CN117531382A - Preparation method and application of repeatedly tearing and recasting composite conductive film - Google Patents
Preparation method and application of repeatedly tearing and recasting composite conductive film Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000005266 casting Methods 0.000 claims abstract description 22
- 239000002033 PVDF binder Substances 0.000 claims abstract description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 11
- 238000002791 soaking Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004745 nonwoven fabric Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000000614 phase inversion technique Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 description 22
- 241000195493 Cryptophyta Species 0.000 description 21
- 239000000243 solution Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000001471 micro-filtration Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 241000195634 Dunaliella Species 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000006056 electrooxidation reaction Methods 0.000 description 4
- 230000002779 inactivation Effects 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000015271 coagulation Effects 0.000 description 1
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- 239000000356 contaminant Substances 0.000 description 1
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- 238000011010 flushing procedure Methods 0.000 description 1
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- 244000005700 microbiome Species 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
- B01D71/441—Polyvinylpyrrolidone
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/20—Prevention of biofouling
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention belongs to the technical field of conductive films, and particularly relates to a preparation method and application of a repeatedly tearable heavy casting conductive film. The preparation method of the composite conductive film comprises the following steps: (1) Dissolving polyvinylidene fluoride and polyvinylpyrrolidone in N-methyl pyrrolidone, stirring and mixing uniformly, and standing for defoaming to obtain an organic film casting solution; (2) And (3) assembling the electrode substrate on a supporting material, uniformly coating the organic film casting solution prepared in the step (1) on the electrode substrate and the supporting material, then soaking the electrode substrate and the supporting material in a deionized water bath, and performing phase inversion at room temperature to obtain the composite conductive film. The conductive film material prepared by the invention can remove the supporting material and the organic film by repeated tearing, the electrode is cleaned, the electrode can be repeatedly utilized, the use cost of the conductive film is greatly saved, the conductive film subjected to repeated tearing and recasting has stable performance and low film pollution, and the marine microalgae can be successfully inactivated and removed.
Description
Technical Field
The invention belongs to the technical field of conductive films, and particularly relates to a preparation method and application of a repeatedly-tearable and recast composite conductive film.
Background
In recent years, low pressure membrane filtration (such as Microfiltration (MF) and Ultrafiltration (UF)) has become one of the dominant technologies for water/wastewater treatment due to the advantages of high water output, small floor space, and low life costs. Wherein, the aperture range of the microfiltration membrane is 0.1-1 mu m, which can effectively intercept microorganisms, and researches show that the efficiency of the microfiltration membrane for intercepting algae can reach 100%, and the microfiltration membrane has great potential in the aspect of algae-containing water removal. However, the complex biological, organic and inorganic components in the water body can cause serious membrane pollution, and on one hand, algae can only be enriched but cannot be further inactivated, so that secondary pollution can be generated; the other side of the membrane pollution causes the water flux to be reduced, and the water treatment cost can be obviously increased by the membrane cleaning and replacement. Therefore, it is important to couple MF with other technologies to improve algae removal efficiency and membrane pollution in MF process.
Electrocatalytic Filtration (EF) is a process that integrates the advantages of chemical oxidation and membrane separation, and has been attracting attention in recent years. In EF process, mass transfer of target pollutant from bulk solution to membrane surface is obviously enhanced due to forced convection effect of filtration, and electrochemical oxidation of pollutant on anode of conductive membrane can be greatly promoted due to a large number of active reaction sites on anode, and membrane pollution problem can be effectively alleviated, and service life of membrane can be prolonged. The EF technology has the advantages of large treatment capacity, good dynamic performance, moderate energy consumption, high treatment efficiency and the like, and has wide application prospect in future water treatment.
For the electrocatalytic filtration process, the conductive film material is a core component, and the current research on the preparation method of the conductive film mainly comprises conductive modification of a film substrate, conductive nano material loading and the like, and the methods have the advantages of complex modification process, high preparation cost, poor film stability, easiness in secondary pollution and low reusability, and prevent the large-scale application of the conductive film. Therefore, the development of the conductive film material which is simple in preparation, low in cost, stable in performance and reusable is of great significance.
