Preparation method, product and application of barium titanate / ethynyl conjugated polymer composite material

Abstract

The invention provides a preparation method of a barium titanate / ethynyl conjugated polymer composite material, a product prepared by the preparation method and application of the product. According to the method, a simple solvothermal reaction is adopted, barium titanate is loaded on an ethynyl conjugated polymer, and therefore the heterojunction composite material with efficient photocatalysis and piezoelectric activity is formed. The material can efficiently generate hydroxyl free radicals (. OH) and superoxide free radicals (. O2-) in situ under piezoelectric-photocatalysis to quickly react with refractory organic pollutants, so that efficient removal of the organic pollutants is realized. The barium titanate / ethynyl conjugated polymer composite material provided by the invention can be recycled after being used for degrading persistent organic pollutants, and is more energy-saving and environment-friendly.

Description

Technical Field

[0001] The present invention belongs to the technical field of nanomaterials, and particularly relates to a preparation method of a barium titanate / ethynyl conjugated polymer composite material, its product and application. Background Art

[0002] Industrialization and urbanization are important components of modern civilization, but they also pose challenges to the natural environment. The industrial production process is often accompanied by the discharge of a large amount of organic sewage, which has brought great harm to human health and the environment. Therefore, the degradation and treatment of organic pollutants have become important issues that scientists are committed to solving. The molecular structure of organic pollutants is complex and variable, and they are more difficult to decompose compared to some small molecule pollutants. Among various methods for degrading organic pollutants, photocatalysis has received extensive attention due to its energy-saving, efficient and environmental-friendly characteristics. However, in traditional semiconductor photocatalytic reactions, the rapid recombination of photoelectrons (e - ) and holes (h + ) in the photocatalyst seriously hinders its application in industry. Therefore, how to improve the effective separation of photoinduced carriers is the key to further improving photocatalytic performance.

[0003] In recent years, the use of the built-in electric field generated by the ferroelectric, pyroelectric or piezoelectric effect of piezoelectric materials (such as barium titanate (BaTiO 3 )) has been proven to be an effective method for improving the separation and migration of photoinduced carriers. Therefore, by combining piezoelectric materials with semiconductors, the generation, transport and separation of carriers can be controlled at the interface between the piezoelectric material and the semiconductor, thereby optimizing photocatalytic activity. This new catalytic mechanism is called "piezo-photocatalysis". BaTiO 3 is the most classic piezoelectric and ferroelectric material, which can cause crystal deformation through mechanical strain or stress, thereby generating an internal piezoelectric potential. Pure BaTiO 3 has very poor photocatalytic performance due to its wide bandgap (E g > 3.1 eV). Therefore, it is necessary to form a heterojunction with other materials having a narrow bandgap and high photocatalytic activity through appropriate means to improve its piezo-photocatalytic performance. Summary of the Invention

[0004] In view of the above problems, the present invention proposes a preparation method of a novel barium titanate / ethynyl conjugated polymer composite material and applies its product to a piezo-photocatalytic system. This method uses a simple solvothermal reaction to load BaTiO 3 onto an ethynyl conjugated polymer (pDEB), thereby forming a heterojunction composite material with both high photocatalytic and piezoelectric activities. This material can efficiently generate hydroxyl radicals (·OH) and superoxide radicals (·O 2-), rapidly oxidize the refractory organic pollutants on its surface, thereby achieving efficient removal of organic pollutants.

[0005] In a first aspect, the present invention provides a method for preparing a barium titanate / ethynyl conjugated polymer composite, the steps of which include:

[0006] A1. Dissolve 1,4-diethynylbenzene and cuprous chloride in pyridine and ultrasonically treat for 5 - 30 minutes to obtain a homogeneous mixed solution; the molar ratio of 1,4-diethynylbenzene, cuprous chloride and pyridine is 1:0.5 - 5:0.5 - 2;

[0007] A2. Add BaTiO 3 to the mixed solution and react under vigorous stirring for 1 - 3 hours to ensure that 1,4-diethynylbenzene is coated on the surface of the BaTiO 3 to obtain a mixture; the molar ratio of the BaTiO 3 to the 1,4-diethynylbenzene described in step A1 is 1:0.1 - 0.6;

[0008] A3. Transfer the mixture to an oven and heat at 50 - 80 °C for 12 - 48 hours; centrifuge and filter the obtained reaction mixture to collect the solid material, and purify the solid material by Soxhlet extraction in solvents of pyridine, dichloromethane and methanol for 4 - 24 hours each; finally, take out the purified solid material and dry it in vacuo at 40 - 80 °C to obtain the barium titanate / ethynyl conjugated polymer composite.

