CN114699931B - Antibacterial conductive composite film for water treatment and preparation method and application thereof - Google Patents

Antibacterial conductive composite film for water treatment and preparation method and application thereof Download PDF

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CN114699931B
CN114699931B CN202210408626.0A CN202210408626A CN114699931B CN 114699931 B CN114699931 B CN 114699931B CN 202210408626 A CN202210408626 A CN 202210408626A CN 114699931 B CN114699931 B CN 114699931B
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film
antibacterial
base film
conductive
composite film
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CN114699931A (en
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孙境求
胡承志
赵凯
芦超杰
曲久辉
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Research Center for Eco Environmental Sciences of CAS
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • 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
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/26—Electrical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention provides an antibacterial conductive composite film for water treatment, 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 antibacterial conductive layer comprises a conductive material and a sterilizing material; by doping the antibacterial conductive layer with the conductive material and the bactericidal material, the problem of poor operation persistence which is easy to generate when the base film is used alone 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 produce a synergistic effect, so that the antibacterial pollution resistance of the finally obtained antibacterial conductive composite film is improved under the condition 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

Antibacterial conductive composite film for water treatment and preparation method and application thereof
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an antibacterial conductive composite film for water treatment, and a preparation method and application thereof.
Background
At present, membrane pollution generated in the water treatment process is the biggest problem existing in the application of membrane technology, wherein biological pollution is the most common, and microorganisms widely exist in places such as air, water, soil and the like. Therefore, in the membrane technology, the raw material liquid inevitably contains active microorganisms, and the microorganisms tend to form colonies or bacterial membranes to resist the severe change of external conditions, so that the survival of the microorganisms is facilitated, therefore, when the raw material liquid is contacted with the surface of the membrane, favorable conditions are provided for the adhesion of the microorganisms on the surface of the membrane, and even 99.99% of the microorganisms in the pretreatment are killed, the residual 0.01% of the microorganisms can cause serious consequences, so that the biofouling of the membrane is an urgent technical problem to be solved in the membrane technology.
The membrane surface modification method is a common method for solving the problem of biological pollution of the membrane, and the membrane surface modification method refers to a chemical or physical method which is adopted to endow the membrane with new properties (such as hydrophilicity and antibacterial property) on the premise of keeping the properties of a material body unchanged. CN103464011a discloses an aromatic polyamide composite membrane with salicylaldehyde and tertiary amine groups on the surface, and the aromatic polyamide composite membrane with amino groups on the surface is prepared by condensation reaction of acyl chloride groups on the surface of the aromatic polyamide composite membrane and organic polyamine; then, carrying out Mannich reaction on the aromatic polyamide composite membrane with the amino group on the surface, formaldehyde and salicylaldehyde to prepare the aromatic polyamide composite membrane with the salicylaldehyde and tertiary amino group on the surface; finally, the aromatic polyamide composite membrane with the surface containing the salicylaldehyde and the tertiary amino group is prepared through quaternization reaction of the aromatic polyamide composite membrane with the surface containing the quaternary ammonium salt and the salicylaldehyde and the quaternary ammonium salt of an alkylating reagent, so that the hydrophilicity of the surface of the aromatic polyamide composite membrane can be improved, and the biocidal and antibacterial properties of the aromatic polyamide composite membrane can be improved. However, although quaternary ammonium salts have antibacterial activity, the deactivated bacteria continue to accumulate on the membrane surface during the continuous filtration process, gradually diminishing the contact sterilizing ability.
In addition, by preparing a conductive film and applying a negative voltage, film contamination can be suppressed by a method of electrostatic repulsion. Since contaminants and microorganisms in water are mostly electronegative, the movement of the microorganisms to the membrane surface can be hindered by electrostatic repulsive force. The conductive film refers to a multifunctional film having both permeability and conductive properties. CN110465209a discloses a polypyrrole/carbon nano tube/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 the polyethersulfone flat membrane, a carbon nano tube film is deposited by utilizing pressure, polypyrrole is synthesized on the carbon nano tube film in situ by adopting a chemical polymerization method, and a conductive layer is formed on the polyethersulfone 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. Polypyrrole is polymerized on the surface of the membrane in situ, so that the hydrophilicity of the membrane and the stability of the conducting 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, no need of complex reaction and high temperature, low cost and strong operability. However, when the surface of the composite conductive film provided by the prior art is attached with the metabolically active microorganism, the electrostatic effect is disabled, and the microorganism can rapidly grow on the surface of the film to cause obvious reduction of the film flux.
