CN114699931A - Antibacterial conductive composite membrane for water treatment and preparation method and application thereof - Google Patents
Antibacterial conductive composite membrane for water treatment and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/48—Antimicrobial properties
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention provides an antibacterial conductive composite film for water treatment and a preparation method and application thereof, wherein the antibacterial conductive composite film comprises a base film and an antibacterial conductive layer arranged on the surface of the base film; the material of the antibacterial conducting layer comprises a conducting material and a sterilizing material; by doping the conductive material and the sterilization material in the antibacterial conducting layer, the problem of poor operation continuity easily caused by singly using the base film is successfully solved, and the service life of the base film is further effectively prolonged; and the conductive material and the bactericidal material of the antibacterial conductive layer can generate a synergistic effect, so that the antibacterial pollution resistance of the finally obtained antibacterial conductive composite film is improved under the condition of ensuring that the pure water film flux of the antibacterial conductive composite film is not reduced, and the antibacterial conductive composite film has important research significance.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an antibacterial conductive composite membrane for water treatment as well as a preparation method and application thereof.
Background
At present, membrane pollution generated in the water treatment process is the biggest problem in the application of membrane technology, wherein biological pollution is the most common, and microorganisms are widely present in places such as air, water bodies, soil and the like. Therefore, in the film technology, active microorganisms are inevitably contained in the raw material liquid, and the survival of the microorganisms is facilitated because the microorganisms tend to form colonies or a bacterial film is resistant to drastic changes in external conditions, so that favorable conditions are provided for the adhesion of the microorganisms to the film surface when the raw material liquid is in contact with the film surface, and since the microorganisms can rapidly grow and propagate, even if 99.99% of the microorganisms in the pretreatment are killed, 0.01% of the remaining microorganisms can cause serious consequences, and thus the biofouling of the film becomes a technical problem which is urgently needed to be solved in the film technology.
The membrane surface modification method is a commonly used method for solving biological pollution resistance of the membrane, and the membrane surface modification method is to endow new properties (such as hydrophilicity and antibacterial property) to the membrane surface by adopting a chemical or physical method on the premise of keeping the properties of the material body unchanged. CN103464011A discloses an aromatic polyamide composite membrane with a surface containing salicylaldehyde and tertiary amino, wherein an acyl chloride group on the surface of the aromatic polyamide composite membrane is subjected to condensation reaction with organic polyamine to prepare an aromatic polyamide composite membrane with a surface containing amino; then the aromatic polyamide composite membrane with the surface containing amino is subjected to Mannich reaction with formaldehyde and salicylaldehyde to prepare an aromatic polyamide composite membrane with the surface containing salicylaldehyde and tertiary amine group; and finally, performing quaternary salination reaction on the aromatic polyamide composite membrane with the surface containing salicylaldehyde and tertiary amine groups and an alkylating agent to obtain the aromatic polyamide composite membrane with the surface containing quaternary ammonium salt and salicylaldehyde, so that the hydrophilicity of the surface of the aromatic polyamide composite membrane can be improved, and the biocidal and antibacterial performance of the aromatic polyamide composite membrane can be improved. However, although quaternary ammonium salts have antibacterial activity, the inactivated bacteria continue to accumulate on the membrane surface during continuous filtration, gradually diminishing the contact sterilization ability.