[0009] Further, in A1, the molar ratio of 1,4-diethynylbenzene, cuprous chloride and pyridine is 1:1:1, and in A2, the molar ratio of the BaTiO 3 to the 1,4-diethynylbenzene is 1:0.4.

[0010] Still further, the duration of ultrasonic treatment in step A1 is 20 minutes.

[0011] Even further, in step A2, the reaction time of the mixed solution and BaTiO 3 under vigorous stirring is 2 hours.

[0012] The present invention recommends that the heating temperature of the mixture in step A3 in the oven is 60 °C and the heating time is 24 hours; the purification time in pyridine, dichloromethane and methanol by Soxhlet extraction in step A3 is 12 hours each; the vacuum drying temperature in step A3 is 60 °C.

[0013] Second aspect, the present invention provides a product of a preparation method of a barium titanate / ethynyl conjugated polymer composite material, namely, the barium titanate / ethynyl conjugated polymer composite material. The product comprises a nanosheet structure formed by stacked layers of ethynyl conjugated polymers, and barium titanate is embedded in the interlayer of the nanosheet structure to form a heterojunction hybrid structure, thereby improving the separation efficiency of photo-generated carriers.

[0014] Third aspect, the present invention provides an application of the barium titanate / ethynyl conjugated polymer composite material in a piezophotocatalytic reaction.

[0015] The steps include:

[0016] B1. Disperse the barium titanate / ethynyl conjugated polymer composite material in a solution containing persistent organic pollutants, and stir for 10 - 60 minutes in a lightless environment to achieve adsorption-desorption equilibrium; the total mass concentration of the persistent organic pollutants contained in the persistent organic pollutant solution is adjusted to 5 - 20 mg / L in advance.

[0017] B2. Turn on a xenon lamp (300 W, λ≥420 nm, average intensity: 100 mW / cm 2 ) and an ultrasonic cleaner (KQ5200DE, 200 W, 40 kHz) for the above organic pollution solution, and keep the temperature in the ultrasonic cleaner at 25 ± 5 °C to carry out the piezophotocatalytic degradation of organic pollutants reaction; usually, ice bags are placed in the ultrasonic cleaner to maintain the temperature.

[0018] B3. Determine the content of organic pollutants in the persistent organic pollutant solution after the piezophotocatalytic degradation of organic pollutants reaction for the organic pollutant solution by high performance liquid chromatography. It is recommended to select the chromatographic column as Agilent XDB-C18.

[0019] Furthermore, the organic pollutants in the persistent organic pollutant solution are one or more of bisphenol A, norfloxacin, p-nitrophenol or carbamazepine.

[0020] In addition, it is recommended that the addition amount of the barium titanate / ethynyl conjugated polymer composite material is 1 - 4 g / 5 g based on the total theoretical mass of the contained organic pollutants; the higher the proportion of the barium titanate / ethynyl conjugated polymer composite material, the better the effect on organic pollutants.

[0021] The barium titanate / ethynyl conjugated polymer composite material of the present invention can also be reused after use. After the piezophotocatalytic degradation of organic pollutants reaction is completed, the reaction solution is centrifuged and washed to recover the barium titanate / ethynyl conjugated polymer composite material, and it is dried in a freeze dryer for 48 hours for use in other degradation experiments.

[0022] The beneficial effects of the present invention are as follows: By combining barium titanate with a wide bandgap 3 and an ethynyl conjugated polymer with a narrow bandgap to prepare a highly efficient heterojunction composite material with photocatalytic and piezoelectric activities, hydroxyl radicals with strong oxidation ability can be rapidly generated during the photocatalytic process, and the charge utilization rate and transfer efficiency are significantly improved, significantly enhancing the degradation rate of organic pollutants. After the barium titanate / ethynyl conjugated polymer composite material of the present invention is used to degrade persistent organic pollutants, it can also be recycled and reused, which is more energy-saving and environmentally friendly. Description of the Drawings

[0023] Figure 1 is a scanning electron microscope image of the barium titanate / ethynyl conjugated polymer composite material of the present invention.

