pollutants from the modified carbon-based material supported organic photovoltaic material prepared in this example is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and the removal rate is 99.5% after 40 minutes.

[0046] Example 3

[0047] The preparation method of the photocatalyst for removing fluorine-containing pollutants from the modified carbon-based material supported organic photovoltaic material of the present invention is operated according to the following steps:

[0048] A. Put 10 g of carbon material into a blender and crush it for 11 h to obtain carbon powder with a mesh size of 7000;

[0049] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain a mixed solution A;

[0050] C. In an ice bath environment (water temperature is 6 °C), slowly add 12 g of concentrated sulfuric acid dropwise to the mixed solution A, and mechanically stir it at a rotation speed of 650 r / min for 30 min to obtain a mixed solution B;

[0051] D. Add the mixed solution B to 1 / 3 of a polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0052] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0053] F. Mix 0.015 g of the organic photovoltaic material PTQ10:PY-IT with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:PY-IT is obtained by mixing PTQ10 and PY-IT in a weight ratio of 1:1;

[0054] G. Uniformly coat the obtained organic photocatalyst mixed solution in step F on the modified carbon-based material, and obtain the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material of the present invention after drying at 60 °C for 24 h, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0055] The photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material prepared in this example is used for the degradation of fluorine-containing pollutants (perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and the removal rate is 99.5% after 40 minutes.

[0056] Example 4

[0057] The preparation method of the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material of the present invention is operated according to the following steps:

[0058] A. Put 10 g of carbon material into a wall breaker and crush it for 11 h to obtain carbon powder with a mesh size of 7000;

[0059] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain mixed solution A;

[0060] C. In an ice bath environment (water temperature is 6 °C), gradually add 12 g of concentrated sulfuric acid dropwise to mixed solution A, and mechanically stir at a rotation speed of 650 r / min for 30 min to obtain mixed solution B;

[0061] D. Add mixed solution B to 1 / 3 of a polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0062] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0063] F. Mix 0.015 g of organic photovoltaic material PTQ10:XS6 with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, wherein PTQ10:XS6 is obtained by mixing PTQ10 and XS6 according to a weight ratio of 1:1;

[0064] G. Uniformly coat the obtained organic photocatalyst mixed solution in step F on the modified carbon-based material, and then dry it at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material of the present invention, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0065] The photocatalyst for removing fluorine-containing pollutants prepared in this example, which is a modified carbon-based supported organic photovoltaic material, is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.). After 40 minutes, the removal rate is 99.1%.

[0066] Example 5

[0067] The preparation method of the photocatalyst for removing fluorine-containing pollutants by the modified carbon-based supported organic photovoltaic material of the present invention is operated according to the following steps:

[0068] A. Put 10 g of carbon material into a wall breaker and crush it for 11 h to obtain carbon powder with a mesh size of 7000;

[0069] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain a mixed solution A;

[0070] C. In an ice bath environment (water temperature is 6 °C), gradually add 12 g of concentrated sulfuric acid dropwise to the mixed solution A, and mechanically stir at a rotation speed of 650 r / min for 30 min to obtain a mixed solution B;

[0071] D. Add the mixed solution B to 1 / 3 of a polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0072] E. Filter the solution in step D (that is, collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain a modified carbon-based material;

[0073] F. Mix 0.015 g of the organic photovoltaic material PTQ10:MeIC with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:MeIC6 is obtained by mixing PTQ10 and MeIC in a weight ratio of 1:1;

[0074] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it in an oven at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants by the modified carbon-based supported organic photovoltaic material of the present invention, where the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0075] The photocatalyst for removing fluorine-containing pollutants prepared in this example, which is a modified carbon-based supported organic photovoltaic material, is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.). After 40 minutes, the removal rate is 99.3%.

[0076] Example 6

[0077] The preparation method of the photocatalyst for removing fluorine-containing pollutants by the modified carbon-based supported organic photovoltaic material of the present invention is operated according to the following steps:

[0078] A. Put 10 g of carbon material into a wall breaker and crush it for 11 h to obtain carbon powder with a particle size of 7000 mesh;

[0079] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain mixed solution A;

[0080] C. In an ice bath environment (water temperature is 6 °C), slowly add 12 g of concentrated nitric acid dropwise to mixed solution A, and mechanically stir at a rotation speed of 650 r / min for 30 min to obtain mixed solution B;

[0081] D. Add mixed solution B to 1 / 3 of a polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0082] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0083] F. Mix 0.015 g of organic photovoltaic material PTQ10:Y6:PY-IT with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:Y6:PY-IT is obtained by mixing PTQ10, Y6, and PY-IT in a weight ratio of 1:1:1;

[0084] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it in an oven at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based material supported with organic photovoltaic material of the present invention, where the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0085] The photocatalyst for removing fluorine-containing pollutants of the modified carbon-based material supported with organic photovoltaic material prepared in this example is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and the removal rate is 100% after 40 minutes.