In addition, by preparing a conductive film and applying a negative voltage, film contamination can be suppressed by a method of electrostatic repulsion. Because pollutants and microorganisms in water are mostly electronegative, the movement of the microorganisms to the surface of the membrane can be hindered by electrostatic repulsion. The conductive film refers to a multifunctional film having both permeability and conductive properties. CN110465209A discloses a polypyrrole/carbon nanotube/polyethersulfone composite conductive film for water treatment and a preparation method thereof. At present, the conductive film used for water treatment has the defects of difficult preparation and low conductivity. According to the invention, on the basis of manufacturing of the polyether sulfone flat membrane, the carbon nanotube film is deposited by using pressure, polypyrrole is synthesized in situ on the carbon nanotube film by adopting a chemical polymerization method, and a conductive layer is formed on the polyether sulfone flat membrane, so that the conductive composite membrane is obtained. The addition of the high-conductivity carbon nano tube greatly improves the conductivity of the composite film. The polypyrrole is polymerized on the surface of the membrane in situ, so that the hydrophilicity of the membrane and the stability of the conductive layer are enhanced, and the anti-pollution performance of the membrane is improved. The conductive film has the characteristics of high conductivity, flexibility, stability and long service life. The preparation method has simple process, does not need complex reaction and high temperature, and has low cost and strong operability. However, once the surface of the composite conductive film provided by the above prior art is adhered with metabolically active microorganisms, the electrostatic action thereof is disabled, and the microorganisms rapidly grow on the surface of the film, so that the film flux is obviously reduced.
Therefore, it is an urgent technical problem in the art to develop an antibacterial conductive composite membrane having durable and excellent antibacterial properties, maintaining a stable membrane flux.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antibacterial conductive composite membrane for water treatment and a preparation method and application thereof; the antibacterial conductive composite film comprises a base film and an antibacterial conductive layer arranged on the surface of the base film; the material of the antibacterial conducting layer comprises a conducting material and a sterilizing material; the conductive material and the sterilization material are combined, so that the obtained antibacterial conductive composite membrane is used for slowing down the attenuation of pure water membrane flux in the water treatment process, and has excellent and lasting biological pollution resistance effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an antibacterial conductive composite film for water treatment, comprising a base film and an antibacterial conductive layer disposed on the surface of the base film;
the material of the antibacterial conducting layer comprises a combination of a conducting material and a sterilizing material.
The invention provides an antibacterial conductive composite film for water treatment, wherein an antibacterial conductive layer is coated on the surface of a base film; the material of the antibacterial conducting layer comprises the combination of a conducting material and a sterilizing material, and an electrochemical group is combined with an antibacterial group, so that the problem of poor long-term running continuity easily caused by single use of the base film is successfully solved, and the service life of the base film is effectively prolonged; and the conductive material and the sterilization material of the antibacterial conductive layer can generate a synergistic effect, so that the antibacterial pollution resistance of the finally obtained antibacterial conductive composite film can be improved under the condition of ensuring that the flux of the pure water film is not reduced, the residual bacteria on the surface of the film after use is reduced, and the antibacterial conductive composite film has important research significance.
Preferably, the base film includes an organic base film or an inorganic base film.
Preferably, the organic base membrane includes any one of a polyvinylidene fluoride membrane, a polyethersulfone membrane, a polytetrafluoroethylene membrane, a polycarbonate membrane, or a mixed cellulose membrane.
Preferably, the inorganic base film includes a ceramic film.
Preferably, the ceramic membrane comprises a porous alumina ceramic membrane.
Preferably, the mass ratio of the conductive material to the sterilization material is 1 (1-5), such as 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4 or 1: 4.5.
As a preferred technical scheme, when the mass ratio of the conductive material to the bactericidal material of the antibacterial conductive layer is 1 (1-5), the obtained antibacterial conductive composite membrane has the most excellent anti-pollution performance, and on one hand, if the dosage of the conductive material is relatively low, the conductivity of the antibacterial conductive composite membrane is reduced, the membrane flux is reduced, and more bacteria are remained; on the other hand, if the dosage of the sterilizing material is relatively low, the anti-pollution performance of the antibacterial conductive composite membrane is reduced, and the membrane flux after pollution is reduced.
Preferably, the conductive material comprises a polymeric conductive material.
Preferably, the polymeric conductive material comprises any one of polyaniline, polypyrrole or polythiophene, or a combination of at least two thereof.
Preferably, the bactericidal material comprises any one of or a combination of at least two of nano silver particles, quaternary ammonium salt bactericides or photocatalytic bactericides.
Preferably, the quaternary ammonium salt bactericide comprises 3-chloro-2-hydroxypropyl trimethyl ammonium chloride.
Preferably, the photocatalytic bactericide comprises titanium dioxide.
