Photoresponse type boron carbide-based nano-particle catalytic material as well as preparation method and application of photoresponse type boron carbide-based nano-particle catalytic material

Abstract

The invention provides a photoresponse type boron carbide-based nanoparticle catalytic material and a preparation method and application thereof.The preparation method comprises the steps that boron carbide, cobalt-nickel alloy and zinc oxide are taken to be mixed and subjected to ball milling, and then a mixture is obtained; the preparation method comprises the following steps: adding absolute ethyl alcohol into polyvinylpyrrolidone, stirring, adding tetrabutyl titanate, and continuously stirring to obtain a mixed solution; mixing the mixture with the mixed solution, transferring into a reaction kettle containing graphene, putting into the reaction kettle for hydrothermal reaction, cooling, collecting solid particles, drying, sintering with inert gas, and cooling to obtain the light response type boron carbide-based nano-particle catalytic material. The light response type boron carbide-based nanoparticle catalytic material prepared from boron carbide, cobalt-nickel alloy, zinc oxide and the photocatalyst is high in specific surface area, can improve the photocatalytic activity, and has a good catalytic degradation effect on artificially synthesized dyes such as rhodamine B.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic materials, and in particular to a light-responsive boron carbide-based nanoparticle catalytic material and a preparation method and application thereof. Background Art

[0002] Rhodamine B, also known as Rose Red B, commonly known as flower pink, is a synthetic organic dye with a bright pink color. Rhodamine B has strong fluorescence in solution and is often used as a cell fluorescent dye in laboratories, colored glass, special fireworks and firecrackers, etc. Although Rhodamine B has a wide range of applications in certain industrial and scientific research fields, it has been found in mouse experiments that Rhodamine B can cause sarcomas in subcutaneous tissue and is considered a potential carcinogen.

[0003] At present, photocatalytic materials have been widely used to treat organic pollutants in water, among which zinc oxide is the most widely used material in photocatalytic materials. However, zinc oxide itself tends to increase the recombination rate of electrons and holes, affecting the overall catalytic efficiency of photocatalytic materials. Therefore, when using zinc oxide to prepare photocatalytic materials, the ability of such catalytic materials to adsorb and degrade organic pollutants should be improved. Summary of the invention

[0004] In view of this, the purpose of the present invention is to provide a light-responsive boron carbide-based nanoparticle catalytic material and a preparation method and application thereof.

[0005] The technical solution of the present invention is achieved in this way:

[0006] A method for preparing a light-responsive boron carbide-based nanoparticle catalytic material comprises the following steps:

[0007] S1: Boron carbide, cobalt-nickel alloy and zinc oxide are mixed and ball-milled to obtain a mixture;

[0008] S2: adding anhydrous ethanol-acetic acid solution to polyvinyl pyrrolidone, stirring, adding tetrabutyl titanate, and continuing to stir to obtain a mixed solution;

[0009] S3: mixing the mixture with the mixed solution, transferring the mixture to a reactor containing graphene, placing the mixture in the reactor for hydrothermal reaction, collecting solid particles after cooling, drying, sintering with an inert gas, and cooling to obtain a light-responsive boron carbide-based nanoparticle catalytic material; the inert gas can be argon, helium or nitrogen.

[0010] A further solution is that the mass ratio of the boron carbide, the cobalt-nickel alloy and the zinc oxide is 6-10:1-2:1-2;

[0011] The dosage ratio of the polyvinyl pyrrolidone, anhydrous ethanol-acetic acid solution and tetrabutyl titanate is 1-2 g: 10-15 mL: 3-5 g;

[0012] The mass ratio of the mixture, the mixed solution and the graphene is 2-3:1:5-8.

[0013] A further solution is that in the cobalt-nickel alloy, the mass ratio of cobalt to nickel is 1:1-3; and in the anhydrous ethanol-acetic acid solution, the volume ratio of anhydrous ethanol to acetic acid is 5-6:1.

[0014] A further solution is that the ball milling conditions are: a rotation speed of 100 to 300 rpm, and ball milling to a particle size of 60 to 100 μm.

[0015] A further solution is that the conditions of the hydrothermal reaction are: reaction temperature is 120-150° C., and reaction time is 6-8 hours.

[0016] A further solution is that the sintering conditions are: a sintering temperature of 250 to 280° C. and a sintering time of 1 to 1.5 hours.

[0017] A further solution is that the drying conditions are: a drying temperature of 60 to 70° C. and a drying time of 2 to 3 hours.

