CN110756067B - Preparation method and application of graphene oxide-based two-dimensional composite membrane embedded with sulfonated polymer cross-linked network - Google Patents

Preparation method and application of graphene oxide-based two-dimensional composite membrane embedded with sulfonated polymer cross-linked network Download PDF

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CN110756067B
CN110756067B CN201911045580.5A CN201911045580A CN110756067B CN 110756067 B CN110756067 B CN 110756067B CN 201911045580 A CN201911045580 A CN 201911045580A CN 110756067 B CN110756067 B CN 110756067B
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冉瑾
吴玉莹
黄强
张朋朋
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Hefei University of Technology
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Abstract

The invention discloses a graphene oxide based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network and preparation and application thereof. Compared with the prior art, the graphene oxide-based two-dimensional composite membrane embedded with the sulfonated polymer cross-linked network has higher ion permeation rate and more excellent selectivity.

Description

Preparation method and application of graphene oxide-based two-dimensional composite membrane embedded with sulfonated polymer cross-linked network
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to a preparation method and application of a graphene oxide-based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network.
Background
With the improvement of the industrialization level, the separation and recycling of metal ions in wastewater have attracted extensive attention, and the current methods for separating metal ions in wastewater mainly include an activated carbon adsorption method, a precipitation method, a membrane separation technology and the like. Although the activated carbon adsorption method has the advantages of low investment and small occupied area, the activated carbon adsorption speed is low, the adsorption capacity is small, and the method is not suitable for treating wastewater with high pollutant concentration; although the precipitation method has wide ion removal range and high efficiency, the precipitation method is easy to generate secondary pollution and consume a large amount of precipitator in the treatment process; the membrane separation technology plays an increasingly important role in wastewater treatment due to the advantages of simple process, high efficiency, low cost and low energy consumption.
The core of the membrane separation technology is the selection of membrane materials, and a two-dimensional membrane constructed by graphene oxide has the advantages of regular two-dimensional channels, controllable interlamination, rich oxygen-containing functional groups and the like, so that the research interest of people is aroused. However, the graphene oxide membrane is easily swollen in an aqueous solution, resulting in low selectivity between metal ions. Meanwhile, graphene oxide lamellae are prone to interact with ions, and therefore transmission of the ions is hindered, and ion flux is low. Therefore, graphene oxide membranes need to be modified and controlled to improve ion flux and selectivity.
Journal of Carbon materials (Carbon,2016,101, 290) -295) reports that different sieving of metal ions is realized by constructing a graphene oxide membrane with a cross-linked structure, and the graphene oxide membrane is sequentially soaked in a dicarboxylic acid and diamine solution under the action of an acid catalyst so as to realize cross-linking of graphene oxide. Compared with a pure graphene oxide membrane, the screening performance of the crosslinked graphene oxide membrane on metal ions with different valence states is improved, but the ion flux is still lower and is only 10-2mol·m-2·h-1And the preparation process is complicated, the membrane controllability is poor, and the mass production is not facilitated.
CN108295812A discloses a graphene oxide composite membrane for selectively removing metal ions in water and a preparation method thereof, wherein the method mainly comprises the steps of uniformly dispersing graphene oxide, an ammonia-carboxyl complexing agent and an organic polymeric flocculant in a solvent to obtain a mixed dispersion liquid, and preparing the mixed dispersion liquid into a membrane. Although this method can remove heavy metal ions in water, it does not have a sieving effect on metal ions among alkali metals, alkaline earth metals, and transition metals.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a graphene oxide-based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network, aiming at obtaining a two-dimensional composite membrane with higher ion permeation rate and excellent selectivity.
