Manufacturing method of waterwheel baffle and water treatment device comprising waterwheel baffle
By preparing a waterwheel baffle with a Co-SnS catalyst, a photo-piezoelectric catalytic water treatment device was constructed, solving the problems of poor light absorption and difficult recovery of photo-piezoelectric catalytic materials, and realizing the large-scale green and environmentally friendly application of efficient degradation of pollutants.
Patent Information
- Application Number
- CN202511634425.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-10
- Publication Date
- 2026-01-09
AI Technical Summary
Existing photo-piezoelectric catalytic materials have poor light absorption, insufficient degradation performance, and are difficult to recycle, which limits their promotion in large-scale environmental applications.
By using Co-SnS catalyst, a water treatment device with photo-piezoelectric catalytic response was constructed by preparing a waterwheel baffle and utilizing the mechanical vibration of the piezoelectric material and light energy to simultaneously drive the catalytic reaction, thereby enhancing the catalytic degradation performance.
It achieves efficient degradation of pollutants, especially RhB, is suitable for large-scale environmental applications, is green and environmentally friendly, and utilizes solar energy and water impact performance.
Smart Images
Figure CN121292572A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photo-piezo-catalytic degradation of pollutants, specifically the method for manufacturing a waterwheel baffle and a water treatment device including the waterwheel baffle. Background Technology
[0002] Piezocatalysis is an emerging catalytic technology whose concept was clearly proposed in the early 21st century. It utilizes the deformation of piezoelectric materials under mechanical vibration (such as ultrasound, water flow, wind, etc.) to generate a piezoelectric potential. Photocatalytic materials absorb light energy, exciting the generation of free radicals, which in turn simultaneously drive the catalytic reaction. This technology converts mechanical and light energy into chemical energy, providing a completely new energy utilization pathway for environmental pollution control.
[0003] However, there are still two main problems in the application of photo-piezoelectric catalytic materials: (1) how to develop efficient photo-piezoelectric materials; (2) how to efficiently utilize mechanical vibration and light energy to construct processing devices. Currently, researchers mostly use catalytic materials such as BaTiO3, ZnO, and MoS2, but their light absorption is poor and their degradation performance needs further improvement. Some studies have pointed out that SnS has an ultra-high piezoelectric coefficient, which is larger than previously reported. Therefore, constructing SnS-based piezoelectric catalytic materials is of greater significance. Currently, piezoelectric-photocatalytic materials are difficult to recycle and are generally not suitable for large-scale environmental applications. Summary of the Invention
[0004] Purpose of the invention: In order to overcome the shortcomings of the existing technology, the purpose of this invention is to provide a method for preparing a waterwheel baffle that can efficiently degrade RhB. Another purpose of this invention is to provide a water treatment device with photo-piezoelectric catalytic response suitable for large-scale environmental applications.
[0005] Technical solution: The present invention provides a method for preparing a waterwheel baffle, comprising the following steps:
[0006] Step 1: Urea and thioacetamide are added to pure water and stirred. SnCl2 is added and stirred again. Cobalt acetate tetrahydrate is added and stirred again to obtain a yellowish-gray suspension. The suspension is then subjected to high pressure reaction and kept warm to obtain Co-SnS catalyst.
[0007] Step 2: Weigh polyvinylidene fluoride and Co-SnS catalyst, then add N,N-dimethylformamide, stir in an oil bath to obtain a polyvinylidene fluoride solution;
[0008] Step 3: After dissolving polyvinylpyrrolidone, polyethylene glycol, and N,N-dimethylformamide by stirring, add them to the polyvinylidene fluoride solution and stir in an oil bath.
[0009] Step 4: After mixing well, pour into a mold and use ethanol to set the shape to obtain the waterwheel baffle.
[0010] Furthermore, in step one, the mass-to-volume ratio of urea, thioacetamide, SnCl2, cobalt acetate tetrahydrate, and pure water is 1~2g:1.5g:0.2~0.3g:18mg:60mL.
[0011] Furthermore, in step one, the stirring speed is 100~200 rpm and the stirring time is 10~30 min.
[0012] Furthermore, in step one, the high-pressure reaction temperature is 140~160℃, and the holding time is 16~20 hours.
[0013] Furthermore, in step two, the mass-to-volume ratio of polyvinylidene fluoride, Co-SnS catalyst, and N,N-dimethylformamide is 1.2 g: 0.05~0.2 g: 8 mL.