[0018] The present invention selects boron carbide, cobalt-nickel alloy, zinc oxide, and tetrabutyl titanate to prepare TiO2 nanoparticles, and undergoes ball milling, hydrothermal treatment, and sintering steps. The parameters of the steps are scientifically adjusted to promote the migration of electrons and holes to the surface of the catalytic material. Carbon defects can increase the separation rate of electrons and holes. At the same time, the crystal structure of boron carbide can exist stably in a large range, reducing the movement of molecules and atoms during the calcination process, limiting the growth of grains, and introducing TiO2 nanoparticles to load TiO2 on graphene, thereby further improving the photocatalytic performance of the material.

[0019] The present invention provides a light-responsive boron carbide-based nanoparticle catalytic material prepared by the above-mentioned preparation method.

[0020] The light-responsive boron carbide-based nanoparticle catalytic material provided by the invention can be applied in the photocatalytic degradation of Rhodamine B dye.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The light-responsive boron carbide-based nanoparticle catalytic material prepared by the invention through boron carbide, cobalt-nickel alloy, zinc oxide and a photocatalyst has a high specific surface area, can improve the photocatalytic activity, and has a good catalytic degradation effect on artificial synthetic dyes such as Rhodamine B.

[0023] The light-responsive boron carbide-based nanoparticle catalytic material prepared by the present invention has readily available and relatively cheap raw materials, a simple preparation method, a controllable reaction process, and is environmentally friendly.

[0024] The present invention selects boron carbide, cobalt-nickel alloy, zinc oxide, and tetrabutyl titanate to prepare TiO2 nanoparticles, and undergoes ball milling, hydrothermal treatment, and sintering steps. The parameters of the steps are scientifically adjusted to promote the migration of electrons and holes to the surface of the catalytic material. Carbon defects can increase the separation rate of electrons and holes. At the same time, the crystal structure of boron carbide can exist stably in a large range, reducing the movement of molecules and atoms during the calcination process, limiting the growth of grains, and introducing TiO2 nanoparticles to load TiO2 on graphene, thereby further improving the photocatalytic performance of the material. DETAILED DESCRIPTION

[0025] In order to better understand the technical content of the present invention, specific embodiments are provided below to further illustrate the present invention.

[0026] Unless otherwise specified, the experimental methods used in the embodiments of the present invention are all conventional methods.

[0027] Unless otherwise specified, the materials, reagents, etc. used in the embodiments of the present invention can be obtained from commercial sources.

[0028] In cobalt-nickel alloy, the mass ratio of cobalt to nickel is 1:3.

[0029] Example 1

[0030] (1) 80 g of boron carbide, 15 g of cobalt-nickel alloy and 12 g of zinc oxide were ball-milled at a speed of 200 rpm until the average particle size was 80 to 100 μm;

[0031] (2) Mix 50 mL of anhydrous ethanol and 10 mL of acetic acid, add 6 g of polyvinyl pyrrolidone, stir evenly with a magnetic stirrer, then add 18 g of tetrabutyl titanate, and continue stirring until evenly mixed to obtain a mixed solution;

[0032] (3) After mixing 80 g of the ball-milled mixture with 40 g of the mixed solution, the mixture was transferred to a reactor containing 200 g of graphene, placed in a stainless steel reactor, sealed, and subjected to hydrothermal treatment at a temperature of 120°C for 6 h. The solid particles were collected by centrifugation and placed in an oven for drying at 60-70°C for 2 h. The solid particles were then added to a sintering furnace for sintering in an argon atmosphere at 280°C for 1 h. The solid particles were cooled to obtain a light-responsive boron carbide-based nanoparticle catalytic material.

[0033] According to the test method for purification performance of aqueous solution of photocatalytic material (GB / T23762-2020), 100 mL of Rhodamine B solution with a concentration of 20 ppm was prepared, 50 mg of the light-responsive boron carbide-based nanoparticle catalytic material of Example 1 was added to the Rhodamine B solution, stirred to adsorption equilibrium, and then placed under light for photocatalytic degradation. The material was taken out, centrifuged, the supernatant was taken, the absorbance value was measured at 550 nm, and the degradation rate was calculated.

[0034] The results showed that after 2 hours of reaction under light, the degradation rate of Rhodamine B was 86.8%.

[0035] Example 2

[0036] (1) 80 g of boron carbide, 15 g of cobalt-nickel alloy and 12 g of zinc oxide were ball-milled at a speed of 200 rpm until the average particle size was 60 to 80 μm;

[0037] (2) Mix 50 mL of anhydrous ethanol and 10 mL of acetic acid, add 6 g of polyvinyl pyrrolidone, stir evenly with a magnetic stirrer, then add 18 g of tetrabutyl titanate, and continue stirring until evenly mixed to obtain a mixed solution;

[0038] (3) After mixing 80 g of the ball-milled mixture with 40 g of the mixed solution, the mixture was transferred to a reactor containing 200 g of graphene, placed in a stainless steel reactor, sealed, and subjected to hydrothermal treatment at a temperature of 150°C for 6 hours. The solid particles were collected by centrifugation and placed in an oven for drying at 60-70°C for 2 hours. The solid particles were then added to a sintering furnace for sintering in an argon atmosphere at 280°C for 1 hour. The solid particles were cooled to obtain a light-responsive boron carbide-based nanoparticle catalytic material.

