A photocatalytic Cu2O@SnS2 composite material, a preparation method thereof and application thereof

Abstract

The application discloses a kind of photocatalytic Cu2O@SnS2 composite material and its preparation method and application, to provide a kind of with higher photocatalytic performance and better stability, the effective management of organic pollutants in water, after 4 times cycle degradation, degradation rate can still be kept at 90% above photocatalytic Cu2O@SnS2 composite material, its technical scheme is positive cubic crystal Cu2O material and petal-like SnS2 material, positive cubic crystal Cu2O material is evenly distributed on the surface of petal-like SnS2 and forms composite photocatalytic material;It belongs to the technical field of inorganic material synthesis.

Description

Technical Field

[0001] This invention relates to the field of photocatalytic degradation technology, and in particular to a photocatalytic Cu2O@SnS2 composite material. This invention also relates to the preparation method and application of this material. Background Technology

[0002] With rapid societal progress and continuous technological development, environmental issues and the energy crisis have garnered significant public attention. Water pollution is particularly severe, with dye wastewater being a prime example. The dispersion of soluble and insoluble pigments in dye wastewater results in various water colors, seriously impacting the safety and sustainable use of water resources. Photocatalysis utilizes clean, renewable sunlight as a driving force. In recent years, photocatalytic oxidation has achieved remarkable results in mitigating water pollution, demonstrating its high efficiency, cleanliness, and green technological characteristics. Nanoscale catalysts have shown excellent performance in photocatalytic degradation, exhibiting even higher degradation efficiency for colored pollutants. This breakthrough not only improves the efficiency of pollutant treatment but also provides new ideas and methods for solving water pollution problems. With continuous technological advancements and increasing societal emphasis on environmental protection, photocatalysis technology has broad application prospects in water pollution control and will make a greater contribution to solving environmental pollution problems such as dye wastewater.

[0003] For example, Chinese Patent 103623845 A discloses a method for preparing a nanocomposite photocatalyst for treating hexavalent chromium wastewater. The method is as follows: 1) Mix and dissolve an aqueous solution of thioacetamide, tin tetrachloride pentahydrate, and citric acid monohydrate, place the mixture in a stainless steel autoclave lined with polytetrafluoroethylene, seal it, place it in an electric oven, heat it at 140°C for 12 hours, stop heating, and allow it to cool naturally to room temperature. Filter out the precipitate obtained from the reaction, wash it with deionized water, and dry it in a vacuum drying oven at 100°C to obtain SnS2 nanoparticles; 2) Disperse the SnS2 nanoparticles ultrasonically in water to form a SnS2 suspension; 3) Mix and react the copper acetate aqueous solution with the SnS2 suspension, filter out the precipitate obtained from the reaction, wash it with deionized water, and dry it in a vacuum drying oven at 100°C to obtain the nanocomposite photocatalyst. This method first prepares SnS2 nanoparticles, and then reacts them with copper acetate water to obtain SnS2 / CuS nanocomposite photocatalyst material. This nanocomposite photocatalyst is a solid nanomaterial with a small catalyst contact area and its catalytic activity is not ideal.

[0004] Therefore, it is particularly necessary to develop a catalyst with high photocatalytic performance and good stability for the effective treatment of organic pollutants in water. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide a photocatalytic Cu2O@SnS2 composite material, which exhibits high photocatalytic performance and good stability, effectively treating organic pollutants in water. After four cycles of degradation, the degradation rate can still be maintained above 90%.

[0006] The second objective of this invention is to provide a method for preparing the above-mentioned photocatalytic Cu2O@SnS2 composite material.

[0007] The second objective of this invention is to provide applications of the above-mentioned photocatalytic Cu2O@SnS2 composite material.

[0008] The first technical solution provided by this invention is as follows:

[0009] A photocatalytic Cu2O@SnS2 composite material comprises cubic crystalline Cu2O material and petal-shaped SnS2 material, wherein the cubic crystalline Cu2O material is uniformly distributed on the surface of the petal-shaped SnS2 to form a composite photocatalytic material.

[0010] Furthermore, in the aforementioned photocatalytic Cu2O@SnS2 composite material, cubic Cu2O is directly synthesized on petal-shaped SnS2.

[0011] The second technical solution provided by this invention is as follows:

[0012] A method for preparing a photocatalytic Cu2O@SnS2 composite material, comprising the following steps in sequence:

[0013] S1: Thioacetamide (TAA) and SnCl4·5H2O were dissolved in ethanol solution at room temperature and stirred evenly. The reaction solution was then transferred to a hydrothermal synthesis reactor and hydrothermally reacted at 150~200 ℃ for 10~16 h. After the reaction was completed, the product was cooled to room temperature, the precipitate was collected by centrifugation, and the collected precipitate was washed and vacuum dried to obtain SnS2 solid material.