In order to realize the purpose of the invention, the following technical scheme is adopted:
the invention discloses a preparation method of a graphene oxide-based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network, which is characterized by comprising the following steps: adding sodium styrene sulfonate and divinylbenzene into a colloidal solution of graphene oxide, carrying out free radical polymerization under the initiation of an initiator azobisisobutyronitrile, and depositing a polymerized mixed dispersion liquid on a porous substrate to obtain the graphene oxide-based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network. The method specifically comprises the following steps:
step 1, ultrasonically dispersing graphene oxide powder in an organic solvent to obtain a graphene oxide nanosheet dispersion liquid;
step 2, dissolving sodium styrene sulfonate in an organic solvent to obtain a sodium styrene sulfonate solution; the structural formula of the sodium styrene sulfonate is as follows:
Figure BDA0002254052090000021
step 3, pouring the sodium styrene sulfonate solution obtained in the step 2 into the graphene oxide nanosheet dispersion liquid obtained in the step 1 to obtain a mixed solution;
step 4, adding divinylbenzene into the mixed solution obtained in the step 3, uniformly mixing, then adding azobisisobutyronitrile, and heating and reacting at 60-110 ℃ for 2-6 hours to obtain a mixed membrane liquid; the structural formula of divinylbenzene is as follows:
Figure BDA0002254052090000022
and 5, loading the mixed membrane liquid obtained in the step 4 on a porous base membrane through a nanosheet assembly technology, and drying to remove redundant solvent to obtain the graphene oxide-based two-dimensional composite membrane embedded in the sulfonated polymer cross-linked network. The sulfonated polymer cross-linked network has the following structural formula:
Figure BDA0002254052090000023
further: in the step 3, the concentration of the mixed solution is 0.01-1mg/mL, and the mass ratio of the sodium styrene sulfonate to the graphene oxide in the mixed solution is 1: 0.1-50; in the step 4, the mass ratio of the added divinylbenzene to the sodium styrene sulfonate is 0.005-0.1:1, and the mass ratio of the added azobisisobutyronitrile to the sodium styrene sulfonate is 0.01-0.2: 1.
Further, in the step 1, the ultrasonic temperature is 20-50 ℃ and the ultrasonic time is 0.5-3 h.
Further, in step 5, the nanosheet assembly technique is vacuum filtration, spin coating, spraying or evaporation drying.
Further, in the step 5, the drying is carried out for 12-48h at the temperature of 40-80 ℃.
Further, the organic solvent in step 1 and step 2 is N, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
Further, in step 5, the porous base membrane is selected from one of a nylon membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane, a polycarbonate membrane, an anodic aluminum oxide membrane and a polyacrylonitrile membrane, and the pore diameter of the porous base membrane is 50-450 nm.
The invention also discloses an application of the graphene oxide-based two-dimensional composite membrane embedded with the sulfonated polymer cross-linked network prepared by the preparation method, and the graphene oxide-based two-dimensional composite membrane is used for separating metal ions with different sizes and charge properties in water.
Further, the metal ion includes Na+、K+、Li+、Ca2+、Mg2+、Cd2+、Cu2+、Al3+、Fe3+、Cr3+。
Compared with the prior art, the invention has the beneficial effects that:
1. the two-dimensional ordered channel of the graphene oxide membrane can effectively improve the permeation rate of ions, the polymer with the sulfonic acid group has different affinities with different metal ions, and the metal ions can be screened after the sulfonated polymer cross-linked network is formed. The invention constructs the graphene oxide based two-dimensional composite membrane embedded with the sulfonated polymer cross-linked network by combining the two, thereby improving the ion permeability and the selectivity.
2. Compared with journal of Carbon materials (Carbon,2016,101, 290-one) 295, the graphene oxide-based two-dimensional composite membrane embedded in the sulfonated polymer cross-linked network can regulate and control the interlayer spacing by changing the intercalation amount of the sodium styrene sulfonate, thereby obviously improving the ion flux, and compared with a pure graphene oxide membrane, the permeation rate can reach 10-1mol·m-2·h-1The improvement is one order of magnitude; meanwhile, the raw materials are cheap, and the operation process is simple.
3. Compared with the graphene oxide composite membrane for selectively removing metal ions in water and the preparation method thereof disclosed in the Chinese patent CN108295812A, the graphene oxide-based two-dimensional composite membrane embedded with the sulfonated polymer cross-linked network can remove heavy metal ions, the separation factor between alkali metal ions and alkaline earth metal ions can reach 5, the separation factor between alkali metal ions and transition metal ions can reach 10 at most, and the screening among the alkali metal ions, the alkaline earth metal ions and the transition metal ions can be realized.
