Preparation method and application of a cuprous oxide composite glycollate vanadate photocatalyst

Abstract

The invention discloses a preparation method and application of a cuprous oxide composite glycolate vanadium ester photocatalyst, relates to the technical field of photocatalyst preparation, and specifically comprises the following steps: S1: preparing a copper ion solution: placing copper nitrate trihydrate in a beaker, adding ethylene glycol and anhydrous ethanol, and stirring until the solution presents a light blue color and no solid particles remain; S2: preparing a Cu2O-C2H4O3V composite material: adding V2O5 powder to the copper ion solution prepared in step S1, and after ultrasonication, obtaining a mixed solution A; transferring the mixed solution A to a hydrothermal reactor with a polytetrafluoroethylene liner, reacting at a constant temperature in an electric blast drying oven, cooling to room temperature after the reaction is completed, washing 3 times with deionized water and anhydrous ethanol, drying, and grinding to obtain a cuprous oxide composite glycolate vanadium ester photocatalyst. The photocatalyst of the present invention has stable performance, good degradation effect on metronidazole, and the raw materials used are all low-priced and pollution-free, with short preparation time and low energy consumption.

Description

Technical Field

[0001] The present invention relates to the technical field of photocatalyst preparation, and specifically relates to a preparation method and application of a cuprous oxide composite glycolic acid vanadate photocatalyst. Background Art

[0002] With the development of science and technology, the usage of antibiotics in agriculture and medicine has gradually increased, resulting in a gradual increase in the content of metronidazole in the ecological environment, and there is a widespread situation of exceeding the standard. Research shows that residues of metronidazole and its intermediate molecules have been found in the soil, surface water, and groundwater in different regions. These metronidazoles will accumulate continuously along the food chain, damaging the ecosystem and easily leading to antibiotic resistance in the human body, seriously endangering people's health. The treatment of environmental metronidazole pollution is a worldwide problem. Traditional technologies such as adsorption, biological treatment, and semi-permeable membranes are difficult to completely degrade metronidazole in the ecological environment, and there are problems such as high cost, slow reaction, easy to cause secondary pollution, and inability to completely eliminate pollutants.

[0003] Photocatalytic technology using semiconductors and their derivative materials as a medium, as a sustainable, pollution-free, and cost-effective means, can utilize clean and sustainable solar energy to treat toxic substances such as wastewater and waste gas in the environment, improve environmental cleanliness, and thus effectively solve the environmental problems faced by human society. According to literature reports, Weeks et al. prepared purple VO(OCH2CH2O) crystals by compounding vanadium pentoxide with LiOH in ethylene glycol as a solvent and heating at 200 °C for 48 h. However, the preparation process of this catalyst has problems such as long time consumption and high temperature.

[0004] Based on this, developing an easily prepared and excellent-performance photocatalytic composite material is a technical problem that needs to be solved urgently by those skilled in the art. Summary of the Invention

[0005] The present invention aims at the above problems and provides a preparation method and application of a cuprous oxide composite glycolic acid vanadate photocatalyst.

[0006] In order to achieve the above object, the technical solutions adopted by the present invention are as follows:

[0007] As shown in the Figure 1 accompanying drawings, the present invention provides a preparation method of a ultrathin sheet-like cuprous oxide composite glycolic acid vanadate photocatalyst, which specifically includes the following steps:

[0008] S1: Prepare a copper ion solution: Place copper nitrate trihydrate in a beaker, add ethylene glycol and absolute ethanol, and stir until the solution shows a light blue color and there is no solid particle residue;

[0009] S2: Preparation of Cu₂O-C₂H₄O₃V composite material: Add V₂O₅ powder to the copper ion solution prepared in step S1. After ultrasonic treatment, a mixed solution A is obtained. Transfer the mixed solution A to a hydrothermal reaction kettle with a polytetrafluoroethylene liner, and carry out a constant-temperature reaction in an electric blast drying oven. After the reaction is completed, cool it to room temperature, wash it 3 times with deionized water and absolute ethanol, dry it, and grind it to obtain a cuprous oxide composite glycollate vanadate photocatalyst.

[0010] Further, in the step S1, the amount of copper nitrate trihydrate is one of 0.203 g, 0.441 g, 0.694 g, 0.979 g, 1.651 g, and 2.482 g.