[0024] Figure 2 is a scanning electron microscope image of the ethynyl conjugated polymer material of the present invention.

[0025] Figure 3 is a photoluminescence spectrum of barium titanate, ethynyl conjugated polymer and barium titanate / ethynyl conjugated polymer composite material of the present invention.

[0026] Figure 4 is a time graph of the removal rate of pollutants in the piezoelectric photocatalytic reaction of the present invention.

[0027] Figure 5 is a cyclic experiment graph of the piezoelectric photocatalytic reaction of the present invention. Detailed Embodiments

[0028] The content of the present invention will be further described below with reference to specific embodiments, but it should not be construed as a limitation to the present invention. Without departing from the spirit and essence of the present invention, simple modifications or substitutions made to the methods, steps or conditions of the present invention all fall within the scope of the present invention. If not specifically specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

[0029] The materials, reagents, etc. used in the following embodiments can be obtained from commercial channels without special instructions.

[0030] Example 1

[0031] In this example, pDEB without barium titanate was prepared as a control example, and the specific steps are as follows:

[0032] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0033] (2) Transfer the mixed solution to an oven, heat to 60 °C and keep for 24 hours, then cool to room temperature to obtain a reaction mixture.

[0034] (3) After centrifuging and collecting the obtained reaction mixture, the solid substance was taken and purified by Soxhlet extraction with pyridine, dichloromethane, and methanol for 12 hours each to remove the solvents.

[0035] (4) The purified solid substance was dried in vacuo at 60 °C to obtain 5 mg of the final product.

[0036] Figure 2 This is the scanning electron microscope image of the ethynyl conjugated polymer prepared in Example 1 of the present invention. As Figure 2 shown, the ethynyl conjugated polymer material has a structure of stacked nanosheets.

[0037] Example 2

[0038] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0039] (1) 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride were dissolved in 10 mL of pyridine and sonicated for 20 minutes to obtain a mixed solution.

[0040] (2) 233.0 mg of BaTiO 3 was added to the mixed solution and reacted under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene was successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0041] (3) The mixture was transferred to an oven, heated to 60 °C and maintained for 24 hours, and then cooled to room temperature to obtain a reaction mixture.

[0042] (4) After centrifuging and collecting the obtained reaction mixture, it was purified by Soxhlet extraction with pyridine, dichloromethane, and methanol for 12 hours each to remove the solvents.

[0043] (5) The purified solid substance was dried in vacuo at 60 °C to obtain 235 mg of the final product.

[0044] Example 3

[0045] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0046] (1) 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride were dissolved in 10 mL of pyridine and sonicated for 20 minutes to obtain a mixed solution.

[0047] (2) 116.5 mg of BaTiO 3 was added to the mixed solution and reacted under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene was successfully coated on the surface of BaTiO3 The surface of the mixture.

[0048] (3) Transfer the mixture to an oven, heat it to 60 °C and keep it for 24 hours, then cool it to room temperature to obtain a reaction mixture.

[0049] (4) After centrifugally collecting the obtained reaction mixture, purify it for 12 hours respectively with pyridine, dichloromethane and methanol by Soxhlet extraction method, and remove the solvent.

[0050] (5) Dry the purified solid substance in vacuo at 60 °C to obtain 110 mg of the final product.

[0051] Example 4

[0052] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0053] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of cuprous chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0054] (2) Add 58.3 mg of BaTiO 3 to the mixed solution and react under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene is successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0055] (3) Transfer the mixture to an oven, heat it to 60 °C and keep it for 24 hours, then cool it to room temperature to obtain a reaction mixture.

[0056] (4) After centrifugally collecting the obtained reaction mixture, purify it for 12 hours respectively with pyridine, dichloromethane and methanol by Soxhlet extraction method, and remove the solvent.

[0057] (5) Dry the purified solid substance in vacuo at 60 °C to obtain 55 mg of the final product.

