CN114917773A - Method for in-situ preparation of graphdiyne separation membrane - Google Patents

Method for in-situ preparation of graphdiyne separation membrane Download PDF

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CN114917773A
CN114917773A CN202210494826.2A CN202210494826A CN114917773A CN 114917773 A CN114917773 A CN 114917773A CN 202210494826 A CN202210494826 A CN 202210494826A CN 114917773 A CN114917773 A CN 114917773A
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graphite alkyne
coating
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CN114917773B (en
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王同华
李琳
刘晓玮
项楠
齐洋
王子昊
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Dalian University of Technology
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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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • 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
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract

The invention relates to a method for preparing a graphite alkyne separation membrane in situ, belonging to the technical field of membrane separation. A method for preparing a graphite alkyne separation membrane in situ comprises the steps of preparing impermeable grooves which are regularly distributed on a surface B of a flat metal substrate, and coating a protective layer on the surface B; preparing a graphite alkyne film on the surface A of the other surface of the metal substrate by a liquid phase synthesis method, and coating a porous polymer on the surface of the graphite alkyne film to serve as a supporting layer; and removing the protective layer on the surface B, and enabling the original impermeable groove to form a through hole to obtain the graphite alkyne separation membrane. The graphite alkyne separation membrane prepared by the method can effectively protect the ultrathin graphite alkyne membrane, avoids the problem that a two-dimensional membrane needs to be transferred, effectively avoids defects caused in the transfer process of the graphite alkyne separation membrane, further improves the separation performance of the graphite alkyne membrane, lays a foundation for in-situ preparation of other ultrathin material separation membranes, and is relatively simple in process conditions, convenient to operate and suitable for popularization and application.

Description

Method for in-situ preparation of graphite alkyne separation membrane
Technical Field
The invention relates to a method for preparing a graphite alkyne separation membrane in situ, belonging to the technical field of membrane separation.
Background
Graphyne (GDY) is prepared from graphene, graphene oxide, MXene, and MoS 2 After waiting for the two-dimensional material, a new two-dimensional material is provided. The graphoynes are a large family, and the predicted structures are many, including graphoynes, alpha-graphoynes (alpha-GDY), beta-graphoynes (beta-GDY), gamma-graphoynes (gamma-GDY), and the like. Different from other two-dimensional materials which realize separation tasks through the defect holes of the sheet layers and the distance between the adjusting layers, the separation device can adjust the size of the hole structure through changing different synthetic monomers so as to realize various separation requirements. The graphdiyne is a novel all-carbon film material, is a natural high-selectivity separation material at the molecular level due to a unique layered structure and a rich distributed pore structure, and is an ideal separation film material for realizing various gas separation requirements.
The current graphite alkyne prepared by liquid phase synthesis (application patent No. CN201010102048.5) grows on a metal substrate and cannot be directly used for gas separation. The graphite alkyne synthesized on the metal substrate needs to be peeled and transferred from the compact metal substrate through a plurality of steps, and the steps are easy to cause cracks or defects on the ultrathin graphite alkyne film, thereby seriously affecting the gas separation performance of the graphite alkyne film. If a graphite alkyne membrane synthesized on a metal substrate can be used directly for gas separation, the intrinsic separation performance of the graphite alkyne membrane is largely maintained.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a graphite alkyne separation membrane in situ aiming at the defects in the prior art. The technical scheme of the invention is as follows:
a method for preparing a graphite alkyne separation membrane in situ comprises the steps of preparing impermeable grooves which are regularly distributed on one surface (marked as a surface B) of a flat metal substrate, and coating a protective layer on the surface; preparing a graphite alkyne film on the other surface (marked as surface A) of the metal substrate by a liquid phase synthesis method, and coating a porous polymer on the surface of the graphite alkyne film to be used as a supporting layer; and removing the protective layer on the surface B, and enabling the original impermeable groove to form a through hole to obtain the graphite alkyne separation membrane.
