Zinc selenide nanorod film material, preparation method and application thereof, and industrial wastewater treatment method
By preparing zinc selenide nanorod film materials with high specific surface area as photocatalysts, the problem of low adsorption efficiency of existing photocatalysts is solved, and the effect of efficient dye degradation is achieved. It is suitable for printing and dyeing wastewater treatment, and has the advantages of environmental protection and easy industrial production.
Patent Information
- Application Number
- CN202510372136.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-27
- Publication Date
- 2025-06-20
AI Technical Summary
The existing photocatalysts are less efficient when adsorbing dye molecules, making it difficult to effectively treat printing and dyeing wastewater. The traditional treatment methods have problems such as high cost and easy secondary pollution.
The zinc selenide nanorod film material is used as a photocatalyst to prepare nanorod films by laser deposition and heat treatment to improve their specific surface area and chemical stability, thereby enhancing the adsorption and degradation ability of dye molecules.
Zinc selenide nanorod film materials can efficiently degrade dyes under light conditions, maintain efficient catalytic performance for a long time, are environmentally friendly and easy to reuse, and are suitable for industrial wastewater treatment, especially printing and dyeing wastewater.
Smart Images
Figure CN120172655A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of materials, and particularly relates to a zinc selenide nanorod thin film material, a preparation method and application thereof, and an industrial wastewater treatment method. Background Art
[0002] With the rapid and stable development of China's economy, the domestic textile dye industry has also further developed. Printing and dyeing wastewater has triple effects, and if not properly treated, it will harm the environment and human health. There are many deficiencies in traditional dye wastewater treatment methods. For example, physical methods have high costs, chemical methods are prone to secondary pollution, and biological methods have poor effects on certain dyes. Therefore, there is an urgent need to develop a new type of efficient and environmentally friendly treatment technology. Photocatalytic oxidation has received extensive attention due to its advantages such as effectively utilizing sunlight, completely degrading organic matter, and fast reaction rate, and it is a dye wastewater treatment technology with great application prospects. However, the existing photocatalysts have problems with poor adsorption efficiency, so there is a need to provide a new photocatalyst with good adsorption efficiency. Summary of the Invention
[0003] To solve the above technical problems, the present invention provides a zinc selenide nanorod thin film material. This zinc selenide nanorod thin film material has a high specific surface area, can provide more active sites, and is conducive to the adsorption and degradation of dye molecules.
[0004] The present invention also provides a preparation method of the zinc selenide nanorod thin film material.
[0005] The present invention also provides an application of the above zinc selenide nanorod thin film material as a photocatalyst.
[0006] The present invention also provides an industrial wastewater treatment method.
[0007] To achieve the above object, the present invention adopts the following technical solutions:
[0008] A zinc selenide nanorod thin film material, in which the zinc selenide nanorods in the zinc selenide nanorod thin film material are arranged in a reticular disordered manner. The zinc selenide nanorod thin film of the present invention can absorb ultraviolet light and part of visible light, generate photoinduced carriers to participate in the catalytic reaction; it has high chemical stability and strong anti-deliquescence ability, and is not prone to structural damage or activity reduction during the photocatalytic degradation of dyes, and can maintain high-efficiency catalytic performance for a long time; in particular, the zinc selenide nanorod thin film material of the present invention has a high specific surface area, can provide more active sites, and is conducive to the adsorption and degradation of dye molecules.
[0009] Wherein, the thickness of the zinc selenide nanorod thin film material is 1 - 2.
[0010] Among them, the diameter of the nanorods in the zinc selenide nanorod thin film material is 100 - 300 nm, and the length is 6 - 20 μm.
[0011] The preparation method of the above zinc selenide nanorod thin film material, the method comprises the following steps:
[0012] S1: Deposit a zinc selenide thin film with a certain thickness on a substrate by laser deposition; preferably, a zinc selenide crystal block with a purity of 99.99% is selected as the raw material for laser deposition of the zinc selenide thin film.
[0013] S2: Heat-treat the zinc selenide thin film to obtain the zinc selenide nanorod photocatalytic thin film material; wherein the heat-treatment temperature is 60 - 80 °C and the time is 8 - 15 hours. The heat-treatment can be carried out by direct heating and can be carried out in a water bath. Specifically, the prepared zinc selenide thin film is placed in a temperature-controlled water bath (deionized water), and this process lasts for a certain time to ensure the growth of zinc selenide nanorods.
[0014] Preferably, the thickness of the deposited zinc selenide thin film is 1 - 2 μm. It has been found through experiments that too thin a thickness (less than 1 μm) will affect the diameter and length of the nanorods.
[0015] Preferably, while performing the heat-treatment on the zinc selenide thin film, an ultrasonic oscillation treatment is carried out on the zinc selenide thin film, and the frequency of the ultrasonic oscillation treatment is 80 - 120 kHz. The purpose of the ultrasonic oscillation treatment is to make its growth more uniform.