[0086] Example 7

[0087] The preparation method of the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based material supported with organic photovoltaic material of the present invention is operated according to the following steps:

[0088] A. Put 10 g of carbon material into a wall breaker and crush it for 11 h to obtain carbon powder with a particle size of 7000 mesh;

[0089] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain mixed solution A;

[0090] C. In an ice bath environment (water temperature is 6 °C), slowly add 12 g of concentrated hydrochloric acid dropwise to mixed solution A, and mechanically stir at a rotation speed of 650 r / min for 30 min to obtain mixed solution B;

[0091] D. Add the mixed solution B to 1 / 3 of the polytetrafluoroethylene reactor and heat it in an oven at 80 °C for 24 h;

[0092] E. Filter the solution from step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0093] F. Mix 0.015 g of the organic photovoltaic materials PTQ10:Y6:PY-IT with 15 ml of chloroform to obtain a mixed solution of the organic photocatalyst, where PTQ10:Y6:PY-IT is obtained by mixing PTQ10, Y6, and PY-IT in a weight ratio of 1:1:1;

[0094] G. Uniformly coat the mixed solution of the organic photocatalyst obtained in step F on the modified carbon-based material and dry it in an oven at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants by the modified carbon-based material supported organic photovoltaic material of the present invention, where the weight ratio of the mixed solution of the organic photocatalyst to the modified carbon-based material is 1:7500.

[0095] The photocatalyst for removing fluorine-containing pollutants by the modified carbon-based material supported organic photovoltaic material prepared in this example is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and the removal rate is 100% after 40 minutes.

[0096] Example 8

[0097] The preparation method of the photocatalyst for removing fluorine-containing pollutants by the modified carbon-based material supported organic photovoltaic material of the present invention is operated according to the following steps:

[0098] A. Put 10 g of carbon materials into a blender and crush them for 11 h to obtain carbon powder with a particle size of 7000 mesh;

[0099] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain a mixed solution A;

[0100] C. In an ice bath environment (water temperature is 6 °C), gradually add 12 g of polyethyleneimine to the mixed solution A and mechanically stir it at a rotation speed of 650 r / min for 30 min to obtain a mixed solution B;

[0101] D. Add the mixed solution B to 1 / 3 of the polytetrafluoroethylene reactor and heat it in an oven at 80 °C for 24 h;

[0102] E. Filter the solution from step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0103] F. Mix 0.015 g of the organic photovoltaic material PTQ10:Y6:PY-IT with 15 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:Y6:PY-IT is obtained by mixing PTQ10, Y6, and PY-IT in a weight ratio of 1:1:1;

[0104] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants from the modified carbon-based material loaded with organic photovoltaic materials of the present invention, where the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:7500.

[0105] The photocatalyst for removing fluorine-containing pollutants from the modified carbon-based material loaded with organic photovoltaic materials prepared in this example is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.), and the removal rate is 100% after 40 minutes.

[0106] Example 9

[0107] The preparation method of the photocatalyst for removing fluorine-containing pollutants from the modified carbon-based material loaded with organic photovoltaic materials of the present invention is operated according to the following steps:

[0108] A. Put 10 g of carbon material into a wall breaker and crush it for 10 h to obtain carbon powder with a mesh size of 6000;

[0109] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain a mixed solution A;

[0110] C. In an ice bath environment (water temperature is 2 °C), slowly add 10 g of concentrated sulfuric acid dropwise to the mixed solution A, and mechanically stir it at a rotation speed of 500 r / min for 30 min to obtain a mixed solution B;

[0111] D. Add the mixed solution B to 1 / 3 of a polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h;

[0112] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 5 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material;

[0113] F. Mix 0.01 g of the organic photovoltaic material PTQ10:Y6:PY-IT with 10 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:Y6:PY-IT is obtained by mixing PTQ10, Y6, and PY-IT in a weight ratio of 1:1:1;

[0114] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material of the present invention. The weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:5000.

[0115] The photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material prepared in this example is used for the degradation of fluorine-containing pollutants (perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.). The removal rate is 99.3% after 40 minutes.

[0116] Example 10

[0117] The preparation method of the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material of the present invention is operated according to the following steps:

[0118] A. Put 10 g of carbon material into a wall breaker and crush it for 12 h to obtain carbon powder with a particle size of 8000 mesh.

[0119] B. Put 10 g of carbon powder into 100 ml of deionized water to obtain mixed solution A.