[0058] Example 5

[0059] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0060] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of cuprous chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0061] (2) Add 38.8 mg of BaTiO 3 to the mixed solution and react under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene is successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0062] (3) Transfer the mixture to an oven, heat it to 60 °C and keep it for 24 hours, then cool it to room temperature to obtain a reaction mixture.

[0063] (4) After centrifugally collecting the obtained reaction mixture, purify it with pyridine, dichloromethane and methanol for 12 hours respectively by Soxhlet extraction method, and remove the solvent.

[0064] (5) Dry the purified solid substance in vacuo at 60 °C to obtain 35 mg of the final product.

[0065] Example 6

[0066] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0067] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0068] (2) Add 58.3 mg of BaTiO 3 to the mixed solution and react under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene is successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0069] (3) Transfer the mixture to an oven, heat it to 50 °C and keep it for 12 hours, then cool it to room temperature to obtain a reaction mixture.

[0070] (4) After centrifugally collecting the obtained reaction mixture, purify it with pyridine, dichloromethane and methanol for 12 hours respectively by Soxhlet extraction method, and remove the solvent.

[0071] (5) Dry the purified solid substance in vacuo at 60 °C to obtain 55 mg of the final product.

[0072] Example 7

[0073] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0074] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0075] (2) Add 58.3 mg of BaTiO 3 to the mixed solution and react under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene is successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0076] (3) Transfer the mixture to an oven, heat it to 80 °C and keep it for 48 hours, then cool it to room temperature to obtain a reaction mixture.

[0077] (4) After centrifugally collecting the obtained reaction mixture, purify it with pyridine, dichloromethane and methanol for 12 hours respectively by Soxhlet extraction method, and remove the solvent.

[0078] (5) Dry the purified solid substance in vacuo at 60 °C to obtain 55 mg of the final product.

[0079] Example 8

[0080] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0081] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0082] (2) Add 58.3 mg of BaTiO 3 to the mixed solution and react under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene is successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0083] (3) Transfer the mixture to an oven, heat it to 60 °C and keep it for 24 hours, then cool it to room temperature to obtain a reaction mixture.

[0084] (4) After centrifugally collecting the obtained reaction mixture, purify it with pyridine, dichloromethane and methanol for 12 hours respectively by Soxhlet extraction method, and remove the solvent.

[0085] (5) Dry the purified solid substance in vacuo at 40 °C to obtain 55 mg of the final product.

[0086] Example 9

[0087] In this example, a barium titanate / ethynyl conjugated polymer composite material was prepared, and the specific steps are as follows:

[0088] (1) Dissolve 12.6 mg of 1,4-diethynylbenzene and 9.9 mg of copper(I) chloride in 10 mL of pyridine, and ultrasonically treat for 20 minutes to obtain a mixed solution.

[0089] (2) Add 58.3 mg of BaTiO 3 to the mixed solution and react under vigorous stirring for 2 hours to ensure that 1,4-diethynylbenzene is successfully coated on the surface of BaTiO 3 to obtain a mixture.

[0090] (3) Transfer the mixture to an oven, heat it to 60 °C and keep it for 24 hours, then cool it to room temperature to obtain a reaction mixture.

[0091] (4) After centrifugally collecting the obtained reaction mixture, purify it for 12 hours with pyridine, dichloromethane and methanol respectively by Soxhlet extraction method, and remove the solvent.

[0092] (5) Dry the purified solid substance in vacuo at 80 °C to obtain 55 mg of the final product.

[0093] The covalent triazine framework materials obtained in Examples 1 and 4 were characterized morphologically by scanning electron microscopy, and the results are as Figure 1 、 Figure 2 shown. It can be seen from Figure 1 that the ethynyl conjugated polymer material is a stacked nanosheet structure. It can be seen from Figure 1 that in the barium titanate / ethynyl conjugated polymer composite, barium titanate is largely embedded in the interlayer of the ethynyl conjugated polymer to form a heterojunction hybrid structure, thereby optimizing the energy band structure ( Figure 3 ), and improving the separation efficiency of photo-generated carriers ( Figure 3 ).

