CN113797761A - Method for regulating and controlling performance of graphene oxide-based composite membrane - Google Patents

Method for regulating and controlling performance of graphene oxide-based composite membrane Download PDF

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CN113797761A
CN113797761A CN202110807502.5A CN202110807502A CN113797761A CN 113797761 A CN113797761 A CN 113797761A CN 202110807502 A CN202110807502 A CN 202110807502A CN 113797761 A CN113797761 A CN 113797761A
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graphene oxide
membrane
solution
based composite
solvent
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神领弟
孙雨菲
张雨停
郭静
黎素宏
黄荣
何婧
卞思琪
赖超
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Jiangsu Normal University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0079Manufacture of membranes comprising organic and inorganic components
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12Composite membranes; Ultra-thin membranes

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Abstract

A method for regulating and controlling the performance of a graphene oxide-based composite membrane comprises the following steps: spinning a polymer material into filaments, and then carrying out cold pressing treatment to obtain a nanofiber base membrane; depositing the graphene oxide nanosheet or the mixed solution of the graphene oxide nanosheet/polyelectrolyte on the electrostatic spinning nanofiber base membrane in a vacuum filtration and coating mode to form a membrane by filtration, then standing at room temperature, and drying in the shade to obtain the graphene oxide-based composite membrane. According to the method, high-flux electrostatic spinning nano-fibers are used as a base film, graphene oxide nano-sheets are used as a barrier layer, and the interlayer spacing of the graphene oxide nano-sheets is finely regulated and controlled by adopting flexible long-chain polyelectrolyte to construct a high-permeability composite filter membrane, so that the problems of extremely low permeability, poor stability and the like of the traditional graphene oxide-based composite filter membrane are solved. The preparation method is simple, feasible, effective and environment-friendly, can realize effective regulation and control of the graphene oxide lamellar nano material barrier layer, and is suitable for large-scale low-cost production of the composite nanofiltration membrane.

