Preparation of two-dimensional piezoelectric semiconductor doped piezoelectric polymer material and application of two-dimensional piezoelectric semiconductor doped piezoelectric polymer material in degrading perfluorinated compounds

Abstract

The invention discloses preparation of a two-dimensional piezoelectric semiconductor doped piezoelectric polymer material and application of the two-dimensional piezoelectric semiconductor doped piezoelectric polymer material to degradation of perfluorinated compounds, a method comprises the steps that a simple physical method is used for doping a two-dimensional piezoelectric semiconductor into a piezoelectric polymer to enhance electron transfer in a polymer matrix, and the synthesis method is simple. Piezoelectric catalysis is driven by ultrasonic mechanical force to realize degradation of perfluorinated compound pollutants in water. The two-dimensional piezoelectric semiconductor doped piezoelectric polymer material prepared by the method has relatively high catalytic activity, shows excellent degradation capacity on perfluorinated compound pollutants (perfluorooctanoic acid, perfluorooctanoic acid, perfluorodecyl acid and perfluorododecyl carboxylic acid), is low in energy consumption and easy to recycle, and avoids secondary pollution.

Description

[Technical field]

[0001] The present invention belongs to the technical field of catalytic materials, and relates to the preparation of a two-dimensional piezoelectric semiconductor doped piezoelectric polymer material and its application in the field of water treatment. The two-dimensional piezoelectric semiconductor doped piezoelectric polymer has enhanced electron transmission ability and is designed for application in the field of interfacial catalytic reaction and water purification, and belongs to the preparation of new functional materials. [Background technology]

[0002] Perfluorinated compounds (PFAS) are a class of compounds containing a perfluorinated carbon chain structure with excellent stability, surface activity and hydrophobicity. They are widely used in many industrial and consumer applications, including waterproof materials, anti-pollution agents, lubricants and flame retardants. At the same time, PFAS contains a large number of CF bonds, which is one of the most stable chemical bonds. Due to the presence of CF bonds, PFAS is difficult to degrade even under extreme conditions and has high thermal stability and chemical stability. This characteristic determines that they are not easily naturally hydrolyzed, photolyzed or biodegraded in the environment, so they are persistent and can exist for a long time. Once released into the environment, PFAS will be extremely difficult to degrade and will exist in soil, water and organisms for a long time, posing a serious threat to ecological environmental safety and human health.

[0003] Piezoelectric catalysis is an emerging research direction in recent years. It is a catalytic technology that converts mechanical vibration into chemical energy. Piezoelectric catalysis is based on the triboelectric effect. It uses mechanical forces generated by stirring, ultrasound, friction and extrusion to polarize the piezoelectric material internally, induce the separation of electrons and holes, generate surface potential at the material interface, form an internal electric field, and the isolated surface charges react with OH- and O2 in water to produce highly oxidizing free radicals (such as ·OH and ·O2-), thereby achieving the purpose of oxidative degradation of pollutants. At present, there are relatively few studies on the effective degradation of persistent perfluorinated compound pollutants through piezoelectric catalysis, and the scope of application is limited.

[0004] Patent CN202310074315.X discloses a method for piezoelectrically degrading various perfluorinated and polyfluorinated compounds in water using polytetrafluoroethylene powder. Polytetrafluoroethylene is used as a piezoelectric catalyst, and various perfluorinated and polyfluorinated compounds in water are piezoelectrically degraded through ultrasonic vibration. Patent CN202210809941.4 discloses a method for removing perfluorinated compounds from groundwater using a photoelectrocatalytic coordinated PRB method. First, a TiO2 nanotube array photoelectrode is prepared, and a photoelectrocatalytic system PEC is constructed and processed. PEC and PRB synergistically treat PFOA and PFOS. After the groundwater contaminated with PFOA and PFOS is treated by the PEC system, it is treated by the permeable reaction wall PRB technology, and the removal rate can reach more than 99%. [Summary of the invention]

[0005] [Technical issues to be solved]

[0006] In order to solve the problem of environmental pollution caused by perfluorinated compounds, the present invention provides a method for preparing a two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material.

[0007] [Technical solution]

[0008] A method for preparing a two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material, characterized in that the preparation of the two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material and the application of degrading perfluorinated compounds, comprises the following steps:

[0009] (1) Preparation of two-dimensional piezoelectric semiconductors:

[0010] 7.5 mg Pt(acac)2 and 2.5 mg Fe(acac)3 were dissolved in 8 ml n-octanoic acid. Subsequently, 10 mg Mo(CO)6 was added to the mixture and stirred for 30 minutes. The solution was heated in a 90 °C oil bath for 2 hours, and finally centrifuged and washed 5 times with n-hexane;

[0011] (2) Preparation of two-dimensional piezoelectric semiconductor doped piezoelectric polymer:

[0012] 0.1g polyvinylidene fluoride and 1.2mL DMF were placed in a beaker, and then a certain mass of PtFe bimetallic olefin was added to the mixture. The solution was placed in a 50℃ oil bath and heated for 0.5h, stirring continuously during the heating process, and then ultrasonically removed bubbles. The prepared solution was poured onto a clean glass slide, spread evenly according to a certain size, put into water, and stored.