The substrate of the invention mainly comprises a flat metal material which can be used for producing the graphite alkyne film in the prior art, such as one of copper foil, silver foil, aluminum foil, zinc foil and nickel foil.
Preferably, coating a surface A of the flat metal substrate with a protective layer and a surface B of the flat metal substrate with a porous template layer; dropwise adding reaction liquid on the surface B of the metal substrate, allowing the reaction liquid to react with the metal substrate through the porous template layer, forming opaque grooves which are regularly distributed on the surface B of the substrate, washing off the protective layer and the template layer of the substrate by using organic washing liquid, and coating the protective layer on the surface B of the substrate; preparing the graphite alkyne on the surface A by a liquid phase synthesis method, coating a porous polymer on the surface of the graphite alkyne to be used as a supporting layer, removing and cleaning a protective layer on the surface B of the substrate by using organic washing liquid, reacting the surface B of the substrate in reaction liquid again, reacting the original groove to form a through hole, and cleaning and drying to obtain the graphite alkyne separation membrane.
Preferably, the protective layer is formed by dissolving the high molecular polymer in an organic solvent to form a solution, coating the solution on the substrate, and then evaporating the solvent, wherein the organic solvent is one of N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and N, N-Dimethylformamide (DMF); the high polymer is one of Polysulfone (PSF), Polytetrafluoroethylene (PTEF), Polyacrylonitrile (PAN), Polyimide (PI), Polyurethane (PU), polyvinylidene fluoride (PVDF) and polyether sulfone (PES).
Preferably, the support layer is obtained by solvent diffusion and continuous phase transformation of a high molecular polymer dissolved in an organic solvent, the organic solvent is one of DMAc, NMP and DMF, and the high molecular polymer is one of polyisophthaloyl metaphenylene diamine (PMIA), polyvinyl alcohol (PVA), polyvinylidene fluoride (PVDF), Polyethersulfone (PES) and Polyacrylonitrile (PAN).
Preferably, the template layer is prepared by coating a polypropylene acrylate solution on a metal substrate, exposing the metal substrate under a black dot matrix shading point, and then carrying out NaHCO (NaHCO) treatment 3 And cleaning the solution, and reacting with the reaction solution to obtain a template layer with uniform through holes on the metal substrate.
Preferably, the reaction liquid is an aqueous solution of ammonium persulfate, sodium persulfate, ferric trichloride or nitric acid.
Preferably, the organic washing solution is one of DMAc, NMP, DMF.
Preferably, the drying method is one of ordinary drying, vacuum drying or freeze drying.
The beneficial effects of the invention are as follows: the method utilizes directional pore-forming to prepare the graphite alkyne separation membrane in situ, and reacts the metal substrate for pore-forming on the premise of not damaging the graphite alkyne film to obtain the porous metal substrate, the graphite alkyne and the substrate are not separated in the preparation process, and the porous polymer plays a role in supporting and protecting.
Drawings
FIG. 1 is a digital photograph of a groove impermeable surface of the copper foil described in example 1;
fig. 2 is a photograph of the graphdiyne separation membrane prepared in example 1 (a), a digital photograph, and (b) a surface enlarged view.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but will not limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
A preferred technical scheme of the invention is as follows:
a method for preparing a graphite alkyne separation membrane in situ mainly comprises the following steps:
1) coating a protective layer: the polymer solution is stirred to completely dissolve the polymer in the organic solvent, the polymer solution is coated on one surface (A surface) of the metal substrate, and a compact protective layer is formed after the solvent is evaporated.
2) Coating a template layer: coating the solution of the poly (propyl acrylate) on the surface (surface B) of the metal substrate, drying the coated ink in the dark, printing black shading points by using film paper, and exposing the shading points and the metal substrate coated with the solution of the poly (propyl acrylate) under an ultraviolet lamp; with NaHCO 3 The solution washes off the residual ink to obtain a template layer with uniform through holes on the metal substrate.