Description

Method for regulating and controlling performance of graphene oxide-based composite membrane
Technical Field
The invention relates to preparation of a separation composite membrane, in particular to a method for regulating and controlling the performance of a graphene oxide-based composite membrane.
Background
In recent years, graphene oxide attracts much attention due to its advantages of high specific surface area, special two-dimensional nanostructure, and rich hydrophilic oxygen-containing groups (hydroxyl, carboxyl, etc.), and they are a class of soft materials with polymer, thin film, colloid, and amphiphilic properties, and are easy to form into films, convenient for mass production, and have a broad application prospect in the technical field of membrane separation. Graphene oxide is often used as a polymer membrane additive to construct water permeation channels and increase the hydrophilicity of the surface of the composite membrane. However, as a planar two-dimensional material, the sheets of the planar two-dimensional material are closely packed to form a dense graphene oxide film after being directly filtered and filtered into a film, so that the permeability is very poor. In addition, the interaction between the sheets is weak, resulting in poor stability in water.
Disclosure of Invention
The invention aims to provide a method for effectively regulating and controlling the interlayer spacing of graphene oxide nano materials, which aims to solve the problems of poor permeability, poor stability and low water treatment efficiency of the traditional graphene oxide composite membrane in the prior art.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for regulating and controlling the performance of a graphene oxide-based composite membrane comprises the following steps:
(1) preparing a nanofiber-based membrane: dissolving a proper amount of polymer in a solvent to prepare a uniform solution with the concentration of 1-50 wt%, preparing nano fibers by using an electrostatic spinning technology, and performing cold pressing treatment to obtain a nano fiber base film;
(2) preparing a graphene oxide functional barrier layer: ultrasonically dispersing a proper amount of graphene oxide nano sheets in a solvent to prepare a solution A with the concentration of 0.001-20 mg/mL; dissolving a proper amount of long-chain polyelectrolyte in a solvent to prepare a solution B with the mass fraction of 0.01-20 wt%; ultrasonically and uniformly mixing the prepared solution A and the prepared solution B according to a certain ratio (1:0-1:500) to form a mixed solution C; depositing the solution C on the surface of the nanofiber base membrane in the step (1) in a vacuum filtration or coating mode, and drying in the shade to obtain the graphene oxide-based composite filter membrane; and soaking the prepared composite filter membrane in deionized water for later use.
Further, the polymer material in step (1) includes, but is not limited to, one or more of polysulfone, polyethersulfone, polyvinyl alcohol, polyacrylonitrile, polyvinyl alcohol, polystyrene, polyvinylidene fluoride, and the like.
Further, the polyelectrolyte in the step (2) includes, but is not limited to, one or more of polyethyleneimine, chitosan, poly (allylamine hydrochloride), polyamide, polyvinylamine, polyvinylpyridine, polydimethyldiallylammonium chloride, polyvinylpyrrolidone, polycarboxymethyl cellulose, gelatin, polystyrene sulfonate, sodium alginate, polyacrylamide, polymethacrylic acid (salt), polyvinyl sulfonic acid (salt), polyvinyl phosphoric acid (salt), carboxymethyl cellulose (salt), polyphosphate, polysilicic acid, and the like.
Further, the solvent in steps (1) and (2) includes, but is not limited to, one or more of deionized water, aqueous acetic acid, N-dimethylformamide, hexane, N-dimethylacetamide, toluene, acetone, diethyl ether, and the like.
The invention also provides the graphene oxide-based composite filter membrane prepared by the method.
Compared with the prior art, the invention has the beneficial technical effects that:
according to the method, the long-chain flexible polymer electrolyte is used as a regulator to modify the graphene oxide nanosheet functional barrier layer, so that the method has good application potential in the aspect of efficient water treatment;
the method provided by the invention has the advantages that the polyelectrolyte is used for regulating and controlling the lamella spacing of the graphene oxide nanosheets, the stability of the functional layer of the nanosheets is improved, the permeability of the functional layer of the nanosheets is improved, the method is simple and effective, energy-saving and environment-friendly, and the fine regulation and control of the surface aperture of the functional barrier layer on the surface of the composite membrane can be realized;
the invention adopts the high-permeability porous nanofiber membrane as the base membrane and has an ultrathin nanosheet barrier layer, wherein the flexible polymer can effectively regulate and control the lamella spacing, and more water permeation channels are provided, so that the prepared composite membrane has high permeability as a whole.
Drawings