Therefore, developing an antibacterial conductive composite membrane with durable and excellent antibacterial performance, which maintains stable membrane flux, is a technical problem that needs to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an antibacterial conductive composite film 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 antibacterial conductive layer comprises a conductive material and a sterilizing material; the conductive material and the bactericidal material are combined, so that the attenuation of the flux of the pure water film used in the water treatment process of the obtained antibacterial conductive composite film is slowed down, and the antibacterial conductive composite film has excellent and durable biological pollution resistance.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an antimicrobial conductive composite film for water treatment, the antimicrobial conductive composite film comprising a base film and an antimicrobial conductive layer disposed on a surface of the base film;
the material of the antibacterial conductive layer comprises a combination of conductive material and antibacterial material.
The invention provides an antibacterial conductive composite film for water treatment, which is characterized in that an antibacterial conductive layer is coated on the surface of a base film; the material of the antibacterial conductive layer comprises a combination of a conductive material and a sterilizing material, and an electrochemical group and an antibacterial group are combined, so that the problem of poor long-term operation persistence easily caused when the base film is used alone 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 produce a synergistic effect, so that the antibacterial pollution resistance of the finally obtained antibacterial conductive composite film can be improved under the condition that the flux of a pure water film is not reduced, the number of bacteria remained on the surface of the film after the film is used 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 film includes any one of a polyvinylidene fluoride film, a polyethersulfone film, a polytetrafluoroethylene film, a polycarbonate film, or a mixed cellulose film.
Preferably, the inorganic base film comprises a ceramic film.
Preferably, the ceramic membrane comprises a porous alumina ceramic membrane.
Preferably, the mass ratio of the conductive material to the bactericidal 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, etc.
As the preferable technical scheme of the invention, when the mass ratio of the conductive material and the bactericidal material of the antibacterial conductive layer is 1 (1-5), the obtained antibacterial conductive composite film has the most excellent anti-pollution performance, on one hand, if the consumption of the conductive material is relatively low, the conductivity of the antibacterial conductive composite film is reduced, the film flux is reduced and the bacteria residue is more; on the other hand, if the amount of the bactericidal 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 or a combination of at least two of polyaniline, polypyrrole or polythiophene.
Preferably, the bactericidal material comprises any one 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 biocide comprises titanium dioxide.
Preferably, the material of the antibacterial conductive layer further comprises a dopant.
As the preferable technical scheme of the invention, the material of the antibacterial conductive layer also comprises a doping agent, and the doping agent can further improve the conductivity of the finally obtained antibacterial conductive composite film, thereby being beneficial to improving the anti-pollution performance of the antibacterial conductive composite film.
Preferably, the dopant comprises any one or a combination of at least two of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, or sodium dodecyl sulfate.
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 steps of:
(1) Immersing the base film into a mixed solution containing a sterilizing material, an oxidant and optionally a doping agent to obtain a surface-treated base film;
(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.
In the preparation method of the antibacterial conductive composite film, a base film is immersed into a mixed solution containing a sterilizing material, an oxidant and optionally a doping agent, so that the sterilizing material and the oxidant are attached to the surface of the base film, and the surface-treated base film is obtained; and immersing the surface-treated base film into a solution containing conductive raw materials, wherein the conductive raw materials in the solution can be subjected to oxidation reaction under the action of an oxidant to generate conductive materials, and then the conductive materials are coated on the surface of the base film to form a conductive layer, and meanwhile, optional doping agents and sterilizing materials attached to the surface of the base film can be doped in the conductive layer, so that the conductive materials and the sterilizing materials can play a synergistic effect, and the antibacterial performance of the antibacterial conductive composite film is further effectively improved.