3) Substrate directional reaction pore-forming: and dropwise adding the reaction liquid on the surface of the template layer, so that the reaction liquid performs directional reaction pore-forming on the substrate through the template layer hole to form a uniform and impermeable groove. And washing the protective layer on the surface A of the metal substrate by using an organic washing solution, washing the template layer on the surface B of the metal substrate by using a NaOH solution, and washing residual solvent by using deionized water.
4) Preparing graphdiyne: coating a compact protective layer on the B surface of the metal substrate according to the method of the step 1), and performing liquid phase synthesis (application patent number: CN201010102048.5) preparing graphite alkyne on the A surface, uniformly coating the surface of the graphite alkyne with a high molecular polymer solution, and putting the graphite alkyne into water for solvent diffusion and continuous phase conversion to obtain the membrane protected by the porous polymer coating.
5) Preparing a through hole: washing the protective layer on the surface B of the membrane obtained in the step 4) by using organic washing liquid, then washing by using deionized water, and then dropwise adding reaction liquid on the surface B of the metal substrate again, wherein the reaction liquid is subjected to directional reaction to penetrate through the groove to form a through hole.
6) Cleaning and drying: and 5) cleaning and drying the membrane sheet obtained in the step 5) to obtain the graphite alkyne separation membrane.
In the above scheme, the high molecular polymer solution in step 1) is obtained by dissolving a high molecular polymer in an organic solvent, and stirring, removing impurities, and defoaming, wherein the organic solvent is one of DMAc, NMP, and DMF, and the high molecular polymer is one of PSF, PTEF, PVA, PAN, PI, PU, PVDF, and PES.
In the scheme, the polymer solution in the step 1) is used after being subjected to centrifugal impurity removal by a high-speed centrifugal machine, and the centrifugal time is 7000-9000 rmp at the centrifugal speed for 15-60 min.
In the scheme, the polymer solution in the step 1) needs to be subjected to vacuum defoaming before coating, and the defoaming time is 5-30 min.
In the above scheme, the concentration of the polymer solution in the step 1) is 5 wt.% to 40 wt.%.
In the scheme, the stirring speed of the polymer solution in the step 1) is 200-1200 rmp during preparation, the stirring temperature is 20-100 ℃, and the stirring time is 2-48 h.
In the scheme, the solvent evaporation temperature in the step 1) is 30-80 ℃, and the evaporation time is 12-48 h.
In the scheme, the solution of poly (propyl acrylate) in step 2) is obtained by dissolving polyacrylate in an organic solvent and stirring, wherein the organic solvent is one of DMAc, NMP and DMF.
In the scheme, the stirring speed of the polypropylene acrylate solution in the step 2) is 200-1200 rmp during preparation, the stirring temperature is 20-50 ℃, and the stirring time is 2-48 h.
In the scheme, the concentration of the polypropylene acrylate solution in the step 2) is 5-30 wt.%.
In the scheme, the drying in the dark in the step 2) is carried out, the drying temperature is 20-60 ℃, and the drying time is 5-120 min.
In the scheme, the exposure temperature in the step 2) is 25 ℃, and the exposure time is 5-120 min.
In the scheme, NaHCO is used in step 2) 3 The concentration of the solution is 3-15 wt.%, the temperature of the solution is 25 ℃, and the cleaning time is 5-120 min.
In the scheme, the reaction liquid in the step 3) is an aqueous solution of one of ammonium persulfate, sodium persulfate, ferric trichloride and nitric acid, the concentration of the reaction liquid is 0.05-5 mol/L, the reaction temperature is 25 ℃, and the reaction time is 0.5-96 h.
In the scheme, the organic washing solution in the step 3) is one of DMAc, NMP and DMF.
In the scheme, the solubility of the NaOH solution in the step 3) is 3-15 wt.%, the temperature of the solution is 25 ℃, and the cleaning time is 15-60 min.
In the scheme, the cleaning in the step 3) is performed for 3-5 times by using deionized water, and the water temperature is 25 ℃.
