CN112915787A - Preparation method of porous graphene oxide nanofiltration membrane - Google Patents
Preparation method of porous graphene oxide nanofiltration membrane Download PDFInfo
- Publication number
- CN112915787A CN112915787A CN202110183596.3A CN202110183596A CN112915787A CN 112915787 A CN112915787 A CN 112915787A CN 202110183596 A CN202110183596 A CN 202110183596A CN 112915787 A CN112915787 A CN 112915787A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- membrane
- porous graphene
- concentrated acid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0039—Inorganic membrane manufacture
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a porous graphene oxide nanofiltration membrane, wherein in-plane pore-forming of graphene oxide nanosheets is realized by chemically etching the graphene oxide nanosheets with concentrated acid, the concentrated acid and the graphene oxide are mainly used as basic materials, and under the action of ultrasonic crushing force, the concentrated acid can react with unsaturated carbon atoms at the existing defect positions and edge positions of the graphene oxide, so that part of carbon atoms are separated from the graphene oxide sheets, and finally in-plane pore-forming of the graphene oxide nanosheets is realized. Pumping the prepared porous graphene oxide nanosheet through a vacuum-assisted self-assembly processAnd filtering to obtain the porous graphene oxide nanofiltration membrane on the base membrane. The preparation method is simple and convenient, and compared with a graphene oxide membrane, the pure water permeation flux of the membrane is from 20.0Lm‑2h‑1bar‑1Increased to 120.9Lm‑2h‑ 1bar‑1The retention rate of methyl blue, chrome black T, Congo red and Alxin blue is more than 95%; can be widely used in the field of dye separation.
Description
Technical Field
The invention relates to a preparation method of a porous graphene oxide nanofiltration membrane, and belongs to the technical field of membrane separation.
Background
With the growth of population, water shortage has become the second greatest challenge of energy supply worldwide after 21 st century, and water quality deterioration is a common challenge facing mankind. About 12 million people around the world face the problems of insufficient water for drinking and the like. Meanwhile, the shortage of water resources seriously threatens the industries of food, energy and the like, and is related to the production, living and environment of human beings. With the development of society, economic growth and improvement of human living standard, human activities are more frequent, and the problems of water ecological environment damage and water resource shortage are more and more severe, so that resource development and utilization of water resources become urgent requirements for sustainable development of modern industry.
In recent years, to address the global water pollution challenge, pressure-driven water treatment membranes have been developed, one of the most common membrane technologies in water treatment applications. The pressure driving membrane technology has the advantages of convenient operation, compact structure, strong shock resistance, small chemical storage tank and water supply facility, low chemical discharge amount and the like while obtaining high-quality water by treatment. The pressure-driven membrane can be classified into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane according to the difference of pore diameters. The pore size of the micro-filtration membrane is generally more than 50nm, and the micro-filtration membrane can be used for removing suspended solids, microorganisms and bacteria in water. The pore diameter of the ultrafiltration membrane is between 2 and 50nm, and the ultrafiltration membrane can be used for oil-water separation and virus and some gel removal. Nanofiltration membranes have a pore size of about 2nm and are commonly used for removing water-soluble organic substances such as dyes. The reverse osmosis membrane has a pore diameter of 1nm or less (about 0.3 to 0.6nm), and is widely used in desalination and ultrapure water production processes.
The dye used in the fields of spinning, rubber, paper making, leather tanning and the like in the world has more than 10000 varieties and the annual production capacity is 7 multiplied by 105Ton. The annual dye yield of China is about 15 ten thousand tons, which is the first major country in the printing and dyeing textile industry, and 10% -15% of dye is discharged in the form of waste water. Taking the textile industry as an example, 1 ton of products are produced, and the average yield is highGrow about 300m3The wastewater of (2). According to incomplete statistics, the daily discharge amount of the printing and dyeing wastewater in China is about 3 multiplied by 106m3. Dye molecules are considered as the largest pollution source of printing and dyeing wastewater, the transparency and the oxygen content of water can be influenced to a certain extent when the printing and dyeing wastewater with color is directly discharged into a freshwater system, and the dye has the characteristics of high molecular structure, high molecular weight, low biodegradability, mutagenicity and carcinogenicity and has toxic and side effects on animals and plants existing in a water body. Therefore, the requirements of energy conservation and emission reduction are considered, if the part of wastewater is recycled by the nanofiltration membrane technology, on one hand, the pollution and the harm of dye can be reduced, and on the other hand, the water consumption of the printing and dyeing industry can be effectively saved.
