CN113479901B - Preparation method for synthesizing special-morphology 13X molecular sieve by assistance of silicon quantum dots - Google Patents
Preparation method for synthesizing special-morphology 13X molecular sieve by assistance of silicon quantum dots Download PDFInfo
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Abstract
A preparation method for synthesizing a 13X molecular sieve with a special morphology by using silicon quantum dots in an auxiliary manner belongs to the field of adsorption separation materials. The invention aims to solve the technical problems that the conventional hydrothermally synthesized molecular sieve serving as an adsorption material is insufficient in shape growth, not large in specific surface area and not good in adsorption performance. The method comprises the steps of taking sodium ascorbate as a reducing agent and a silane coupling agent as a silicon source, and synthesizing silicon quantum dots by adopting a one-step hydrothermal method to obtain a silicon quantum dot solution; silicon quantum dots are introduced in the hydrothermal synthesis process to synthesize the 13X molecular sieve with special morphology. The invention changes the appearance of the molecular sieve into a special ball shape when the crystal structure of the molecular sieve is formed, obviously increases the specific surface area, ensures that the particle size distribution is more uniform, the aperture is reduced, the pore volume is increased, the application effect of the molecular sieve on gas adsorption and screening is enhanced, and the application range is expanded.
Description
Technical Field
The invention belongs to the field of adsorption separation materials, and particularly relates to a preparation method for synthesizing a 13X molecular sieve with a special morphology by using silicon quantum dots in an auxiliary manner.
Background
For many years, industry development has continued to rely on fossil energy, the consumption of which results in CO2The emission increases year by year, the global warming is caused by the greenhouse effect, the ecological balance is destroyed, and people gradually realize effective CO treatment2The pollution problem is crucial to the development of human society. At present, the CO is mainly treated by the aqueous solution of amine compounds in industry2The neutralization treatment is carried out, the process usually needs high-temperature operation above 100 ℃ so as to develop CO with low energy consumption and high efficiency2Adsorbent materials and techniques have been the subject of scientific and industrial circles. At present, it can be used for CO2The adsorbent for gas capture is mainly porous material, such as active carbon, active carbon fiber, diatomite, mesoporous silica, Metal Organic Frameworks (MOFs), molecular sieve and the like, and under the background, the molecular sieve has unique adsorption characteristic in CO2AdsorptionThe field plays an important role.
Zeolite molecular sieves have played an important role in the fields of adsorption separation, petrochemical industry and the like as adsorbents, ion exchange materials, catalysts and the like, and therefore preparation methods of high-performance zeolite molecular sieves are receiving more and more attention. The element ratio is (3-7.5) NaO2:Al2O3:(3-5)SiO2:(81-300)H2Suitable conditions within the O range can form 13X molecular sieve.
The existing molecular sieve synthesis methods mainly comprise: the hydrothermal synthesis method, the ion exchange method, the gas phase transfer method, the dry glue method and the like are commonly used because the hydrothermal synthesis method has the advantages of simple operation, extremely low cost, high product purity, good dispersibility and easy particle size control, and can synthesize the nanocrystalline with special appearance and excellent performance.
At present, the raw materials for hydrothermal synthesis of 13X molecular sieve consist of a silicon source and an aluminum source, wherein the silicon source is usually silica sol and sodium hydroxide, and the aluminum source is sodium aluminate. However, the molecular sieve synthesized by the conventional hydrothermal method is insufficient in shape growth, large in specific surface area and poor in adsorption performance when used as an adsorption material. Therefore, a simple method capable of forming a special shape and increasing the specific surface area is needed to be found on the basis of hydrothermal synthesis of the molecular sieve.
Disclosure of Invention
The invention mainly solves the technical problem of overcoming the potential defects which are not researched, proves that the silicon quantum dots can form a molecular sieve structure with special appearance on the basis of hydrothermal synthesis, the surfaces of the silicon quantum dots are provided with a large number of active groups, the nucleation and crystallization processes of hydrothermal are changed, and simultaneously, the surface effect of the silicon quantum dots has obvious effects of changing the appearance of the molecular sieve, improving the surface area and further reducing the pore diameter of micropores on the basis of the quantum effect of the quantum dots and the particle size in a nanometer level, lays a foundation for the subsequent adsorption and separation application of small molecules, and is particularly suitable for the adsorption and separation of CO2 for the 13X molecular sieve.