[0013] (3) Degradation performance test of perfluorinated compounds:

[0014] Firstly, the mobile phase was methanol and ammonium acetate (70:30), the flow rate was 0.4 mL / min, the column temperature was 35 °C, the injection volume was 100 μL, and the absorption wavelength was 210 nm. The perfluorinated compounds of different concentrations were measured in a high performance liquid chromatography, and the measurement results were plotted as a standard curve; the prepared two-dimensional piezoelectric semiconductor doped piezoelectric polymer material was placed in a beaker, 50 mL of perfluorinated compound pollutants were added, and the perfluorinated compounds were degraded under the mechanical force of ultrasound. Samples were taken every 10 minutes and measured in a high performance liquid chromatography. The measurement results were substituted into the standard curve to obtain the concentration. According to C t / C0 is the ordinate and time is the abscissa, and the degradation performance is plotted in Origin.

[0015] [Beneficial Effects]

[0016] The purpose of the present invention is to solve the problem in the field of catalysis that powdered catalytic materials are difficult to recycle, easily cause secondary pollution and have low catalytic efficiency. Two-dimensional piezoelectric semiconductor doped piezoelectric polymer materials can overcome this shortcoming, thereby improving the stability and catalytic performance of the material.

Brief Description of the Drawings

[0017] Figure 1 This is a SEM image of the two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material in Example 1.

[0018] Figure 2 This is the degradation curve of the piezoelectric catalytic degradation of perfluorinated compounds in Example 1. [Specific implementation method]

[0019] Embodiment 1:

[0020] (1) Preparation of two-dimensional piezoelectric polymers:

[0021] 7.5 mg Pt(acac)2 and 2.5 mg Fe(acac)3 were dissolved in 8 ml n-octanoic acid. Subsequently, 10 mg Mo(CO)6 was added to the mixture and stirred for 30 minutes. The solution was heated in a 90 °C oil bath for 2 hours, and finally centrifuged and washed 5 times with n-hexane;

[0022] (2) Preparation of two-dimensional piezoelectric semiconductor doped piezoelectric polymer:

[0023] 0.15g polyvinylidene fluoride and 1.2mL DMF were placed in a beaker, and then 0.1g PtFe bimetallic olefin was added to the mixture. The solution was placed in a 50℃ oil bath and heated for 0.5h, stirring continuously during the heating process, and then ultrasonically removed bubbles. The prepared solution was poured onto a clean glass slide, spread evenly according to a certain size, put into water, and stored;

[0024] (3) Degradation performance test of perfluorinated compounds:

[0025] Firstly, the mobile phase was methanol and ammonium acetate (70:30), the flow rate was 0.4 mL / min, the column temperature was 35 °C, the injection volume was 100 μL, and the absorption wavelength was 210 nm. The perfluorinated compounds of different concentrations were measured in a high performance liquid chromatography, and the measurement results were plotted as a standard curve; the prepared two-dimensional piezoelectric semiconductor doped piezoelectric polymer material was placed in a beaker, 50 mL of perfluorinated compound pollutants were added, and the perfluorinated compounds were degraded under the mechanical force of ultrasound. Samples were taken every 10 minutes and measured in a high performance liquid chromatography. The measurement results were substituted into the standard curve to obtain the concentration. According to C t / C0 is the ordinate and time is the abscissa, and the degradation performance is plotted in Origin.

[0026] Embodiment 2:

[0027] (1) Preparation of two-dimensional piezoelectric polymers:

[0028] 7.5 mg Pt(acac)2 and 2.5 mg Fe(acac)3 were dissolved in 8 ml n-octanoic acid. Subsequently, 10 mg Mo(CO)6 was added to the mixture and stirred for 30 minutes. The solution was heated in a 90 °C oil bath for 2 hours, and finally centrifuged and washed 5 times with n-hexane;

[0029] (2) Preparation of two-dimensional piezoelectric semiconductor doped piezoelectric polymer:

[0030] 0.15g polyvinylidene fluoride and 1.2mL DMF were placed in a beaker, and then 0.3g PtFe bimetallic olefin was added to the mixture. The solution was placed in a 50℃ oil bath and heated for 0.5h, stirring continuously during the heating process, and then ultrasonically removed bubbles. The prepared solution was poured onto a clean glass slide, spread evenly according to a certain size, put into water, and stored;

[0031] (3) Degradation performance test of perfluorinated compounds:

[0032] Firstly, the mobile phase was methanol and ammonium acetate (70:30), the flow rate was 0.4 mL / min, the column temperature was 35 °C, the injection volume was 100 μL, and the absorption wavelength was 210 nm. The perfluorinated compounds of different concentrations were measured in a high performance liquid chromatography, and the measurement results were plotted as a standard curve; the prepared two-dimensional piezoelectric semiconductor doped piezoelectric polymer material was placed in a beaker, 50 mL of perfluorinated compound pollutants were added, and the perfluorinated compounds were degraded under the mechanical force of ultrasound. Samples were taken every 10 minutes and measured in a high performance liquid chromatography. The measurement results were substituted into the standard curve to obtain the concentration. According to C t / C0 is the ordinate and time is the abscissa, and the degradation performance is plotted in Origin.

