ZnS photocatalytic nanomaterial, and preparation method and application thereof
By simplifying the preparation process and controlling the morphology, highly efficient photocatalytic nanomaterials were prepared, solving the problem of poor photocatalytic effect of ZnS nanomaterials under sunlight, and realizing the application of efficient degradation of organic pollutants in water.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- BCEG ENVIRONMENTAL REMEDIATION CO LTD
- Filing Date
- 2024-12-20
- Publication Date
- 2026-05-29
Smart Images
Figure CN119733532B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photocatalytic nanomaterials technology, specifically to a ZnS photocatalytic nanomaterial, its preparation method, and its applications. Background Technology
[0002] ZnS, a typical wide-bandgap semiconductor material, is one of the most reactive metal sulfides and is widely used in sensors, photodetectors, and photocatalysis due to its superior performance. In photocatalysis, numerous studies have shown that the catalytic performance of materials is closely related to their morphology, size, and crystal form. Therefore, the controllable preparation of ZnS nanomaterials, considering their morphology, size, and crystal form, has become an important approach to regulating their performance.
[0003] However, although numerous methods exist for preparing ZnS nanomaterials with different morphologies, sizes, and crystal forms, most methods suffer from drawbacks such as complex and cumbersome preparation processes, the need for template agents, and poor controllability leading to low yields. Furthermore, commercially available ZnS materials generally exhibit photoresponsiveness in the ultraviolet region, and their photocatalytic performance under simulated sunlight is not ideal and requires improvement. These factors significantly limit the promotion and practical application of ZnS nanomaterials. Summary of the Invention
[0004] Therefore, the technical problem to be solved by the present invention is to overcome the shortcomings of existing ZnS materials, such as poor photocatalytic effect under sunlight irradiation, complicated preparation process, need for template agent, and poor controllability, so as to provide a ZnS photocatalytic nanomaterial, its preparation method and application to solve the above problems.
[0005] To achieve the above objectives, the present invention provides the following technical solution:
[0006] In a first aspect, the present invention provides a method for preparing ZnS photocatalytic nanomaterials, comprising:
[0007] Obtain a mixture of organic acid zinc salt, triethylenetetramine, and solvent;
[0008] The sulfur source was dissolved in a mixed solution to obtain a reaction precursor solution, and then reacted to prepare ZnS photocatalytic nanomaterials.
[0009] Preferably, the organic acid zinc salt includes zinc acetate;
[0010] And / or, the sulfur source includes thiourea;
[0011] And / or, the mixture also includes sodium tartrate;
[0012] And / or, the volume ratio of the solvent to triethylenetetramine is (4-1):1, preferably (3-2):1;
[0013] And / or, the solvent is water or an aqueous alcohol solution; preferably, the aqueous alcohol solution includes an aqueous ethanol solution; more preferably, the concentration of ethanol in the aqueous ethanol solution is ≤25 vol%.
[0014] Preferably, based on a total volume of 40 ml of triethylenetetramine and solvent, the amount of sodium tartrate is 0.05-0.2 g.
[0015] Preferably, based on a total volume of 40 ml of triethylenetetramine and solvent, the amount of the organic acid zinc salt is 0.5-0.8 g;
[0016] And / or, the mass ratio of the organic acid zinc salt to the sulfur source is (0.5-0.8):(0.1-0.3);
[0017] And / or, the process of obtaining the mixture includes: dissolving an organic zinc acid salt in a solution of triethylenetetramine and a solvent to obtain the mixture.
[0018] Preferably, the reaction is a hydrothermal reaction or a solvothermal reaction;
[0019] And / or, the temperature of the reaction is 130-160°C;
[0020] And / or, the reaction duration is 10-14 h;
[0021] And / or, the mixture is also stirred during the preparation process;
[0022] And / or, during the acquisition of the reaction precursor solution, a stirring process is also performed;
[0023] And / or, after the reaction, cooling, washing, and drying processes are also performed.