[0120] C. In an ice bath environment (water temperature is 10 °C), slowly add 15 g of concentrated sulfuric acid dropwise to mixed solution A, and mechanically stir at a rotation speed of 800 r / min for 30 min to obtain mixed solution B.

[0121] D. Add mixed solution B to 1 / 3 of a polytetrafluoroethylene reaction kettle and heat it in an oven at 80 °C for 24 h.

[0122] E. Filter the solution in step D (i.e., collect the carbon-based material using a filter paper with a pore size of 0.1 - 1 μm), wash it 3 times with deionized water, and then dry it in an oven at 60 °C for 24 h to obtain the modified carbon-based material.

[0123] F. Mix 0.02 g of organic photovoltaic materials PTQ10:Y6:PY-IT with 20 ml of chloroform to obtain an organic photocatalyst mixed solution, where PTQ10:Y6:PY-IT is obtained by mixing PTQ10, Y6, and PY-IT in a weight ratio of 1:1:1.

[0124] G. Uniformly coat the organic photocatalyst mixed solution obtained in step F on the modified carbon-based material, and dry it at 60 °C for 24 h to obtain the photocatalyst for removing fluorine-containing pollutants of the modified carbon-based supported organic photovoltaic material of the present invention. The weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:10000.

[0125] The photocatalyst for removing fluorine-containing pollutants prepared in this example, which is a modified carbon-based supported organic photovoltaic material, is used for the degradation of fluorine-containing pollutants (such as perfluorooctanoic acid, perfluorooctane sulfonyl compounds, etc.). The removal rate is 100% after 40 minutes.

Claims

1. A method for preparing a photocatalyst for removing fluorine-containing pollutants from a modified carbon-based organic photovoltaic material, characterized in that: The method comprises the following steps: A. Grind the carbon material into 6000-8000 mesh to obtain carbon powder; B. Mix the carbon powder in step A with deionized water in the following weight ratio to obtain a mixed solution A: 10 g carbon powder and 100 ml deionized water; C. placing the mixed solution A in an ice bath, and then adding concentrated acid / amino-rich material dropwise, and uniformly stirring by mechanical means to obtain a mixed solution B; the amount of the concentrated acid / amino-rich material added is 8-15% of the weight of the mixed solution A, and the concentrated acid / amino-rich material is concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid or polyethyleneimine; D. Place the mixed solution B into a polytetrafluoroethylene reactor and heat it in an oven for 24 hours; E. filtering, washing and drying the solution after the reaction in step D to obtain a modified carbon-based material; F. Mixing an organic photovoltaic material and chloroform in the following weight ratio to obtain an organic photocatalyst mixed solution: 0.01-0.02 g of organic photovoltaic material: 10-20 ml of chloroform; the organic photovoltaic material is PTQ10:Y6, PTQ10:PY-IT, PTQ10:XS6, PTQ10:MeIC or PTQ10:Y6:PY-IT; G. The organic photocatalyst mixed solution obtained in step F is uniformly coated on the modified carbon-based material, wherein the weight ratio of the organic photocatalyst mixed solution to the modified carbon-based material is 1:5000-10000, and after drying at 60° C. for 24 hours, a photocatalyst for removing fluorine-containing pollutants from a modified carbon-based loaded organic photovoltaic material is obtained.

2. The method for preparing a photocatalyst for removing fluorine-containing pollutants from modified carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In the step A, the carbon material is placed in a planetary ball mill for crushing, and the carbon material crushing time is 10 to 12 hours.

3. The method for preparing a photocatalyst for removing fluorine-containing pollutants by modified carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In step C, the water temperature of the ice bath environment is 2-10° C.; the rate of the mechanical stirring is 500-800 r / min, and the stirring time is 30 min.

4. The method for preparing a photocatalyst for removing fluorine-containing pollutants by modified carbon-based supported organic photovoltaic materials according to claim 1 or 2, characterized in that: In the step D, the volume of the mixed solution B occupies 1 / 3 of the reactor, and the temperature of the oven is heated to 80°C.

5. The method for preparing a photocatalyst for removing fluorine-containing pollutants by modified carbon-based organic photovoltaic materials according to claim 1 or 2, characterized in that: In the step E, the filtration is to collect the carbon-based material using a 0.1-1 μm caliber filter paper; The collected carbon-based materials were washed with deionized water for 3 to 5 times; and dried in an oven at 60° C. for 24 hours.

6. The method for preparing a photocatalyst for removing fluorine-containing pollutants by modified carbon-based supported organic photovoltaic materials according to claim 1 or 2, characterized in that: In step F, the PTQ10:Y6, PTQ10:PY-IT, PTQ10:XS6, and PTQ10:MeIC are mixed at a weight ratio of 1:1, and the PTQ10:Y6:PY-IT is mixed at a weight ratio of 1:1:1.

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