[0014] Furthermore, in step three, the mass-to-volume ratio of polyvinylpyrrolidone, polyethylene glycol, and N,N-dimethylformamide is 200 mg: 170~180 mg: 4 mL.
[0015] Furthermore, in step three, the temperature of the oil bath stirring is 60~80℃.
[0016] Furthermore, in step three, the oil bath stirring speed is 100~200 rpm, and the time is 8~12 hours.
[0017] The water treatment device with photo-piezoelectric catalytic response obtained by the waterwheel baffle preparation method of the present invention further includes a rotating shaft and a waterwheel frame. The waterwheel baffle and the rotating shaft are arranged in the waterwheel frame, and the waterwheel baffle is evenly spaced along the circumference of the rotating shaft.
[0018] Furthermore, the waterwheel baffle occupies 15-20% of the length of the waterwheel frame.
[0019] High-efficiency degradation principle: It mainly utilizes piezoelectric catalysis to degrade pollutants. First, the catalyst is mixed and fixed in a PVDF baffle. Figure 3 Then, the highly efficient piezoelectric properties of the catalyst are utilized to enhance catalytic degradation. Co 2+ The ionic radius is much smaller than that of Sn. 2+ This induces lattice distortion, breaks symmetry, and enhances spontaneous polarization.
[0020] Beneficial effects: Compared with the prior art, the present invention has the following significant features: it constructs a highly efficient photo-piezoelectric catalytic device, which is suitable for large-scale environmental applications; at the same time, it utilizes solar energy and water impact performance, making it green and environmentally friendly. Attached Figure Description
[0021] Figure 1 This is a schematic diagram of the structure of the waterwheel operating device of the present invention;
[0022] Figure 2 This is the XRD pattern of the Co-SnS catalytic material of this invention;
[0023] Figure 3 These are scanning electron microscope images of the Co-SnS catalytic material on the membrane, where a represents the surface morphology of the membrane without catalyst and b represents the surface morphology of the membrane after catalysis with Co-SnS additive. Detailed Implementation
[0024] Unless otherwise specified, all materials and reagents used in the following embodiments are commercially available. Experimental methods not specifically described in the embodiments are generally performed under standard conditions or as recommended by the manufacturer.
[0025] like Figure 1 As shown, the waterwheel baffle and rotating shaft of the water treatment device with photo-piezoelectric catalytic response are set inside the waterwheel frame, and the waterwheel baffle is evenly spaced at 45° intervals along the circumference of the rotating shaft.
[0026] Figure 2 The structural changes of XRD before and after Co doping are shown. Obviously, the positions of the XRD peaks remain basically unchanged, but the intensity of some peaks of Co-SnS changes and some new peaks appear. This may be due to the change of SnS lattice caused by doping.
[0027] Figure 3 The changes on the membrane surface before and after the catalyst was incorporated into the membrane were shown. Clearly, the catalyst entering the membrane is the main reason for the improved catalytic degradation performance.
[0028] Example 1
[0029] A method for preparing a waterwheel baffle includes the following steps:
[0030] S1. Add 1.68 g of urea and 1.5 g of thioacetamide to 60 mL of pure water respectively. After stirring at 100 r / min for 10 min, add 0.27 g of SnCl2 and continue stirring for 10 min. Then add 18 mg of cobalt acetate tetrahydrate and continue stirring for 30 min to obtain a yellowish-gray suspension. Transfer the suspension to a high-pressure reactor and keep it in an oven at 160 ℃ for 18 hours to obtain the Co-SnS catalyst.
[0031] S2. Weigh 1.2g (14.6wt%) of polyvinylidene fluoride and 0.13g of Co-SnS catalyst, then add 8mL of N,N-dimethylformamide, and stir in an oil bath at 70℃ for 8 hours to obtain a polyvinylidene fluoride solution.
[0032] S3. Dissolve 200 mg polyvinylpyrrolidone (K30), 173 mg polyethylene glycol and 4 mL N,N-dimethylformamide by stirring, then add to polyvinylidene fluoride solution. Stir again in an oil bath at 70°C for 8 hours at a stirring speed of 100 r / min.
[0033] S4. After mixing, pour into a mold and use ethanol to set, thus obtaining a waterwheel baffle.
[0034] Application Example 1
[0035] The water treatment device with photo-piezoelectric catalytic response, prepared from the waterwheel baffle obtained in Example 1, was used. The water level submerged 10% below the waterwheel frame, and water flowed down from directly above baffle No. 2 to a height of 2 cm above the waterwheel frame. The submersible pump flow rate was 200 L / h. After degrading a 5 mg / L RhB solution, the removal rates were 85.8% and 97.2% after 3 hours of operation under darkness and light (150 W) conditions, respectively.
