CN111574735B - Polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film and preparation and application thereof - Google Patents
Polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film and preparation and application thereof Download PDFInfo
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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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
- C08J2465/00—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 provides a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, and a preparation method and application thereof, and belongs to the technical field of wastewater treatment. The polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film comprises polyvinylidene fluoride and poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate coated on the surface of the polyvinylidene fluoride; the mass ratio of the polyvinylidene fluoride to the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate is (9.5-10.8): 1. In the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film provided by the invention, the thiophene sulfur group contained in the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate can reduce heavy metal ions on the surface of the composite film into a metal simple substance, so that the removal of the heavy metal ions is realized, and the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film has a wide application prospect in the field of wastewater treatment.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, and preparation and application thereof.
Background
The existing methods for treating wastewater containing heavy metals mainly comprise the following steps: chemical, physical and biological processes. Wherein, the chemical method mainly comprises a chemical precipitation method and an electrolysis method and is mainly suitable for treating the wastewater containing heavy metal ions with higher concentration; the chemical precipitation method is to convert heavy metals in a dissolved state in wastewater into heavy metal compounds insoluble in water through chemical reaction, and remove precipitates from an aqueous solution through filtration and separation, and has the defects of complex treatment process and easy generation of secondary pollution; the electrolytic method is to utilize the electrochemical property of metal, and metal ions can be separated from a relatively high-concentration solution during electrolysis and then utilized; the electrolysis method is mainly used for treating electroplating wastewater, and has the defect that the concentration of heavy metal ions in the wastewater cannot be reduced very low. Therefore, the electrolytic method is not suitable for treating wastewater containing heavy metal ions at a relatively low concentration.
The physical treatment method mainly comprises a solvent extraction method, an ion exchange method, a membrane separation technology and an adsorption method; the solvent extraction method needs to select an extracting agent with higher selectivity, heavy metals in the wastewater generally exist in a cation or anion form, and the method has limitation and cannot be widely popularized; the ion exchange method is a method for removing heavy metal ions in wastewater by exchanging heavy metal ions with an ion exchanger, wherein the ion exchange group in the method is easy to oxidize and lose efficacy, the regeneration is frequent, and the operation cost is high; the membrane separation technology is a method for separating or concentrating a solvent and a solute by utilizing a special semipermeable membrane under the action of external pressure on the basis of not changing the chemical form in a solution, and the method has the defects of electrode polarization, easy scaling and corrosion of the membrane and the like; the adsorption method mainly utilizes porous solid substances to adsorb and remove heavy metal ions in water, the key technology of the adsorption method is the selection of an adsorbent, the traditional adsorbent is activated carbon, but the regeneration efficiency of the activated carbon is low, the treated water quality is difficult to meet the recycling requirement, the price is high, and the application is limited.
The biological treatment method is a method for removing heavy metals in wastewater by the flocculation, absorption, accumulation, enrichment and other actions of microorganisms or plants, and comprises the methods of biological adsorption, biological flocculation, plant restoration and the like; the biological adsorption method is a method for adsorbing metal ions by organisms by means of chemical action, and has the defects that the adsorption capacity is easily influenced by environmental factors, and various harmful heavy metals contained in heavy metal wastewater influence the action of microorganisms, limit the application and the like; the bioflocculation method is a decontamination method for performing flocculation precipitation by using microorganisms or metabolites produced by the microorganisms, and has the defect that the characteristics of the microorganisms are easily influenced by the environment; the phytoremediation method is an effective method for treating the environment by using ecological engineering, and has the defects of large engineering quantity and low economic benefit.
Therefore, it is of great significance to develop a novel material for heavy metal wastewater treatment, which can treat wastewater with low metal ion concentration and has low engineering quantity.
Disclosure of Invention
The invention aims to provide a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, and a preparation method and application thereof, wherein the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film has better heavy metal ion selectivity, and can achieve the purposes of selectively separating and removing heavy metal ions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, which comprises polyvinylidene fluoride and poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate coated on the surface of the polyvinylidene fluoride; the mass ratio of the polyvinylidene fluoride to the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate is (9.5-10.8): 1.