Preferably, the material of the antibacterial conductive layer further comprises a dopant.
As a preferable technical scheme of the present invention, the material of the antibacterial conductive layer further includes a dopant, and the addition of the dopant can further improve the conductivity of the finally obtained antibacterial conductive composite film, thereby contributing to the improvement of the anti-pollution performance of the antibacterial conductive composite film.
Preferably, the dopant comprises any one of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide or sodium dodecyl sulfate or a combination of at least two of the foregoing.
In a second aspect, the present invention provides a method for preparing the antibacterial conductive composite film according to the first aspect, the method comprising the following steps:
(1) immersing the base film in a mixed solution containing a sterilization material, an oxidant and optionally a dopant to obtain a surface-treated base film;
(2) and (2) immersing the surface-treated base film obtained in the step (1) into a solution containing a conductive raw material to obtain the antibacterial conductive composite film.
The preparation method of the antibacterial conductive composite film provided by the invention comprises the steps of firstly immersing a base film into a mixed solution containing a sterilizing material, an oxidant and optionally a dopant, so that the sterilizing material and the oxidant are attached to the surface of the base film, and obtaining the base film after surface treatment; and then the base film after surface treatment is immersed in a solution containing a conductive raw material, the conductive raw material in the solution can generate an oxidation reaction under the action of an oxidant to generate a conductive material, and then the conductive material is coated on the surface of the base film to form a conductive layer, and meanwhile, an optional dopant and a bactericidal material attached to the surface of the base film can be doped in the conductive layer, so that the conductive material and the bactericidal material can play a synergistic role to effectively improve the antibacterial performance of the antibacterial conductive composite film.
Preferably, in the present invention, the oxidizing agent may be any substance capable of causing an oxidation reaction of the conductive material, such as iron oxide.
Preferably, the amount of the oxidizing agent is 1 to 1.5mol, such as 1.05mol, 1.1mol, 1.15mol, 1.2mol, 1.25mol, 1.3mol, 1.35mol, or 1.4mol, based on 1L of the mixed solution in the step (1), and specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
Preferably, the immersion time in step (1) is 20-40 min, such as 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min or 38min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the range.
Preferably, the method further comprises a step of drying the surface-treated polytetrafluoroethylene-based film obtained in the step (1) before the step (2).
Preferably, the pyrrole is used in an amount of 0.25 to 1mol, such as 0.3mol, 0.35mol, 0.4mol, 0.45mol, 0.5mol, 0.55mol, 0.6mol, 0.65mol, 0.7mol, 0.8mol, or 0.9mol, based on the volume of the pyrrole solution of step (2) being 1L, and specific points therebetween are not exhaustive, and the invention is not limited to the specific points included in the range for brevity and conciseness.
Preferably, the immersion time in step (2) is 0.5-1.5 h, such as 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h or 1.4h, and the specific values therebetween are not exhaustive, and for brevity and clarity, the invention is not exhaustive.
In a third aspect, the present invention provides the use of an antimicrobial conductive composite membrane according to the first aspect in a material separation apparatus.
Preferably, the antibacterial conductive film serves as a cathode of the substance separating apparatus.
Compared with the prior art, the invention has the following beneficial effects:
(1) the antibacterial conductive composite membrane for water treatment provided by the invention comprises a base membrane and an antibacterial conductive layer arranged on the surface of the base membrane, wherein the antibacterial conductive layer is made of a combination of a conductive material and a sterilization material; through the surface cladding conducting material and the bactericidal material of base film for the two takes place the synergism, has successfully overcome the poor problem of base film persistence in long-term operation, has improved the life of base film, still helps promoting the antipollution performance of antibiotic electrically conductive complex film, and can not influence the pure water flux of base film itself.
