CN111841341A - Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof - Google Patents

Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof Download PDF

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CN111841341A
CN111841341A CN201911020685.5A CN201911020685A CN111841341A CN 111841341 A CN111841341 A CN 111841341A CN 201911020685 A CN201911020685 A CN 201911020685A CN 111841341 A CN111841341 A CN 111841341A
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graphene oxide
amino acid
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metal complex
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CN111841341B (en
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王炳涛
舒婷
周福平
高德
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Ningbo Institute of Technology of ZJU
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/022Metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14Ultrafiltration; Microfiltration
    • B01D61/145Ultrafiltration
    • 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
    • B01D69/12Composite membranes; Ultra-thin membranes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02Inorganic material
    • B01D71/021Carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract

The invention discloses a composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and a preparation method thereof, and is characterized in that: the ultrafiltration membrane is prepared by chemically bonding amino acid and metal ions on the surface of graphene oxide, dispersing the formed graphene oxide-amino acid-metal ion complex in a high molecular solution, and then preparing the graphene oxide-amino acid-metal ion complex by a non-solvent phase conversion method. The method has the advantages of overcoming the defects of easy adhesion of organic pollutants to block membrane pores, low separation efficiency, difficult cleaning, low flux recovery rate and the like of the traditional polymer membrane material in the ultrafiltration separation process.

Description

Composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and preparation method thereof
Technical Field
The invention belongs to the technical field of functional high-molecular-weight membrane materials, and particularly relates to a composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide and a preparation method thereof.
Background
The gradual shortage of fresh water resources seriously restricts the development of global economy and the improvement of the living standard of people. The recycling of domestic sewage and industrial wastewater can effectively relieve the water resource crisis. The membrane separation technology is favored by people because of energy conservation, high efficiency, simple operation and no chemical pollution, and becomes an important means for treating the urban domestic sewage. However, the traditional polymer membrane material is very easy to generate membrane pollution in the sewage treatment process due to the hydrophobic property of the traditional polymer membrane material, so that the problems of membrane pore blockage, water flux reduction, separation efficiency reduction, difficulty in cleaning and the like are caused, and the application of the membrane separation technology is greatly limited.
The prior research proves that the introduction of a hydrophilic component into a membrane matrix and the improvement of the self-hydrophilic performance of the membrane material are important means for improving the anti-pollution performance of the membrane material. Graphene is a novel carbon nanomaterial consisting of a single layer of carbon atoms and having a lamellar structure, the thickness of the graphene is only 1nm, and the graphene has ultrahigh strength, large specific surface area and excellent gas-liquid separation performance. Graphene oxide GO is an important derivative of graphene, and the surface of the graphene oxide GO is rich in a large number of polar groups such as hydroxyl, carboxyl, epoxy and the like, so that the graphene oxide GO has good hydrophilic performance and can stably exist in an aqueous solution for a long time. Adding silver-loaded graphene oxide GO into a polyvinyl alcohol ultrafiltration membrane as reported in patent CN106582327A, a membrane separation material with excellent anti-pollution performance is obtained; however, the introduction effect of the single hydrophilic substance is not ideal, and the high flux and strong anti-fouling performance are not ideal.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the composite ultrafiltration membrane of the amino acid-metal complex bonded graphene oxide, which can overcome the defects that organic pollutants are easy to adhere to block membrane pores, the separation efficiency is low, the membrane is not easy to clean, the flux recovery rate is low and the like in the ultrafiltration separation process of the traditional polymer membrane material.
In order to achieve the purpose, the invention adopts the technical scheme that: the composite ultrafiltration membrane is prepared by chemically bonding amino acid and metal ions on the surface of graphene oxide, dispersing the formed graphene oxide-amino acid-metal ion complex in a high molecular solution, and then preparing the graphene oxide-amino acid-metal ion complex by a non-solvent phase conversion method.
The amino acid is one or more of lysine, arginine, serine and glutamic acid, and lysine is preferred.
