CN110628060A - Poly-3, 4-ethylenedioxythiophene modified film and preparation method and application thereof - Google Patents
Poly-3, 4-ethylenedioxythiophene modified film and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
- C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
Abstract
The invention discloses a poly-3, 4-ethylenedioxythiophene modified film and a preparation method and application thereof, wherein a polyvinylidene fluoride base film is prepared on a supporting material; mixing Fe3+Taking an ethanol solution of soluble salt as an oxidant, and uniformly coating the oxidant on the polyvinylidene fluoride base membrane to obtain the polyvinylidene fluoride base membrane coated with the oxidant; carrying out gas-phase polymerization reaction on a 3, 4-ethylene dioxythiophene monomer on a polyvinylidene fluoride base film coated with an oxidant to obtain a poly-3, 4-ethylene dioxythiophene modified film; the invention is prepared by mixing Fe3+Soluble in waterThe salt ethanol solution is used as an oxidant, the volatility of ethanol is utilized, the oxidant can be conveniently coated and dried in time, and liquid flow does not occur in the drying process, so that the coating uniformity of the oxidant is ensured, the gas-phase polymerization effect is ensured, and the quality of a modified film is ensured; the invention can realize the removal of pollutants generated by the mineralization and decomposition of the pollutants through photocatalysis, reduces the pollution of films and has good photoelectric synergistic effect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic or photoelectrocatalytic film composite materials, and particularly relates to a poly-3, 4-ethylenedioxythiophene modified film and a preparation method and application thereof.
Background
Poly-3, 4-ethylenedioxythiophene is a conductive polymer developed by bayer corporation, and has been widely noticed in the field of conductive polymers due to its advantages of excellent environmental stability, high conductivity, easy processing into a film, etc., and poly-3, 4-ethylenedioxythiophene is often used as a filter membrane modification material in the form of a thin film.
The existing poly-3, 4-ethylenedioxythiophene modified film usually adopts an in-situ polymerization method, wherein a vapor deposition polymerization method is easy to control, and the prepared poly-3, 4-ethylenedioxythiophene molecule has the characteristics of good regularity, high conductivity and strong adhesion with a base material; however, in the vapor deposition polymerization, the 3, 4-ethylenedioxythiophene monomer is required to be evaporated after the oxidant is coated to realize the preparation, and in the process, the existing coating method has the defects of uneven oxidant coating, so that the polymerization effect is poor, and the quality of the modified film cannot be ensured.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a poly-3, 4-ethylenedioxythiophene modified film, a preparation method and application thereof, so as to solve the technical problem of poor polymerization effect caused by uneven coating of an oxidant in the prior art and improve the quality of the modified film.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a poly-3, 4-ethylenedioxythiophene modified film, which comprises the following steps:
step 1, preparing a polyvinylidene fluoride base membrane on a supporting material;
step 2, preparing Fe3+Taking a soluble salt ethanol solution as an oxidant, and uniformly coating the oxidant on the polyvinylidene fluoride base film to obtain the polyvinylidene fluoride base film coated with the oxidant;
and 3, carrying out gas-phase polymerization reaction on the 3, 4-ethylene dioxythiophene monomer on the polyvinylidene fluoride base film coated with the oxidant to obtain the poly-3, 4-ethylene dioxythiophene modified film.
Further, when preparing the polyvinylidene fluoride substrate in the step 1, the method comprises the following steps:
step 11, dissolving polyvinylpyrrolidone and polyvinylidene fluoride in N, N-dimethylacetamide in sequence, and stirring until bubbles are eliminated to obtain a casting solution;
and 12, coating the casting solution obtained in the step 1 on the surface of a supporting material, immersing the supporting material into a solidification solution until the casting solution forms a film, and cleaning to obtain the polyvinylidene fluoride base membrane.
Further, in step 2, Fe3+Soluble salt in ethanol solution Fe3+The volume concentration of the soluble salt is 5-30%.
Further, Fe3+The soluble salt ethanol solution adopts FeCl3·6H2O ethanol solution, Fe2(SO4)3Ethanol solution and ferric ethyl benzene sulfonate ethanol solution.