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FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of a graphene oxide-based two-dimensional composite membrane (1:1) embedded with a sulfonated polymer crosslinked network obtained in example 1;
FIG. 2 is a graph showing the surface-scanning element distribution (Mapping) of the graphene oxide-based two-dimensional composite membrane (1:1) intercalated with a crosslinked network of a sulfonated polymer obtained in example 1.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) embedded in a sulfonated polymer crosslinked network was prepared as follows:
step 1, weighing 20mg of graphene oxide powder, and ultrasonically dispersing the graphene oxide powder in N, N-dimethylformamide to obtain graphene oxide nanosheet dispersion liquid, wherein the ultrasonic temperature is 30 ℃ and the ultrasonic time is 1 h;
step 2, weighing 20mg of sodium styrene sulfonate powder (the mass ratio of the graphene oxide to the sodium styrene sulfonate is 1:5), and dispersing the powder in N, N-dimethylformamide to obtain a sodium styrene sulfonate solution;
step 3, pouring the sodium styrene sulfonate solution obtained in the step 2 into the graphene oxide nanosheet dispersion liquid to obtain a mixed solution, wherein the concentration of the mixed solution is 0.5 mg/mL;
step 4, adding N, N-dimethylformamide into the divinylbenzene solution, diluting to the concentration of 9.6mg/mL, then adding 0.1mL into the mixed solution obtained in the step 3, adding 0.96mg of azobisisobutyronitrile after uniformly mixing, finally placing into a three-neck flask, and introducing N2Making protective gas, and reacting for 4 hours at 85 ℃ in an oil bath pan to obtain mixed membrane liquid;
and 5, loading the mixed membrane liquid obtained in the step 4 on a Nylon (Nylon) base membrane with the aperture of 220nm by a vacuum filtration method, drying at 60 ℃ for 12h, and removing redundant solvent to obtain the graphene oxide-based two-dimensional composite membrane (1:1) embedded with the sulfonated polymer cross-linked network.
FIG. 1 is a Scanning Electron Microscope (SEM) cross-sectional view of the two-dimensional composite film (1:1) obtained in this example, showing a uniform two-dimensional layered structure and a film thickness of about 5 μm.
FIG. 2 is a graph showing the surface scanning element distribution (Mapping) of the two-dimensional composite film (1:1) obtained in this example, in which S elements are uniformly distributed between layers.
The two-dimensional composite membrane (1:1) of this example was applied to a salt solution for separating NaCl: the two-dimensional composite membrane (1:1) obtained in this example was charged into a diffusion dialysis apparatus, and a salt solution of NaCl at a concentration of 0.2mol/L and a deionized water solution were charged into both sides of the membrane, respectively. The results show that the permeation rate of the sulfonated polymer crosslinked network-intercalated graphene oxide-based two-dimensional composite membrane (1:1) obtained in the example to NaCl is 0.144mol m-2·h-1While the permeation rate of pure graphene oxide membrane to NaCl is only 0.021 mol.m-2·h-1The permeation rate was increased by a factor of 7.
Example 2
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 1.
The two-dimensional composite membrane (1:1) of this example was applied to a salt solution for separation of LiCl: the two-dimensional composite membrane (1:1) obtained in this example was charged into a diffusion dialysis apparatus, and a salt solution of LiCl and a deionized water solution at a concentration of 0.2mol/L were charged into both sides of the membrane, respectively. As a result, the permeation rate of the sulfonated polymer crosslinked network-intercalated graphene oxide-based two-dimensional composite membrane (1:1) obtained in this example to LiCl was 0.171 mol. m-2·h-1While the permeation rate of pure graphene oxide film to LiCl is only 0.027mol · m-2·h-1The permeation rate was increased by 8 times.
Example 3
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 1.
The two-dimensional composite membrane (1:1) of this example was applied to a salt solution for separation of KCl: the two-dimensional composite membrane (1:1) obtained in this example was charged into a diffusion dialysis apparatus, and a salt solution of KCl with a concentration of 0.2mol/L and a deionized water solution were charged into both sides of the membrane, respectively. The results show that the permeation rate of the sulfonated polymer crosslinked network-intercalated graphene oxide-based two-dimensional composite membrane (1:1) obtained in the example to KCl is 0.024mol · m-2·h-1While the permeation rate of pure graphene oxide film to KCl is only 0.011 mol.m-2·h-1。
Example 4
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 1.