(2) The preparation method of the antibacterial conductive composite membrane provided by the invention is simple, the preparation cost is low, the composite membrane can be used as a cathode to generate electrostatic repulsion on microorganisms in water when in use, so that the accumulation of the microorganisms on the surface of the membrane is prevented, once the microorganisms move to the surface of the membrane, the microorganisms can be inactivated under the sterilization effect, the attachment and the growth of the microorganisms on the surface of the membrane are prevented, the formation of a biological membrane is avoided, and meanwhile, the inactivated microorganisms can fall off from the surface of the membrane under the electrostatic repulsion effect, so that the pure water flux and the antibacterial performance of the composite membrane are improved.
(3) Specifically, the resistance of the antibacterial conductive composite film provided by the invention is 64.4-270 k omega, and the pure water film flux is 820-1072L/m2H, contaminationThe pure water flux is 692-991L/m2H, the number of bacteria extracted from the membrane surface after filtration is 0-67 CFU/mL.
Drawings
Fig. 1 is a schematic structural diagram of a dead-end/cross-flow filtration membrane module provided by the present invention, wherein 1-anode, 2-cathode of conductive membrane, 3-dc power supply, 4-water inlet, and 5-water outlet.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
An antibacterial conductive composite membrane for water treatment, which consists of a polytetrafluoroethylene-based membrane (Millipore, 100nm) and an antibacterial conductive layer arranged on the surface of the polytetrafluoroethylene-based membrane;
the material of the antibacterial conducting layer comprises polypyrrole, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and sodium dodecyl benzene sulfonate, wherein the mass ratio of the polypyrrole to the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is 1: 3;
the preparation method of the antibacterial conductive composite membrane for water treatment provided by the embodiment comprises the following steps:
(1) soaking the polytetrafluoroethylene-based membrane into a mixed aqueous solution of 1mol/L ferric chloride, 0.0025mol/L sodium dodecyl benzene sulfonate and 0.0025 mol/L3-chloro-2-hydroxypropyl trimethyl ammonium chloride for 30min to obtain a polytetrafluoroethylene-based membrane after surface treatment;
(2) and (2) drying the polytetrafluoroethylene-based membrane subjected to surface treatment obtained in the step (1), immersing the dried polytetrafluoroethylene-based membrane into 0.5mol/L pyrrole aqueous solution for 1h, and taking out the dried polytetrafluoroethylene-based membrane to obtain the antibacterial conductive composite membrane for water treatment.
Example 2
An antibacterial conductive composite membrane for water treatment is different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 1:1, and other parameters and steps are the same as those of example 1.
Example 3
An antibacterial conductive composite membrane for water treatment, which is different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 1:5, and other parameters and steps are the same as those of example 1.
Example 4
An antibacterial conductive composite membrane for water treatment, which is different from example 1 only in that the concentration of iron oxide in step (1) of the preparation method is 0.5mol/L, and other parameters and steps are the same as those of example 1.
Example 5
An antibacterial conductive composite membrane for water treatment, which is different from example 1 only in that the concentration of iron oxide in step (1) of the preparation method is 2mol/L, and other parameters and steps are the same as those of example 1.
Example 6
An antibacterial conductive composite membrane for water treatment, which is different from example 1 only in that titanium dioxide is used instead of 3-chloro-2-hydroxypropyltrimethylammonium chloride, and other parameters and steps are the same as those of example 1.
Example 7
An antibacterial conductive composite membrane for water treatment, which is different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 1:6, and other parameters and steps are the same as those of example 1.
Example 8
An antibacterial conductive composite membrane for water treatment is different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyltrimethylammonium chloride is 1:0.5, and other parameters and steps are the same as those of example 1.
Example 9
An antibacterial conductive composite membrane for water treatment is different from the composite membrane in example 1 only in that sodium dodecylbenzene sulfonate is not added to the antibacterial conductive layer, and other parameters and steps are the same as those in example 1.
Comparative example 1
A conductive polytetrafluoroethylene membrane which is different from example 1 in that 3-chloro-2-hydroxypropyltrimethylammonium chloride is not added to the antibacterial conductive layer and other parameters and steps are the same as example 1.
Comparative example 2
An antibacterial polytetrafluoroethylene film which is different from the one in example 1 in that no polypyrrole is added to the antibacterial conductive layer and other parameters and steps are the same as those of example 1.