The invention provides a preparation method of a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, which comprises the following steps:
and coating the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution on the surface of the polyvinylidene fluoride membrane, and drying to obtain the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite membrane.
Preferably, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution is obtained by mixing a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and an ethanol solution, and the dosage ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution to the polyvinylidene fluoride basal membrane is (16-28) mL:0.396 g.
Preferably, the mass concentration of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution is 1g/mL, and the mass concentration of the ethanol solution is 95%; the volume ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution to the ethanol solution is 1 (5-8).
Preferably, the mixing is carried out under the condition of stirring, the rotating speed of the stirring is 600-700 rpm, and the stirring time is more than or equal to 0.5 h.
Preferably, the coating mode is coating by using a liquid-transfering gun.
Preferably, the drying mode is vacuum drying, the drying temperature is 70-100 ℃, and the drying time is 8-12 hours.
The invention provides an application of the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film or the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film prepared by the preparation method in the technical scheme in treating heavy metal-containing wastewater.
Preferably, the method of application comprises the steps of:
and placing the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film in a penetration device, and respectively pouring water and heavy metal ion solution into two sides of the penetration device to remove heavy metal ions.
The invention provides a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, which comprises polyvinylidene fluoride and poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate coated on the surface of the polyvinylidene fluoride; the mass ratio of the polyvinylidene fluoride to the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate is (9.5-10.8): 1. In the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film provided by the invention, the thiophene sulfur group contained in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate can reduce heavy metal ions to metal simple substances on the surface of the composite film, so that the heavy metal ions can be removed, and the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film has a wide application prospect in the field of wastewater treatment.
The invention provides a preparation method of the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, and the preparation method adopts a coating film preparation mode, so that a film preparation process is simplified.
The invention provides application of the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film in the technical scheme in treatment of heavy metal-containing wastewater. When the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film provided by the invention is used for carrying out metal ions in heavy metal wastewater, the removal reaction rate is high, and the removal rate is high; meanwhile, the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film provided by the invention has different interception effects on different heavy metal ions, so that the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film has better heavy metal ion selectivity, is easy to separate specific heavy metal ions from wastewater, and achieves the aim of selectively separating the heavy metal ions.
Drawings
FIG. 1 is a schematic view showing the effect of removing heavy metal ions in application example 1;
FIG. 2 is a schematic view showing the effect of removing heavy metal ions in application example 2;
FIG. 3 is a schematic view showing the effect of removing heavy metal ions in application example 3;
FIG. 4 is a schematic view showing the effect of removing heavy metal ions in application example 4;
fig. 5 is a schematic view of the effect of removing heavy metal ions in application example 5.
Detailed Description
The invention provides a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, which comprises polyvinylidene fluoride and poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate coated on the surface of the polyvinylidene fluoride; the mass ratio of the polyvinylidene fluoride to the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate is (9.5-10.8): 1.
In the present invention, the required raw materials are all commercially available products well known to those skilled in the art, unless otherwise specified.
The polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film provided by the invention comprises polyvinylidene fluoride (PVDF). In the present invention, the polyvinylidene fluoride is preferably a commercially available polyvinylidene fluoride membrane. The specification of the polyvinylidene fluoride film is not particularly limited in the present invention, and commercially available products well known in the art may be used. The polyvinylidene fluoride is used as the base film of the composite film.
The polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film provided by the invention comprises poly (3, 4-ethylenedioxythiophene) (PEDOT) -polystyrene sulfonate (PSS) coated on the surface of polyvinylidene fluoride. According to the invention, poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate is coated on the polyvinylidene fluoride base film, and the reduction of heavy metal ions on the surface of the composite film into a metal simple substance can be realized by using a thiophene sulfur group contained in the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate, so that the removal of the heavy metal ions is realized.
In the invention, the mass ratio of the polyvinylidene fluoride to the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate is (9.5-10.8): 1, preferably (9.8-10.6): 1, and more preferably (10.2-10.4): 1.
The invention provides a preparation method of a polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film, which comprises the following steps:
and coating the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution on the surface of the polyvinylidene fluoride membrane, and drying to obtain the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite membrane.