[0024] Preferably, the stirring speed is 150-500 r / min;
[0025] And / or, the duration of the stirring treatment is 20-40 min;
[0026] And / or, during the washing process, the water and anhydrous ethanol are used for centrifugal washing 4-6 times respectively;
[0027] And / or, the drying process is carried out at a temperature of 50-70°C;
[0028] And / or, the drying process lasts for ≥12 hours.
[0029] Preferably, the centrifugal cleaning speed is 4000-6000 r / min;
[0030] And / or, the duration of the centrifugal washing is 2-5 minutes.
[0031] Secondly, the present invention also provides a ZnS photocatalytic nanomaterial, which is prepared by the above-described method for preparing ZnS photocatalytic nanomaterials.
[0032] Thirdly, the present invention also provides the application of the above-mentioned ZnS photocatalytic nanomaterials in the photocatalytic degradation of organic pollutants in water.
[0033] Preferably, the organic pollutant is an antibiotic; alternatively, the antibiotic includes tetracycline.
[0034] The technical solution of this invention has the following advantages:
[0035] 1. A method for preparing ZnS photocatalytic nanomaterials, comprising: obtaining a mixture of an organic acid zinc salt, triethylenetetramine, and a solvent; dissolving a sulfur source in the mixture to obtain a reaction precursor solution and reacting it to obtain ZnS photocatalytic nanomaterials. The ZnS nanomaterials prepared by this invention possess a unique three-dimensional nanoparticle assembly micron-sized spherical structure with uniform size and good dispersibility. They exhibit excellent and stable photocatalytic performance, with a photocatalytic degradation efficiency of tetracycline far exceeding that of existing ZnS materials (under simulated sunlight for 300 min, the ZnS nanomaterials of this invention can degrade tetracycline at a concentration of 10 mg / L by more than 44.2%, even reaching 80.5%, while existing commercially available ZnS materials only achieve a tetracycline degradation rate of 25.5%). Furthermore, the preparation method provided by this invention is simple to operate, requires no template agent, and has good controllability (the ZnS nanomaterials prepared by this invention have high purity and crystallinity, and few impurities). The preparation is rapid, with abundant raw material sources, low cost, and environmental friendliness, possessing broad industrial application prospects.
[0036] 2. When the ZnS photocatalytic nanomaterials of the present invention are used in the photocatalytic degradation of organic pollutants in water, they differ from existing composite materials of ZnS nanomaterials with other carriers (e.g., carbon materials). The present invention can exhibit highly efficient photocatalytic degradation of tetracycline under sunlight irradiation, and has broad application prospects in the field of water treatment. At the same time, it provides a strong theoretical basis for the practical application of wide bandgap semiconductor nanomaterials under natural light. Attached Figure Description
[0037] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.
[0038] Figure 1The image shows the XRD pattern of the ZnS photocatalytic nanomaterial prepared in Example 1 of this invention.
[0039] Figure 2 This is a SEM image (scale bar is 2 μm) of the ZnS photocatalytic nanomaterials prepared in Example 1 of the present invention;
[0040] Figure 3 This is a SEM image (scale bar is 500 nm) of the ZnS photocatalytic nanomaterials prepared in Example 1 of the present invention;
[0041] Figure 4 The diagram shows the photocatalytic degradation of tetracycline by the ZnS photocatalytic nanomaterial prepared in Example 1 of this invention, as well as the commercially available ZnS material and the blank control group. Detailed Implementation
[0042] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.
[0043] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.
[0044] Example 1
[0045] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials, the specific steps of which are as follows:
[0046] 1) Obtaining the mixture: Under room temperature conditions, weigh 0.658 g of zinc acetate dihydrate and 0.1 g of sodium tartrate and dissolve them in 40 ml of triethylenetetramine aqueous solution (the volume ratio of water to triethylenetetramine is 3:1). Then, stir the mixture at a constant speed (300 r / min) on a magnetic stirrer for 30 min.