Comparative example 3
A conductive polytetrafluoroethylene membrane which is different from example 1 in that 3-chloro-2-hydroxypropyltrimethylammonium chloride and sodium dodecylbenzenesulfonate are not added to the antibacterial conductive layer, and other parameters and steps are the same as those of example 1.
And (3) performance testing:
(1) conductivity: testing the film surface resistance by adopting a four-probe method;
(2) pure water membrane flux: by measuring the volume of percolate over a certain period of time, according to formula J0The pure water membrane flux was calculated as V/A.times.T, where J0For pure water flux, V represents the volume of leachate, A represents the effective area of the membrane, and T represents time;
(3) and (3) antibacterial property: shearing the obtained antibacterial conductive composite membrane into 1 × 1cm, and placing into diluted bacterial solution (Escherichia coli, 5 × 10) containing 100mL6CFU/mL) in a beaker, standing at room temperature for 3h for adsorption, gently washing off bacteria not adsorbed on the surface of the membrane by using a PBS solution, putting the wet membrane into the beaker containing 10mL of 0.01M PBS buffer solution for ultrasonic treatment for 15min, and completely dispersing the bacteria adsorbed on the surface of the membrane into the solution; coating the bacterial sample on a solid culture medium by a dilution coating plate method, culturing at 37 ℃ for 24h, and observing the number of live bacteria adhered to a membrane by a plate counting method;
(4) pure water membrane flux after contamination: the experiment adopts a self-made dead-end/cross-flow filtration membrane component, and the specific structural schematic diagram is shown in figure 1, wherein 1 represents an anode which is a titanium plate, 2 represents a conductive film cathode which is an antibacterial conductive composite membrane provided by the invention, 3 represents a direct-current power supply, 4 represents a water inlet, and 5 represents a water outlet; the specific operation is to carry out a solution filtration experiment containing escherichia coli under the groove pressure of 10V, and after the experiment is finished, the pollutants on the membrane are reserved and are not cleaned, and the flux of the polluted pure water membrane is tested.
The composite films obtained in examples 1 to 9 and comparative examples 1 to 3 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1: the antibacterial conductive composite membrane for water treatment provided by the invention has excellent anti-pollution performance, and does not influence the pure water flux of the base membrane. Specifically, the antibacterial conductive composite films provided in examples 1 to 9 have a resistance of 64.4 to 270k Ω and a pure water film flux of 820 to 1072L/m2H, the flux of the polluted pure water membrane is 692-991L/m2H, the number of residual bacteria on the surface after contamination is 0-67 CFU/mL.
Comparing example 1 with comparative examples 1 and 3, it can be seen that the conductive polytetrafluoroethylene films obtained without adding 3-chloro-2-hydroxypropyltrimethylammonium chloride (comparative example 1), without adding 3-chloro-2-hydroxypropyltrimethylammonium chloride and sodium dodecylbenzenesulfonate (comparative example 3) have a decreased flux of pure water film after contamination and a large number of residual bacteria, indicating that the composite film has poor contamination resistance.
As can be seen from comparison of example 1 and comparative example 2, no addition of the conductive material during the preparation process resulted in failure to form a film.
Further comparing example 1 with examples 4 to 5, it can be seen that when the concentration of iron oxide in step (1) of the preparation method is too low (example 4), the resistance of the obtained antibacterial conductive composite film is large, and the number of bacteria remaining on the surface of the film is large, which affects the antibacterial property of the composite film; on the other hand, when the concentration of iron oxide in the step (1) of the production method is too high (example 5), the pure water flux of the membrane is decreased, and further, the pure water flux after the membrane is contaminated is decreased, so that the number of bacteria remaining on the membrane surface is increased, and the antibacterial property is impaired.
Further comparison between example 1 and example 6 shows that the titanium dioxide is used to replace 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, which results in a general antibacterial effect of the composite membrane under the condition of no ultraviolet light.
Further comparison of examples 1 and 7 to 8 reveals that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyltrimethylammonium chloride not falling within the preferred range defined in the present invention also results in a composite film having poor antibacterial properties.