In the above scheme, the support layer in step 4) is obtained by dissolving a high molecular polymer in an organic solvent, and performing solvent diffusion and continuous phase conversion in water, wherein the organic solvent is one of DMAc, NMP, and DMF, and the high molecular polymer is one of PMIA, PVA, PVDF, PES, and PAN.
In the scheme, the polymer solution in the step 4) is used after being subjected to centrifugal impurity removal by a high-speed centrifuge, and the centrifugal time is 7000-9000 rmp for 15-60 min.
In the scheme, the polymer solution in the step 4) needs to be subjected to vacuum defoaming before coating, and the defoaming time is 5-30 min.
In the above scheme, the solubility of the polymer solution in step 4) is 5 wt.% to 25 wt.%.
In the scheme, the stirring speed of the polymer solution in the step 4) is 200-1200 rmp during preparation, the stirring temperature is 30-80 ℃, and the stirring time is 2-48 h.
In the scheme, the solvent diffusion and continuous phase conversion time in the step 4) is 12-48 h.
In the scheme, the organic washing solution in the step 5) is the same as that in the step 3).
In the scheme, the reaction solution in the step 5) is the same as the reaction solution in the step 3); the reaction concentration is 0.1-2 mol/L, the reaction temperature is 25 ℃, and the reaction time is 3-60 min.
In the scheme, the cleaning in the step 6) is performed for 3-5 times by using deionized water, and the water temperature is 25 ℃.
In the scheme, the drying method in the step 6) is one of ordinary drying, vacuum drying or freeze drying, the ordinary drying temperature is 40 ℃, and the drying time is 4-24 hours; the vacuum drying temperature is 25 ℃, the vacuum degree is 0.1MPa, and the drying time is 2-12 h; the freeze drying temperature is-40 ℃, and the drying time is 12-48 h under the vacuum degree of 20 Pa.
Example 1:
1) coating a protective layer: a certain amount of PSF was weighed into DMAc and mechanically stirred at 50 ℃ at 1000rmp for 4h to give a homogeneous and stable solution of 15 wt.% PSF. And centrifuging the PSF solution at 7000rmp of rotation speed for 60min, taking the upper layer solution, and carrying out vacuum defoamation for 5 min. And uniformly coating the solution of the PSF on one surface (surface A) of the copper foil, and evaporating the solvent at 40 ℃ for 24 hours to form a layer of compact protective layer on the surface of the copper foil by the PSF polymer.
2) Coating a template layer: uniformly coating 15 wt% of a polypropylene acrylate solution on the other surface (B surface) of the copper foil, and drying the coated printing ink in a dark place at the drying temperature of 40 ℃ for 15 min; printing shading points with film paper, and exposing the shading points and the copper foil coated with the solution of polypropylene acrylate under an ultraviolet lamp at 25 ℃ for 5 min. 3% NaHCO at 25 deg.C 3 And cleaning in the solution for 60min to obtain a template layer with uniform through holes on the copper foil.
3) Substrate directional reaction pore-forming: FeCl of 0.05mol/L 3 The reaction liquid is dripped on the surface of the copper foil B covered by the template layer, the reaction liquid reacts with the copper foil substrate through the uniform through holes, and uniform impermeable grooves are formed after 96 hours at the temperature of 25 ℃. And washing the protective layer on the surface A of the copper foil by using a DMAc washing solution, washing the template layer on the surface B of the copper foil by using a 15% NaOH solution, washing for 3 times in deionized water at 25 ℃, and washing away residual solvent.
4) Preparing graphyne: coating a compact protective layer on the B surface of the copper foil according to the method in the step 1), and synthesizing a layer of graphdiyne on the A surface by adopting a liquid phase synthesis method. An amount of PMIA was weighed out and dissolved in DMAc and stirred mechanically at 80 ℃ and 200rmp for 48h to give a homogeneous and stable solution of 25 wt.% PMIA. And (3) centrifuging the PMIA solution at the rotating speed of 7000rmp for 60min, taking the upper layer solution, and defoaming in vacuum for 30 min. And uniformly coating the solution of PMIA on the surface of the graphite alkyne layer, and putting the graphite alkyne layer into water for solvent diffusion and continuous phase transformation for 48 hours to obtain the membrane protected by the porous polymer coating.