Disclosure of Invention
The invention aims to solve the problems of complex modification process, high preparation cost, poor film stability, easiness in causing secondary pollution and low reusability in the preparation method of the conductive film.
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for preparing a composite conductive film which can be repeatedly torn and re-cast, and an application thereof, wherein the conductive film is simple to prepare, low in cost, stable in performance, and less in film pollution, and can be repeatedly torn and re-cast after use.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the invention provides a preparation method of a composite conductive film, which comprises an electrode substrate, a supporting material and an organic film;
the preparation method of the composite conductive film comprises the following steps:
(1) Preparing an organic film casting solution:
dissolving polyvinylidene fluoride (PVDF) and polyvinylpyrrolidone (PVP) in N-methyl pyrrolidone (NMP), stirring, mixing uniformly, standing and defoaming to obtain an organic film casting solution;
(2) Preparing a composite conductive film by using a phase inversion method:
and (3) assembling the electrode substrate on a supporting material, uniformly coating the organic film casting solution prepared in the step (1) on the electrode substrate and the supporting material, then soaking the electrode substrate and the supporting material in a deionized water bath, and performing phase inversion at room temperature to obtain the composite conductive film.
Preferably, the electrode substrate comprises a Pt/Ti metal electrode and SnO 2 Ti metal electrode, ruO 2 Ti metal electrode, pbO 2 One of the Ti metal electrodes has a thickness of 50-200 μm, and provides excellent conductivity and electrocatalytic properties to the organic film.
Preferably, the support material is one of a nonwoven fabric and a carbon cloth, and more preferably, the support material is a nonwoven fabric.
Preferably, in the step (1), the weight percentages of the raw materials in the organic film casting solution are: 8-15% of polyvinylidene fluoride (PVDF), 1-7% of polyvinylpyrrolidone (PVP) and 78-91% of N-methylpyrrolidone (NMP), and more preferably, the weight percentages of polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP) and N-methylpyrrolidone (NMP) are respectively as follows: 8%, 3% and 89%.
Preferably, in the step (1), the stirring time is 18 to 24 hours, more preferably 24 hours, and the standing time is 24 to 48 hours, more preferably 24 hours.
Preferably, in the step (2), the casting blade gap for coating the organic film casting solution is 120 to 240. Mu.m, more preferably 180. Mu.m.
Preferably, in step (1) and step (2), the polyvinylidene fluoride (PVDF) and support material are dried at 80 ℃ for 2 hours to remove moisture.
In another aspect, the present invention provides a recasting method for a composite conductive film obtained by the above preparation method, in which the support material and the organic film are removed by tearing the used composite conductive film, the electrode substrate is immersed in an organic solvent for cleaning, and the steps (1) and (2) described in claim 1 are repeated to recast the conductive film.
Preferably, the organic solvent includes any one of dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), and N-N Dimethylformamide (DMF), and further preferably dimethyl sulfoxide (DMSO).
Preferably, the soaking time is 5-10min.
The invention also provides an application of the composite conductive film prepared by the preparation method, wherein the composite conductive film is used as an anode, a Ti net is used as a cathode, and an electrocatalytic filtration system is constructed to inactivate marine microalgae.
Compared with the prior art, the invention has the beneficial effects that:
1. polyvinylidene fluoride (PVDF) is a widely used polymer membrane material, the PVDF membrane has good corrosion resistance and stable physical and chemical properties, but the PVDF membrane has low mechanical strength and does not have conductivity.
2. The preparation method is simple and easy to operate.
3. The composite conductive film prepared by the invention can remove the supporting material and the organic film by repeated tearing, the electrode is soaked and cleaned, the electrode can be reused, and the use cost of the conductive film is greatly saved.