[0011] Further, in the step S1, the volume of absolute ethanol is 34 mL, and the volume of ethylene glycol is 16 mL.

[0012] Further, in the step S2, the molar mass of V₂O₅ is 0.01 mol; the ultrasonic time is 10 min; the volume of polytetrafluoroethylene is 100 mL; the constant-temperature reaction temperature is 160 °C, and the constant-temperature reaction time is 6 h; the drying temperature is 80 °C, and the drying time is 8 h.

[0013] The present invention also provides an application of the above-mentioned cuprous oxide composite glycollate vanadate photocatalyst, and the cuprous oxide composite glycollate vanadate photocatalyst catalyzes the degradation of metronidazole under visible light.

[0014] Further, the mass ratio of the cuprous oxide composite glycollate vanadate photocatalyst to metronidazole is 25:1.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0016] The method of the present invention for the first time uses cuprous oxide composite glycollate vanadate to modify the vanadium-based catalyst. By utilizing the appropriate bandgap positions of glycollate vanadate flakes and cuprous oxide, the composite of cuprous oxide is used to excite persulfate to capture photogenerated electrons, improve the lifetimes of photogenerated electrons and holes, promote the transport of photogenerated charges, accelerate the rapid separation of photogenerated electrons and holes, thereby inhibiting the recombination of photogenerated carriers and improving the photocatalytic performance of the photocatalyst. The photocatalyst prepared by the method of the present invention has stable performance, good degradation effect on metronidazole, high utilization rate of light source, low-cost and pollution-free raw materials used, short preparation time, and low energy consumption, and has good application prospects in solving environmental pollution, energy crisis and photocatalytic application fields, and can be mass-produced. Description of the Drawings

[0017] Figure 1 It is a transmission electron microscope image of the Cu₂O-C₂H₄O₃V composite material of the present invention;

[0018] Figure 2 It is the degradation effect diagram of metronidazole photocatalyzed by different catalysts of the present invention under visible light. Specific Embodiments

[0019] In order to make the purpose and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0020] For the instruments, reagents, materials, etc. involved in the following embodiments, unless otherwise specified, they are all conventional instruments, reagents, materials, etc. existing in the prior art and can be obtained through regular commercial channels. For the experimental methods, detection methods, etc. involved in the following embodiments, unless otherwise specified, they are all conventional experimental methods, detection methods, etc. existing in the prior art.

[0021] Example 1

[0022] This example provides a preparation method of a cuprous oxide composite glycollate vanadate photocatalyst, which specifically includes the following steps:

[0023] S1: Prepare a copper ion solution: Place 0.203 g of copper nitrate trihydrate in a 100 mL beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and stir until the solution shows a light blue color and there is no solid particle residue;

[0024] S2: Prepare a Cu2O-C2H4O3V composite material: Add 1.82 g of V2O5 powder to the copper ion solution prepared in step S1, ultrasonicate for 10 min to obtain a mixed solution A; transfer the mixed solution A to a hydrothermal reaction kettle with a 100 mL polytetrafluoroethylene inner liner, keep it at a constant temperature of 160 °C in an electric blast drying oven for 6 h, cool to room temperature after the reaction is completed, wash it 3 times with deionized water and absolute ethanol, dry it at 80 °C for 8 h, and grind it to obtain a Cu2O-C2H4O3V composite material (5 wt% Cu2O-C2H4O3V), that is, a cuprous oxide composite glycollate vanadate photocatalyst, denoted as 5-Cu-V.

[0025] This example also provides an application of the above cuprous oxide composite glycollate vanadate photocatalyst. This photocatalyst catalyzes the degradation of metronidazole under visible light, wherein the mass ratio of the photocatalyst to metronidazole is 25:1.

[0026] Example 2

[0027] This example provides a preparation method of a cuprous oxide composite glycollate vanadate photocatalyst, which specifically includes the following steps:

[0028] S1: Preparation of copper ion solution: Place 0.441 g of copper nitrate trihydrate in a 100 mL beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and stir until the solution turns light blue and no solid particles remain.