[0016] In one embodiment, the laser deposition method is femtosecond laser deposition; the femtosecond laser deposition is carried out in a vacuum chamber; the vacuum degree of the vacuum chamber is 1 10 -7 -2 10 -7 Torr. Specifically, the femtosecond laser deposition is carried out in a vacuum chamber, the air pressure in the vacuum chamber is reduced to a certain atmospheric pressure by using a mechanical and molecular vacuum pump, and the substrate is heated to a high temperature; then a titanium sapphire regenerative amplifier mode-locked femtosecond laser (Coherent Inc., central wavelength 800 nm, pulse width ~45 fs, repetition frequency 1 KHz) is used to ablate the target; a zinc selenide thin film with a certain thickness can be deposited on the substrate.
[0017] More preferably, the laser energy on the target in the femtosecond laser deposition is 0.16 - 0.2 J / cm 2 , the deposition time is 30 - 40 min, and the distance between the substrate and the target is 8 - 10 cm.
[0018] Among them, the temperature of the substrate during the deposition process is 450 - 550 °C.
[0019] Among them, the preparation method further includes the step of cleaning and drying the substrate before deposition. Specifically, the substrate is ultrasonically cleaned in a polar aprotic solvent and a polar protic solvent respectively, then rinsed in flowing deionized water for 10 - 20 min, dried in an inert gas, and then the substrate is placed on a rotatable and fixed substrate. Preferably, the substrate is ultrasonically cleaned with a polar aprotic solvent and a polar protic solvent. The polar aprotic solvents are acetone, chloroform, tetrahydrofuran, etc., and the polar protic solvent is methanol or ethanol. The inert gas used in the above drying treatment is nitrogen, argon or helium.
[0020] The substrate of the present invention can be fused quartz, silicon wafer, germanium wafer, calcium fluoride, etc. Preferably, the substrate is fused quartz glass.
[0021] The application of the above zinc selenide nanorod thin film material as a photocatalyst.
[0022] An industrial wastewater treatment method, which uses the above zinc selenide nanorod thin film material for treatment under illumination conditions.
[0023] The beneficial effects of the present invention are as follows:
[0024] (1) The zinc selenide nanorod thin film material of the present invention can effectively degrade dyes under light irradiation and is convenient for recycling and reuse; therefore, the zinc selenide nanorod thin film material of the present invention can be applied to industrial wastewater treatment, especially the treatment of wastewater containing a large amount of organic dyes such as printing and dyeing wastewater.
[0025] (2) The zinc selenide nanorod thin film material of the present invention is environmentally friendly and convenient for repeated use.
[0026] (3) The preparation method of the zinc selenide nanorod thin film material of the present invention is simple, can meet the requirements of low cost and easy industrial production, and has a very broad application prospect. Description of the Drawings
[0027] Figure 1 Scanning electron microscope images of the zinc selenide thin film and the zinc selenide nanorod thin film material prepared in Example 1, where Figure 1 a in is the scanning electron microscope image of the zinc selenide thin film prepared in step S1 of Example 1; Figure 1 b in is the scanning electron microscope image of the zinc selenide nanorod thin film material prepared in step S2.
[0028] Figure 2 It is a schematic diagram of the effect of treating wastewater with the zinc selenide nanorod thin film material prepared in Example 1. Detailed Embodiments
[0029] In order to make the objectives, technical solutions and advantages of the present invention more clear and understandable, the present invention will be further described in detail below in conjunction with the accompanying drawings and 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. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0030] For the test methods without specific conditions noted in the embodiments, they are generally carried out under conventional conditions or according to the conditions recommended by the manufacturer.
[0031] Example 1
[0032] I. Preparation steps:
[0033] (1) The fused silica glass used as the substrate was ultrasonically cleaned in acetone and alcohol respectively, then rinsed in flowing deionized water for 10 min, and dried in nitrogen.
[0034] (2) In order to ensure the uniformity and quality homogeneity of the film, the fused silica substrate was placed on a rotatable fixed substrate.
[0035] (3) A zinc selenide crystal block with a purity of 99.99% was selected as the raw material for preparing the zinc selenide thin film by laser deposition and was mounted on the target.
[0036] II. Preparation process:
[0037] S1: Laser deposition: First, control the vacuum degree in the vacuum chamber (reduce it to 1 10 -7 Torr atmospheric pressure) by using a mechanical and molecular vacuum pump. At the same time, the fused silica substrate was heated to 450 °C. A titanium sapphire regenerative amplifier mode-locked femtosecond laser (Coherent Inc., central wavelength 800 nm, pulse width ~45 fs, repetition frequency 1 KHz) was used to ablate the target. The laser energy on the target was 0.16 J / cm 2 , the deposition time was 35 min, and the distance between the substrate and the target was 8.0 cm. During the femtosecond laser deposition in step S1, a zinc selenide thin film was prepared.