Application of the two-dimensional composite membrane (1:1) of this example to the separation of MgCl2Salt solution: the two-dimensional composite membrane (1:1) obtained in this example was placed in a diffusion dialysis apparatus, and MgCl was placed at a concentration of 0.2mol/L on each side of the membrane2Salt solution and deionized water solution. ResultsIt is shown that the graphene oxide-based two-dimensional composite membrane (1:1) vs. MgCl embedded with the sulfonated polymer crosslinked network obtained in this example2Has a permeation rate of 0.034mol · m-2·h-1While pure graphene oxide film pairs MgCl2Has a penetration rate of only 0.011mol m-2·h-1The permeation rate of the composite membrane is improved by 3 times, and Li+/Mg2+A separation factor of 5 is reached.
Example 5
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 1.
The two-dimensional composite membrane (1:1) of the embodiment is applied to separating CaCl2Salt solution: the two-dimensional composite membrane (1:1) obtained in this example was placed in a diffusion dialysis apparatus, and CaCl was placed at a concentration of 0.2mol/L on each side of the membrane2Salt solution and deionized water solution. The results show that the sulfonated polymer crosslinked network-embedded graphene oxide-based two-dimensional composite membrane (1:1) prepared in the example is aligned with CaCl2Has a penetration rate of 0.032mol · m-2·h-1And pure graphene oxide film on CaCl2Has a penetration rate of only 0.013mol · m-2·h-1。
Example 6
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 1.
The two-dimensional composite membrane (1:1) of the present example was applied to the separation of CrCl3Salt solution: the two-dimensional composite membrane (1:1) obtained in this example was placed in a diffusion dialysis apparatus, and CrCl was placed at a concentration of 0.2mol/L on each side of the membrane3Salt solution and deionized water solution. The results show that the sulfonated polymer crosslinked network-embedded graphene oxide-based two-dimensional composite membrane (1:1) versus CrCl prepared in the example3Has a permeation rate of 0.024mol · m-2·h-1And pure graphene oxide film pair CrCl3Has a penetration rate of only 0.007mol m-2·h-1。
Example 7
In this example, a graphene oxide-based two-dimensional composite membrane (1:1) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 1.
The two-dimensional composite membrane (1:1) of the embodiment is applied to separating FeCl3Salt solution: the two-dimensional composite membrane (1:1) obtained in this example was placed in a diffusion dialysis apparatus, and FeCl was placed at a concentration of 0.2mol/L on each side of the membrane3Salt solution and deionized water solution. The results show that the graphene oxide-based two-dimensional composite membrane (1:1) embedded with the sulfonated polymer cross-linked network obtained in the example is paired with FeCl3Has a permeation rate of 0.029mol m-2·h-1While pure graphene oxide film pairs FeCl3Has a penetration rate of only 0.003mol m-2·h-1。
Example 8
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) embedded in a sulfonated polymer crosslinked network was prepared as follows:
step 1, weighing 20mg of graphene oxide powder, and ultrasonically dispersing the graphene oxide powder in N, N-dimethylformamide to obtain graphene oxide nanosheet dispersion liquid, wherein the ultrasonic temperature is 30 ℃ and the ultrasonic time is 1 h;
step 2, weighing 100mg of sodium styrene sulfonate powder (the mass ratio of graphene oxide to sodium styrene sulfonate is 1:5), and dispersing in N, N-dimethylformamide to obtain a sodium styrene sulfonate solution;
step 3, pouring the sodium styrene sulfonate solution obtained in the step 2 into the graphene oxide nanosheet dispersion liquid to obtain a mixed solution, wherein the concentration of the mixed solution is 0.5 mg/mL;
step 4, adding N, N-dimethylformamide into the divinylbenzene solution, diluting to the concentration of 9.6mg/mL, then adding 0.5mL into the mixed solution obtained in the step 3, adding 5mg of azobisisobutyronitrile after uniformly mixing, then placing into a three-neck flask, introducing N2Making protective gas, and reacting for 4 hours at 85 ℃ in an oil bath pan to obtain mixed membrane liquid;
and 5, loading the mixed membrane liquid obtained in the step 4 on a Nylon (Nylon) base membrane with the aperture of 220nm by a vacuum filtration method, drying at 60 ℃ for 12h, and removing redundant solvent to obtain the graphene oxide-based two-dimensional composite membrane (1:5) embedded with the sulfonated polymer cross-linked network.