[0029] S2: Preparation of Cu2O-C2H4O3V composite material: Add 1.82 g of V2O5 powder to the copper ion solution prepared in step S1. After ultrasonic treatment for 10 min, obtain a mixed solution A. Transfer the mixed solution A to a hydrothermal reaction kettle with a 100 mL polytetrafluoroethylene liner, and react at a constant temperature of 160 °C in an electric blast drying oven for 6 h. After the reaction is completed, cool to room temperature, wash 3 times with deionized water and absolute ethanol, dry at 80 °C for 8 h, and grind to obtain the Cu2O-C2H4O3V composite material (10 wt% Cu2O-C2H4O3V), that is, copper oxide composite glycollate vanadate photocatalyst, denoted as 10-Cu-V.

[0030] This example also provides an application of the above copper oxide composite glycollate vanadate photocatalyst. This photocatalyst catalyzes the degradation of metronidazole under visible light, where the mass ratio of the photocatalyst to metronidazole is 25:1.

[0031] Example 3

[0032] This example provides a preparation method of a copper oxide composite glycollate vanadate photocatalyst, which specifically includes the following steps:

[0033] S1: Preparation of copper ion solution: Place 0.694 g of copper nitrate trihydrate in a 100 mL beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and stir until the solution turns light blue and no solid particles remain.

[0034] S2: Preparation of Cu2O-C2H4O3V composite material: Add 1.82 g of V2O5 powder to the copper ion solution prepared in step S1. After ultrasonic treatment for 10 min, obtain a mixed solution A. Transfer the mixed solution A to a hydrothermal reaction kettle with a 100 mL polytetrafluoroethylene liner, and react at a constant temperature of 160 °C in an electric blast drying oven for 6 h. After the reaction is completed, cool to room temperature, wash 3 times with deionized water and absolute ethanol, dry at 80 °C for 8 h, and grind to obtain the Cu2O-C2H4O3V composite material (15 wt% Cu2O-C2H4O3V), that is, copper oxide composite glycollate vanadate photocatalyst, denoted as 15-Cu-V.

[0035] This example also provides an application of the above copper oxide composite glycollate vanadate photocatalyst. This photocatalyst catalyzes the degradation of metronidazole under visible light, where the mass ratio of the photocatalyst to metronidazole is 25:1.

[0036] Example 4

[0037] This embodiment provides a method for preparing a cuprous oxide composite glycollate vanadate photocatalyst, which specifically includes the following steps:

[0038] S1: Prepare a copper ion solution: Place 0.979 g of copper nitrate trihydrate in a 100 mL beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and stir until the solution shows a light blue color and there is no solid particle residue;

[0039] S2: Prepare the Cu2O-C2H4O3V composite material: Add 1.82 g of V2O5 powder to the copper ion solution prepared in step S1, ultrasonicate for 10 min to obtain a mixed solution A; Transfer the mixed solution A to a hydrothermal reaction kettle with a 100 mL polytetrafluoroethylene liner, keep it at a constant temperature of 160 °C in an electric blast drying oven for 6 h, after the reaction is completed, cool it to room temperature, wash it 3 times with deionized water and absolute ethanol, dry it at 80 °C for 8 h, and grind it to obtain the Cu2O-C2H4O3V composite material (20 wt% Cu2O-C2H4O3V), that is, the cuprous oxide composite glycollate vanadate photocatalyst, denoted as 20-Cu-V.

[0040] This embodiment also provides an application of the above cuprous oxide composite glycollate vanadate photocatalyst. This photocatalyst catalyzes the degradation of metronidazole under visible light, wherein the mass ratio of the photocatalyst to metronidazole is 25:1.

[0041] Example 5

[0042] This embodiment provides a method for preparing a cuprous oxide composite glycollate vanadate photocatalyst, which specifically includes the following steps:

[0043] S1: Prepare a copper ion solution: Place 1.651 g of copper nitrate trihydrate in a 100 mL beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and stir until the solution shows a light blue color and there is no solid particle residue;

[0044] S2: Prepare the Cu2O-C2H4O3V composite material: Add 1.82 g of V2O5 powder to the copper ion solution prepared in step S1, ultrasonicate for 10 min to obtain a mixed solution A; Transfer the mixed solution A to a hydrothermal reaction kettle with a 100 mL polytetrafluoroethylene liner, keep it at a constant temperature of 160 °C in an electric blast drying oven for 6 h, after the reaction is completed, cool it to room temperature, wash it 3 times with deionized water and absolute ethanol, dry it at 80 °C for 8 h, and grind it to obtain the Cu2O-C2H4O3V composite material (30 wt% Cu2O-C2H4O3V), that is, the cuprous oxide composite glycollate vanadate photocatalyst, denoted as 30-Cu-V.