[0014] S2: CuSO4·5H2O, sodium citrate, and the petal-shaped SnS2 solid obtained in S1 were dissolved in deionized water at room temperature and stirred evenly to obtain mixture A. Sodium hydroxide solution was added to mixture A to obtain a suspension. L-ascorbic acid solution was then added to the suspension and stirred evenly to obtain mixture B. Mixture B was aged at room temperature for 1 h, and the precipitate was collected by centrifugation. The collected precipitate was then washed and vacuum dried to obtain the photocatalytic Cu2O@SnS2 composite.

[0015] Furthermore, in the above-mentioned method for preparing a photocatalytic Cu2O@SnS2 composite material, the amount of TAA used in S1 is 0.8~1.5 g; the amount of SnCl4·5H2O used is 0.5~0.9 g; and the volume of the ethanol solution is 60~100 mL.

[0016] Furthermore, in the above-mentioned method for preparing a photocatalytic Cu2O@SnS2 composite material, the amount of CuSO4·5H2O in S2 is 0.3–0.6 g; the amount of sodium citrate is 0.1–0.3 g; the amount of the petal-shaped SnS2 solid obtained in S1 is 0.06–1.00 g; the volume of deionized water is 60–100 mL; and the concentration of the sodium hydroxide solution is 0.5–2 mol·L⁻¹. -1 The volume is 10–30 mL; the concentration of the L-ascorbic acid solution is 20–40 mol·mL⁻¹. -1 The volume is 40–60 mL.

[0017] Furthermore, in the above-mentioned method for preparing a Cu2O@SnS2 composite material, in S1: the stirring time is 25-40 min, and the magnetic stirring time is 3-8 min.

[0018] Furthermore, in the above-mentioned method for preparing a photocatalytic Cu2O@SnS2 composite material, the vacuum degree during drying of S1, S2, S3, and S3 is 2500 kPa, the temperature is 50~70℃, and the time is 10~16 h.

[0019] Furthermore, in the above-mentioned method for preparing a photocatalytic Cu2O@SnS2 composite material, the washing described in S1 and S2 involves first centrifuging with deionized water 2-3 times, and then washing with ethanol 2-3 times.

[0020] The third technical solution provided by this invention is the application of the aforementioned photocatalytic Cu2O@SnS2 composite material as a photocatalyst.

[0021] Compared with the prior art, the technical solution provided by the present invention has the following technical advantages:

[0022] 1. The Cu2O cubic crystal material provided by this invention is uniformly distributed on the surface of petal-shaped SnS2, forming a photocatalytic Cu2O@SnS2 composite material. The petal-shaped structure has a large catalyst contact area and high catalytic degradation performance; after light irradiation, the degradation rate of Cu2O@SnS2 is [missing information]. It can reach 90%. This indicates that Cu2O@SnS2 composite materials can effectively improve the photocatalytic effect of materials.

[0023] 2. The technical solution provided by this invention uses inexpensive raw materials and can efficiently utilize solar energy resources to degrade organic pollutants, showing potential application prospects in environmental protection and wastewater treatment.

[0024] 3. The technical solution provided by this invention is to obtain a photocatalytic Cu2O@SnS2 composite material through a combination of simple chemical reaction synthesis and hydrothermal method. Its preparation process is simple and easy to industrialize. Attached Figure Description

[0025] Figure 1 SEM image of the photocatalytic Cu2O@SnS2 composite material prepared in Example 1;

[0026] Figure 2 SEM images of the photocatalytic Cu2O@SnS2 composite materials prepared in Examples 2-4;

[0027] Figure 3 The degradation rate of methylene orange (MO) by different catalysts under full light irradiation is shown in the figure.

[0028] Figure 4 The recycling performance of Cu2O@SnS2 composite catalyst for photocatalysis;

[0029] Figure 5 The graph shows the degradation rate of methylene orange (MO) under full light irradiation with different catalyst contents. Detailed Implementation

[0030] To make the technical problems, technical solutions and advantages of the present invention clearer, a detailed description will be given below in conjunction with specific embodiments.