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 oxidizing agent is used in an amount of 1 to 1.5mol, for example 1.05mol, 1.1mol, 1.15mol, 1.2mol, 1.25mol, 1.3mol, 1.35mol, or 1.4mol, based on 1L of the volume of the mixed solution in step (1), and the specific point values between the above point values are limited in length and for the sake of brevity, the present invention is not exhaustive list of the specific point values included in the range.
Preferably, the time of immersion in step (1) is 20-40 min, such as 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min or 38min, and the specific point values between the above point values, which are limited in space and for brevity, the present invention is not exhaustive.
Preferably, the step (2) is preceded by a step of drying the surface-treated polytetrafluoroethylene-based film obtained in the step (1).
Preferably, the pyrrole is used in an amount of 0.25 to 1mol, for example 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 1L of the volume of the pyrrole solution of step (2), and the specific point values between the above point values are limited in space and for the sake of brevity, the invention does not exhaustively enumerate the specific point values included in the range.
Preferably, the time of immersion in step (2) is between 0.5 and 1.5 hours, such as 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hours, 1.1 hours, 1.2 hours, 1.3 hours or 1.4 hours, and the specific point values between the above point values, are limited in length and for the sake of brevity, the invention is not exhaustive of the specific point values comprised in the range.
In a third aspect, the present invention provides the use of an antimicrobial conductive composite membrane as described in the first aspect in a substance separation device.
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 film for water treatment provided by the invention comprises a base film and an antibacterial conductive layer arranged on the surface of the base film, wherein the antibacterial conductive layer comprises a combination of a conductive material and a sterilizing material; the surface of the base film is coated with the conductive material and the bactericidal material, so that the conductive material and the bactericidal material have synergistic effect, the problem of poor persistence of the base film in long-term operation is successfully overcome, the service life of the base film is prolonged, the anti-pollution performance of the antibacterial conductive composite film is also improved, and the pure water flux of the base film is not influenced.
(2) The preparation method of the antibacterial conductive composite membrane provided by the invention is simple, the preparation cost is low, and the antibacterial conductive composite membrane can be used as a cathode to generate electrostatic repulsion on microorganisms in water when in application, so that the microorganisms are prevented from accumulating on the surface of the membrane, once the microorganisms move to the surface of the membrane, the microorganisms are deactivated under the sterilization effect, the adhesion 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 deactivated microorganisms fall off 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 kΩ, and the pure water film flux is 820-1072L/m 2 H, the pure water flux after pollution is 692 to 991L/m 2 H, the number of bacteria extracted from the surface of the membrane after filtration is 0 to 67CFU/mL.
Drawings
FIG. 1 is a schematic diagram of a dead-end/cross-flow filtration membrane module provided by the invention, wherein the dead-end/cross-flow filtration membrane module comprises a 1-anode, a 2-conductive membrane cathode, a 3-DC power supply, a 4-water inlet and a 5-water outlet.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
An antibacterial conductive composite film for water treatment, which consists of a polytetrafluoroethylene-based film (Millipore, 100 nm) and an antibacterial conductive layer arranged on the surface of the polytetrafluoroethylene-based film;
the antibacterial conductive 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 film for water treatment provided by the embodiment comprises the following steps:
(1) Immersing a polytetrafluoroethylene base 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 base membrane after surface treatment;
(2) And (3) drying the polytetrafluoroethylene base film subjected to surface treatment obtained in the step (1), immersing the dried polytetrafluoroethylene base film into a pyrrole aqueous solution with the concentration of 0.5mol/L for 1h, and taking out the polytetrafluoroethylene base film to obtain the antibacterial conductive composite film for water treatment.
Example 2
An antibacterial conductive composite film for water treatment is different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyl trimethylammonium chloride is 1:1, and other parameters and steps are the same as in example 1.
Example 3
An antibacterial conductive composite film for water treatment was different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyl trimethylammonium chloride was 1:5, and other parameters and steps were the same as in example 1.
Example 4
An antibacterial conductive composite film for water treatment, which is different from example 1 only in that the concentration of iron oxide in step (1) of the production method is 0.5mol/L, and other parameters and steps are the same as those of example 1.
Example 5
An antibacterial conductive composite film for water treatment was different from example 1 only in that the concentration of iron oxide in step (1) of the production method was 2mol/L, and other parameters and steps were the same as those of example 1.