[0094] Example 10

[0095] For the piezoelectric photocatalytic degradation experiment of persistent organic pollutants of BaTiO 3 、pDEB (Example 1) and barium titanate / ethynyl conjugated polymer composite (Examples 2 - 5) of the present invention, the specific steps are as follows:

[0096] Disperse 25 mg of the barium titanate / ethynyl conjugated polymer composite in 50 mL of bisphenol A solution with a concentration of 10 mg / L, and stir it in the dark for 30 minutes at a temperature of 25 °C to achieve adsorption - desorption equilibrium. Then, turn on the xenon lamp (300 W, λ≥420 nm, average intensity: 100 mW / cm 2 ) and an ultrasonic cleaner (KQ5200DE, 200 W, 40 kHz) to carry out the piezoelectric photocatalytic degradation reaction of organic pollutants. Place an ice pack in the ultrasonic cleaner to keep the temperature within the range of 25 ± 5 °C. At given time intervals, take 1 mL of the solution and immediately filter it with a 0.22 - micron syringe filter for detection. The concentration of bisphenol A is determined by high - performance liquid chromatography (Shimadzu, LC - 16), and the instrument parameters are set as follows: the chromatographic column is Agilent XDB - C18, the column temperature is set at 30 °C, the detection wavelength is 225 nm. The mobile phase is methanol / water (volume ratio 7:3), the total flow rate is 1 mLmin -1 , and the detection time is 4 min.

[0097] The results are as follows Figure 4 shown. The data from -20 min to 0 min were omitted according to the needs of graphing. The barium titanate / ethynyl conjugated polymer composite material described in Example 4 achieved a removal rate of 98.6% of BPA within 20 minutes, far higher than that of BaTiO 3 (61.0%) and pDEB (61.1%), indicating that loading an appropriate content of barium titanate on the ethynyl conjugated polymer material can effectively enhance the activity of the material in the piezoelectric photocatalytic reaction system, thereby improving the removal efficiency of the system for organic pollutants.

[0098] Example 11

[0099] The stability experiment of the barium titanate / ethynyl conjugated polymer composite material (Example 4) of the present invention for piezoelectric photocatalytic degradation of organic pollutants was carried out as follows:

[0100] After the barium titanate / ethynyl conjugated polymer composite material prepared in Example 4 was subjected to piezoelectric photocatalytic degradation experiment according to the steps described in Example 6, the reaction solution was centrifuged and washed. The recovered composite material was dried in a freeze dryer for 48 hours, and then put into the reactor again for the next degradation experiment. Except for the material, the remaining degradation reaction conditions and the experimental setup program of the first piezoelectric photocatalytic degradation performance evaluation experiment remained the same; after the second reaction was completed, the above steps were repeated for four degradation experiments.

[0101] As Figure 5 shown, in the four stability experiments, the barium titanate / ethynyl conjugated polymer composite material (Example 4) was able to remove 98.6%, 95.2%, 92.5% and 90.1% of bisphenol A pollutants respectively, indicating that the barium titanate / ethynyl conjugated polymer composite material prepared by the present invention has good chemical stability and catalytic stability, and has good application prospects.

[0102] The above results show that loading barium titanate nanoparticles with piezoelectric catalytic activity on the ethynyl conjugated polymer can effectively improve the piezoelectric photocatalytic activity of the material, thereby realizing the efficient degradation of organic pollutants.

[0103] The embodiments described above are only a preferred solution of the present invention, rather than limiting the present invention. For example, in the embodiment, barium titanate is selected as the precursor to enhance the piezocatalytic performance of the material. However, it does not mean that only barium titanate can be loaded on the ethynyl conjugated polymer described herein to improve the highly efficient piezophotocatalytic activity of the composite material. The effect of the present invention can be achieved by selecting broadband gap piezocatalytic nanomaterials with a structure similar to that of barium titanate. Another example is that bisphenol A is selected as the organic pollutant to be degraded in the piezophotocatalytic reaction of the present invention. However, it does not mean that the embodiments described in the present invention only have the ability to degrade bisphenol A. Organic pollutants of the same type as bisphenol A can all be effectively removed in the piezophotocatalytic degradation experiment described in the present invention.

[0104] Therefore, those skilled in the art can make various changes without departing from the basic method of the present invention. However, if an inventive solution is obtained by an equivalent or equivalent replacement method, it is within the protection scope of the present invention.