The metal ion is Cu2+、Mg2+、Zn2+、Ni2+Preferably Zn2+
The polymer of the present invention is preferably polysulfone PSf (polysulfone is a thermoplastic resin containing a chain unit in the main chain of the molecule).
The invention also provides a preparation method of the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane, which comprises the following steps:
(1) uniformly dispersing Graphene Oxide (GO) in an aqueous solution, adding A NHS (N-hydroxysuccinimide)/EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) catalyst to activate A carboxyl functional group on the surface of GO, adding an amino acid, and reacting to generate amino acid surface modified graphene oxide GO-A;
(2) Respectively dispersing the GO-A prepared in the step 1) and metal salts in water, then dropwise adding the metal salts (metal salt aqueous solution) into the GO-A aqueous dispersion to obtain A mixed reaction solution, after completely mixing, adding ethanol, violently stirring, centrifuging, filtering and drying to obtain graphene oxide-amino acid-metal ion complex GO-A-M;
(3) selecting A high molecular polymer as A membrane matrix, dissolving the membrane matrix in dimethylacetamide (DMAc), adding GO-A-M and A pore-forming agent PVP-K30, ultrasonically dispersing, standing, vacuum defoaming, pouring the mixed solution on A glass plate, scraping the mixed solution into A liquid membrane with the thickness of 150 mu M, and then immersing the liquid membrane into A coagulating bath to be solidified into A membrane to obtain the ultrafiltration membrane.
In the invention, the graphene oxide aqueous solution in the step (1), the GO-A in the step (2) and the metal salt are respectively dispersed in water, and preferably ultrasonically dispersed.
The graphene oxide in the step (1) of the present invention: the mass ratio of the amino acids is 5: 1-1: 5, preferably 1: 1; the molar ratio of NHS/EDC in the NHS/EDC catalyst in the step (1) is 1:1, and the mass ratio of EDC to graphene oxide is 4: 1.
In the step (2), the mass ratio of GO-A to metal salt is 15: 1-5: 1, and 8:1 is preferred.
The metal ion of the metal salt in the step (2) of the invention is Cu 2+、Mg2+、Zn2+、Ni2+Preferably Zn2+
The adding amount of the ethanol in the step (2) is 1-10 mL, preferably 3 mL; the amount of ethanol added was in accordance with the ratio of the mixed reaction solution, and 30ml of the mixed reaction solution: 1-10 mL of ethanol; the specific amount of addition herein is not limited by unit, as long as the ethanol satisfies the above mixing ratio.
The addition amount of the GO-A-M in the step (3) is 0.1-3% (mass percentage content), and preferably 1%. GO-A-M is herein its content in the mixture of the final polymer, dimethylacetamide, GO-A-M and porogen PVP-K30.
The adding amount of the pore-foaming agent PVP-K30 in the step (3) is 1-5% by mass; the porogen here is its content in the final polymer, dimethylacetamide, GO-A-M and the porogen PVP-K30.
All materials of the coagulation bath in the step (3) of the invention are one or more of deionized water, ethanol and isobutanol, and deionized water is preferred.
The invention has the advantages and beneficial effects that:
1. according to the invention, the amino acid-metal ion complex is adopted to modify the graphene oxide, the modification mode further improves the polar components on the surface of the graphene oxide, and endows the graphene oxide with better hydrophilic performance, the reaction condition is mild, the operation is simple and convenient, the graphene oxide can be uniformly dispersed in a polymer ultrafiltration membrane matrix through conventional solution blending, the agglomeration phenomenon is avoided, and the compatibility is good.
2. The ultrafiltration membrane containing graphene-amino acid prepared by the invention has large water flux (the highest pure water flux is 215 L.m)-2·h-1) The removal rate of organic pollutants is high (the highest retention rate of bovine serum albumin BSA can reach 95%), the cleaning is easy after pollution, the recovery rate of water flux is high (the lowest irreversible pollution proportion is 7.3%, the highest recovery rate of water flux can reach 94%), and the like. In addition, the ultrafiltration membrane still keeps higher membrane flux and pollution resistance after multiple tests, and the ultrafiltration membrane has simple preparation process, good repeatability and easy realization of large-scale production.