Further, step 3 specifically includes the following steps:
step 31, tightly pasting the polyvinylidene fluoride base coated with the oxidant on the bottom of the box cover of the airtight box, and placing the 3, 4-ethylene dioxythiophene monomer on the upper part of the box bottom of the airtight box;
and step 32, fully closing the airtight box, placing the airtight box at a constant temperature of 40-80 ℃ for gas phase polymerization, taking out the airtight box after reacting for 4-6 hours, cooling and cleaning the airtight box to obtain the poly-3, 4-ethylenedioxythiophene modified film.
Further, in the step 2, an oxidizing agent is uniformly coated on the polyvinylidene fluoride basement membrane by using a mechanical arm.
Further, in step 12, the membrane casting solution is scraped on the surface of the non-woven fabric by a membrane scraping knife; the non-woven fabric is fixedly arranged on the flat substrate.
Further, in step 12, deionized water is used as the solidification liquid, and deionized water is used for cleaning after film formation; the prepared polyvinylidene fluoride base membrane is stored in deionized water.
Further, the mass ratio of the polyvinylpyrrolidone to the polyvinylidene fluoride is (1-2): 5.
the invention also provides a poly-3, 4-ethylenedioxythiophene modified film, and the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film is 1 × 1e-4-4×1e-4A。
The invention also provides application of the poly-3, 4-ethylenedioxythiophene modified film in sewage or wastewater treatment under the photoelectric action.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a poly-3, 4-ethylenedioxythiophene modified film, which adopts Fe3+The ethanol solution of soluble salt is used as an oxidant, the volatility of ethanol is utilized, the oxidant is conveniently coated and dried in time, liquid flow does not occur in the drying process, the coating uniformity of the oxidant is ensured, the gas-phase polymerization effect is further ensured, and the quality of the poly-3, 4-ethylenedioxythiophene modified film is ensured.
Furthermore, the oxidant is uniformly attached to the surface of the polyvinylidene fluoride base membrane by adopting mechanical arm controlled physical coating in the oxidant coating process.
The invention also provides a poly-3, 4-ethylenedioxythiophene modified film, wherein the poly-3, 4-ethylenedioxythiophene modified film is prepared by the vapor deposition polymerization of a 3, 4-ethylenedioxythiophene monomer on the surface of the polyvinylidene fluoride base surface, and the poly-3, 4-ethylenedioxythiophene modified film is a modified conductive film; the photocurrent density of the poly-3, 4-ethylenedioxythiophene modified film reaches 1 × 1e-4-4×1e-4A。
The invention also provides an application of the poly-3, 4-ethylenedioxythiophene modified film, the poly-3, 4-ethylenedioxythiophene modified film has excellent photoelectric performance under visible light irradiation, and the specific performance is high photocurrent density, conductivity and stable filtering performance, the poly-3, 4-ethylenedioxythiophene modified film not only can remove pollutants generated by mineralization and decomposition of the pollutants through photooxidation, but also can reduce film pollution in the filtering process to a certain extent, and shows good photoelectric synergistic effect in practical application.
Drawings
FIG. 1 is a schematic view of the structure of an airtight box in the preparation method of a poly-3, 4-ethylenedioxythiophene modified film according to the present invention;
FIG. 2 is an SEM image of a poly-3, 4-ethylenedioxythiophene modified film prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a poly-3, 4-ethylenedioxythiophene modified film prepared in example 2 of the present invention;
FIG. 4 is an SEM image of a poly-3, 4-ethylenedioxythiophene modified film prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
As shown in the attached figure 1, the invention provides a preparation method of a poly-3, 4-ethylenedioxythiophene modified film, which comprises the following steps:
step 1, preparing a polyvinylidene fluoride base membrane on a supporting material; specifically, the method comprises the following steps:
step 11, dissolving polyvinylpyrrolidone and polyvinylidene fluoride in N, N-dimethylacetamide in sequence, and stirring until bubbles are eliminated to obtain a casting solution; the mass ratio of the polyvinylpyrrolidone to the polyvinylidene fluoride is (1-2): 5; stirring at the speed of 200-300 r/min for 24-36 h;
12, adopting a 200-300 mu m film scraping knife to scrape the film from the film casting solution obtained in the step 1 on a non-woven fabric, wherein the non-woven fabric is fixedly arranged on the surface of the flat substrate; and then, soaking the non-woven fabric coated with the casting solution in deionized water at normal temperature until the casting solution is solidified to obtain the polyvinylidene fluoride base membrane.