The two-dimensional composite membrane (1:5) of this example was applied to a salt solution for separating NaCl: the two-dimensional composite membrane (1:5) obtained in this example was charged into a diffusion dialysis apparatus, and a salt solution of NaCl at a concentration of 0.2mol/L and a deionized water solution were charged into both sides of the membrane, respectively. As a result, the permeation rate of the sulfonated polymer crosslinked network-intercalated graphene oxide-based two-dimensional composite membrane (1:5) obtained in this example to NaCl was 0.210 mol. m-2·h-1While the permeation rate of pure graphene oxide membrane to NaCl is only 0.021 mol.m-2·h-1The permeation rate was increased by a factor of 10.
Example 9
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 8.
The two-dimensional composite membrane (1:5) of this example was applied to a salt solution for separation of LiCl: the two-dimensional composite membrane (1:5) obtained in this example was charged into a diffusion dialysis apparatus, and a salt solution of LiCl and a deionized water solution at a concentration of 0.2mol/L were charged into both sides of the membrane, respectively. As a result, the permeation rate of the sulfonated polymer crosslinked network-intercalated graphene oxide-based two-dimensional composite membrane (1:5) obtained in this example to LiCl was 0.229 mol. m-2·h-1While the permeation rate of pure graphene oxide film to LiCl is only 0.027mol · m-2·h-1The permeation rate was increased by a factor of 10.
Example 10
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 8.
The two-dimensional composite membrane (1:5) of this example was applied to a salt solution for separation of KCl: the two-dimensional composite membrane (1:5) obtained in this example was charged into a diffusion dialysis apparatus, and a salt solution of KCl with a concentration of 0.2mol/L and a deionized water solution were charged into both sides of the membrane, respectively. The results show that the permeation rate of the sulfonated polymer crosslinked network-intercalated graphene oxide-based two-dimensional composite membrane (1:5) obtained in the example to KCl is 0.111mol·m-2·h-1While the permeation rate of pure graphene oxide film to KCl is only 0.011 mol.m-2·h-1The permeation rate of the composite membrane is improved by 10 times.
Example 11
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 8.
Application of the two-dimensional composite membrane (1:5) of this example to the separation of MgCl2Salt solution: the two-dimensional composite membrane (1:5) obtained in this example was placed in a diffusion dialysis apparatus, and MgCl was placed at a concentration of 0.2mol/L on each side of the membrane2Salt solution and deionized water solution. The results show that the graphene oxide-based two-dimensional composite membrane (1:5) embedded with the sulfonated polymer cross-linked network obtained in the example is aligned to MgCl2Has a permeation rate of 0.052mol · m-2·h-1While pure graphene oxide film pairs MgCl2Has a penetration rate of only 0.011mol m-2·h-1The permeation rate of the composite membrane is improved by 5 times, and Li+/Mg2+A separation factor of 4 is reached.
Example 12
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 8.
The two-dimensional composite membrane (1:5) of the embodiment is applied to separating CaCl2Salt solution: the two-dimensional composite membrane (1:5) obtained in this example was placed in a diffusion dialysis apparatus, and CaCl was placed at a concentration of 0.2mol/L on each side of the membrane2Salt solution and deionized water solution. The results show that the sulfonated polymer crosslinked network-embedded graphene oxide-based two-dimensional composite membrane (1:5) prepared in the example is aligned with CaCl2Has a permeation rate of 0.076mol m-2·h-1And pure graphene oxide film on CaCl2Has a penetration rate of only 0.013mol · m-2·h-1The permeation rate of the composite membrane is improved by 7 times.
Example 13
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 8.
The two-dimensional composite membrane (1:5) of the present example was used for separating CrCl3Salt solution: the two-dimensional composite membrane (1:5) obtained in this example was placed in a diffusion dialysis apparatus, and CrCl was placed at a concentration of 0.2mol/L on each side of the membrane3Salt solution and deionized water solution. The results show that the sulfonated polymer crosslinked network-embedded graphene oxide-based two-dimensional composite membrane (1:5) versus CrCl prepared in the example3Has a permeation rate of 0.034mol · m-2·h-1And pure graphene oxide film pair CrCl3Has a penetration rate of only 0.007mol m-2·h-1The permeation rate of the composite membrane is improved by 5 times.