The preparation method for synthesizing the 13X molecular sieve with the special morphology by the aid of the silicon quantum dots comprises the following steps:
step one, Sodium Ascorbate (SA) is used as a reducing agent, a silane coupling agent is used as a silicon source, and a one-step hydrothermal method is adopted to synthesize silicon quantum dots to obtain a silicon quantum dot solution;
step two, mixing silica sol, sodium hydroxide powder and deionized water, heating while stirring to obtain a clear transparent gel solution, and then stirring at room temperature to obtain a silicon source solution;
mixing sodium hydroxide powder, a sodium aluminate solution and deionized water, and stirring until the sodium hydroxide powder, the sodium aluminate solution and the deionized water are dissolved to obtain an aluminum source solution;
step four, dropwise adding the aluminum source solution into the silicon source solution at room temperature under stirring, continuously stirring after dropwise adding is finished, performing ultrasonic treatment, and aging at room temperature;
step five, putting the mixture into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating for reaction, performing suction filtration, washing until the pH value of the filtrate is 8-9, and drying to obtain a pompon-shaped 13X molecular sieve;
wherein, the silicon quantum dot solution is added and mixed with the silica sol, the sodium hydroxide powder and the deionized water in the second step, or mixed with the sodium hydroxide powder, the sodium aluminate powder and the deionized water in the third step; or step four is added after the stirring is continued and before the ultrasonic treatment.
Step one the method for synthesizing the silicon quantum dot solution is completed by the following steps:
step 1, dissolving 1.0g of sodium ascorbate in 15ml of deionized water under stirring at a rotating speed of 300r/min-1000r/min to prepare an SA solution with the concentration of 0.067 g/ml;
step 2, taking 12ml of SA solution obtained in the step one and 2.5ml of silane coupling agent KH-550 together, adding into 50ml of deionized water, and stirring at the rotating speed of 300r/min-1000r/min at room temperature until the mixture is uniformly mixed;
and 3, putting the mixed solution obtained in the step 2 into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 180 ℃ to obtain a silicon quantum dot solution.
In the second step, the dosage of the 40% silica sol is 7.5g to 12.5g, the dosage of the sodium hydroxide powder is 1.8g to 6.0g, and the dosage of the deionized water is 10.1g to 39.6 g.
Step two, stirring and heating for 10min at the rotating speed of 300-.
The dosage of the silicon quantum dot solution is 2.0-20.0% of the total mass of the silicon source solution obtained in the second step and the aluminum source solution obtained in the third step.
The dosage of the sodium hydroxide powder is 0.8g to 2.8g, the mass concentration of the sodium aluminate solution is 1.2 percent to 22 percent, the dosage is 0.5g to 3g, and the dosage of the deionized water is 10.4g to 41 g.
In the third step, stirring is carried out for 30min at the rotating speed of 300r/min-1000 r/min.
Step four, dropwise adding the aluminum source solution into the silicon source solution at room temperature and stirring at the speed of 1000r/min-1500 r/min; stirring for 30min after the dropwise addition; performing ultrasonic treatment at 40KHz for 15 min; aging at room temperature for 6 h.
In step five, the mixture is heated at 90 ℃ for 12 h.
And step five, drying at the temperature of 80 ℃.
The silicon quantum dots (quantum dots) obtained by the method are low-dimensional nano semiconductor materials, the surfaces of the silicon quantum dots are provided with a large number of active groups, and the silicon quantum dots have the quantum effect of the silicon quantum dots.
According to the invention, the silicon quantum dots are introduced in the hydrothermal synthesis process, so that the molecular sieve has a changed morphology and a higher specific surface area. By introducing silicon quantum dots and ultrasonically treating a reaction system, the nucleation and crystallization growth processes of the molecular sieve are changed, and the hydrothermal temperature does not need to be increased or the hydrothermal time does not need to be prolonged. And then filtering and washing the product by using a suction filtration device to reach a certain PH value, and drying the product to obtain the 13X molecular sieve with the special feature of a hair ball shape.