[0047] 2) Under stirring conditions, 0.228 g of thiourea was added to the mixture obtained in step 1), and the mixture was stirred continuously (at a speed of 300 r / min) for 30 min until it was uniformly mixed to obtain the reaction precursor solution;
[0048] 3) The reaction precursor solution obtained in step 2) was transferred to a polytetrafluoroethylene high-temperature reactor and subjected to hydrothermal reaction at 150°C for 12 h. After the reaction was completed and cooled to room temperature, the product was washed 4 times by centrifugation with water (5000 r / min for 3 min) and then washed 4 times by centrifugation with anhydrous ethanol (5000 r / min for 3 min). The product was collected and dried at 60°C for 12 h to obtain ZnS photocatalytic nanomaterials.
[0049] The XRD pattern of the ZnS photocatalytic nanomaterials prepared in this embodiment is shown below. Figure 1 As shown, from Figure 1 As can be seen above, typical diffraction peaks of the ZnS (111), (220), and (311) crystal planes appeared at 2θ of 28.79°, 47.5°, and 56.3°, which is consistent with the ZnS (JCPDS No. 05-0566) standard card. Furthermore, the diffraction peaks are sharp and free of impurity peaks, indicating that the prepared ZnS nanomaterials have high purity and crystallinity.
[0050] SEM images of the ZnS photocatalytic nanomaterials prepared in this embodiment are shown below. Figure 2 and Figure 3 As shown, from Figure 2 and Figure 3 As can be seen above, this material possesses a unique three-dimensional structure, generally exhibiting a micron-sized spherical structure assembled from nanoparticles. This microstructure gives the ZnS material a larger specific surface area, providing more active sites and thus enhancing its catalytic activity.
[0051] Example 2
[0052] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials, the specific steps of which are as follows:
[0053] 1) Obtaining the mixture: Under room temperature conditions, weigh 0.658 g of zinc acetate dihydrate and 0.1 g of sodium tartrate and dissolve them in 40 ml of triethylenetetramine aqueous solution (the volume ratio of water to triethylenetetramine is 2:1). Then, stir the mixture at a constant speed (300 r / min) on a magnetic stirrer for 30 min.
[0054] 2) Under stirring conditions, 0.228 g of thiourea was added to the mixture obtained in step 1), and the mixture was stirred continuously (at a speed of 300 r / min) for 30 min until it was uniformly mixed to obtain the reaction precursor solution;
[0055] 3) The reaction precursor solution obtained in step 2) was transferred to a polytetrafluoroethylene high-temperature reactor and subjected to hydrothermal reaction at 150°C for 12 h. After the reaction was completed and cooled to room temperature, the product was washed 4 times by centrifugation with water (5000 r / min for 3 min) and then washed 4 times by centrifugation with anhydrous ethanol (5000 r / min for 3 min). The product was collected and dried at 60°C for 12 h to obtain ZnS photocatalytic nanomaterials.
[0056] Example 3
[0057] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials, the specific steps of which are as follows:
[0058] 1) Obtaining the mixture: Under room temperature conditions, weigh 0.658 g of zinc acetate dihydrate and 0.1 g of sodium tartrate and dissolve them in 40 ml of triethylenetetramine aqueous solution (the volume ratio of water to triethylenetetramine is 3:1). Then, stir the mixture at a constant speed (300 r / min) on a magnetic stirrer for 30 min.
[0059] 2) Under stirring conditions, 0.228 g of thiourea was added to the mixture obtained in step 1), and the mixture was stirred continuously (at a speed of 300 r / min) for 30 min until it was uniformly mixed to obtain the reaction precursor solution;
[0060] 3) The reaction precursor solution obtained in step 2) was transferred to a polytetrafluoroethylene high-temperature reactor and subjected to hydrothermal reaction at 130℃ for 12 h. After the reaction was completed and cooled to room temperature, the product was washed 4 times by centrifugation with water (5000 r / min for 3 min) and then washed 4 times by centrifugation with anhydrous ethanol (5000 r / min for 3 min). The product was collected and dried at 60℃ for 12 h to obtain ZnS photocatalytic nanomaterials.