[0038] S2: Heat treatment + oscillation treatment: The prepared zinc selenide thin film was placed in a temperature-controlled water bath (deionized water), the temperature was controlled at 60 °C, and at the same time, continuous ultrasonic action was carried out during the heat treatment. The heat treatment time was 12 hours, and a zinc selenide nanorod photocatalyst thin film material was obtained.
[0039] The scanning electron microscope image of the zinc selenide thin film prepared in step S1 is shown in Figure 1a in; The scanning electron microscope image of the zinc selenide nanorod photocatalyst thin film material prepared in step S2 is shown in Figure 1 b in. Comparing Figure 1 a in and Figure 1 b in, it can be seen that nanorods grow on the surface of the zinc selenide thin film, showing a disordered network distribution.
[0040] The zinc selenide nanorod photocatalyst thin film material prepared in Example 1 was used for the photocatalytic dye degradation experiment. In the photocatalytic dye degradation experiment, methyl orange (MO) was used as the dye to be photocatalytically degraded, and the solution concentration was 5 10 -5 M. At room temperature, the samples were respectively placed in 5 ml solutions containing MO dye, and irradiated with ultraviolet light, and the incident light intensity was 5 mW cm -2 . The UV-Vis absorption intensity was used to evaluate the change in the concentration of MO, and the test results are as Figure 2 shown. It can be seen from Figure 2 that in the test group containing the zinc selenide nanorod photocatalyst thin film, after 3 hours of ultraviolet light irradiation, 60% of MO was degraded. From the comparison curve, the zinc selenide nanorod thin film prepared in Example 1 had the largest reduction in the concentration of photocatalytic degradation of methyl orange under ultraviolet light irradiation. Followed by the zinc selenide thin film irradiated with ultraviolet light catalyzing methyl orange. In the two control experiments without light irradiation and with light irradiation but without a photocatalyst, the concentration of the methyl orange solution basically did not decrease.
[0041] Example 2
[0042] I. Preparation work:
[0043] (1) The fused silica glass of the substrate was ultrasonically cleaned in acetone and alcohol respectively, then rinsed in flowing deionized water for 15 min, and dried in helium gas.
[0044] (2) To ensure the uniformity and quality homogeneity of the thin film, the fused silica substrate was placed on a rotatable fixed substrate.
[0045] (3) A zinc selenide crystal block with a purity of 99.99% was selected as the raw material for preparing the zinc selenide thin film by laser deposition.
[0046] II. Preparation process:
[0047] S1: Laser deposition: First, control the air pressure in the vacuum chamber and reduce it to 2 10 -7Under a Torr atmospheric pressure, the fused silica substrate was heated to 500 °C. A titanium sapphire regenerative amplified mode-locked femtosecond laser (Coherent Inc., central wavelength 800 nm, pulse width ~45 fs, repetition rate 1 KHz) was used to ablate the target. The laser energy on the target was 0.18 J / cm 2 , the deposition time was 40 min, and the distance between the substrate and the target was 9.0 cm. During the S1 femtosecond laser deposition process, zinc selenide thin films were prepared.
[0048] S2: Heat treatment + Oscillation treatment: The prepared zinc selenide thin film was placed in a temperature-controlled water bath (deionized water) with the temperature controlled at 70 °C. At the same time, continuous ultrasonic action was carried out during the heat treatment process. The heat treatment time was 15 hours, and a zinc selenide nanorod photocatalyst thin film was obtained.
[0049] Similarly, the photocatalytic treatment effect was verified using the photocatalytic dye degradation experiment, and the experimental method was the same as that in Example 1. In the test group containing the zinc selenide nanorod photocatalyst thin film of this example, after 3 hours of ultraviolet light irradiation, the degradation of MO was 62%.
[0050] Example 3
[0051] I. Preparation work:
[0052] (1) The fused silica glass of the substrate was ultrasonically cleaned in acetone and alcohol respectively, then rinsed in flowing deionized water for 10 min, and dried in nitrogen.
[0053] (2) To ensure the uniformity and quality homogeneity of the thin film, the fused silica substrate was placed on a rotatable fixed substrate.
[0054] (3) A zinc selenide crystal block with a purity of 99.99% was used as the raw material for preparing the zinc selenide thin film by laser deposition.
[0055] II. Preparation process:
[0056] S1: Laser deposition: First, control the air pressure in the vacuum chamber and reduce it to 1 10 -7 Under a Torr atmospheric pressure, the fused silica substrate was heated to 450 °C. A titanium sapphire regenerative amplified mode-locked femtosecond laser (Coherent Inc., central wavelength 800 nm, pulse width ~45 fs, repetition rate 1 KHz) was used to ablate the target. The laser energy on the target was 0.16 J / cm 2 , the deposition time was 30 min, and the distance between the substrate and the target was 9.0 cm. During the first-step femtosecond laser deposition process, zinc selenide thin films were prepared.