In the present invention, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution is preferably obtained by mixing an aqueous solution of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate and an ethanol solution. In the present invention, the mass concentration of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution (PEDOT: PSS) is preferably 1g/mL, and the source of the PEDOT: PSS is not particularly limited in the present invention, and any commercially available product known in the art may be used. In the present invention, the ethanol solution preferably has a mass concentration of 95% (commercially available). In the invention, the volume ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution to the ethanol solution is preferably 1 (5-8). According to the invention, the PEDOT PSS is dissolved by using an ethanol solution.
In the invention, the mixing of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and the ethanol solution is preferably carried out under a stirring condition, the rotation speed of the stirring is preferably 600-700 rpm, more preferably 650rpm, and the stirring time is preferably not less than 0.5h, more preferably 1-2 h. According to the invention, the stirring condition is controlled within the range, so that the PEDOT/PSS is fully diluted in the ethanol solution, the dispersion uniformity of the PEDOT/PSS is improved, and the PEDOT/PSS is easy to follow-up film coating.
After the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and the ethanol solution are mixed, the obtained materials are preferably subjected to impurity removal in sequence to obtain a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution. The invention preferably adopts a suction filtration method to remove impurities; the suction filtration process is not particularly limited, and a suction filtration device well known in the field is selected for suction filtration. The insoluble PEDOT and PSS flaky colloid in the mixed solution is filtered by suction filtration, so that the influence of the PEDOT and PSS flaky colloid on heavy metal removal reaction is eliminated.
In the invention, the dosage ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution to the polyvinylidene fluoride base membrane is preferably (16-28) mL to 0.396g, more preferably (18-25) mL to 0.396g, and after conversion, the mass ratio of the polyvinylidene fluoride base membrane to the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution is preferably 1 (7-8), and more preferably 1 (7.2-7.6).
After the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution is obtained, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution is coated on the polyvinylidene fluoride base film. In the present invention, the polyvinylidene fluoride-based membrane is preferably previously laid on the surface of the filter element of the filtration apparatus; the present invention is not particularly limited to the filter device, and a filter device known in the art may be used; the process of tiling is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the invention, the coating mode is preferably to use a liquid-transfering gun for coating until the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution completely permeates from the upper surface to the lower surface of the polyvinylidene fluoride basal membrane. In the coating process, the invention preferably performs suction filtration at the same time, the liquid transferring gun transfers the solution to the upper surface of the polyvinylidene fluoride basal membrane, and simultaneously the solution rapidly passes through the polyvinylidene fluoride basal membrane by suction filtration and enters the inner part and the lower surface of the membrane. In the invention, the basis of complete permeation is that no bubbles are generated on the lower surface of the polyvinylidene fluoride-based membrane. The suction filtration process is not particularly limited, and a suction filtration device well known in the field is selected for suction filtration. The invention adopts a suction filtration mode to coat PEDOT (Poly ethylene terephthalate) (PSS) on the surface of the PVDF base film, simplifies the film preparation process and effectively improves the economic benefit.
After the coating is finished, the film obtained is dried to obtain the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film. In the invention, the drying mode is preferably vacuum drying, the drying temperature is preferably 70 ℃, the drying time is preferably 8-12 h, and more preferably 9-10 h; the drying is preferably carried out in a vacuum drying oven.
In the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film prepared by using polyvinylidene fluoride as a base film and poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate as coating agents, the polyvinylidene fluoride is used as a substrate, the poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate are used as active components, and thiophene sulfur groups contained in the poly 3, 4-ethylenedioxythiophene and polystyrene sulfonate can reduce heavy metal ions to metal simple substances on the surface of the composite film, so that the heavy metal ions are removed.
The invention provides an application of the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film or the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film prepared by the preparation method in the technical scheme in treating heavy metal-containing wastewater.
In the present invention, the method of application preferably comprises the steps of:
and placing the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film in a penetration device, and respectively pouring water and heavy metal ion solution into two sides of the penetration device to remove heavy metal ions.