[0033] Embodiment 3:

[0034] (1) Preparation of two-dimensional piezoelectric polymers:

[0035] 7.5 mg Pt(acac)2 and 2.5 mg Fe(acac)3 were dissolved in 8 ml n-octanoic acid. Subsequently, 10 mg Mo(CO)6 was added to the mixture and stirred for 30 minutes. The solution was heated in a 90 °C oil bath for 2 hours, and finally centrifuged and washed 5 times with n-hexane;

[0036] (2) Preparation of two-dimensional piezoelectric semiconductor doped piezoelectric polymer:

[0037] 0.15g polyvinylidene fluoride and 1.2mL DMF were placed in a beaker, and then 0.5g PtFe bimetallic olefin was added to the mixture. The solution was placed in a 50℃ oil bath and heated for 0.5h, stirring continuously during the heating process, and then ultrasonically removed bubbles. The prepared solution was poured onto a clean glass slide, spread evenly according to a certain size, put into water, and stored;

[0038] (3) Degradation performance test of perfluorinated compounds:

[0039] Firstly, different concentrations of perfluorinated compounds were measured in a high performance liquid chromatography with methanol and ammonium acetate (70:30) as the mobile phase, a flow rate of 0.4 mL / min, a column temperature of 35°C, an injection volume of 100 μL, and an absorption wavelength of 210 nm, and the measurement results were plotted as a standard curve; the prepared two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material was placed in a beaker, and 50 mL of perfluorinated compound pollutants were added. The perfluorinated compounds were degraded under the action of ultrasound as a mechanical force. Samples were taken every 10 minutes and measured in a high performance liquid chromatography. The measurement results were substituted into the standard curve to obtain the concentration, and the degradation performance was plotted in Origin based on Ct / C0 as the ordinate and time as the abscissa.

Claims

1. A method for preparing a two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material, characterized in that The preparation of a two-dimensional piezoelectric semiconductor doped piezoelectric polymer material and its application in degrading perfluorinated compounds include the following steps: (1) Preparation of two-dimensional piezoelectric semiconductors: 7.5 mg Pt(acac)2 and 2.5 mg Fe(acac)3 were dissolved in 8 ml n-octanoic acid. Subsequently, 10 mg Mo(CO)6 was added to the mixture and stirred for 30 minutes. The solution was heated in a 90 °C oil bath for 2 hours, and finally centrifuged and washed 5 times with n-hexane; (2) Preparation of two-dimensional piezoelectric semiconductor doped piezoelectric polymer: 0.1g polyvinylidene fluoride and 1.2mL DMF were placed in a beaker, and then a certain mass of PtFe bimetallic olefin was added to the mixture. The solution was placed in a 50℃ oil bath and heated for 0.5h, stirring continuously during the heating process, and then ultrasonically removed bubbles. The prepared solution was poured onto a clean glass slide, spread evenly according to a certain size, put into water, and stored. (3) Degradation performance test of perfluorinated compounds: Firstly, different concentrations of perfluorinated compounds were measured in a high performance liquid chromatography with methanol and ammonium acetate (70:30) as the mobile phase, a flow rate of 0.4 mL / min, a column temperature of 35°C, an injection volume of 100 μL, and an absorption wavelength of 210 nm, and the measurement results were plotted as a standard curve; the prepared two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material was placed in a beaker, and 50 mL of perfluorinated compound pollutants were added. The perfluorinated compounds were degraded under the action of ultrasound as a mechanical force. Samples were taken every 10 minutes and measured in a high performance liquid chromatography. The measurement results were substituted into the standard curve to obtain the concentration, and the degradation performance was plotted in Origin based on Ct / C0 as the ordinate and time as the abscissa.

2. The preparation of the two-dimensional piezoelectric semiconductor-doped piezoelectric polymer according to claim 1, characterized in that The mass ratio of Pt(acac)2 and Fe(acac)3 in the preparation of two-dimensional piezoelectric semiconductors is 3:

1.

3. The preparation of the two-dimensional piezoelectric semiconductor-doped piezoelectric polymer material and its application in degrading perfluorinated compounds according to claim 1, characterized in that The mass ratio of polyvinylidene fluoride to DMF in the preparation of two-dimensional piezoelectric semiconductor-doped piezoelectric polymer is 1:10-12.

4. According to the two-dimensional piezoelectric semiconductor doped piezoelectric polymer material prepared in claim 1, 50 mL of perfluorinated pollutants are measured and placed in a beaker together, and the perfluorinated pollutants in water are degraded under the mechanical force of ultrasound, and the solutions at different times are absorbed to measure the concentration of the pollutants. The perfluorinated pollutants can be perfluorooctenic acid, perfluorooctanoic acid, perfluorodecanoic acid, and perfluorododecyl carboxylic acid.

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