[0045] This embodiment also provides an application of the above copper oxide composite glycolic acid vanadate photocatalyst, which photocatalytically degrades metronidazole under visible light. Among them, the mass ratio of the photocatalyst to metronidazole is 25:1.

[0046] Example 6

[0047] This embodiment provides a preparation method of a copper oxide composite glycolic acid vanadate photocatalyst, which specifically includes the following steps:

[0048] S1: Prepare a copper ion solution: Place 2.482 g of copper nitrate trihydrate in a 100 mL beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and stir until the solution shows a light blue color and there is no solid particle residue;

[0049] S2: Prepare the Cu2O-C2H4O3V composite material: Add 1.82 g of V2O5 powder to the copper ion solution prepared in step S1. After ultrasonic treatment for 10 min, obtain the mixed solution A; transfer the mixed solution A to a hydrothermal reaction kettle with a 100 mL polytetrafluoroethylene lining, and react at a constant temperature of 160 °C in an electric blast drying oven for 6 h. After the reaction is completed, cool to room temperature, wash 3 times with deionized water and absolute ethanol, dry at 80 °C for 8 h, and grind to obtain the Cu2O-C2H4O3V composite material (40 wt% Cu2O-C2H4O3V), that is, the copper oxide composite glycolic acid vanadate photocatalyst, denoted as 40-Cu-V.

[0050] This embodiment also provides an application of the above copper oxide composite glycolic acid vanadate photocatalyst, which photocatalytically degrades metronidazole under visible light. Among them, the mass ratio of the photocatalyst to metronidazole is 25:1.

[0051] Comparative Example 1

[0052] The pure C2H4O3V composite material photocatalyst is prepared as follows: Place 1.82 g of commercially available V2O5 powder in a 100 ml beaker, add 16 mL of ethylene glycol and 34 mL of absolute ethanol, and perform ultrasonic treatment for 10 min to obtain a mixed solution. Transfer the mixed solution to a hydrothermal reaction kettle with a 100 ml polytetrafluoroethylene lining, and perform a solvothermal reaction at 160 °C for 6 h. After the reaction is completed, cool to room temperature, wash, dry, and grind to obtain the C2H4O3V photocatalyst.

[0053] The photocatalysts prepared in Examples 1-6 and Comparative Example 1 above were respectively used to degrade metronidazole dissolution under visible light conditions. The specific steps are as follows: Take 25 mg of the photocatalyst sample and add it to 50 mL of a 20 mg / L metronidazole solution (the mass ratio of metronidazole to the photocatalyst is 1:25). Ultrasonic for 3 min and add a magnetic stir bar. Start the photocatalytic instrument, turn on the revolution, and turn on the stirring. Place the reaction system in the photocatalytic instrument and stir in the dark for 10 min so that the catalyst and metronidazole reach the adsorption and desorption equilibrium. Take 5-6 mL of samples every 5 min, for a total of 2 times. After sampling, turn on the circulating water, add 20 mg of sodium persulfate (PDS), and turn on the xenon light source. Take samples once every 5 min, for a total of 4 times, 5-6 mL each time. After the experiment, turn off the light source, turn off the photocatalytic instrument, and turn off the circulating water. After filtering the sample solution, use an ultraviolet spectrophotometer to detect the absorbance. The results are shown in the appendix Figure 2 . The calculation formula is: , where C0 is the initial concentration, C t is the metronidazole concentration at time t, A0 is the initial absorbance of the metronidazole solution, and A t is the absorbance of the metronidazole solution at time t. In the appendix Figure 2 , Vis is the degradation trend of the metronidazole solution in simulated visible light, Vis+PDS is the degradation trend of the metronidazole solution in visible light after adding persulfate, and 30-Cu-V / Dark is the adsorption and desorption equilibrium of the 30-Cu-V catalyst.