[0031] Example 1

[0032] This embodiment provides a photocatalytic Cu2O@SnS2 composite material, which is prepared by the following method:

[0033] 1) Dissolve 1.0 g of thioacetamide (TAA) and 0.7 g of SnCl4·5H2O in an ethanol solution at room temperature and stir evenly for 5 min. Then transfer the reaction solution to a hydrothermal synthesis reactor and hydrothermally react at 160 °C for 12 h. After the reaction is completed, cool the product to room temperature, centrifuge to collect the precipitate, wash it three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry it at 60 °C for 12 h to obtain SnS2 solid material.

[0034] 2) Dissolve 0.375 g CuSO4·5H2O, 0.147 g sodium citrate, and 0.08 g of the petal-shaped SnS2 solid material obtained in step 1) in deionized water at room temperature and stir evenly to obtain mixture A. Add 20 mL of 1.25 mol / L sodium hydroxide solution to mixture A to obtain a suspension. Then add 50 mL of 0.03 mol / L L-ascorbic acid solution to the suspension and stir for 3 min to obtain mixture B. Age mixture B at room temperature (25 ℃) for 1 h, centrifuge to collect the precipitate, wash three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry at 60 ℃ for 12 h to obtain the photocatalytic Cu2O@SnS2 composite. See the SEM image for details. Figure 1 .

[0035] Example 2

[0036] This embodiment provides a photocatalytic Cu2O@SnS2 composite material, which is prepared by the following method:

[0037] 1) Dissolve 0.9 g of thioacetamide (TAA) and 0.9 g of SnCl4·5H2O in ethanol solution at room temperature and stir evenly for 5 min. Then transfer the reaction solution to a hydrothermal synthesis reactor and hydrothermally react at 160 ℃ for 12 h. After the reaction is completed, cool the product to room temperature, centrifuge to collect the precipitate, wash it three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry it at 60 ℃ for 12 h to obtain SnS2 solid material.

[0038] 2) Dissolve 0.6 g CuSO4·5H2O, 0.3 g sodium citrate, and 1.0 g of the petal-shaped SnS2 solid material obtained in step 1) in deionized water at room temperature and stir evenly to obtain mixture A. Add 30 mL of 2 mol / L sodium hydroxide solution to mixture A to obtain a suspension. Then add 60 mL of 30 mol / L ascorbic acid solution to the suspension and stir for 3 min to obtain mixture B. Age mixture B at room temperature (25 ℃) for 1 h, centrifuge to collect the precipitate, wash three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry at 60 ℃ for 12 h to obtain the photocatalytic Cu2O@SnS2 composite. See the SEM image for details. Figure 2 (a).

[0039] Example 3

[0040] This embodiment provides a photocatalytic Cu2O@SnS2 composite material, which is prepared by the following method:

[0041] 1) Dissolve 0.8 g of thioacetamide (TAA) and 0.5 g of SnCl4·5H2O in an ethanol solution at room temperature and stir evenly for 5 min. Then transfer the reaction solution to a hydrothermal synthesis reactor and hydrothermally react at 160 °C for 12 h. After the reaction is completed, cool the product to room temperature, centrifuge to collect the precipitate, wash it three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry it at 60 °C for 12 h to obtain SnS2 solid material.

[0042] 2) Dissolve 0.3 g CuSO4·5H2O, 0.1 g sodium citrate, and 0.06 g of the petal-shaped SnS2 solid material obtained in step 1) in deionized water at room temperature and stir evenly to obtain mixture A. Add 10 mL of 0.5 mol / L sodium hydroxide solution to mixture A to obtain a suspension. Then add 40 mL of 0.02 mol / L L-ascorbic acid solution to the suspension and stir for 3 min to obtain mixture B. Age mixture B at room temperature (25 ℃) for 1 h, centrifuge to collect the precipitate, wash three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry at 60 ℃ for 12 h to obtain the photocatalytic Cu2O@SnS2 composite. See the SEM image for details. Figure 2 (b)

[0043] Example 4

[0044] This embodiment provides a photocatalytic Cu2O@SnS2 composite material, which is prepared by the following method:

[0045] 1) Dissolve 1.0 g of thioacetamide (TAA) and 0.7 g of SnCl4·5H2O in an ethanol solution at room temperature and stir evenly for 5 min. Then transfer the reaction solution to a hydrothermal synthesis reactor and hydrothermally react at 160 °C for 12 h. After the reaction is completed, cool the product to room temperature, centrifuge to collect the precipitate, wash it three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry it at 70 °C for 16 h to obtain SnS2 solid material.