Step 2, adding Fe3+Dissolving soluble salt or persulfate in absolute ethyl alcohol to prepare Fe3+Ethanol solution of soluble salt or ethanol solution of persulfate, wherein Fe3+Soluble salt in ethanol solution Fe3+The volume concentration of the soluble salt is 5-30%, Fe3 +A soluble salt ethanol solution is used as an oxidant; fe3+The soluble salt ethanol solution adopts FeCl3·6H2O ethanol solution, Fe2(SO4)3One of ethanol solution and ferric ethyl methyl benzene sulfonate ethanol solution, wherein the persulfate ethanol solution is sodium persulfate ethanol solution; then, uniformly coating an oxidant on the polyvinylidene fluoride base film by adopting a mechanical arm to obtain the polyvinylidene fluoride base film coated with the oxidant;
step 3, tightly pasting the polyvinylidene fluoride base membrane coated with the oxidant to the bottom of the box cover of the airtight box, and placing the 3, 4-ethylene dioxythiophene monomer on the upper part of the box bottom of the airtight box; fully closing the airtight box, and then placing the airtight box under the constant temperature condition of 40-80 ℃ to perform gas phase polymerization reaction; taking out after reacting for 4-6h, cooling, washing with deionized water, and then washing with deionized water to obtain the poly-3, 4-ethylenedioxythiophene modified film.
The invention provides a preparation method of a poly-3, 4-ethylenedioxythiophene modified film, which adopts Fe3+Soluble salt or persulfate is dissolved in ethanol to prepare an oxidant, the oxidant is conveniently coated and dried in time by utilizing the volatility of the ethanol, and liquid flow does not occur in the drying process, so that the coating uniformity of the oxidant is ensured, the gas-phase polymerization effect is further ensured, and the quality of the film is ensured; the oxidant is uniformly attached to the bottom surface of the polyvinylidene fluoride base through physical coating controlled by a mechanical arm in the oxidant coating process.
The invention also provides a poly-3, 4-ethylenedioxythiophene modified film, wherein the poly-3, 4-ethylenedioxythiophene modified film is prepared by the vapor deposition polymerization of a 3, 4-ethylenedioxythiophene monomer on the surface of the polyvinylidene fluoride base surface, and the poly-3, 4-ethylenedioxythiophene modified film is a modified conductive film; the photocurrent density of the poly-3, 4-ethylenedioxythiophene modified film reaches 1 × 1e-4-4×1e-4A；
The invention also provides an application of the poly-3, 4-ethylenedioxythiophene modified film, the poly-3, 4-ethylenedioxythiophene modified film has excellent photoelectric performance under the irradiation of visible light, and the specific expression is higher photocurrent density and conductivity, the modified film not only can remove pollutants generated by mineralization and decomposition of the pollutants through photooxidation, but also lightens the film pollution caused in the filtering process to a certain extent, and shows good photoelectric synergistic effect in practical application.
Example 1
The invention provides a poly-3, 4-ethylenedioxythiophene modified film, which comprises the following steps:
step 1, preparing a casting solution
Dissolving 6g of polyvinylpyrrolidone and 15g of polyvinylidene fluoride in 100mL of N, N-dimethylacetamide at room temperature, and stirring until bubbles are eliminated to obtain a casting solution; wherein the stirring speed is 300r/min, and the stirring time is 24 h;
step 2, selecting clean non-woven fabrics with the size of 16cm multiplied by 18cm as a supporting material of the polyvinylidene fluoride substrate, and fixing the non-woven fabrics on a smooth and flat glass sheet; adopting a 300-micron film scraping knife to scrape the film casting solution on the surface of the non-woven fabric; then, soaking the non-woven fabric coated with the membrane casting solution in normal-temperature deionized water until the membrane casting solution is solidified, and then cleaning the non-woven fabric with deionized water to obtain a polyvinylidene fluoride base membrane;
step 3, preparing oxidant solution
5g of FeCl3·6H2Dissolving O in 100mL of absolute ethanol to prepare FeCl with the volume concentration of 5 percent3·6H2O ethanol solution, FeCl3·6H2Using O ethanol solution as oxidant;
step 4, filling a proper amount of oxidant into a spray pen, fixing the spray pen filled with the oxidant on a V5 EGGBOT Chinese board writing robot arm, setting a motion track of the robot arm by adopting INKSCAPE software, and coating the oxidant on the surface of the polyvinylidene fluoride base film by the spray pen; airing at room temperature to obtain the polyvinylidene fluoride base membrane coated with the oxidant; the motion trail parameters of the mechanical arm are as follows: the curve is smooth by 10.0, the turning speed factor is 10.0, and the motion trail is as follows: 15cm reciprocating straight lines with the interval of 0.5 cm;
step 5, tightly pasting the polyvinylidene fluoride base membrane coated with the oxidant to the bottom of a stainless steel airtight box cover, adding 0.1mL of 3, 4-ethylenedioxythiophene monomer into a glass culture dish by using a pipette, and placing the glass culture dish on the upper part of the bottom of the stainless steel airtight box;
step 6, fully closing the stainless steel airtight box, and placing the stainless steel airtight box at a constant temperature of 40 ℃ to enable the 3, 4-ethylenedioxythiophene monomer to generate gas-phase polymerization reaction on the polyvinylidene fluoride base membrane coated with the oxidant; after 4h of gas phase polymerization, washing with deionized water for 5 times to remove excessive Fe3+And obtaining the poly-3, 4-ethylenedioxythiophene modified film.