FIG. 1 is an SEM photograph of the surface morphology of the GO-PEI/PAN nanofiber-based composite membrane of example 1;
FIG. 2 is the GO: influence of mass ratio of PEI on separation effect of GO-PEI/PAN composite membrane.
FIG. 3 is the separation effect of GO-CTS/PAN composite membranes on different dyes in example 2.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
Example 1
A preparation method of a high-flux graphene oxide-Polyethyleneimine (PEI)/polyacrylonitrile nanofiber-based composite filter membrane comprises the following steps:
1. dissolving polyacrylonitrile in an N, N-dimethylformamide solvent to prepare a 10 wt% solution, preparing nanofibers in an electrostatic spinning mode, and obtaining a PAN nanofiber base membrane after cold pressing;
2. dissolving PEI in deionized water to prepare a uniform solution with the mass fraction of 1%;
3. dispersing graphene oxide in water to prepare a solution of 0.05 mg/L;
4. preparing a mixed solution according to the mass ratio of GO to PEI, taking a proper amount of the mixed solution, depositing the mixed solution on the PAN nano-fiber in a vacuum filtration mode, and drying in the shade to form the GO-PEI/PAN nano-fiber composite filter membrane (figure 1).
As shown in figure 2, when the GO/PEI mass ratio is 1:0, 1:15 and 1:25 in sequence, the permeation flux of the composite filter membrane under 0.3MPa is 411.1, 173.8 and 89.2L/m respectively2h, the retention rates are 70.9%, 99.6% and 99.8% respectively. It can be found that when the mass ratio of GO to PEI is 1:15, the prepared GO-PEI/PAN nanofiber-based composite filter membrane has the best filtration performance, and the graphene oxide interlayer spacing is increased after PEI modification
Figure BDA0003166902410000031
The penetration flux is reduced by less than 30 percent after 24h test, and the antifouling paint has good antifouling performance.
Example 2
A preparation method of a high-flux Graphene Oxide (GO) -Chitosan (CTS)/Polyacrylonitrile (PAN) nanofiber-based composite filter membrane comprises the following steps:
1. dissolving polyacrylonitrile in an N, N-dimethylformamide solvent to prepare a 12 wt% solution, preparing nanofibers in an electrostatic spinning mode, and obtaining a PAN nanofiber base membrane after cold pressing;
2. dissolving chitosan in acetic acid water solution to prepare coating solution with the mass fraction of 1.0%;
3. dispersing graphene oxide in water to prepare a solution of 0.02 mg/L;
4. preparing a mixed solution according to the mass ratio of GO to CTS, taking a proper amount of the mixed solution, depositing the mixed solution on the PAN nano-fiber in a vacuum filtration mode, and drying in the shade to form the GO-CTS/PAN nano-fiber composite filter membrane.
As shown in fig. 3, the graphene oxide-chitosan/polyacrylonitrile nanofiber-based composite filter membrane was used for the filtration test of direct red 80 dye: the mass ratio of GO to CTS is 1:75, 1:100 and 0 when the mass ratio of GO to CTS is 1:125 in sequence.The permeation flux of the composite filter membrane under 3MPa is 112.9, 246.9 and 369.8L/m respectively2h, the retention rates are 99.0%, 98.2% and 99.3% respectively. It can be found that when the mass ratio of GO to CTS is 1:125, the prepared GO-CTS/PAN nanofiber-based composite filter membrane has the best filtration performance, and the graphene oxide interlayer spacing is increased after chitosan modification
Figure BDA0003166902410000032
And the permeation flux is still maintained at a higher level (141.2L/m) after 24h test2h) And the antifouling paint shows good antifouling performance.
For pure GO membrane, when the retention rate is more than 99%, the permeation flux is only 28.5L/m under 0.3MPa2h, the result shows that the method is really effective in regulating and controlling the graphene oxide functional barrier layer.
Example 3
A preparation method of a high-flux GO-polyacrylic acid (PAA)/polyether sulfone (PES) nanofiber-based composite filter membrane comprises the following steps:
1. dissolving polyether sulfone in an N, N-dimethylacetamide solvent to prepare a 26 wt% solution, preparing nanofibers through an electrostatic spinning mode, and obtaining a PES nanofiber base membrane after cold pressing;
2. dissolving PAA in deionized water to prepare a uniform solution with the mass fraction of 0.2%;
3. dispersing GO in water to prepare a 0.1mg/L solution;
4. preparing a mixed solution according to the GO/PAA mass ratio, taking a proper amount of the mixed solution, depositing the mixed solution on PES nano fibers in a vacuum filtration mode, and drying in the shade to form the GO-PAA/PES nano fiber composite filter membrane.
When the mass ratio of GO to PAA is 1:0.25, 1:0.5 and 1:0.75 in sequence, the permeation flux of the composite filter membrane under 0.1MPa is respectively 256.2, 271.3 and 275.9L/m2h, the retention rates are 86.5%, 98.9% and 96.3% respectively. It can be found that when the mass ratio of GO to PAA is 1:0.5, the prepared GO-PAA/PES nanofiber-based composite filter membrane has the best filtration performance, and the interlayer spacing of graphene oxide modified by PAA is increased after analysis
Figure BDA0003166902410000041