[0046] 2) Dissolve 0.375 g CuSO4·5H2O, 0.147 g sodium citrate, and 0.08 g of the petal-shaped SnS2 solid material obtained in step 1) in deionized water at room temperature and stir evenly to obtain mixture A. Add 20 mL of 1.25 mol / L sodium hydroxide solution to mixture A to obtain a suspension. Then add 50 mL of 0.03 mol / L ascorbic acid solution to the suspension and stir for 3 min to obtain mixture B. Age mixture B at room temperature (25 °C) for 1 h, centrifuge to collect the precipitate, wash three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry at 70 °C for 16 h to obtain the photocatalytic Cu2O@SnS2 composite. See the SEM image for details. Figure 2 (c)

[0047] Example 5

[0048] This embodiment provides a photocatalytic Cu2O@SnS2 composite material, which is prepared by the following method:

[0049] 1) Dissolve 1.0 g of thioacetamide (TAA) and 0.7 g of SnCl4·5H2O in an ethanol solution at room temperature and stir evenly for 5 min. Then transfer the reaction solution to a hydrothermal synthesis reactor and hydrothermally react at 160 °C for 12 h. After the reaction is completed, cool the product to room temperature, centrifuge to collect the precipitate, wash it three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry it at 70 °C for 16 h to obtain SnS2 solid material.

[0050] 2) Dissolve 0.375 g CuSO4·5H2O, 0.147 g sodium citrate, and 0.08 g of the petal-shaped SnS2 solid material obtained in step 1) in deionized water at room temperature and stir evenly to obtain mixture A. Add 20 mL of 1.25 mol / L sodium hydroxide solution to mixture A to obtain a suspension. Then add 50 mL of 0.03 mol / L L-ascorbic acid solution to the suspension and stir for 3 min to obtain mixture B. Age mixture B at room temperature (25 ℃) for 1 h, centrifuge to collect the precipitate, wash three times with water and three times with ethanol, wash the collected precipitate again, and vacuum dry at 70 ℃ for 16 h to obtain the photocatalytic Cu2O@SnS2 composite. See the SEM image for details. Figure 2 (d)

[0051] To demonstrate the effectiveness of the technical solution provided in this application, the following experimental data on its photocatalytic degradation performance are presented:

[0052] 1. Degradation efficiency of methylene orange (MO) by photocatalytic Cu2O@SnS2 composite material.

[0053] 24 mg of Cu₂O cubic crystals, 24 mg of SnS₂ nanoparticles, and 24 mg of Cu₂O@SnS₂ catalyst were added to 60 mL of methylene orange (MO). After stirring in the dark for 15 min, the degradation rates of Cu₂O cubic crystals, SnS₂ nanoparticles, and the Cu₂O@SnS₂ composite were 64.4%, 55.1%, and 80.6%, respectively. Clearly, Cu₂O@SnS₂ exhibited a higher degradation rate for methylene orange (MO) than other substances. Furthermore, after 15 min of illumination, the degradation rate of Cu₂O@SnS₂ reached as high as 80%, indicating that constructing the Cu₂O@SnS₂ composite can effectively improve the photocatalytic effect of the material. Figure 3 As shown.

[0054] 15 mg, 18 mg, 24 mg, 30 mg, and 60 mg of the photocatalytic Cu2O@SnS2 complex prepared in Example 1 were respectively added to 60 mL of methylene orange (MO). The mixtures were then subjected to full-light irradiation under a 300 W xenon lamp for 60 min to degrade the compounds. The absorbance was measured every 5 min. The results are as follows: Figure 5 As shown, after 5 min of degradation in the dark with stirring, the degradation rates of Cu2O, SnS2, and Cu2O@SnS2 complexes were as follows. After 90 min of degradation under full light irradiation, the degradation rates of Cu2O, SnS2, and Cu2O@SnS2 complexes were 55.1%, 64.4%, and 94.7%, respectively. The degradation rate of MO by Cu2O@SnS2 complex was significantly higher than that of Cu2O and SnS2. This is presumably due to the larger specific surface area and more active sites after Cu2O and SnS2 are combined, resulting in higher degradation efficiency.

[0055] The photocatalytic degradation rate of the Cu2O@SnS2 nanocomposite material prepared in Example 1 of this invention is shown in the figure below. Figure 4 As shown, from Figure 5 It can be seen that after 60 min of illumination, the degradation rate was 80.4% for 15 mg, 85.8% for 18 mg, 92.2% for 24 mg, 92.9% for 30 mg, and 93% for 60 mg. The fact that the degradation rate at 30 mg was greater than that at 15 mg, 18 mg, 24 mg, and 60 mg under the same illumination time indicates that 30 mg of Cu2O@SnS2 represents the optimal catalyst concentration for this degradation process.