Example 6
An antibacterial conductive composite film for water treatment was different from example 1 only in that titanium dioxide was used instead of 3-chloro-2-hydroxypropyl trimethylammonium chloride, and other parameters and steps were the same as in example 1.
Example 7
An antibacterial conductive composite film for water treatment was different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyl trimethylammonium chloride was 1:6, and other parameters and steps were the same as in example 1.
Example 8
An antibacterial conductive composite film for water treatment was different from example 1 only in that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyl trimethylammonium chloride was 1:0.5, and other parameters and steps were the same as in example 1.
Example 9
An antibacterial conductive composite film for water treatment was different from example 1 only in that sodium dodecylbenzenesulfonate was not added to the antibacterial conductive layer, and other parameters and steps were the same as in example 1.
Comparative example 1
A conductive polytetrafluoroethylene film differing from example 1 in that the antibacterial conductive layer was free of addition of 3-chloro-2-hydroxypropyl trimethylammonium chloride, and the other parameters and steps were the same as in example 1.
Comparative example 2
An antibacterial polytetrafluoroethylene film differing from example 1 in that polypyrrole was not added to the antibacterial conductive layer, and other parameters and steps were the same as those of example 1.
Comparative example 3
An electroconductive polytetrafluoroethylene film differing from example 1 in that the antibacterial electroconductive layer was free of 3-chloro-2-hydroxypropyl trimethylammonium chloride and sodium dodecylbenzenesulfonate added, and the other parameters and steps were the same as in example 1.
Performance test:
(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 period of time, according to formula J 0 Calculate the pure water film flux, where J 0 For pure water flux, V represents the volume of percolate, A represents the effective area of the membrane, and T represents time;
(3) Antibacterial properties: the obtained antibacterial conductive composite film was cut into 1X 1cm and placed in a diluted bacterial solution (E.coli, 5X 10) containing 100mL 6 CFU/mL), standing at room temperature for adsorption for 3 hours, gently flushing bacteria which are not adsorbed on the surface of the membrane by using a PBS solution, then placing the wetted membrane into a beaker containing 10mL of PBS buffer solution with the concentration of 0.01M for ultrasonic treatment for 15 minutes, and dispersing all bacteria which are adsorbed on the surface of the membrane into the solution; coating the bacterial sample in a solid culture medium by a dilution coating flat plate method, culturing for 24 hours at 37 ℃, and observing the number of living bacteria adhered to the membrane by a flat plate counting method;
(4) Pure water membrane flux after contamination: the experiment adopts a self-made dead-end/cross-flow filtering membrane component, and a specific structural schematic diagram is shown in figure 1, wherein 1 represents an anode, a titanium plate, 2 represents a conductive membrane cathode, 3 represents a direct current power supply, 4 represents a water inlet, and 5 represents a water outlet; the specific operation is that a solution filtration experiment containing escherichia coli is carried out under the cell pressure of 10V, pollutants on the membrane are reserved after the experiment is finished, the membrane is 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 methods, and the test results are shown in table 1:
TABLE 1
From the data in table 1, it can be seen that: the antibacterial conductive composite film for water treatment provided by the invention has excellent anti-pollution performance, and the pure water flux of the base film is not affected. Specifically, the antibacterial conductive composite films provided in examples 1 to 9 have a resistance of 64.4 to 270kΩ and a pure water film flux of 820 to 1072L/m 2 H, the flux of the pure water membrane after pollution is 692-991L/m 2 H, after contaminationThe number of residual bacteria on the surface is 0-67 CFU/mL.
As can be seen from comparative example 1 and comparative examples 1 and 3, the conductive polytetrafluoroethylene film obtained without adding 3-chloro-2-hydroxypropyl trimethylammonium chloride (comparative example 1), 3-chloro-2-hydroxypropyl trimethylammonium chloride and sodium dodecylbenzenesulfonate (comparative example 3) had a decreased pure water film flux after contamination and a large number of residual bacteria, indicating that the composite film had poor contamination resistance.
As can be seen from comparing example 1 with comparative example 2, the absence of the conductive material added during the preparation process resulted in the inability to form a film.