[0039] According to the test method for purification performance of aqueous solution of photocatalytic material (GB / T23762-2020), 100 mL of Rhodamine B solution with a concentration of 20 ppm was prepared, 50 mg of the light-responsive boron carbide-based nanoparticle catalytic material of Example 2 was added to the Rhodamine B solution, stirred to adsorption equilibrium, and then placed under light for photocatalytic degradation. The material was taken out, centrifuged, the supernatant was taken, the absorbance value was measured at 550 nm, and the degradation rate was calculated.

[0040] The results showed that after 2 hours of reaction under light, the degradation rate of rhodamine B was 85.5%.

[0041] Example 3

[0042] (1) 80 g of boron carbide, 15 g of cobalt-nickel alloy and 12 g of zinc oxide were ball-milled at a speed of 300 rpm until the average particle size was 80 to 100 μm;

[0043] (2) Mix 50 mL of anhydrous ethanol and 10 mL of acetic acid, add 6 g of polyvinyl pyrrolidone, stir evenly with a magnetic stirrer, then add 18 g of tetrabutyl titanate, and continue stirring until evenly mixed to obtain a mixed solution;

[0044] (3) After mixing 80 g of the ball-milled mixture with 40 g of the mixed solution, the mixture was transferred to a reactor containing 200 g of graphene, placed in a stainless steel reactor, sealed, and subjected to hydrothermal treatment at a temperature of 150°C for 8 h. The solid particles were collected by centrifugation and placed in an oven for drying at 60-70°C for 2 h. The solid particles were then added to a sintering furnace for sintering in an argon atmosphere at 280°C for 1 h. The solid particles were cooled to obtain a light-responsive boron carbide-based nanoparticle catalytic material.

[0045] According to the test method for purification performance of aqueous solution of photocatalytic material (GB / T23762-2020), 100 mL of Rhodamine B solution with a concentration of 20 ppm was prepared, 50 mg of the light-responsive boron carbide-based nanoparticle catalytic material of Example 3 was added to the Rhodamine B solution, stirred to adsorption equilibrium, and then placed under light for photocatalytic degradation. The material was taken out, centrifuged, the supernatant was taken, the absorbance value was measured at 550 nm, and the degradation rate was calculated.

[0046] The results showed that after 2 hours of reaction under light, the degradation rate of Rhodamine B was 85.3%.

[0047] Example 4

[0048] (1) 80 g of boron carbide, 15 g of cobalt-nickel alloy and 12 g of zinc oxide were ball-milled at a speed of 200 rpm until the average particle size was 80 to 100 μm;

[0049] (2) Mix 50 mL of anhydrous ethanol and 10 mL of acetic acid, add 6 g of polyvinyl pyrrolidone, stir evenly with a magnetic stirrer, then add 18 g of tetrabutyl titanate, and continue stirring until evenly mixed to obtain a mixed solution;

[0050] (3) After mixing 80 g of the ball-milled mixture with 40 g of the mixed solution, the mixture was transferred to a reactor containing 200 g of graphene, placed in a stainless steel reactor, sealed, and subjected to hydrothermal treatment at a temperature of 120°C for 6 hours. The solid particles were collected by centrifugation and placed in an oven for drying at 60-70°C for 2 hours. The solid particles were then added to a sintering furnace for sintering in an argon atmosphere at 250°C for 1.5 hours. The solid particles were cooled to obtain a light-responsive boron carbide-based nanoparticle catalytic material.

[0051] According to the test method for purification performance of aqueous solution of photocatalytic material (GB / T23762-2020), 100 mL of Rhodamine B solution with a concentration of 20 ppm was prepared, 50 mg of the light-responsive boron carbide-based nanoparticle catalytic material of Example 4 was added to the Rhodamine B solution, stirred to adsorption equilibrium, and then placed under light for photocatalytic degradation. The material was taken out, centrifuged, the supernatant was taken, the absorbance value was measured at 550 nm, and the degradation rate was calculated.

[0052] The results showed that after 2 hours of reaction under light, the degradation rate of rhodamine B was 82.6%.