5) Preparing a through hole: washing the protective layer on the B surface of the membrane sheet obtained in the step 4) by using DMAc washing liquid, washing the membrane sheet in deionized water at 25 ℃ for 3 times, and washing away residual solvent. FeCl of 2mol/L is dripped on the B surface of the copper foil again 3 The reaction solution is reacted for 3min at 25 ℃, and the grooves of the copper foil are reacted and penetrated to form through holes.
6) Cleaning and drying: washing the membrane obtained in the step 5) in deionized water at 25 ℃ for 5 times, and carrying out common drying at 40 ℃ for 24 hours to obtain the graphite alkyne separation membrane, wherein the separation performance of the graphite alkyne separation membrane is shown in Table 1.
Examples 2 to 8:
according to the experimental method of the embodiment 1, the difference from the step 1) and the step 4) in the embodiment 1 is that a certain amount of PTEF, PVA, PAN, PI, PU, PVDF and PES are respectively weighed, mechanically stirred for 12 hours at 50 ℃ and 400rmp to be completely dissolved in DMAc to obtain polymer solutions with the concentration of 15 wt.%, different polymers are respectively coated on the surface of copper foil, and the solvent is evaporated for 24 hours at 40 ℃ to form a compact protective layer. The permeability of the prepared graphdiyne separation membrane is shown in table 1.
TABLE 1 separation Performance of graphite acetylene separation membranes with different protective layers
Figure BDA0003632321220000061
Examples 9 to 12:
according to the experimental method of the embodiment 1, the difference from the experimental method of the embodiment 1 is that a silver foil, an aluminum foil, a zinc foil and a nickel foil are respectively selected as metal substrates; the difference from the step 3) and the step 5) in the example 1 is that 0.5mol/L nitric acid solution is prepared and is dripped on the surfaces of different metal substrates for reaction, and the permeability of the prepared graphite alkyne separation membrane is shown in the table 2.
TABLE 2 separation Performance of graphdine separation membranes on different metal substrates
Figure BDA0003632321220000062
Examples 13 to 16:
according to the experimental method of example 1, the difference from step 3) and step 5) of example 1 is that 0.5mol/L ammonium persulfate, sodium persulfate, ferric trichloride and a nitric acid solution are respectively prepared and added dropwise to the surface of the copper foil for reaction, and the difference from step 3) and step 5) of example 1 is that NMP is used as an organic washing liquid for cleaning the protective layer. The permeability of the prepared graphdiyne separation membrane is shown in table 3.
TABLE 3 separation Performance of the graphdiyne separation membranes prepared using different reaction solutions
Figure BDA0003632321220000063
Figure BDA0003632321220000071
Examples 17 to 21:
the experimental procedure of example 1 was followed, except that amounts of PVDF, PES, PMIA, PVA and PAN were separately weighed and dissolved in DMAc and mechanically stirred at 50 ℃ and 400 rpm for 12 hours, to obtain a homogeneous stable solution of 13 wt.% of different polymers, in contrast to step 4) of example 1. And centrifuging different polymer solutions at 8000rmp for 15min, taking the upper layer solution, and defoaming for 5min in vacuum. The different solutions were uniformly coated on the side with the synthetic graphdine and placed in water for solvent diffusion and continuous phase transformation for 24 h. The difference from step 3) and step 5) in example 1 is that DMF was used as the organic washing solution for cleaning the protective layer. The permeation performance of the prepared graphdiyne separation membrane is shown in table 4.
TABLE 4 separation Performance of the graphdiyne separation membranes of different support layers
Figure BDA0003632321220000072
Examples 22 to 24:
the experimental procedure of example 1 was followed, except that the sample was dried by drying the film sheet under atmospheric pressure, vacuum drying and freeze drying, respectively, in step 6) of example 1, and except that 0.5mol/L of sodium persulfate solution was prepared and added dropwise to the surface of the copper foil to react, respectively, in step 3) and step 5) of example 1. The permeation performance of the prepared graphdiyne separation membrane is shown in table 5.