[0036] Application Example 2
[0037] The water treatment device with photo-piezoelectric catalytic response, prepared from the waterwheel baffle obtained in Example 1, was used with the water surface submerging 15% of the area below the waterwheel frame. Water flowed down from directly above baffle No. 2, reaching a height of 2 cm above the waterwheel frame, and the submersible pump flow rate was 200 L / h. After operating for 3 hours under illumination (150 W) conditions, the removal rate of a 5 mg / L RhB solution was 98.6%.
[0038] Application Example 3
[0039] The water treatment device with photo-piezoelectric catalytic response, prepared from the waterwheel baffle obtained in Example 1, was used. The water level submerged 20% of the waterwheel frame, and water flowed down directly above baffle No. 2, reaching a height of 2 cm above the waterwheel frame. The submersible pump flow rate was 200 L / h. After operating for 3 hours under illumination (150 W) conditions, the removal rate of a 5 mg / L RhB solution was 98.2%.
[0040] Application Example 4
[0041] The water treatment device with photo-piezoelectric catalytic response, prepared from the waterwheel baffle obtained in Example 1, was used with the water surface submerging 15% of the area below the waterwheel frame. Water flowed down from directly above baffle No. 2, reaching a height of 5 cm above the waterwheel frame, and the submersible pump flow rate was 200 L / h. After operating for 3 hours under illumination (150 W) conditions, the removal rate of a 5 mg / L RhB solution was 98.9%.
[0042] Application Example 5
[0043] The water treatment device with photo-piezoelectric catalytic response, prepared from the waterwheel baffle obtained in Example 1, was used. The water level submerged 20% of the waterwheel frame, and water flowed down directly above baffle No. 2, reaching a height of 2 cm above the waterwheel frame. The submersible pump flow rate was 200 L / h. After degrading a 5 mg / L RhB solution under illumination (150 W) for 3 hours, the removal rate was 99.6%.
[0044] Comparative Example 1
[0045] Weigh 1.2 g (14.6 wt%) of polyvinylidene fluoride (PVDF), then add 8 mL of N,N-dimethylformamide. Place the mixture in an oil bath at 70°C and stir for 8-12 h. Simultaneously, dissolve 200 mg of polyvinylpyrrolidone (K30), 173 mg of polyethylene glycol, and 4 mL of N,N-dimethylformamide by stirring, then add this solution to the PVDF mixture. Stir again in the oil bath at 70°C for 8-12 h. After thorough mixing, pour the mixture into a mold and set with ethanol to create a waterwheel baffle.
[0046] A catalyst-free waterwheel baffle was prepared, with the water level submerging 10% of the waterwheel frame. Water flowed down from directly above baffle No. 2 to a height of 2 cm above the waterwheel frame, and the submersible pump flow rate was 200 L / h. The degradation of a 5 mg / L RhB solution resulted in removal rates of 8.6% and 9.4% after 3 hours of operation under darkness and light (150 W) conditions, respectively.
[0047] Comparative Example 2
[0048] Weigh 1.2 g (14.6 wt%) of polyvinylidene fluoride (PVDF) and 0.13 g of SnS catalyst, then add 8 mL of N,N-dimethylformamide. Place the mixture in an oil bath at 70°C and stir for 8–12 h. Simultaneously, dissolve 200 mg of polyvinylpyrrolidone (K30), 173 mg of polyethylene glycol, and 4 mL of N,N-dimethylformamide by stirring, then add this solution to the PVDF mixture. Stir again in the oil bath at 70°C for 8 h. After thorough mixing, pour the mixture into a mold and set with ethanol to create a waterwheel baffle.
[0049] The water level was 10% below the waterwheel frame, and the water flowed down from directly above baffle No. 2 to a height of 2 cm above the waterwheel frame. The submersible pump flow rate was 200 L / h. The catalyst-free waterwheel baffle degraded a 5 mg / L RhB solution, achieving removal rates of 56.1% and 64.8% after 3 hours of operation under dark and light (150 W) conditions, respectively.
[0050] Example 2
[0051] A method for preparing a waterwheel baffle includes the following steps:
[0052] S1. Add 1g of urea and 1.5g of thioacetamide to 60mL of pure water respectively. Stir at 100 r / min for 10min, then add 0.2g of SnCl2 and continue stirring for 10min. Then add 18mg of cobalt acetate tetrahydrate and continue stirring for 30min to obtain a yellowish-gray suspension. Transfer the suspension to a high-pressure reactor and keep it in an oven at 150℃ for 16 hours to obtain the Co-SnS catalyst.