Drawings
FIG. 1 is a schematic structural view of a composite conductive film;
wherein: 1. the organic film I, 2, electrode substrate, 3, non-woven fabrics, 4 is organic film II;
FIG. 2 is a schematic view of a membrane module structure;
wherein: 1. a composite conductive film, 2, a Ti net;
FIG. 3 shows the microalgae inactivation effect under different conditions in comparative example 1, example 1 and example 2;
FIG. 4 is the TMP change when the composite conductive film of example 3 continuously inactivated microalgae;
FIG. 5 shows the microalgae inactivating effect when the composite conductive film of examples 4-12 is reused.
Detailed Description
The invention will be further described with reference to the drawings and specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Furthermore, it will be appreciated that those skilled in the art, upon reading the teachings of the present invention, may make various changes or modifications thereto, and that such equivalents will fall within the scope of the invention as claimed.
Example 1
A preparation method of a composite conductive film comprises the following steps:
(1) Preparing a casting solution by taking PVDF as an organic film material:
dissolving 8wt% of polyvinylidene fluoride (PVDF) and 3wt% of polyvinylpyrrolidone (PVP) in 89wt% of N-methylpyrrolidone (NMP), stirring the solution for 24 hours, mixing uniformly, and standing for 24 hours for defoaming to obtain an organic film casting solution;
(2) Preparing a conductive film by using a phase inversion method:
the Pt/Ti electrode of 4cm multiplied by 4cm is assembled on a non-woven fabric supporting material, the gap of a casting knife is adjusted to 180 mu m, the organic film casting solution is uniformly coated on the non-woven fabric and the electrode, the non-woven fabric and the electrode stay for 2 minutes, and then the composite conductive film is obtained by immersing the composite conductive film in a deionized water bath (coagulation bath) and performing phase inversion at room temperature.
The composite conductive film prepared in example 1 was used as an anode, a titanium mesh was used as a cathode, and a film module was used for assembly, and the film module structure is schematically shown in fig. 2.
At an algae density of 1×10 4 The Dunaliella algae in cells/mL is taken as a model pollutant, and the electrocatalytic filtering effect of the prepared conductive film anode is examined in an electrocatalytic filtering system. As shown in fig. 2, in the EF system, the distance between the cathode and the anode is 1cm, the algae cells pass through the titanium mesh cathode, a part of the algae cells are electrostatically repelled by the cathode, the rest of the algae cells then reach the anode conductive film for membrane filtration and electrochemical oxidation, and the permeate is pumped out from the anode side through the peristaltic pump. Under applied voltage, the current density was 30mA/cm 2 The flow rate was 10mL/min, pH 8.0, salinity 3.4%, and removal rate was-2.84 at 180min, as shown by curve a in FIG. 3.
Example 2
The composite conductive film obtained in example 1 was mounted in a film package having an alga density of 1X 10 as in example 1 4 The cell/mL Dunaliella is taken as model pollutant,the membrane separation effect of the composite conductive membrane produced in example 1 was examined in a filtration system. Wherein, the flow rate is 10mL/min, the pH is 8.0, and the salinity is 3.4%.180min, the removal rate was-0.50 as shown in curve b of FIG. 3.
Example 3
The composite conductive film obtained in example 1 was mounted in a film package having an alga density of 1X 10 as in example 1 4 The cell/mL Dunaliella is taken as a model pollutant, and the electrocatalytic filtering effect of the anode of the conductive film is examined in an electrocatalytic filtering system. As shown in fig. 2, in the EF system, the distance between the cathode and the anode is 1cm, the algae cells pass through the titanium mesh cathode, a part of the algae cells are electrostatically repelled by the cathode, the rest of the algae cells then reach the anode conductive film for membrane filtration and electrochemical oxidation, and the permeate is pumped out from the anode side through the peristaltic pump. Wherein the current density is 30mA/cm 2 The flow rate was 10mL/min, pH 8.0, salinity 3.4%, and the transmembrane pressure (TMP) change during the 9h continuous inactivation experiment was recorded. When the anode of the conductive film was continuously deactivated for 9 hours, the transmembrane pressure was 0.0045MPa as shown in FIG. 4.