TABLE 5 separation Performance of the graphdiyne separation membranes prepared by different drying methods
Figure BDA0003632321220000073
Figure BDA0003632321220000081
Examples 25 to 27:
the experimental procedure of example 1 was followed, except that the organic solvents required for the preparation of the polymer were DMAc, DMF and NMP, respectively, in comparison with step 1) and step 4) of example 1. A PSF solution with a concentration of 15 wt.% and a PMIA solution with a concentration of 13 wt.% are obtained; different from the steps 3) and 5) in the example 1, 0.5mol/L of sodium persulfate solution is respectively prepared and added dropwise to the surface of the copper foil to react. The permeation performance of the prepared graphdiyne separation membrane is shown in table 6.
TABLE 6 separation Performance of the graphdiyne separation membranes prepared with different organic solvents
Figure BDA0003632321220000082

Claims (8)

1. A method for preparing a graphite alkyne separation membrane in situ is characterized by comprising the following steps: preparing opaque grooves which are regularly distributed on a surface B of a flat metal substrate, and coating a protective layer on the surface B; preparing a graphite alkyne film on the surface A of the other surface of the metal substrate by a liquid phase synthesis method, and coating a porous polymer on the surface of the graphite alkyne film to serve as a supporting layer; and removing the protective layer on the surface B, and enabling the original impermeable groove to form a through hole to obtain the graphite alkyne separation membrane.
2. The method of claim 1, wherein: coating a protective layer on the surface A of the flat metal substrate, and coating a porous template layer on the surface B; dripping reaction liquid on the surface B of the metal substrate, allowing the reaction liquid to react with the metal substrate through the porous template layer to form opaque grooves which are regularly distributed on the surface B of the substrate, washing off the protective layer and the template layer of the substrate by using organic washing liquid, and coating the protective layer on the surface B of the substrate; preparing the graphdiyne on the surface A by a liquid phase synthesis method, coating a porous polymer on the surface of the graphdiyne to be used as a supporting layer, removing and cleaning a protective layer on the surface B of the substrate by using organic washing liquor, reacting the surface B of the substrate in reaction liquid again, reacting the original groove to form a through hole, and cleaning and drying to obtain the graphdiyne separation membrane.
3. The method according to claim 1 or 2, characterized in that: the protective layer is formed by dissolving a high molecular polymer in an organic solvent to form a solution, coating the solution on a substrate and evaporating the solvent, wherein the organic solvent is one of N, N-dimethylacetamide, N-methylpyrrolidone and N, N-dimethylformamide; the high molecular polymer is one of polysulfone, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyurethane, polyvinylidene fluoride and polyether sulfone.
4. The method according to claim 1 or 2, characterized in that: the supporting layer is obtained by dissolving a high molecular polymer in an organic solvent through solvent diffusion in water and continuous phase transformation, wherein the organic solvent is one of DMAc, NMP and DMF; the high molecular polymer is one of polyisophthaloyl metaphenylene diamine, polyvinyl alcohol, polyvinylidene fluoride, polyether sulfone and polyacrylonitrile.
5. The method of claim 2, wherein: the template layerThe method comprises the steps of coating a polypropylene acrylate solution on a metal substrate, exposing the metal substrate under a black dot matrix shading point, and then carrying out NaHCO 3 And cleaning the solution, and reacting with the reaction solution to obtain a template layer with uniform through holes on the metal substrate.
6. The method of claim 1, wherein: the reaction liquid is an aqueous solution of ammonium persulfate, sodium persulfate, ferric trichloride or nitric acid.
7. The method of claim 1, wherein: the substrate is one of copper foil, silver foil, aluminum foil, zinc foil and nickel foil.
8. The method of claim 1, wherein: the organic washing solution is one of DMAc, NMP and DMF.
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