Further comparing example 1 with examples 4 to 5, it can be seen that too low a concentration of iron oxide in step (1) of the preparation method (example 4) results in a larger resistance of the obtained antibacterial conductive composite film, and further a larger number of bacteria remained on the film surface, affecting the antibacterial property of the composite film; in the preparation method, when the concentration of iron oxide in the step (1) (example 5) is too high, the pure water flux of the membrane is reduced, the pure water flux after pollution is reduced, the number of bacteria remained on the surface of the membrane is increased, and the antibacterial property of the membrane is affected.
It can be seen from a further comparison of examples 1 and 6 that the use of titanium dioxide instead of 3-chloro-2-hydroxypropyl trimethylammonium chloride resulted in a composite film having a generally antimicrobial effect without ultraviolet irradiation.
Further comparing example 1 with examples 7 to 8, it was found that the mass ratio of polypyrrole to 3-chloro-2-hydroxypropyl trimethylammonium chloride was not within the preferred range defined in the present invention, and the antibacterial property of the resulting composite film was also poor.
Finally, comparing example 1 with example 9, it was found that the pure water membrane flux of the composite membrane obtained without adding sodium dodecylbenzenesulfonate as a dopant was slightly decreased as well as the antibacterial property.
The applicant states that the present invention, by way of the above examples, illustrates an antimicrobial conductive composite film for water treatment and a method of preparing and using the same, but the present invention is not limited to the above process steps, i.e. it is not meant that the present invention must be practiced in dependence upon the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (13)

1. The preparation method of the antibacterial conductive composite film for water treatment is characterized in that 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 conductive layer comprises a combination of a conductive material and a sterilizing material;
the mass ratio of the conductive material to the bactericidal material is 1 (1-5);
the conductive material comprises a polymeric conductive material;
the polymer conductive material comprises any one or a combination of at least two of polyaniline, polypyrrole or polythiophene;
the sterilizing material comprises any one or a combination of at least two of nano silver particles, quaternary ammonium salt bactericides or photocatalysis bactericides;
the material of the antibacterial conductive layer further comprises a doping agent;
the dopant comprises any one or a combination of at least two of sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide or sodium dodecyl sulfate;
the preparation method comprises the following steps:
(1) Immersing the base film into a mixed solution containing a sterilizing material, an oxidant and a doping agent to obtain a surface-treated base film;
(2) Immersing the surface-treated base film obtained in the step (1) into a solution containing a conductive material to obtain the antibacterial conductive composite film for water treatment;
and (3) counting the volume of the mixed solution in the step (1) to 1L, wherein the consumption of the oxidant is 1-1.5 mol.
2. The method of manufacturing according to claim 1, wherein the base film comprises an organic base film or an inorganic base film.
3. The method according to claim 2, wherein the organic base film comprises any one of a polyvinylidene fluoride film, a polyethersulfone film, a polytetrafluoroethylene film, a polycarbonate film, and a mixed cellulose film.
4. The method of manufacturing according to claim 2, wherein the inorganic base film comprises a ceramic film.
5. The method of manufacturing according to claim 4, wherein the ceramic membrane comprises a porous alumina ceramic membrane.
6. The method according to claim 1, wherein the quaternary ammonium salt bactericide comprises 3-chloro-2-hydroxypropyl trimethylammonium chloride.
7. The method of claim 1, wherein the photocatalytic biocide comprises titanium dioxide.
8. The method according to claim 1, wherein the immersion time in step (1) is 20 to 40 minutes.
9. The method according to claim 1, further comprising a step of drying the surface-treated base film obtained in step (1) before performing step (2).
10. The method according to claim 1, wherein the conductive material is used in an amount of 0.25 to 1mol based on the volume of the solution in the step (2) of 1. 1L.
11. The method according to claim 1, wherein the immersion time in step (2) is 0.5 to 1.5 hours.
12. Use of the antibacterial conductive composite film for water treatment prepared by the preparation method according to any one of claims 1 to 11 in a substance separation device.
13. The use according to claim 12, wherein the antimicrobial conductive composite film acts as a cathode for the substance separation device.
CN202210408626.0A 2022-04-19 2022-04-19 Antibacterial conductive composite film for water treatment and preparation method and application thereof Active CN114699931B (en)

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