[0054] It can be seen from the appendix Figure 2 that the 5-Cu-V photocatalyst of Example 1 can degrade 79% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. The 10-Cu-V photocatalyst of Example 2 can degrade 87% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. The 15-Cu-V photocatalyst of Example 3 can degrade 89% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. The 20-Cu-V photocatalyst of Example 4 can degrade 94% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. The 30-Cu-V photocatalyst of Example 5 can degrade 100% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. The 40-Cu-V photocatalyst of Example 6 can degrade 98% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. The C2H4O3V photocatalyst of Comparative Example 1 can degrade 51% of the 20 mg / L metronidazole solution under visible light irradiation for 20 min. Thus, it can be seen that the cuprous oxide composite glycollate vanadate composite photocatalysts prepared in Examples 1-6 of the present invention have good degradation effects on metronidazole.

[0055] The cuprous oxide composite glycollate vanadate composite photocatalyst used in this embodiment modifies glycollate vanadate through the composite of cuprous oxide. By utilizing the appropriate band gap positions of glycollate vanadate flakes and cuprous oxide, the composite cuprous oxide can be used to excite persulfate to capture photo-generated electrons, improving the lifetimes of photo-generated electrons and holes, promoting the transport of photo-generated charges, accelerating the rapid separation of photo-generated electrons and holes, thereby inhibiting the recombination of photo-generated carriers and enhancing its photocatalytic performance. At the same time, the suspension characteristics of the photocatalyst system during the photocatalytic degradation process also effectively improve the utilization rate of the photocatalyst for the light source.

[0056] In summary, the photocatalyst composite material prepared in this embodiment has stable performance, good degradation effect on metronidazole, the raw materials used are all low-cost and pollution-free, the preparation time is short, and the energy consumption is low. It has good application prospects in solving environmental pollution, energy crisis and photocatalytic application fields, and can be mass-produced.

[0057] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a cuprous oxide composite glycollate vanadate photocatalyst, characterized in that: Specifically, it includes the following steps: S1: Prepare a copper ion solution: Place copper nitrate trihydrate in a beaker, add ethylene glycol and absolute ethanol, and stir until the solution shows a light blue color and there is no residual solid particle; S2: Prepare the Cu2O-C2H4O3V composite material: Add V2O5 powder to the copper ion solution prepared in step S1, and after ultrasonic treatment, obtain a mixed solution A; Transfer the mixed solution A to a hydrothermal reaction kettle with a polytetrafluoroethylene inner liner, and carry out a constant temperature reaction in an electric blast drying oven. After the reaction is completed, cool it to room temperature, wash it 3 times with deionized water and absolute ethanol, dry it, and grind it to obtain the cuprous oxide composite glycollate vanadate photocatalyst.

2. The preparation method of a cuprous oxide composite glycolic acid vanadate photocatalyst according to claim 1, characterized in that: In the step S1, the dosage of copper nitrate trihydrate is one of 0.203 g, 0.441 g, 0.694 g, 0.979 g, 1.651 g, 2.482 g.

3. The preparation method of a cuprous oxide composite glycollate vanadate photocatalyst according to claim 1, characterized in that: In the step S1, the volume of absolute ethanol is 34 mL, and the volume of ethylene glycol is 16 mL.

4. The preparation method of a cuprous oxide composite glycolate vanadate photocatalyst according to claim 1, characterized in that: In the step S2, the amount of substance of V2O5 is 0.01 mol; the ultrasonic time is 10 min; the volume of the hydrothermal reaction kettle with a polytetrafluoroethylene inner liner is 100 mL; the constant temperature reaction temperature is 160 °C, and the constant temperature reaction time is 6 h; the drying temperature is 80 °C, and the drying time is 8 h.

5. Use of a cuprous oxide composite glycolic acid vanadate photocatalyst prepared by the preparation method according to any one of claims 1-4, characterized in that: The cuprous oxide composite glycollate vanadate photocatalyst catalyzes the degradation of metronidazole under visible light.

6. The application according to claim 5, wherein: The mass ratio of the cuprous oxide composite glycollate vanadate photocatalyst to metronidazole is 25:1.

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