Drawings
FIG. 1 is an XRD contrast picture of 13X molecular sieves before and after introduction of silicon quantum dots (13X and samples 1,2,3,4, 5);
FIG. 2 is an SEM image of 13X molecular sieves before and after introduction of silicon quantum dots (13X and samples 1,2,3,4, 5);
FIG. 3 is a photograph of adsorption isotherms of 13X molecular sieves before and after introduction of silicon quantum dots (13X and sample 5);
FIG. 4 is a comparison graph of pore sizes of 13X molecular sieves before and after introduction of silicon quantum dots (13X and sample 5);
FIG. 5 shows the adsorptive separation of CO in sample 52/N2A simulation of IAST competitive adsorption of (15%: 85%).
Detailed Description
The experimental reagents and materials used in the examples of the present invention include: 100ml polytetrafluoroethylene lining high pressure water heating kettle, high power ultrasonic cleaner, water bath, magnetic stirrer, beaker, rotor, blast drying box, suction filtration device, liquid-transfering gun, high precision electronic balance, X-ray diffraction instrument (XRD), Scanning Electron Microscope (SEM), specific surface area tester (BET), silica sol (solid content is 40% (mass)), sodium hydroxide, sodium aluminate, Sodium Ascorbate (SA), silane coupling agent KH-550, deionized water, etc.
Example 1: the preparation method for synthesizing the 13X molecular sieve with the special morphology by the aid of the silicon quantum dots comprises the following steps:
step one, synthesizing silicon quantum dots by using Sodium Ascorbate (SA) as a reducing agent and a silane coupling agent as a silicon source through a one-step hydrothermal method to obtain a silicon quantum dot solution;
step two, mixing 10.0g of 40 mass percent silica sol, 2.5g of sodium hydroxide powder, 2.0g of silicon quantum dot solution and 33g of deionized water in a beaker, heating and stirring at the rotating speed of 500r/min for 10min in a water bath kettle at the temperature of 80 ℃ to obtain clear and transparent sodium silicate gel solution, and stirring at the rotating speed of 500r/min for 30min at the room temperature to obtain silicon source solution.
And step three, mixing 1.5g of sodium hydroxide powder with the mass concentration of 15%, 2.9g of sodium aluminate solution and 16.5g of deionized water in a beaker, and stirring and dissolving at the rotating speed of 500r/min for 30min to obtain the aluminum source solution.
And step four, at room temperature, dropwise adding an aluminum source into the silicon source at the stirring speed of 1200r/min, stirring for 30min after the addition is finished, and aging for 6h at room temperature.
And step five, filling the reaction liquid obtained in the step four into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining of 100ml, reacting for 12 hours at 90 ℃ to obtain a molecular sieve crude product, performing suction filtration in a suction filtration device, washing until the PH of the filtrate is 8-9, and drying the molecular sieve at 80 ℃ to obtain a product (sample 1).
In this embodiment, the first step of the method for synthesizing a silicon quantum dot solution is completed by the following steps:
step 1, dissolving 1.0g of sodium ascorbate in 15ml of deionized water under stirring at a rotating speed of 300r/min to prepare an SA solution with the concentration of 0.067 g/ml;
step 2, taking 12ml of SA solution obtained in the step one and 2.5ml of silane coupling agent KH-550, adding into 50ml of deionized water together, and stirring at the rotating speed of 300r/min at room temperature until the mixture is uniformly mixed;
and 3, putting the mixed solution obtained in the step 2 into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 180 ℃ to obtain a silicon-silicon quantum dot solution.
Example 2: the preparation method for synthesizing the 13X molecular sieve with the special morphology by the aid of the silicon quantum dots comprises the following steps:
step one, Sodium Ascorbate (SA) is used as a reducing agent, a silane coupling agent is used as a silicon source, silicon quantum dots are synthesized by adopting a one-step hydrothermal method, and a silicon quantum dot solution is obtained, wherein the step one of preparing the silicon quantum dot solution and parameters are the same as those in the example 1;
step two, mixing 10.0g of silica sol (40%), 2.5g of sodium hydroxide powder and 33g of deionized water in a beaker, heating and stirring the mixture for 10min at a rotating speed of 500r/min in a water bath kettle at a temperature of 80 ℃ to obtain a clear and transparent sodium silicate gel solution, and stirring the clear and transparent sodium silicate gel solution for 30min at a rotating speed of 500r/min at room temperature; to obtain silicon source solution.