The present invention is not particularly limited to the permeation device, and a permeation device known in the art may be used. In the present invention, the volumes of the water and the heavy metal ion solution are preferably the same; both ends of the permeation device are preferably placed on a constant temperature stirrer, the rotating speed of the constant temperature stirrer is preferably 100rpm, and the temperature is preferably room temperature. According to the invention, the permeation device is placed in the constant-temperature stirrer, so that the high-efficiency operation of the heavy metal ion removal reaction can be promoted, the ion removal effect is improved, and the purpose of increasing the removal rate is achieved.
The heavy metal ion solution is not particularly limited, and the heavy metal ion wastewater from sources well known in the field can be obtained; in the embodiment of the invention, the experiment is specifically carried out by taking the heavy metal ion mixed solution as the simulation solution, wherein Ag in the heavy metal ion mixed solution+、Cd2+And Cu2+The concentration of (A) is 5 mg/L; the preparation process of the heavy metal ion mixed solution is not particularly limited, and the heavy metal ion mixed solution can be prepared according to the well-known process in the field.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 3mL of 1g/mL PEDOT PSS aqueous solution and 15mL of 95% ethanol solution into a beaker, placing the obtained mixed solution into a magnetic stirrer, stirring uniformly, regulating the rotation speed to 600rpm, stirring for 0.5h, and filtering the obtained material system by using a suction filtration device to obtain the PEDOT PSS solution;
and flatly paving a PVDF membrane (0.396g) on the surface of a filter element of a filtering device, transferring 3mL of PEDOT: PSS solution by using a liquid transfer gun, coating the solution on the surface of the PVDF membrane until the solution completely permeates from the upper surface to the lower surface of the PVDF membrane, putting the obtained film into a vacuum drying oven, and drying for 12 hours at 70 ℃ to obtain the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film (the mass ratio of PVDF to PEDOT: PSS is 10.1: 1).
Comparative example 1
Adding 2mL of PEDOT (Polytetrafluoroethylene) PSS aqueous solution with the concentration of 1g/mL and 10mL of ethanol solution with the mass concentration of 95% into a beaker, placing the obtained mixed solution into a magnetic stirrer to be stirred and mixed uniformly, regulating the rotating speed to 600rpm, stirring for 0.5h, and filtering the obtained material system by adopting a suction filtration device to obtain a PEDOT (Polytetrafluoroethylene) PSS solution;
and flatly paving a PVDF membrane (0.396g) on the surface of a filter element of a filtering device, transferring 3mL of PEDOT: PSS solution by using a liquid transfer gun, coating the solution on the surface of the PVDF membrane until the solution completely permeates from the upper surface to the lower surface of the PVDF membrane, putting the obtained film into a vacuum drying oven, and drying for 12 hours at 70 ℃ to obtain the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film (the mass ratio of PVDF to PEDOT: PSS is 5: 1).
Comparative example 2
The present comparative example differs from comparative example 1 only in that: PEDOT, PSS aqueous solution 4mL, ethanol solution 20mL, other same as comparative example 1; the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film is prepared (the mass ratio of PVDF to PEDOT: PSS is 10: 1).
Comparative example 3
This comparative example differs from example 1 only in that: the procedure of filtering the mixed solution obtained in example 1 by using a suction filtration apparatus was omitted, and the procedure was otherwise the same as in example 1; the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film is prepared (the mass ratio of PVDF to PEDOT: PSS is 10.1: 1).
Comparative example 4
This comparative example differs from example 1 only in that: the rotation speed is adjusted to 300rpm, and the other steps are the same as those of the embodiment 1; the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite film is prepared (the mass ratio of PVDF to PEDOT: PSS is 10.1: 1).
Application examples 1 to 5
1L of Ag with the concentration of 5mg/L is prepared+、Cd2+And Cu2+Ultrasonically mixing the heavy metal ion mixed solution for later use;
PSS composite films based on PVDF prepared in the example 1 and the comparative examples 1-4 are placed in a permeation device, 350mL of deionized water and the heavy metal ion mixed solution are respectively poured into two sides of the permeation device for removing heavy metal ions, the heavy metal ion removal rate is analyzed through an atomic absorption instrument, the example 1 and the comparative examples 1-4 are respectively and sequentially marked as an application example 1, an application example 2, an application example 3, an application example 4 and an application example 5, and the obtained test results are respectively shown in the figures 1-5.