[0061] Example 4
[0062] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials. The difference from Example 1 is that sodium tartrate is not added to the mixture, while other conditions are the same as in Example 1.
[0063] Example 5
[0064] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials. The difference from Example 1 is that in step 1), zinc acetate dihydrate, sodium tartrate, triethylenetetramine, and water are directly blended to obtain a mixed solution, while other conditions are the same as in Example 1.
[0065] Example 6
[0066] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials, the specific steps of which are as follows:
[0067] 1) Obtaining the mixture: Under room temperature conditions, weigh 0.8 g of zinc acetate dihydrate and 0.2 g of sodium tartrate and dissolve them in 40 ml of triethylenetetramine aqueous solution (the volume ratio of water to triethylenetetramine is 3:1). Then stir the mixture at a constant speed (500 r / min) on a magnetic stirrer for 20 min.
[0068] 2) Under stirring conditions, 0.278 g of thiourea was added to the mixture obtained in step 1), and the mixture was stirred continuously (at a speed of 500 r / min) for 20 min until it was uniformly mixed to obtain the reaction precursor solution;
[0069] 3) The reaction precursor solution obtained in step 2) was transferred to a polytetrafluoroethylene high-temperature reactor and subjected to hydrothermal reaction at 160℃ for 10 h. After the reaction was completed and cooled to room temperature, the product was washed 6 times by centrifugation with water (4000 r / min for 5 min) and then washed 6 times by centrifugation with anhydrous ethanol (4000 r / min for 5 min). The product was collected and dried at 70℃ for 12 h to obtain ZnS photocatalytic nanomaterials.
[0070] Example 7
[0071] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials, the specific steps of which are as follows:
[0072] 1) Obtaining the mixture: Under room temperature conditions, weigh 0.5 g of zinc acetate dihydrate and 0.05 g of sodium tartrate and dissolve them in 40 ml of triethylenetetramine aqueous solution (the volume ratio of water to triethylenetetramine is 3:1). Then, stir the mixture at a constant speed (150 r / min) on a magnetic stirrer for 20 min.
[0073] 2) Under stirring conditions, 0.174 g of thiourea was added to the mixture obtained in step 1), and the mixture was stirred continuously (at a speed of 150 r / min) for 40 min until it was mixed evenly to obtain the reaction precursor solution.
[0074] 3) The reaction precursor solution obtained in step 2) was transferred to a polytetrafluoroethylene high-temperature reactor and subjected to hydrothermal reaction at 150℃ for 14 h. After the reaction was completed and cooled to room temperature, the product was washed 4 times by centrifugation with water (6000 r / min for 2 min) and then washed 4 times by centrifugation with anhydrous ethanol (6000 r / min for 2 min). The product was collected and dried at 50℃ for 12 h to obtain ZnS photocatalytic nanomaterials.
[0075] Example 8
[0076] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials. The difference from Example 1 is that the volume ratio of water to triethylenetetramine in the mixture is 1:1, while other conditions are the same as in Example 1.
[0077] Example 9
[0078] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials. The difference from Example 1 is that the volume ratio of water to triethylenetetramine in the mixture is 4:1, and other conditions are the same as in Example 1.
[0079] Example 10
[0080] This embodiment provides a method for preparing ZnS photocatalytic nanomaterials. The difference from Example 1 is that the water in the mixture is replaced with a 25 vol% aqueous ethanol solution, while other conditions are the same as in Example 1.
[0081] Comparative Example 1
[0082] This comparative example provides a method for preparing ZnS photocatalytic nanomaterials. The difference from Example 1 is that the triethylenetetramine in the mixture is replaced with ethylenediaminetetraacetic acid, while other conditions are the same as in Example 1.