As shown in fig. 2, fig. 2 shows an SEM image of the poly-3, 4-ethylenedioxythiophene modified film prepared in example 1, and it can be seen from fig. 2 that the poly-3, 4-ethylenedioxythiophene modified film has better gas phase polymerization effect when the pores of the base film with a diameter of 0.2 μm are uniformly filled after modification; the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film is detected to be 1 × 1e-4A has excellent photoelectric performance under the irradiation of visible light, and is particularly represented by higher photocurrent density and conductivity.
Example 2
The invention provides a poly-3, 4-ethylenedioxythiophene modified film, which comprises the following steps:
step 1, preparing a casting solution
Dissolving 6g of polyvinylpyrrolidone and 15g of polyvinylidene fluoride in 100mL of N, N-dimethylacetamide at room temperature, and stirring until bubbles are eliminated to obtain a casting solution; wherein the stirring speed is 200r/min, and the stirring time is 36 h;
step 2, selecting clean non-woven fabrics with the size of 16cm multiplied by 18cm as a supporting material of the polyvinylidene fluoride substrate, and fixing the non-woven fabrics on a smooth and flat glass sheet; adopting a 300-micron film scraping knife to scrape the film casting solution on the surface of the non-woven fabric; then, soaking the non-woven fabric coated with the membrane casting solution in normal-temperature deionized water until the membrane casting solution is solidified, and then cleaning the non-woven fabric with deionized water to obtain a polyvinylidene fluoride base membrane;
step 3, preparing oxidant solution
20g of FeCl3·6H2Dissolving O in 100mL of absolute ethanol to prepare FeCl with the volume concentration of 20 percent3·6H2O ethanol solution, FeCl3·6H2Using O ethanol solution as oxidant;
step 4, filling a proper amount of oxidant into a spray pen, fixing the spray pen filled with the oxidant on a V5 EGGBOT Chinese board writing robot arm, setting a motion track of the robot arm by adopting INKSCAPE software, and coating the oxidant on the surface of the polyvinylidene fluoride base film by the spray pen; airing at room temperature to obtain the polyvinylidene fluoride base membrane coated with the oxidant;
step 5, pasting the polyvinylidene fluoride base membrane coated with the oxidant on the bottom of the stainless steel airtight box cover, adding 0.15mL of 3, 4-ethylenedioxythiophene monomer into a glass culture dish by using a pipette, and placing the glass culture dish on the upper part of the box bottom of the stainless steel airtight box;
step 6, fully closing the stainless steel airtight box, and placing the stainless steel airtight box at a constant temperature of 60 ℃ to enable the 3, 4-ethylenedioxythiophene monomer to generate gas-phase polymerization reaction on the polyvinylidene fluoride base membrane coated with the oxidant; after the gas-phase polymerization reaction for 5 hours, washing for 6 times by using deionized water to remove redundant Fe3+And obtaining the poly-3, 4-ethylenedioxythiophene modified film.