3. According to the invention, A specific catalyst is adopted to activate carboxyl functional groups on the surface of GO, and the catalyst enables the carboxyl on the surface of GO to become more active and easy to generate chemical reaction, so that amino acid surface modified graphene oxide GO-A is generated by the reaction, and the combination of the amino acid surface modified graphene oxide GO-A and the graphene oxide GO-A is more compact through the chemical reaction. The ethanol is added in the step (2) of the invention, so that the GO-amino acid-metal salt complex generated after the reaction can be completely dispersed in water, and the complex reaction is more sufficient.
4. In the prior art, amino acid is grafted on graphene oxide by an alkaline method, but the regularity of a carbon sheet layer of the graphene oxide is damaged under an alkaline condition, so that the use effect of the graphene oxide is influenced; in addition, the amino acid is not a chemical reaction but a physical reaction under the alkaline condition, and is combined together through the hydrogen bonding between the graphene oxide and the amino acid, the amino acid connected by the method is not firm and is easy to change along with the change of the pH value of the solution, and the connected amino acid is easy to fall off in the subsequent application process. The method is carried out under a neutral condition, and the amino acid is connected to the graphene oxide through a chemical reaction (carboxyl on the graphene oxide reacts with amine on the amino acid to form an amide chemical bond), so that the graphene oxide is firm and cannot fall off. In addition, metal ions are introduced on the basis of graphene oxide-amino acid, amino acid chemically grafted on the surface of graphene oxide and metal ions are subjected to a complex reaction to form an amino acid-metal ion complex, so that the graphene oxide-amino acid-metal ions are mutually fused on a molecular level and firmly exist without falling, and the simple physical mixing is not performed.
Drawings
FIG. 1 SEM and AFM images of the surface, cross-sectional profile of PSf ultrafiltration membrane and PSf/GO-Lys-Zn ultrafiltration membrane.
FIG. 2 is a graph comparing water flux and BSA retention for PSf ultrafiltration membranes and PSf/GO-Lys-Zn ultrafiltration membranes.
FIG. 3 is a graph comparing the water flux recovery rate and the reversible fouling rate of PSf ultrafiltration membranes and PSf/GO-Lys-Zn ultrafiltration membranes.
Detailed Description
The present invention will be described in further detail below by way of examples, but the present invention is not limited to only the following examples.
As mentioned in the invention
Example 1
Graphene oxide surface lysine-zinc ion functionalization: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.25g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. And then adding 50mg of lysine Lys, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Lys. Then ZnCl is put into2Slowly dripping the aqueous solution into GO-Lys water dispersion (the mass ratio of GO-Lys: ZnCl)2And (8: 1), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Lys-Zn.
Preparation of PSf-based ultrafiltration membrane: uniformly ultrasonically dispersing GO-Lys-Zn with the mass percent concentration of 1% in DMAc solution of polysulfone PSf with the mass percent concentration of 19%, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8h after completely dissolving, pouring the solution after standing on a glass plate, scraping the film with the thickness controlled at 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 215 L.m -2·h-1The retention rate of BSA is 95%, the irreversible contamination ratio is 7.3%, and the recovery rate of water flux is 94%. The methods and standards for detecting the water flux, the retention rate, the reversible pollution and the like are tested according to the GB/T32360-2015 ultrafiltration membrane test method.
Example 2
And (3) carrying out lysine-copper ion functionalization on the surface of graphene oxide: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by ultrasonic wave, and preparingTo a 1mg/mL GO dispersion, 0.25g NHS/EDC catalyst was added and stirred at 20 ℃ for 30 min. And then adding 50mg of lysine Lys, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Lys. Then adding CuCl2Slowly dripping the aqueous solution into GO-Lys water dispersion (the mass ratio of GO-Lys: CuCl)21: 8), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Lys-Cu. Preparation of PSf-based ultrafiltration membrane: uniformly dispersing 1% of GO-Lys-Cu in DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic waves, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after completely dissolving, pouring liquid on a glass plate, scraping the film, controlling the thickness to be 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 197 L.m -2·h-1The retention rate of BSA is 91%, the irreversible contamination ratio is 14%, and the recovery rate of water flux is 90%.