Claims

1. A method for preparing a barium titanate / acetylene conjugated polymer composite material, comprising the steps of: A1. Dissolve 1,4-diethynylbenzene and cuprous chloride in pyridine and ultrasonically treat for 5-30 minutes to obtain a uniform mixed solution; the molar ratio of 1,4-diethynylbenzene, cuprous chloride and pyridine is 1:0.5-5:0.5-2; A2. BaTiO3 is added to the mixed solution, and the reaction is carried out under vigorous stirring for 1-3 hours to ensure that 1,4-diethinylbenzene is coated on the surface of the BaTiO3 to obtain a mixture; the molar ratio of the BaTiO3 to the 1,4-diethinylbenzene in step A1 is 1:0.1-0.6; A3. The mixture is transferred to an oven and heated at 50-80°C for 12-48 hours; the obtained product is centrifuged to collect the solid matter, and the solid matter is purified by Soxhlet extraction using pyridine, dichloromethane and methanol solvents for 4-24 hours; finally, the purified solid matter is taken out and dried in a vacuum at 40-80°C to obtain a barium titanate / acetylene conjugated polymer composite material.

2. The method for preparing the barium titanate / acetylene conjugated polymer composite material according to claim 1, characterized in that: The molar ratio of 1,4-diethynylbenzene, cuprous chloride and pyridine in A1 is 1:1:1, and the molar ratio of BaTiO3 and 1,4-diethynylbenzene in A2 is 1:0.

4.

3. The method for preparing the barium titanate / acetylene conjugated polymer composite material according to claim 1, characterized in that: The duration of ultrasonic treatment in step A1 was 20 minutes.

4. The method for preparing the barium titanate / acetylene conjugated polymer composite material according to claim 1, characterized in that: In step A2, the reaction time of the mixed solution and BaTiO3 under vigorous stirring is 2 hours.

5. The method for preparing the barium titanate / acetylene conjugated polymer composite material according to claim 1, characterized in that: The mixture in step A3 is heated in an oven at 60°C for 24 hours. The purification time in step A3 by Soxhlet extraction in pyridine, dichloromethane and methanol is 12 hours each. The vacuum drying temperature in step A3 is 60°C.

6. The barium titanate / ethynyl conjugated polymer composite material obtained by the method for preparing the barium titanate / ethynyl conjugated polymer composite material according to claim 1.

7. The use of the barium titanate / acetylene conjugated polymer composite material according to claim 6 in the piezoelectric photocatalytic degradation of persistent organic pollutants, comprising the steps of: B1. Dispersing the barium titanate / acetylene conjugated polymer composite material in a solution containing persistent organic pollutants and stirring for 10-60 minutes in a lightless environment to achieve adsorption-desorption equilibrium; the total mass concentration of the persistent organic pollutants contained in the persistent organic pollutant solution is adjusted to 5-20 mg / L in advance; B2. Turn on the xenon lamp and ultrasonic cleaner for the organic contamination solution and maintain the temperature in the ultrasonic cleaner at 25 ± 5 ° C to perform the piezoelectric photocatalytic degradation of organic pollutants; B3. Using high performance liquid chromatography to determine the content of organic pollutants in the persistent organic pollutant solution after the electro-photocatalytic degradation of organic pollutants.

8. The use of the barium titanate / ethynyl conjugated polymer composite material according to claim 7, characterized in that: The organic pollutants in the persistent organic pollutant solution are one or more of bisphenol A, norfloxacin, p-nitrophenol or carbamazepine.

9. The use of the barium titanate / ethynyl conjugated polymer composite material according to claim 7, characterized in that: The addition amount of the barium titanate / ethynyl conjugated polymer composite material is 1-4g / 5g based on the total theoretical mass of organic pollutants contained.

10. The use of the barium titanate / ethynyl conjugated polymer composite material according to claim 7, characterized in that: After the piezoelectric photocatalytic degradation of organic pollutants is completed, the post-reaction solution is centrifuged and washed, and the barium titanate / acetylene conjugated polymer composite material is recovered and dried in a freeze dryer for 48 hours for use in other degradation experiments.

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