As shown in fig. 3, fig. 3 shows an SEM image of the poly-3, 4-ethylenedioxythiophene modified film prepared in example 2, and it can be seen from fig. 3 that the surface of the poly-3, 4-ethylenedioxythiophene modified film has an obvious uniform dot structure, i.e., the gas phase polymerization effect is good; the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film is detected to be 2.9 multiplied by 1e-4A has excellent photoelectric performance under the irradiation of visible light, and is particularly represented by higher photocurrent density and conductivity.
Example 3
The invention provides a poly-3, 4-ethylenedioxythiophene modified film, which comprises the following steps:
step 1, preparing a casting solution
Dissolving 3g of polyvinylpyrrolidone and 15g of polyvinylidene fluoride in 100mL of N, N-dimethylacetamide at room temperature, and stirring until bubbles are eliminated to obtain a casting solution; wherein the stirring speed is 250r/min, and the stirring time is 30 h;
step 2, selecting clean non-woven fabrics with the size of 16cm multiplied by 18cm as a supporting material of the polyvinylidene fluoride substrate, and fixing the non-woven fabrics on a smooth and flat glass sheet; adopting a 200-micron film scraping knife to scrape the film casting solution on the surface of the non-woven fabric; then, soaking the non-woven fabric coated with the membrane casting solution in normal-temperature deionized water until the membrane casting solution is solidified, and then cleaning the non-woven fabric with deionized water to obtain a polyvinylidene fluoride base membrane;
step 3, preparing oxidant solution
30g of FeCl3·6H2Dissolving O in 100mL of absolute ethanol to prepare FeCl with the volume concentration of 30 percent3·6H2O ethanol solution, FeCl3·6H2Using O ethanol solution as oxidant;
step 4, filling a proper amount of oxidant into a spray pen, fixing the spray pen filled with the oxidant on a V5 EGGBOT Chinese board writing robot arm, setting a motion track of the robot arm by adopting INKSCAPE software, and coating the oxidant on the surface of the polyvinylidene fluoride base film by the spray pen; airing at room temperature to obtain the polyvinylidene fluoride base membrane coated with the oxidant;
step 5, tightly pasting the polyvinylidene fluoride base membrane coated with the oxidant to the bottom of a stainless steel airtight box cover, adding 0.2mL of 3, 4-ethylenedioxythiophene monomer into a glass culture dish by using a pipette, and placing the glass culture dish on the upper part of the bottom of the stainless steel airtight box;
step 6, fully closing the stainless steel airtight box, and placing the stainless steel airtight box at a constant temperature of 80 ℃ to enable the 3, 4-ethylenedioxythiophene monomer to generate gas-phase polymerization reaction on the polyvinylidene fluoride base membrane coated with the oxidant; after the gas-phase polymerization reaction for 6 hours, washing with deionized water for 8 times to remove excessive Fe3+And obtaining the poly-3, 4-ethylenedioxythiophene modified film.
As shown in FIG. 4, FIG. 4 shows SEM image of poly-3, 4-ethylenedioxythiophene modified film prepared in example 3As can be seen from the attached figure 4, the surface of the poly-3, 4-ethylenedioxythiophene modified film has an obvious uniform dotted structure, i.e. the gas-phase polymerization effect is good; the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film is detected to be 4 multiplied by 1e-4A has excellent photoelectric performance under the irradiation of visible light, and is particularly represented by higher photocurrent density and conductivity.
Examples 4 to 6
Examples 4 to 6 are basically the same in principle as examples 1 to 3 except that Fe is contained in examples 4 to 63+The soluble salt ethanol solution adopts Fe2(SO4)3Ethanol solution; among them, Fe in examples 4 to 62(SO4)3The volume concentration of the ethanol solution is 5 percent, 20 percent and 30 percent respectively; the poly-3, 4-ethylenedioxythiophene modified films prepared in examples 4 to 6 had good effects of gas phase polymerization on the surface, and the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film was 1 × 1e-4-4×1e-4A, exhibiting higher photocurrent density and conductivity.
Examples 7 to 9
Examples 7 to 9 basically have the same principle as examples 1 to 3 except that Fe is used in examples 4 to 63+The soluble salt ethanol solution is ferric ethyl benzene sulfonate ethanol solution; wherein, the volume concentrations of the ethyl alcohol solution of the iron methylbenzenesulfonate in the examples 4 to 6 are 5 percent, 20 percent and 30 percent respectively; the poly-3, 4-ethylenedioxythiophene modified films prepared in examples 4 to 6 had good effects of gas phase polymerization on the surface, and the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film was 1 × 1e-4-4×1e-4A, exhibiting higher photocurrent density and conductivity.