[0053] S2. Weigh 1.2g (14.6wt%) of polyvinylidene fluoride and 0.05g of Co-SnS catalyst, then add 8mL of N,N-dimethylformamide, and stir in an oil bath at 80℃ for 8 hours to obtain a polyvinylidene fluoride solution.
[0054] S3. Dissolve 200 mg polyvinylpyrrolidone (K30), 180 mg polyethylene glycol and 4 mL N,N-dimethylformamide by stirring, then add to polyvinylidene fluoride solution. Stir in an oil bath at 80°C for 8 hours at a stirring speed of 100 r / min.
[0055] S4. After mixing, pour into a mold and use ethanol to set, thus obtaining a waterwheel baffle.
[0056] Example 3
[0057] A method for preparing a waterwheel baffle includes the following steps:
[0058] S1. Add 2g of urea and 1.5g of thioacetamide to 60mL of pure water respectively. Stir at 100r / min for 10min, then add 0.3g of SnCl2 and continue stirring for 10min. Then add 18g of cobalt acetate tetrahydrate and continue stirring for 30min to obtain a yellowish-gray suspension. Transfer the suspension to a high-pressure reactor and keep it in an oven at 140℃ for 20 hours to obtain the Co-SnS catalyst.
[0059] S2. Weigh 1.2g (14.6wt%) of polyvinylidene fluoride and 0.2g of Co-SnS catalyst, then add 8mL of N,N-dimethylformamide, and stir in an oil bath at 60℃ for 12 hours to obtain a polyvinylidene fluoride solution.
[0060] S3. Dissolve 200 mg polyvinylpyrrolidone (K30), 170 mg polyethylene glycol and 4 mL N,N-dimethylformamide by stirring, then add to polyvinylidene fluoride solution. Stir in an oil bath at 60°C for 12 hours at a stirring speed of 100 r / min.
[0061] S4. After mixing, pour into a mold and use ethanol to set, thus obtaining a waterwheel baffle.
Claims
1. A method for preparing a waterwheel baffle, characterized in that, Includes the following steps: Step 1: Urea and thioacetamide are added to pure water and stirred. SnCl2 is added and stirred again. Cobalt acetate tetrahydrate is added and stirred again to obtain a yellowish-gray suspension. The suspension is then subjected to high pressure reaction and kept warm to obtain Co-SnS catalyst. Step 2: Weigh polyvinylidene fluoride and Co-SnS catalyst, then add N,N-dimethylformamide, stir in an oil bath to obtain a polyvinylidene fluoride solution; Step 3: After dissolving polyvinylpyrrolidone, polyethylene glycol, and N,N-dimethylformamide by stirring, add them to the polyvinylidene fluoride solution and stir in an oil bath. Step 4: After mixing well, pour into a mold and use ethanol to set the shape to obtain the waterwheel baffle.
2. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step one, the mass-to-volume ratio of urea, thioacetamide, SnCl2, cobalt acetate tetrahydrate, and pure water is 1~2g:1.5g:0.2~0.3g:18mg:60mL.
3. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step one, the stirring rate is 100-200 rpm and the stirring time is 10-30 min.
4. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step one, the high-pressure reaction temperature is 140~160℃, and the holding time is 16~20 hours.
5. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step two, the mass-to-volume ratio of polyvinylidene fluoride, Co-SnS catalyst, and N,N-dimethylformamide is 1.2g:0.05~0.2g:8mL.
6. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step three, the mass-to-volume ratio of polyvinylpyrrolidone, polyethylene glycol, and N,N-dimethylformamide is 200 mg: 170-180 mg: 4 mL.
7. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step three, the temperature of the oil bath stirring is 60~80℃.
8. The method for preparing a waterwheel baffle according to claim 1, characterized in that: In step three, the oil bath stirring speed is 100~200 rpm, and the time is 8~12 hours.
9. A water treatment device comprising a waterwheel baffle prepared by any one of claims 1 to 8, having a photo-piezoelectric catalytic response, characterized in that: It also includes a rotating shaft and a waterwheel frame. The waterwheel baffles and the rotating shaft are set inside the waterwheel frame, and the waterwheel baffles are evenly spaced along the circumference of the rotating shaft.
10. A water treatment device with photo-piezoelectric catalytic response according to claim 9, characterized in that: The waterwheel baffle occupies 15-20% of the length of the waterwheel frame.