Example 14
In this example, a graphene oxide-based two-dimensional composite membrane (1:5) having a sulfonated polymer crosslinked network intercalated therein was prepared in the same manner as in example 8.
The two-dimensional composite membrane (1:5) of the embodiment is applied to separating FeCl3Salt solution: the two-dimensional composite membrane (1:5) obtained in this example was placed in a diffusion dialysis apparatus, and FeCl was placed at a concentration of 0.2mol/L on each side of the membrane3Salt solution and deionized water solution. The results show that the graphene oxide-based two-dimensional composite membrane (1:5) embedded with the sulfonated polymer cross-linked network obtained in the example is paired with FeCl3The permeation rate of (A) is 0.026mol · m-2·h-1While pure graphene oxide film pairs FeCl3Has a penetration rate of only 0.003mol m-2·h-1The permeation rate of the composite membrane is improved by 10 times, and Li+/Fe3+Up to a separation factor of 10.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a graphene oxide based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network is characterized by comprising the following steps: adding sodium styrene sulfonate and divinylbenzene into a colloidal solution of graphene oxide, carrying out free radical polymerization under the initiation of an initiator azobisisobutyronitrile, and depositing a polymerized mixed dispersion liquid on a porous substrate to obtain the graphene oxide-based two-dimensional composite membrane embedded with a sulfonated polymer cross-linked network.
2. The method of claim 1, comprising the steps of:
step 1, ultrasonically dispersing graphene oxide powder in an organic solvent to obtain a graphene oxide nanosheet dispersion liquid;
step 2, dissolving sodium styrene sulfonate in an organic solvent to obtain a sodium styrene sulfonate solution;
step 3, pouring the sodium styrene sulfonate solution obtained in the step 2 into the graphene oxide nanosheet dispersion liquid obtained in the step 1 to obtain a mixed solution;
step 4, adding divinylbenzene into the mixed solution obtained in the step 3, uniformly mixing, then adding azobisisobutyronitrile, and heating and reacting at 60-110 ℃ for 2-6 hours to obtain a mixed membrane liquid;
and 5, loading the mixed membrane liquid obtained in the step 4 on a porous base membrane through a nanosheet assembly technology, and drying to remove redundant solvent to obtain the graphene oxide-based two-dimensional composite membrane embedded in the sulfonated polymer cross-linked network.
3. The method of claim 2, wherein:
in the step 3, the concentration of the mixed solution is 0.01-1mg/mL, and the mass ratio of the sodium styrene sulfonate to the graphene oxide in the mixed solution is 1: 0.1-50;
in the step 4, the mass ratio of the added divinylbenzene to the sodium styrene sulfonate is 0.005-0.1:1, and the mass ratio of the added azobisisobutyronitrile to the sodium styrene sulfonate is 0.01-0.2: 1.
4. The method of claim 2, wherein: in the step 1, the ultrasonic temperature is 20-50 ℃ and the ultrasonic time is 0.5-3 h.
5. The method of claim 2, wherein: and in the step 5, the nano sheet assembly technology is vacuum filtration, spin coating, spraying or evaporation drying.
6. The method of claim 2, wherein: in step 5, the drying is carried out for 12-48h at the temperature of 40-80 ℃.
7. The method of claim 2, wherein: in the step 1 and the step 2, the organic solvent is N, N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
8. The method of claim 2, wherein: in the step 5, the porous base membrane is selected from one of a nylon membrane, a polyether sulfone membrane, a polyvinylidene fluoride membrane, a polycarbonate membrane, an anodic aluminum oxide membrane and a polyacrylonitrile membrane, and the aperture of the porous base membrane is 50-450 nm.
9. The application of the graphene oxide-based two-dimensional composite membrane embedded with the sulfonated polymer cross-linked network prepared by the preparation method of any one of claims 1 to 8 is characterized in that: for separating metal ions of different sizes and charge properties.
10. Use according to claim 9, characterized in that: the metal ion comprises Na+、K+、Li+、Ca2+、Mg2+、Ni2+、Cd2+、Cu2+、Al3+、Fe3+、Cr3+。
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