Example 4
The composite conductive film after use in example 1 was subjected to recasting, and the recasting method includes the steps of:
tearing the non-woven fabric and the organic film in the composite conductive film after the use in the embodiment 1, gently rubbing the other organic film covered by the electrode, soaking the electrode in DMSO solution for 5-10min, and finally repeatedly flushing with deionized water to dry the electrode; and assembling the cleaned Pt/Ti electrode on a non-woven fabric bracket, adjusting the clearance of a casting knife to 180 mu m, uniformly coating the prepared organic film casting solution on an electrode substrate and a supporting material, staying for 2 minutes, immersing the electrode in a deionized water bath (coagulating bath), and carrying out phase inversion at room temperature to obtain the composite conductive film.
The composite conductive film obtained by recasting is used as an anode, a titanium net is used as a cathode, and the algae density is 1 multiplied by 10 4 The Dunaliella algae in cells/mL is taken as a model pollutant, and the electrocatalytic filtering effect of the synthesized conductive film anode is examined in an electrocatalytic filtering system. As shown in FIG. 2, in EF system, the distance between cathode and anode electrodeAt 1cm, algae cells pass through a titanium mesh cathode, a part of algae cells are electrostatically repelled by the cathode, the rest algae cells then reach an anode conductive film for membrane filtration and electrochemical oxidation, and permeate is pumped out from the anode side through a peristaltic pump. Wherein the current density is 30mA/cm 2 The flow rate was 10mL/min, pH 8.0, salinity 3.4%, and removal rate of-2.83 at 180min, as shown in FIG. 5.
Example 5
The composite conductive film after the use of example 4 was subjected to recasting, and the removal rate was-2.79 when the recasting method was the same as that of example 4 for 180 minutes, as shown in fig. 4.
Example 6
The composite conductive film after the use of example 5 was subjected to recasting, and the removal rate was-2.75 as shown in FIG. 5 when the recasting method was the same as that of example 4 for 180 minutes.
Example 7
The composite conductive film after the use of example 6 was subjected to recasting, and the removal rate was-2.7 as shown in FIG. 5 when the recasting method was the same as that of example 4 for 180 minutes.
Example 8
The composite conductive film after the use of example 7 was subjected to recasting, and the removal rate was-2.65 as shown in FIG. 5 when the recasting method was the same as that of example 3 for 180 minutes.
Example 9
The composite conductive film after the use of example 8 was subjected to recasting, and the removal rate was-2.62 as shown in FIG. 5 when the recasting method was the same as that of example 4 for 180 minutes.
Example 10
The composite conductive film after the use of example 9 was subjected to recasting, and the removal rate was-2.6 as shown in FIG. 5 when the recasting method was the same as that of example 4 for 180 minutes.
Example 11
The composite conductive film after the use of example 10 was subjected to recasting, and the removal rate was-2.59 as shown in FIG. 5 when the recasting method was the same as that of example 4 for 180 minutes.
Example 12
The composite conductive film after the use of example 11 was subjected to recasting, and the removal rate was-2.59 as shown in FIG. 5 when the recasting method was the same as that of example 4 for 180 minutes.
Comparative example 1
Commercial PVDF membranes (5. Mu. m Membrane Solutions) were purchased and mounted in membrane modules having an algae density of 1X 10 as in example 1 4 Dunaliella algae in cells/mL was used as model contaminant, and the membrane separation effect of commercial microfiltration membranes was examined in a filtration system. Wherein, the flow rate is 10mL/min, the pH is 8.0, and the salinity is 3.4%.180min, the removal rate was-0.34 as shown in curve c of FIG. 3.