FIG. 1 is a schematic diagram showing the effect of removing heavy metal ions in application example 1, and it can be seen from FIG. 1 that the PVDF-based PEDOT/PSS composite film prepared in example 1 has metal ions Ag+Removal rate of (2) is 35%, Cd2+The removal rate of (2) was 17%, Cu2+The removal rate of (2) was 10%.
FIG. 2 is a schematic diagram showing the effect of removing heavy metal ions in application example 2, and it can be seen from FIG. 2 that the PVDF-based PEDOT/PSS composite film prepared in comparative example 1 has metal ions Ag+The removal rate of (2) is 20%, and the removal rate of the metal ions Cu is2+Has a removal rate of 0 with respect to metal ions Cu2+And Ag+The removal rate of (A) is inferior to that of example 1; therefore, the reduction of the addition amount of PEDOT to PSS influences the metal ion Ag+The removal rate of (3).
FIG. 3 is a schematic diagram showing the effect of removing heavy metal ions in application example 3, and it can be seen from FIG. 3 that the PVDF-based PEDOT/PSS composite film prepared in comparative example 2 has metal ions Ag+Removal rate of (2) is 25%, for Cu2+Removal rate of (2) is 5%, for Cd2+The removal rate of (2) is 8%, which is for metal ion Ag+、Cd2+And Cu2+The removal rates of (A) were all inferior to those of example 1; therefore, increasing the addition of PEDOT to PSS affects the removal rate of metal ions.
FIG. 4 is a schematic diagram showing the effect of removing heavy metal ions in application example 4, and it can be seen from FIG. 4 that in comparative example 3, the impurity removal step is directly omitted, and the prepared PVDF-based PEDOT/PSS composite film is used for removing metal ions Ag+Removal rate of (2) was 20%, for Cu2+Removal rate of (2) is 5%, for Cd2+The removal rate of the silver is 17 percent, and the metal Ag is reduced+And Cu2+The removal rate of (3).
FIG. 5 is a schematic diagram showing the effect of removing heavy metal ions in application example 5, and it can be seen from FIG. 5 that the PVDF-based PEDOT/PSS composite film prepared in comparative example 4 has metal ions Ag+The removal rate of (2) is 18%, for Cu2+The removal rate of (2) was 5%, which is greatly different from that of example 1, and therefore the influence of the stirring rotation speed on the removal effect was large.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film comprises polyvinylidene fluoride and poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate loaded on the surface of the polyvinylidene fluoride; the mass ratio of the polyvinylidene fluoride to the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate is (9.5-10.8): 1.
2. The method for preparing the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film according to claim 1, comprising the following steps:
and coating the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution on the surface of the polyvinylidene fluoride membrane, and drying to obtain the polyvinylidene fluoride-based poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate composite membrane.
3. The preparation method of claim 2, wherein the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution is obtained by mixing a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution and an ethanol solution, and the dosage ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate solution to the polyvinylidene fluoride-based membrane is (16-28) mL:0.396 g.
4. The preparation method according to claim 3, wherein the mass concentration of the aqueous solution of poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate is 1g/mL, and the mass concentration of the ethanol solution is 95%; the volume ratio of the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate aqueous solution to the ethanol solution is 1 (5-8).
5. The preparation method according to claim 3, wherein the mixing is carried out under stirring conditions, the stirring speed is 600-700 rpm, and the stirring time is not less than 0.5 h.
6. The method of claim 2, wherein the coating is performed by using a pipette.
7. The preparation method according to claim 2, wherein the drying mode is vacuum drying, the drying temperature is 70-100 ℃, and the drying time is 8-12 h.
8. The polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film as defined in claim 1 or the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film prepared by the preparation method as defined in any one of claims 2 to 7 is applied to treatment of heavy metal-containing wastewater.
9. The application according to claim 8, characterized in that the method of application comprises the steps of:
and placing the polyvinylidene fluoride-based poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate composite film in a penetration device, and respectively pouring water and heavy metal ion solution into two sides of the penetration device to remove heavy metal ions.
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