Claims (11)

1. A method for regulating and controlling the performance of a graphene oxide-based composite membrane is characterized by comprising the following steps:
s1: dissolving a proper amount of polymer in a solvent to prepare a uniform solution, preparing nano fibers through electrostatic spinning, and obtaining a nano fiber base film after cold pressing treatment;
s2: ultrasonically dispersing a proper amount of graphene oxide nanosheets in a solvent to prepare a solution A; dissolving a proper amount of long-chain polyelectrolyte in a solvent to prepare a solution B; ultrasonically and uniformly mixing the prepared solution A and the prepared solution B according to a certain proportion to form a mixed solution C; and depositing the solution C on the surface of the nanofiber base membrane prepared in the step S1, and drying in the shade to obtain the graphene oxide-based composite filter membrane.
2. The method according to claim 1, wherein the step S1 includes: dissolving a proper amount of polymer in a solvent to prepare a uniform solution with the concentration of 1-50 wt%, preparing nano fibers through electrostatic spinning, and performing cold pressing treatment to obtain the nano fiber base film.
3. The method of claim 1, wherein the concentration of solution a is 0.001-20 mg/mL.
4. The method according to claim 1, wherein the mass fraction of the solution B is 0.01 to 20 wt%.
5. The method according to claim 1, wherein the ratio in step S2 is 1:0 to 1: 500.
6. The method of claim 1, wherein the step S2 is carried out by depositing solution C on the surface of the nanofiber-based membrane prepared in step S1 by vacuum filtration or coating.
7. The method as claimed in claim 1, wherein the step S2 further comprises immersing the prepared graphene oxide-based composite filter membrane in deionized water for use.
8. The method of claim 1, wherein the polymer is at least one of polysulfone, polyethersulfone, polyvinyl alcohol, polyacrylonitrile, polyvinyl alcohol, polystyrene, polyethylene oxide, and polyvinylidene fluoride.
9. The method of claim 1, wherein the polyelectrolyte is at least one of polyethyleneimine, chitosan, polyallylamine hydrochloride, polyamide, polyvinylamine, polyvinylpyridine, polydimethyldiallylammonium chloride, polyvinylpyrrolidone, polyacrylic acid/salt, polyacrylic acid carboxymethylcellulose, gelatin, polystyrene sulfonate, sodium alginate, polyacrylamide, polymethacrylic acid/salt, polyvinylsulfonic acid/salt, polyvinylphosphoric acid/salt, carboxymethylcellulose/salt, polyphosphate, polysilicic acid.
10. The method of claim 1, wherein the solvent is at least one of deionized water, aqueous acetic acid, N-dimethylformamide, hexane, N-dimethylacetamide, toluene, acetone, and diethyl ether.
11. A graphene oxide-based composite filtration membrane prepared by the method of any one of claims 1 to 10.
CN202110807502.5A 2021-07-16 2021-07-16 Method for regulating and controlling performance of graphene oxide-based composite membrane Pending CN113797761A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN114774951A (en) * 2022-03-14 2022-07-22 东华大学 Graphene-based bipolar membrane and preparation method and application thereof
CN114887498A (en) * 2022-06-21 2022-08-12 青岛大学 Graphene oxide/sodium alginate composite nanofiltration membrane with controllable water flux or rejection rate
CN115025635A (en) * 2022-06-30 2022-09-09 常州大学 Preparation method of bridge organic silicon/GO composite nanofiltration membrane
CN115121134A (en) * 2022-07-04 2022-09-30 重庆工商大学 Preparation method of novel MXene-based composite membrane
CN117621592A (en) * 2023-12-28 2024-03-01 苏州羽燕特种材料科技有限公司 Antistatic high-barrier TPU film laminated composite fabric and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114774951A (en) * 2022-03-14 2022-07-22 东华大学 Graphene-based bipolar membrane and preparation method and application thereof
CN114887498A (en) * 2022-06-21 2022-08-12 青岛大学 Graphene oxide/sodium alginate composite nanofiltration membrane with controllable water flux or rejection rate
CN114887498B (en) * 2022-06-21 2023-09-22 青岛大学 Graphene oxide/sodium alginate composite nanofiltration membrane with controllable water flux or retention rate
CN115025635A (en) * 2022-06-30 2022-09-09 常州大学 Preparation method of bridge organic silicon/GO composite nanofiltration membrane
CN115025635B (en) * 2022-06-30 2023-08-18 常州大学 Preparation method of bridge organic silicon/GO composite nanofiltration membrane
CN115121134A (en) * 2022-07-04 2022-09-30 重庆工商大学 Preparation method of novel MXene-based composite membrane
CN117621592A (en) * 2023-12-28 2024-03-01 苏州羽燕特种材料科技有限公司 Antistatic high-barrier TPU film laminated composite fabric and preparation method thereof

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