[0083] Test Example 1
[0084] The degradation rate of tetracycline in water by the ZnS photocatalytic nanomaterials and ZnS (commercially available, Aladdin Reagent Company) prepared in the above examples and comparative examples was tested under sunlight irradiation. The test method was as follows: 50 mg of ZnS photocatalytic nanomaterials were used to degrade a tetracycline aqueous solution (50 mL volume) with an initial concentration (C0) of 10 mg / L at room temperature and pressure. The light source was a 500W Xe lamp (simulating sunlight), and the degradation time was 300 min. The tetracycline concentration (C) was measured using a UV-Vis spectrophotometer, and the degradation rate (C / C0) was calculated based on the concentration. In addition, to eliminate the influence of external interference factors, a test was conducted without the addition of ZnS photocatalytic nanomaterials (i.e., tetracycline aqueous solution) as a blank control group. The test results of the ZnS photocatalytic nanomaterials prepared in Example 1, the commercially available ZnS material, and the blank control group are as follows: Figure 4 As shown.
[0085] The test results of each embodiment, comparative example, ZnS (commercially available) material, and blank control group are shown in Table 1 below.
[0086] Table 1
[0087]
[0088]
[0089] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A method for preparing ZnS photocatalytic nanomaterials, characterized in that, include: A mixture of an organic acid zinc salt, triethylenetetramine, and a solvent is obtained; the volume ratio of the solvent to triethylenetetramine is (4-1):1, and the mixture also includes sodium tartrate. A sulfur source is dissolved in a mixed solution to obtain a reaction precursor solution, and then reacted to obtain ZnS photocatalytic nanomaterials; the sulfur source includes thiourea.
2. The preparation method according to claim 1, characterized in that, The organic acid zinc salt includes zinc acetate; And / or, the volume ratio of the solvent to triethylenetetramine is (3-2):1; And / or, the solvent is an aqueous solution of water or alcohol.
3. The preparation method according to claim 2, characterized in that, The alcohol-water solution includes an aqueous solution of ethanol.
4. The preparation method according to claim 3, characterized in that, The concentration of ethanol in the aqueous ethanol solution is ≤25 vol.
5. The preparation method according to claim 2, characterized in that, Based on a total volume of 40 ml of triethylenetetramine and solvent, the amount of sodium tartrate used is 0.05-0.2 g.
6. The preparation method according to claim 1, characterized in that, Based on a total volume of 40 ml of triethylenetetramine and solvent, the amount of the organic acid zinc salt used is 0.5-0.8 g; And / or, the mass ratio of the organic acid zinc salt to the sulfur source is (0.5-0.8):(0.1-0.3); And / or, the process of obtaining the mixture includes: dissolving an organic zinc acid salt in a solution of triethylenetetramine and a solvent to obtain the mixture.
7. The preparation method according to claim 1, characterized in that, The reaction is a hydrothermal reaction or a solvothermal reaction; And / or, the temperature of the reaction is 130-160°C; And / or, the reaction duration is 10-14 h; And / or, the mixture is also stirred during the preparation process; And / or, during the acquisition of the reaction precursor solution, a stirring process is also performed; And / or, after the reaction, cooling, washing, and drying processes are also performed.
8. The preparation method according to claim 7, characterized in that, The stirring speed is 150-500 r / min; And / or, the duration of the stirring treatment is 20-40 min; And / or, during the washing process, the water and anhydrous ethanol are used for centrifugal washing 4-6 times respectively; And / or, the drying process is carried out at a temperature of 50-70°C; And / or, the drying process lasts for ≥12 hours.
9. The preparation method according to claim 8, characterized in that, The centrifugal cleaning speed is 4000-6000 r / min; And / or, the duration of the centrifugal washing is 2-5 minutes.
10. A ZnS photocatalytic nanomaterial, characterized in that, It is prepared by the method for preparing ZnS photocatalytic nanomaterials according to any one of claims 1-9.
11. The application of the ZnS photocatalytic nanomaterial of claim 10 in the photocatalytic degradation of organic pollutants in water.
12. The application according to claim 11, characterized in that, The organic pollutant is an antibiotic.
13. The application according to claim 12, characterized in that, The antibiotics include tetracycline.