And step three, mixing 1.5g of sodium hydroxide powder, 2.9g of sodium aluminate solution and 16.5g of deionized water, and 2.0g of the silicon quantum dot solution obtained in the step one in a beaker, and stirring and dissolving at the rotating speed of 500r/min for 30min to obtain the aluminum source solution.
And step four, at room temperature, dropwise adding an aluminum source into the silicon source at the stirring speed of 1200r/min, continuously stirring for 30min after the addition is finished, and aging for 6h at room temperature.
And step five, filling the obtained reaction liquid into a high-pressure hydrothermal reaction kettle with a 100ml polytetrafluoroethylene lining, reacting for 12 hours at 90 ℃ to obtain a molecular sieve crude product, performing suction filtration in a suction filtration device, washing until the pH of the filtrate is 8-9, and drying the molecular sieve at 80 ℃ to obtain a product (sample 2).
Example 3: the preparation method for synthesizing the 13X molecular sieve with the special morphology by the aid of the silicon quantum dots comprises the following steps:
step one, Sodium Ascorbate (SA) is used as a reducing agent, a silane coupling agent is used as a silicon source, a one-step hydrothermal method is adopted to synthesize silicon quantum dots to obtain a silicon quantum dot solution, and the steps and parameters for preparing the silicon quantum dot solution in the step one are the same as those in the embodiment 1.
Step two, a silicon source: mixing 10.0g of silica sol (40%), 2.5g of sodium hydroxide powder and 33g of deionized water in a beaker, heating the mixture in a water bath kettle at 80 ℃ for 10min, stirring the mixture at a rotating speed of 500r/min to dissolve the mixture to obtain a clear and transparent sodium silicate gel solution, and stirring the clear and transparent sodium silicate gel solution at room temperature for 30min at a rotating speed of 500 r/min.
Step three, aluminum source: 1.5g of sodium hydroxide powder, 2.9g of sodium aluminate solution and 16.5g of deionized water are mixed in a beaker and stirred to dissolve for 30min (the rotating speed is 500 r/min).
And step four, when the temperature is room temperature, dropwise adding an aluminum source into a silicon source at the stirring speed of 1200r/min, stirring for 30min after the addition is finished, adding 2.0g of the silicon quantum dot solution obtained in the step one, performing ultrasonic treatment for 15min (the ultrasonic frequency is 40KHZ), and aging for 6h at room temperature.
And step five, filling the aged reaction solution into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining of 100ml, reacting for 12 hours at 90 ℃ to obtain a molecular sieve crude product, performing suction filtration in a suction filtration device, washing until the pH value of the filtrate is 8-9, and drying the molecular sieve at 80 ℃ to obtain a product (sample 3).
Example 4: the preparation method for synthesizing the 13X molecular sieve with the special morphology by the aid of the silicon quantum dots comprises the following steps:
step one, Sodium Ascorbate (SA) is used as a reducing agent, a silane coupling agent is used as a silicon source, a one-step hydrothermal method is adopted to synthesize silicon quantum dots to obtain a silicon quantum dot solution, and the steps and parameters for preparing the silicon quantum dot solution in the step one are the same as those in the embodiment 1.
Step two, mixing 10.0g of silica sol (40%), 2.5g of sodium hydroxide powder, 0.66g of silicon quantum dot solution obtained in the step one and 33g of deionized water in a beaker, heating the mixture in a water bath kettle at 80 ℃ for 10min, stirring the mixture at a rotating speed of 500r/min, and dissolving the mixture to obtain clear and transparent sodium silicate gel solution, and stirring the mixture at room temperature for 30min at a rotating speed of 500r/min to obtain silicon source solution.
Step three, mixing 1.5g (0.8g-2.8g) of sodium hydroxide powder, 2.9g (2.5g-3g) of sodium aluminate solution and 16.5g (10.4g-41g) of deionized water in a beaker, stirring and dissolving for 30min (the rotating speed is 300-1000r/min) to obtain the aluminum source solution.
And step four, at room temperature, dropwise adding an aluminum source into the silicon source at the stirring speed of 1200r/min, stirring for 30min after the addition is finished, and aging for 6h at room temperature.