Analysis of results:
as can be seen from the above examples 1, 2 and 1, the removal rate of the conductive film prepared by the invention to Dunaliella is higher than that of commercial microfiltration film, which shows that the conductive film material prepared by the invention has better film separation effect; the removal rate under the condition of applying electricity is obviously higher than that under the condition of not applying voltage, which indicates that the conductive film material prepared by the invention has excellent effect and good algae inactivation removal effect under the electrocatalytic filtration system.
As can be seen from the above example 3, when the microalgae is continuously inactivated for 9 hours, as shown in FIG. 4, the transmembrane pressure is relatively low, and only increases from 0.0012MPa to 0.0045MPa, which indicates that the repeatedly tearable heavy casting conductive film prepared by the invention has less film pollution in the use process.
The above examples 4-12 show that the electrode can be reused by tearing the non-woven fabric layer and the organic film layer and soaking and cleaning the non-woven fabric layer and the organic film layer in the organic solvent, the removal rate reaches-2.84 in the first repeated experiment, the conductive film anode is reused for 10 times, the removal rate is only reduced by 8.8%, the removal rate can still reach-2.59, and the conductive film anode in the invention circulates for 10 times, so that the electrocatalytic performance is slightly reduced, the algae inactivation removal effect is good, and the reusability is stable.
The above embodiments are only for illustrating the present invention, and are not limiting of the present invention. While the invention has been described in detail with reference to the embodiments, those skilled in the art will appreciate that various combinations, modifications, and substitutions can be made thereto without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the composite conductive film is characterized in that the composite conductive film comprises an electrode substrate, a supporting material and an organic film;
the preparation method of the composite conductive film comprises the following steps:
(1) Preparing an organic film casting solution:
dissolving polyvinylidene fluoride and polyvinylpyrrolidone in N-methyl pyrrolidone, stirring and mixing uniformly, and standing for defoaming to obtain an organic film casting solution;
(2) Preparing a composite conductive film by using a phase inversion method:
and (3) assembling the electrode substrate on a supporting material, uniformly coating the organic film casting solution prepared in the step (1) on the electrode substrate and the supporting material, then soaking the electrode substrate and the supporting material in a deionized water bath, and performing phase inversion at room temperature to obtain the composite conductive film.
2. The method according to claim 1, wherein the electrode substrate comprises a Pt/Ti metal electrode, snO 2 Ti metal electrode, ruO 2 Ti metal electrode, pbO 2 One of the Ti metal electrodes has a thickness of 50-200 μm.
3. The method according to claim 1, wherein the support material is one of a nonwoven fabric and a carbon cloth.
4. The method according to claim 1, wherein in the step (1), the weight percentages of the raw materials in the organic film casting solution are: 8-15% of polyvinylidene fluoride, 1-7% of polyvinylpyrrolidone and 78-91% of N-methyl pyrrolidone.
5. The method according to claim 1, wherein in the step (1), the stirring time is 18 to 24 hours, and the standing time is 24 to 48 hours.
6. The method according to claim 1, wherein in the step (2), the gap between the casting blades coated with the organic film casting solution is 120 to 240. Mu.m.
7. A recasting method of the composite conductive film produced by the production method according to any one of claims 1 to 6, characterized in that the support material and the organic film are removed by tearing the used composite conductive film, the electrode substrate is immersed in an organic solvent for cleaning, and the steps (1) and (2) according to claim 1 are repeated to perform recasting of the conductive film.
8. The recasting method according to claim 7, wherein said organic solvent comprises any one of dimethyl sulfoxide, N-methylpyrrolidone, and N-N dimethylformamide.
9. The recasting method according to claim 7, wherein the soaking time is 5 to 10 minutes.
10. The application of the composite conductive film prepared by the preparation method according to any one of claims 1 to 6, wherein an electrocatalytic filtration system is constructed to inactivate marine microalgae by taking the composite conductive film as an anode and taking a Ti net as a cathode.
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