[0056] 2. Photocatalytic recycling performance

[0057] The cyclic stability of photocatalysts is one of the key indicators for practical applications. When the concentration of methylene orange (MO) in aqueous solution reaches a certain value, it can cause a series of harms to the human body. This experiment uses methylene orange (MO) as the object and performs photocatalytic degradation under full light irradiation. Therefore, it is necessary to study the cyclic degradation efficiency of methylene orange (MO) on Cu2O@SnS2 under simulated sunlight irradiation. Sunlight was simulated by xenon lamp irradiation. The procedure was as follows: 24 mg of the catalyst prepared in Example 3 was dispersed in 60 mL of 15 mg / L methylene orange (MO) solution, magnetically stirred (in the dark) for 1 min, the xenon lamp was turned on, and the solution temperature was kept stable by external circulating water. Every 5 min, 4.5 mL of the mixture was taken, centrifuged and filtered, and the absorbance value at the maximum absorption wavelength (k = 664 nm) was measured. The precipitate was collected again by centrifugation, washed 3 times with deionized water, and then washed 3 times with ethanol. Figure 4 As shown, after four cycles of degradation, the degradation efficiency of Cu2O@SnS2 remained above 90%. This indicates that the Cu2O@SnS2 composite structure can still maintain a certain degree of crystallinity, and Cu2O@SnS2 exhibits good photocatalytic degradation stability.

Claims

1. A photocatalytic Cu2O@SnS2 composite material, characterized in that, It includes cubic crystalline Cu2O material and petal-shaped SnS2 material. The cubic crystalline Cu2O material is uniformly distributed on the surface of the petal-shaped SnS2 to form a composite photocatalytic material.

2. The photocatalytic Cu2O@SnS2 composite material according to claim 1, characterized in that, Cu2O was directly synthesized on petal-shaped SnS2.

3. A method for preparing a photocatalytic Cu2O@SnS2 composite material, characterized in that, The steps are as follows: S1: Thioacetamide and SnCl4·5H2O were dissolved in ethanol solution at room temperature and stirred evenly. Then the reaction solution was transferred to a hydrothermal synthesis reactor and hydrothermally reacted at 150~200 ℃ for 10~16 h. After the reaction was completed, the product was cooled to room temperature, the precipitate was collected by centrifugation, and the collected precipitate was washed and vacuum dried to obtain petal-shaped SnS2 solid material. S2: CuSO4·5H2O, sodium citrate, and the petal-shaped SnS2 solid obtained in S1 were dissolved in deionized water at room temperature and stirred evenly to obtain mixture A. Sodium hydroxide solution was added to mixture A to obtain a suspension. L-ascorbic acid solution was then added to the suspension and stirred evenly to obtain mixture B. Mixture B was aged at room temperature for 1 h, and the precipitate was collected by centrifugation. The collected precipitate was then washed and vacuum dried to obtain the photocatalytic Cu2O@SnS2 complex.

4. The method for preparing a photocatalytic Cu2O@SnS2 composite material according to claim 3, characterized in that, The amount of thioacetamide used in S1 is 0.8~1.5 g; the amount of SnCl4·5H2O used is 0.5~0.9 g; The volume of the ethanol solution is 60~100 mL.

5. The method for preparing a photocatalytic Cu2O@SnS2 composite material according to claim 3, characterized in that, The amount of CuSO4·5H2O used in S2 is 0.3–0.6 g; the amount of sodium citrate is 0.1–0.3 g; the amount of the petal-shaped SnS2 solid obtained in S1 is 0.06–1.00 g; the volume of deionized water is 60–100 mL; and the concentration of the sodium hydroxide solution is 0.5–2 mol·L⁻¹. -1 The volume is 10–30 mL; the concentration of the L-ascorbic acid solution is 20–40 mol·mL⁻¹. -1 The volume is 40–60 mL.

6. The method for preparing a photocatalytic Cu2O@SnS2 composite material according to claim 3, characterized in that, In S1: the stirring time is 25 to 40 minutes.

7. The method for preparing a photocatalytic Cu2O@SnS2 composite material according to claim 3, characterized in that, During the drying of S1 and S2, the vacuum degree was 2500 kPa, the temperature was 50~70 ℃, and the time was 10~16 h.

8. The method for preparing a photocatalytic Cu2O@SnS2 composite material according to claim 3, characterized in that, The washing described in S1 and S2 involves first centrifuging with deionized water 2-3 times, and then washing with ethanol 2-3 times.

9. The application of the photocatalytic Cu2O@SnS2 composite material as described in claim 1 as a photocatalyst.

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