Finally, comparing example 1 with example 9, it can be seen that the pure water membrane flux and antibacterial property of the composite membrane obtained without adding sodium dodecylbenzenesulfonate as a dopant are also slightly reduced.
The applicant states that the present invention is illustrated by the above examples to provide an antibacterial conductive composite membrane for water treatment, and a preparation method and application thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must be implemented by relying on the above process steps. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. An antibacterial conductive composite film for water treatment is characterized by comprising a base film and an antibacterial conductive layer arranged on the surface of the base film;
the material of the antibacterial conducting layer comprises a combination of a conducting material and a sterilizing material.
2. The antibacterial conductive composite film according to claim 1, wherein the base film comprises an organic base film or an inorganic base film;
preferably, the organic base membrane comprises any one of a polyvinylidene fluoride membrane, a polyether sulfone membrane, a polytetrafluoroethylene membrane, a polycarbonate membrane or a mixed cellulose membrane;
preferably, the inorganic base film comprises a ceramic film;
preferably, the ceramic membrane comprises a porous alumina ceramic membrane.
3. The antibacterial conductive composite film according to claim 1 or 2, wherein the mass ratio of the conductive material to the bactericidal material is 1 (1-5);
preferably, the conductive material comprises a polymeric conductive material;
preferably, the polymeric conductive material comprises any one of polyaniline, polypyrrole or polythiophene, or a combination of at least two thereof.
4. The antibacterial conductive composite film according to any one of claims 1 to 3, wherein the bactericidal material comprises any one of or a combination of at least two of nano-silver particles, quaternary ammonium salt bactericides and photocatalytic bactericides;
preferably, the quaternary ammonium salt bactericide comprises 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
preferably, the photocatalytic bactericide comprises titanium dioxide.
5. The antibacterial conductive composite film according to any one of claims 1 to 4, wherein the material of the antibacterial conductive layer further comprises a dopant;
preferably, the dopant comprises any one of sodium dodecylbenzene sulfonate, cetyltrimethylammonium bromide or sodium dodecyl sulfate or a combination of at least two thereof.
6. A preparation method of the antibacterial conductive composite membrane for water treatment according to any one of claims 1 to 5, characterized by comprising the following steps:
(1) immersing the base film into a mixed solution containing a sterilization material, an oxidant and optionally a dopant to obtain a surface-treated base film;
(2) and (2) immersing the surface-treated base film obtained in the step (1) into a solution containing a conductive raw material to obtain the antibacterial conductive composite film for water treatment.
7. The preparation method according to claim 6, wherein the amount of the oxidant is 1 to 1.5mol based on 1L of the mixed solution in the step (1);
preferably, the immersion time in the step (1) is 20-40 min.
8. The production method according to claim 6 or 7, characterized by further comprising, before the step (2), a step of drying the surface-treated base film obtained in the step (1);
preferably, the amount of the conductive raw material is 0.25-1 mol based on 1L of the solution in the step (2);
preferably, the immersion time in the step (2) is 0.5-1.5 h.
9. Use of an antibacterial conductive composite membrane according to any one of claims 1 to 5 for water treatment in a material separation apparatus.
10. Use according to claim 9, wherein the antimicrobial conductive composite membrane is used as a cathode in the substance separation device.
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| CN115155332A (en) * | 2022-07-07 | 2022-10-11 | 南京大学 | In-situ membrane pollution resisting method for low-voltage electric field coupling conductive ultrafiltration membrane |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1101161A (en) * | 1993-09-30 | 1995-04-05 | 中国科学院化学研究所 | conductive polymer composite film and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115155332A (en) * | 2022-07-07 | 2022-10-11 | 南京大学 | In-situ membrane pollution resisting method for low-voltage electric field coupling conductive ultrafiltration membrane |
| CN115155332B (en) * | 2022-07-07 | 2023-12-19 | 南京大学 | Method for in-situ membrane pollution resistance of low-voltage electric field coupling conductive ultrafiltration membrane |
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| CN114699931B (en) | 2023-07-25 |
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