Example 10
Example 10 is basically the same in principle as example 1, except that the oxidizing agent of example 10 is a persulfate ethanol solution; the poly-3, 4-ethylenedioxythiophene modified film prepared in example 10 has good gas-phase polymerization effect on the surface, and shows high photocurrent density and conductivity.
The above description is only illustrative of the preferred embodiments of the present invention, and any structural changes, improvements, modifications, etc. made without departing from the principle of the present invention are deemed to be within the scope of the present invention.
Claims (10)
1. A preparation method of a poly-3, 4-ethylenedioxythiophene modified film is characterized by comprising the following steps:
step 1, preparing a polyvinylidene fluoride base membrane on a supporting material;
step 2, preparing Fe3+Taking a soluble salt ethanol solution as an oxidant, and uniformly coating the oxidant on the polyvinylidene fluoride base film to obtain the polyvinylidene fluoride base film coated with the oxidant;
and 3, carrying out gas-phase polymerization reaction on the 3, 4-ethylene dioxythiophene monomer on the polyvinylidene fluoride base film coated with the oxidant to obtain the poly-3, 4-ethylene dioxythiophene modified film.
2. The method for preparing the poly-3, 4-ethylenedioxythiophene modified film according to claim 1, wherein the step 1 of preparing the polyvinylidene fluoride substrate comprises the following steps:
step 11, dissolving polyvinylpyrrolidone and polyvinylidene fluoride in N, N-dimethylacetamide in sequence, and stirring until bubbles are eliminated to obtain a casting solution;
and 12, coating the casting solution obtained in the step 1 on the surface of a supporting material, immersing the supporting material into a solidification solution until the casting solution forms a film, and cleaning to obtain the polyvinylidene fluoride base membrane.
3. The method for preparing poly-3, 4-ethylenedioxythiophene modified film according to claim 1, wherein in step 2, Fe3+Soluble salt in ethanol solution Fe3+The volume concentration of the soluble salt is 5-30%.
4. The method for preparing poly-3, 4-ethylenedioxythiophene modified film according to claim 1, wherein Fe3+The soluble salt ethanol solution adopts FeCl3·6H2O ethanol solution, Fe2(SO4)3Ethanol solution and ferric ethyl benzene sulfonate ethanol solution.
5. The method for preparing the poly-3, 4-ethylenedioxythiophene modified film according to claim 1, wherein the step 3 specifically comprises the following steps:
step 31, tightly pasting the polyvinylidene fluoride base coated with the oxidant on the bottom of the box cover of the airtight box, and placing the 3, 4-ethylene dioxythiophene monomer on the upper part of the box bottom of the airtight box;
and step 32, fully closing the airtight box, placing the airtight box at a constant temperature of 40-80 ℃ for gas phase polymerization, taking out the airtight box after reacting for 4-6 hours, cooling and cleaning the airtight box to obtain the poly-3, 4-ethylenedioxythiophene modified film.
6. The method for preparing the poly-3, 4-ethylenedioxythiophene modified film according to claim 2, wherein in step 12, the casting solution is scraped from the surface of the non-woven fabric by a doctor blade; the non-woven fabric is fixedly arranged on the flat substrate.
7. The method for preparing the poly-3, 4-ethylenedioxythiophene modified film according to claim 2, wherein in step 12, deionized water is used as a coagulating liquid, and deionized water is used for cleaning after film formation; the prepared polyvinylidene fluoride base membrane is stored in deionized water.
8. The preparation method of the poly-3, 4-ethylenedioxythiophene modified film according to claim 1, wherein the mass ratio of the polyvinylpyrrolidone to the polyvinylidene fluoride is (1-2): 5.
9. a poly-3, 4-ethylenedioxythiophene modified film, which is characterized by being prepared by the preparation method of the poly-3, 4-ethylenedioxythiophene modified film according to any one of claims 1 to 8; the photoelectric density of the poly-3, 4-ethylenedioxythiophene modified film is 1 × 1e-4-4×1e-4A。
10. The use of the poly-3, 4-ethylenedioxythiophene modified membrane of claim 9 in sewage or wastewater treatment under photoelectric action.
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