[0053] Example 5

[0054] (1) 60 g of boron carbide, 20 g of cobalt-nickel alloy and 20 g of zinc oxide were ball-milled at a speed of 200 rpm until the average particle size was 80 to 100 μm;

[0055] (2) Mix 50 mL of anhydrous ethanol and 10 mL of acetic acid, add 6 g of polyvinyl pyrrolidone, stir evenly with a magnetic stirrer, then add 18 g of tetrabutyl titanate, and continue stirring until evenly mixed to obtain a mixed solution;

[0056] (3) After mixing 100 g of the ball-milled mixture with 40 g of the mixed solution, the mixture was transferred to a reactor containing 250 g of graphene, placed in a stainless steel reactor, sealed, and subjected to hydrothermal treatment at a temperature of 120°C for 6 hours. The solid particles were collected by centrifugation and placed in an oven for drying at 60-70°C for 2 hours. The solid particles were then added to a sintering furnace for sintering in an argon atmosphere at 280°C for 1 hour. The solid particles were cooled to obtain a light-responsive boron carbide-based nanoparticle catalytic material.

[0057] According to the test method for purification performance of aqueous solution of photocatalytic material (GB / T23762-2020), 100 mL of Rhodamine B solution with a concentration of 20 ppm was prepared, 50 mg of the light-responsive boron carbide-based nanoparticle catalytic material of Example 5 was added to the Rhodamine B solution, stirred to adsorption equilibrium, and then placed under light for photocatalytic degradation. The material was taken out, centrifuged, the supernatant was taken, the absorbance value was measured at 550 nm, and the degradation rate was calculated.

[0058] The results showed that after 2 hours of reaction under light, the degradation rate of rhodamine B was 81.2%.

[0059] The above is a preferred embodiment of the present invention. It should be pointed out that a person skilled in the art can make several improvements and modifications without departing from the principle of the present invention. These improvements and modifications are also considered to be within the scope of protection of the present invention.

Claims

1. A method for preparing a light-responsive boron carbide-based nanoparticle catalytic material, characterized in that: The steps include: S1: Boron carbide, cobalt-nickel alloy and zinc oxide are mixed and ball-milled to obtain a mixture; S2: adding anhydrous ethanol-acetic acid solution to polyvinyl pyrrolidone, stirring, adding tetrabutyl titanate, and continuing to stir to obtain a mixed solution; S3: Mix the mixture with the mixed solution, transfer it to a reactor containing graphene, place it in the reactor for hydrothermal reaction, collect solid particles after cooling, dry them, sinter them with inert gas, and cool them to obtain a light-responsive boron carbide-based nanoparticle catalytic material.

2. The method for preparing the light-responsive boron carbide-based nanoparticle catalytic material according to claim 1, characterized in that: The mass ratio of boron carbide, cobalt-nickel alloy and zinc oxide is 6-10:1-2:1-2; The dosage ratio of the polyvinyl pyrrolidone, anhydrous ethanol-acetic acid solution and tetrabutyl titanate is 1-2 g: 10-15 mL: 3-5 g; The mass ratio of the mixture, the mixed solution and the graphene is 2-3:1:5-8.

3. The method for preparing the light-responsive boron carbide-based nanoparticle catalytic material according to claim 2, characterized in that: In the cobalt-nickel alloy, the mass ratio of cobalt to nickel is 1:1-3; in the anhydrous ethanol-acetic acid solution, the volume ratio of anhydrous ethanol to acetic acid is 5-6:

1.

4. The method for preparing a light-responsive boron carbide-based nanoparticle catalytic material according to claim 1, characterized in that: The ball milling conditions are: a rotation speed of 100 to 300 rpm, and ball milling to a particle size of 60 to 100 μm.

5. The method for preparing a light-responsive boron carbide-based nanoparticle catalytic material according to claim 1, characterized in that: The conditions of the hydrothermal reaction are: reaction temperature is 120-150° C., and reaction time is 6-8 hours.

6. The method for preparing a light-responsive boron carbide-based nanoparticle catalytic material according to claim 1, characterized in that: The sintering conditions are as follows: the sintering temperature is 250-280° C. and the sintering time is 1-1.5 h.

7. The method for preparing a light-responsive boron carbide-based nanoparticle catalytic material according to claim 1, characterized in that: The drying conditions are as follows: the drying temperature is 60-70° C. and the drying time is 2-3 hours.

8. A light-responsive boron carbide-based nanoparticle catalytic material prepared according to the method for preparing a light-responsive boron carbide-based nanoparticle catalytic material according to any one of claims 1 to 7.

9. Use of the light-responsive boron carbide-based nanoparticle catalytic material according to claim 8 in photocatalytic degradation of Rhodamine B.