Example 3
Carrying out serine-zinc ion functionalization on the surface of graphene oxide: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.5g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. And then adding 100mg of serine Ser, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Ser. Then ZnCl is put into2Slowly dripping the aqueous solution into GO-Ser water dispersion (the mass ratio of GO-Ser: ZnCl)21: 5), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Ser-Zn. Preparation of PSf-based ultrafiltration membrane: uniformly dispersing 1% of GO-Ser-Zn in DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic waves, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after completely dissolving, pouring liquid on a glass plate, scraping a membrane, controlling the thickness to be 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 173 L.m-2·h-1The retention rate of BSA is 92%, the irreversible contamination ratio is 21%, and the recovery rate of water flux is 89%.
Example 4
Carrying out serine-magnesium ion functionalization on the surface of graphene oxide: uniformly dispersing 50mg of graphene oxide GO in an aqueous solution by using ultrasound to prepare 1mg/mL GO dispersion liquid, then adding 0.5g of NHS/EDC catalyst, and stirring for 30min at 20 ℃. And then adding 100mg of serine Ser, stirring for 24 hours at normal temperature, centrifuging, washing with water, and drying to obtain GO-Ser. Then MgCl2Slowly dripping the aqueous solution into GO-Ser water dispersion (the mass ratio of GO-Ser to MgCl)21: 8), adding 3mL of ethanol after the solution is completely mixed, stirring for 3min, centrifuging, filtering and drying to obtain GO-Ser-Mg. Preparation of PSf-based ultrafiltration membrane: uniformly dispersing 1% of GO-Ser-Mg in DMAc solution with the concentration of 19% of polysulfone PSf by ultrasonic waves, simultaneously adding 3% of PVP-K30 pore-forming agent, standing and defoaming for 8 hours after completely dissolving, pouring liquid on a glass plate, scraping a membrane, controlling the thickness to be 150 mu m, and then immersing the glass plate into deionized water to prepare the ultrafiltration membrane containing graphene-amino acid. The pure water flux of the ultrafiltration membrane is 204 L.m-2·h-1The retention rate of BSA is 91%, the irreversible contamination ratio is 13%, and the recovery rate of water flux is 93%.
FIGS. 1-3 are graphs comparing the structural performance of the ultrafiltration membranes prepared in example 1 (PSf/GO-Lys-Zn ultrafiltration membrane) with that of a pure polymer ultrafiltration membrane (PSf ultrafiltration membrane). As can be seen from the attached figure 1, compared with a pure PSf ultrafiltration membrane, the surface pore density and the pore diameter of the ultrafiltration membrane prepared in the embodiment 1 are both obviously increased, which plays an important role in greatly improving the water flux of the ultrafiltration membrane; furthermore, the example 1 ultrafiltration membrane has longer and denser throughout the fingers of the sub-layer compared to the cross-sectional area of the membrane, which helps to reduce the flow resistance of the permeate water and increase the water flux of the membrane. The cross-sectional view of the ultrafiltration membrane of example 1 shows no agglomerated GO-Lys-Zn particles or lamellae, which is almost the same as the cross-sectional view of a pure PSf ultrafiltration membrane, indicating that the added GO-Lys-Zn has good compatibility with the PSf matrix. The AFM profile of the ultrafiltration membrane of example 1 also clearly shows that the surface roughness of the PSf/GO-Lys-Zn ultrafiltration membrane is not increased but rather decreased compared to the pure PSf ultrafiltration membrane, which indicates that GO-Lys-Zn is well fused with the PSf matrix.
FIG. 2 demonstrates that the ultrafiltration membrane prepared in example 1 of this patent exhibits a greatly improved retention of both water flux and BSA over pure polymer ultrafiltration membranes.