And step five, filling the obtained reaction liquid into a high-pressure hydrothermal reaction kettle with a 100ml polytetrafluoroethylene lining, reacting for 12 hours at 90 ℃ to obtain a molecular sieve crude product, performing suction filtration in a suction filtration device, washing until the pH of the filtrate is 8-9, and drying the molecular sieve at 80 ℃ to obtain a product (sample 4).
Example 4: the preparation method for synthesizing the 13X molecular sieve with the special morphology by the aid of the silicon quantum dots comprises the following steps:
step one, Sodium Ascorbate (SA) is used as a reducing agent, a silane coupling agent is used as a silicon source, a one-step hydrothermal method is adopted to synthesize silicon quantum dots to obtain a silicon quantum dot solution, and the steps and parameters for preparing the silicon quantum dot solution in the step one are the same as those in the embodiment 1.
Step two, mixing 10.0g of silica sol (40%), 2.5g of sodium hydroxide powder, 3.32g of the silicon quantum dot solution obtained in the step one and 33g of deionized water in a beaker, heating the mixture in a water bath kettle at 80 ℃ for 10min, stirring the mixture at a rotating speed of 500r/min, and dissolving the mixture to obtain a clear and transparent sodium silicate gel solution, and stirring the mixture at room temperature for 30min at a rotating speed of 500r/min to obtain a silicon source solution.
And step three, mixing 1.5g of sodium hydroxide powder, 2.9g of sodium aluminate solution and 16.5g of deionized water in a beaker, and stirring and dissolving for 30min (the rotating speed is 500r/min) to obtain the aluminum source solution.
And step four, when the temperature is room temperature, dropwise adding an aluminum source into the silicon source at the stirring speed of 1200r/min, stirring for 30min after the addition is finished, and aging for 6h at room temperature.
And step five, filling the obtained reaction liquid into a high-pressure hydrothermal reaction kettle with a 100ml polytetrafluoroethylene lining, reacting for 12 hours at 90 ℃ to obtain a molecular sieve crude product, performing suction filtration in a suction filtration device, washing until the PH of the filtrate is 8-9, and drying the molecular sieve at 80 ℃ to obtain the product. (sample 5)
The following experiments are adopted to verify the effect of the invention
The phase analysis was performed by X-ray diffraction (XRD), morphology testing by Scanning Electron Microscope (SEM), and specific surface area testing by BET.
1. Characterization of the molecular sieves
(1) XRD: the phase analysis of the sample was performed by X-ray diffraction, and the spectra were compared to a standard card to determine 13X molecular sieve.
(2) SEM: the appearance of the molecular sieve is observed by a scanning electron microscope, and the hair ball shape which is uniformly distributed in a large area appears.
(3) BET: the specific surface area, pore size and pore volume of the sample were measured.
2. Conclusion
XRD contrast pictures of 13X molecular sieves before and after introduction of the silicon quantum dots are shown in figure 1(13X and samples 1,2,3,4 and 5);
SEM images of the 13X molecular sieve before and after introducing the silicon quantum dots are shown in figure 2, figure 2-1 is an SEM image of the 13X molecular sieve without introducing the silicon quantum dots, and figures 2-2, 2-3, 2-4, 2-5 and 2-6 are SEM images of sample 1 to sample 5 respectively;
the pictures of the adsorption isotherms of the 13X molecular sieve before and after introducing the silicon quantum dots are shown in FIG. 3, FIG. 3-1 is the isothermal adsorption curve of the 13X molecular sieve without introducing the quantum dots, and 3-2 is the isothermal adsorption curve of the sample 5;
a comparison graph of the pore diameters of the 13X molecular sieves before and after introduction of the silicon quantum dots is shown in FIG. 4, wherein 4-1 is a pore diameter distribution curve of the 13X molecular sieve without introduction of the quantum dots, and 4-2 is a pore diameter distribution curve of the sample 5;
EXAMPLE 5 adsorptive separation of CO2/N2A graph of a competition adsorption simulation for iatt (15%: 85% by volume) is shown in fig. 5.
The following conclusions can be drawn from the figures:
(1) the 13X molecular sieve with higher crystallinity is synthesized by the method, and other elements and impurities are not introduced.