[0057] S2: Heat treatment + ultrasonic treatment: Then place the prepared zinc selenide thin film in a temperature-controlled water bath (deionized water) at 60 °C, and apply continuous ultrasonic action during the heat treatment for 8 hours.
[0058] Similarly, the photocatalytic treatment effect was verified using the photocatalytic dye degradation experiment, and the experimental method was the same as that in Example 1. For the test group with the zinc selenide nanorod photocatalyst thin film in this example, after 3 hours of ultraviolet light irradiation, 53% of MO was degraded.
[0059] Example 4
[0060] I. Preparation steps:
[0061] (1) Ultrasonically clean the fused silica glass used as the substrate in acetone and alcohol respectively, then rinse it in flowing deionized water for 20 min, and dry it in nitrogen.
[0062] (2) To ensure the uniformity and quality homogeneity of the thin film, place the fused silica substrate on a rotatable fixed substrate.
[0063] (3) Select a zinc selenide crystal block with a purity of 99.99% as the raw material for preparing the zinc selenide thin film by laser deposition and install it on the target.
[0064] II. Preparation process:
[0065] S1: Laser deposition: First, control the vacuum degree in the vacuum chamber (reduce it to 1 10 -7 Torr atmospheric pressure) using a mechanical and molecular vacuum pump, and at the same time heat the fused silica substrate to 550 °C. Use a titanium-sapphire regenerative amplifier mode-locked femtosecond laser (Coherent Inc., central wavelength 800 nm, pulse width ~45 fs, repetition rate 1 KHz) to ablate the target. The laser energy on the target is 0.20 J / cm 2 , the deposition time is 35 min, and the distance between the substrate and the target is 10 cm. During the femtosecond laser deposition in step S1, a zinc selenide thin film was prepared.
[0066] S2: Heat treatment + oscillation treatment: Place the prepared zinc selenide thin film in a temperature-controlled water bath (deionized water) at 80 °C, and apply continuous ultrasonic action during the heat treatment for 15 hours to obtain the zinc selenide nanorod photocatalyst thin film.
[0067] The photocatalytic treatment effect was also verified using the photocatalytic dye degradation experiment, and the experimental method was the same as that in Example 1. For the test group containing the zinc selenide nanorod photocatalyst thin film in this example, after 3 hours of ultraviolet light irradiation, the degradation rate of MO was 58%.
[0068] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention rather than to limit them. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in terms of form and details without departing from the scope defined by the claims of the present invention.
Claims
1. A zinc selenide nanorod thin film material, characterized in that: The zinc selenide nanorods in the zinc selenide nanorod film material are arranged disorderly in a network shape.
2. The zinc selenide nanorod thin film material according to claim 1, characterized in that: The thickness of the zinc selenide nanorod film material is 1-2 μm.
3. The zinc selenide nanorod thin film material according to claim 1, characterized in that: The diameter of the nanorods in the zinc selenide nanorod film material is 100-300 nm, and the length is 6-20 μm.
4. The method for preparing the zinc nanorod thin film material according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: S1: A zinc selenide film of a certain thickness is deposited on a substrate by a laser deposition method; S2: heat-treating the zinc selenide film to obtain the zinc selenide nanorod photocatalytic film material; wherein the heat-treating temperature is 60-80° C. and the time is 8-15 hours.
5. The preparation method according to claim 4, characterized in that: The zinc selenide film is subjected to ultrasonic oscillation treatment while the heat treatment is performed, and the frequency of the ultrasonic oscillation treatment is 80-120 kHz.
6. The preparation method according to claim 4 or 5, characterized in that: The laser deposition method is femtosecond laser deposition; the femtosecond laser deposition is performed in a vacuum chamber; the vacuum degree of the vacuum chamber is 1 10 -7 -2 10 -7 Torr.
7. The preparation method according to claim 6, characterized in that: The laser energy on the target in the femtosecond laser deposition is 0.16-0.2 J / cm 2 , the deposition time is 30-40 min, and the distance between the substrate and the target is 8-10 cm.
8. The preparation method according to claim 4 or 5, characterized in that: The temperature of the substrate during the deposition process is 450-550°C.
9. The preparation method according to claim 4 or 5, characterized in that: The preparation method further comprises the step of cleaning and drying the substrate before deposition.
10. Use of the zinc selenide nanorod thin film material according to any one of claims 1 to 3 as a photocatalyst.
11. A method for treating industrial wastewater, characterized in that: The zinc selenide nanorod film material according to any one of claims 1 to 3 is treated under light conditions.