Fig. 3 shows that the ultrafiltration membrane prepared in the patent example 1 has excellent anti-pollution performance, and the water flux recovery rate is obviously improved compared with that of a pure polymer ultrafiltration membrane, wherein the irreversible pollution rate is greatly reduced, and the reversible pollution rate is greatly improved.

Claims (10)

1. The composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide is characterized in that: the ultrafiltration membrane is prepared by chemically bonding amino acid and metal ions on the surface of graphene oxide, dispersing the formed graphene oxide-amino acid-metal ion complex in a high molecular solution, and then preparing the graphene oxide-amino acid-metal ion complex by a non-solvent phase conversion method.
2. The amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane of claim 1, wherein: the amino acid is one or more of lysine, arginine, serine and glutamic acid, preferably lysine.
3. The amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane of claim 1, wherein: the metal ion is Cu2+、Mg2+、Zn2+、Ni2+Preferably Zn 2+
4. The graphene-amino acid containing high flux anti-pollution ultrafiltration membrane of claim 1, wherein: the polymer in the polymer solution is polysulfone.
5. A preparation method of a composite ultrafiltration membrane of amino acid-metal complex bonded graphene oxide is characterized by comprising the following steps: the method comprises the following steps:
(1) uniformly dispersing Graphene Oxide (GO) in an aqueous solution, adding an NHS/EDC catalyst to activate carboxyl functional groups on the surface of GO, adding amino acid, and reacting to generate amino acid surface modified graphene oxide GO-A;
(2) respectively dispersing the GO-A prepared in the step (1) and metal salt in water, dropwise adding the metal salt into GO-A water dispersion to obtain mixed reaction liquid, after completely mixing, adding ethanol, violently stirring, centrifuging, filtering and drying to obtain graphene oxide-amino acid-metal ion complex GO-A-M;
(3) selecting A high molecular polymer as A membrane matrix, dissolving the membrane matrix in dimethylacetamide, then adding GO-A-M and A pore-forming agent PVP-K30, ultrasonically dispersing, standing, vacuum defoaming, then pouring the mixed solution on A glass plate, scraping into A liquid membrane with the thickness of 150 mu M, and then immersing into A coagulating bath to solidify into A membrane to obtain the ultrafiltration membrane.
6. The method for preparing the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane according to claim 5, wherein the method comprises the following steps: and (3) respectively dispersing the graphene oxide aqueous solution in the step (1), the GO-A in the step (2) and the metal salt in water by adopting ultrasonic dispersion.
7. The method for preparing the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane according to claim 5, wherein the method comprises the following steps: the graphene oxide in the step (1): the mass ratio of the amino acids is 5: 1-1: 5, preferably 1: 1; the molar ratio of NHS/EDC in the NHS/EDC catalyst in the step (1) is 1:1, and the mass ratio of EDC to graphene oxide is 4: 1.
8. The method for preparing the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane according to claim 5, wherein the method comprises the following steps: in the step (2), the mass ratio of GO-A to metal salt is 15: 1-5: 1, and 8:1 is preferred.
9. The method for preparing the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane according to claim 5, wherein the method comprises the following steps: the metal ion of the metal salt in the step (2) is Cu2+、Mg2+、Zn2+、Ni2+Preferably Zn2+
10. The method for preparing the amino acid-metal complex bonded graphene oxide composite ultrafiltration membrane according to claim 5, wherein the method comprises the following steps: the adding amount of the ethanol in the step (2) is 1-10 mL, preferably 3 mL; the addition amount of the GO-A-M in the step (3) is 0.1-3% (mass percentage content), and preferably 1%; the adding amount of the pore-foaming agent PVP-K30 in the step (3) is 1-5% by mass; and (3) all materials of the coagulating bath in the step (3) are one or more of deionized water, ethanol and isobutanol, and preferably deionized water.
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CN113311036A (en) * 2021-05-23 2021-08-27 山东化工职业学院 MOFs/GO composite gas sensitive material and preparation method and application thereof
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