(2) The synthesized 13X molecular sieve has a special feature structure of a fuzzy ball shape, and is distributed more and uniformly.
(3) Compared with the BET test results of the same synthesis process before and after the introduction of the silicon quantum dots, the introduction of the silicon quantum dots obviously improves the specific surface area, increases the pore volume, reduces the pore diameter, increases the number of micropores, and basically has no mesopores and macropores.
(4) By the reaction of CO2/N2(15% by volume: 85%) adsorption-separated IAST competed for adsorption simulation to give a separation factor of 189, which is about 30% -60% higher than the separation factor of about 120-150, which is common in literature values.
Claims (10)
1. A preparation method for synthesizing a 13X molecular sieve with a special morphology by the aid of silicon quantum dots is characterized by comprising the following steps:
step one, synthesizing silicon quantum dots by using sodium ascorbate as a reducing agent and a silane coupling agent as a silicon source through a one-step hydrothermal method to obtain a silicon quantum dot solution;
step two, mixing silica sol, sodium hydroxide powder and deionized water, heating while stirring to obtain a clear transparent gel solution, and then stirring at room temperature to obtain a silicon source solution;
mixing sodium hydroxide powder, a sodium aluminate solution and deionized water, and stirring until the sodium hydroxide powder, the sodium aluminate solution and the deionized water are dissolved to obtain an aluminum source solution;
step four, dropwise adding the aluminum source solution into the silicon source solution at room temperature under stirring, continuously stirring after dropwise adding is finished, performing ultrasonic treatment, and aging at room temperature;
step five, putting the mixture into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, heating for reaction, performing suction filtration, washing until the pH value of the filtrate is 8-9, and drying to obtain a pompon-shaped 13X molecular sieve;
wherein, the silicon quantum dot solution is mixed with the silica sol, the sodium hydroxide powder and the deionized water in the step two, or is mixed with the sodium hydroxide powder, the sodium aluminate powder and the deionized water in the step three; or step four is added after the stirring is continued and before the ultrasonic treatment.
2. The method according to claim 1, wherein the step of synthesizing the silicon quantum dot solution is performed by:
step 1, dissolving 1.0g of sodium ascorbate in 15ml of deionized water under stirring at a rotating speed of 300r/min-1000r/min to prepare an SA solution with the concentration of 0.067 g/ml;
step 2, taking 12ml of SA solution obtained in the step one and 2.5ml of silane coupling agent KH-550 together, adding into 50ml of deionized water, and stirring at the rotating speed of 300r/min-1000r/min at room temperature until the mixture is uniformly mixed;
and 3, putting the mixed solution obtained in the step 2 into a high-pressure hydrothermal reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 180 ℃ to obtain a silicon quantum dot solution.
3. The method according to claim 1, wherein the amount of the 40% silica sol used in the second step is 7.5g to 12.5g, the amount of the sodium hydroxide powder used is 1.8g to 6.0g, and the amount of the deionized water used is 10.1g to 39.6 g.
4. The method according to claim 1, wherein the second step is carried out in a water bath at 80 ℃ under stirring at a rotation speed of 300r/min to 1000r/min for 10 min.
5. The method according to claim 1, wherein the amount of the silicon quantum dot solution is 2.0-20.0% of the total mass of the silicon source solution obtained in the second step and the aluminum source solution obtained in the third step.
6. The preparation method according to claim 1, characterized in that the amount of sodium hydroxide powder is 0.8g-2.8g, the mass concentration of the sodium aluminate solution is 1.2% -22%, and the amount is 0.5g-3g, and the amount of deionized water is 10.4g-41 g.
7. The process according to claim 1, wherein the stirring is carried out at a rotation speed of 300-1000r/min for 30min in step three.
8. The method according to claim 1, wherein the aluminum source solution is added dropwise to the silicon source solution at room temperature under stirring at a speed of 1000r/min to 1500r/min in step four; stirring for 30min after the dropwise addition; performing ultrasonic treatment at 40KHz for 15 min; aging at room temperature for 6 h.
9. The method according to claim 1, wherein the heating is carried out at 90 ℃ for 12 hours in the step five.
10. The method according to claim 1, wherein the drying is carried out at 80 ℃ in the step five.
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