The Graphene Oxide (GO) has the excellent characteristics of strong mechanical property, high specific surface area and flexibility, ultralow water mass transfer resistance, easiness in large-scale production and the like. Since the first report in 2007, GO membranes have been widely used in the fields of gas separation, batteries, water treatment, and seawater desalination. The two-dimensional layered structure forms unique two-dimensional nanopores between GO layers, allowing molecules or ions to selectively pass through. In order to increase the flux of graphene oxide membranes, researchers have conducted two kinds of research. The first is to regulate the lamella spacing and the second is to regulate the channel length. In order to optimize the interlayer spacing of GO membranes for different separation purposes, researchers have designed a variety of intercalants with different physicochemical properties, including ions and small molecules, polymers, nanomaterials, and the like. However, the research on regulating the channel length and reducing the channel length to increase the flux of graphene oxide is relatively few, namely, the thickness of the film is reduced, and the research proves that the flux of the film is exponentially increased along with the reduction of the thickness, namely, the reduction of the channel length, and the graphene oxide film with the thickness of only 8nm is prepared. The thickness of the membrane is further reduced, and the prepared membrane easily generates a penetrating non-selective defect because the diameter of the graphene oxide is far larger than that of a defect hole of 1 nm. Another method is to use ion bombardment or chemical etching, but this method is expensive, has high requirements for reaction conditions, and produces low porosity with only one hole per hundred square nanometer size area, and has non-uniform pore diameter. But even at such porosity, the flux of the membrane is significantly increased, thus demonstrating that increasing the flux of graphene oxide membranes by decreasing the channel length is effective. Therefore, if a graphene oxide film with a porous structure can be prepared in a cheap and efficient pore-forming manner, the graphene oxide film has a wide application prospect in the field of water treatment.
Disclosure of Invention
The invention aims to provide a preparation method of a porous graphene oxide nanofiltration membrane, the preparation method is simple, convenient and easy to operate, the prepared porous graphene oxide nanofiltration membrane has higher permeation flux compared with a pure unmodified graphene oxide membrane, and the rejection rates of methyl blue, Congo red, chrome black T and Alsinoblue are all over 95%, so that the preparation of the porous graphene oxide with excellent separation performance is realized.
In order to solve the technical problem, according to the preparation method of the porous graphene oxide film provided by the invention, the graphene oxide nanosheets are chemically etched by concentrated acid to realize in-plane pore-forming of the graphene oxide nanosheets, so that the porous graphene oxide nanosheets are prepared; and carrying out suction filtration on the obtained porous graphene oxide nanosheet to a base membrane through a vacuum-assisted self-assembly process to obtain the porous graphene oxide nanofiltration membrane.
Further, the realization of the in-plane pore-forming of the graphene oxide nanosheets by the chemical etching of the graphene oxide nanosheets with concentrated acid is as follows: the method is characterized in that concentrated acid and graphene oxide are used as basic materials, and the concentrated acid reacts with unsaturated carbon atoms existing in the graphene oxide under the action of ultrasonic crushing force, so that part of the carbon atoms are separated from graphene oxide sheets, and finally, in-plane pore forming of graphene oxide nanosheets is realized.
The preparation method of the porous graphene oxide film comprises the following specific steps:
step one, mixing concentrated acid and graphene oxide dispersion liquid with the concentration of 0.5-2.5 mg/mL by a chemical concentrated acid etching method under stirring, wherein the volume ratio of the graphene oxide dispersion liquid to the concentrated acid is 1: 1-1: 10; carrying out ultrasonic reaction on the mixture for 0.5-2h, standing at room temperature, removing concentrated acid in the mixture in a centrifugal separation mode to obtain porous graphene oxide nanosheets, and drying for later use;
and step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking a certain amount of porous graphene oxide nanosheet aqueous dispersion, performing suction filtration on the base membrane through a vacuum-assisted self-assembly process, and placing the base membrane in an oven for drying to obtain the porous graphene oxide nanofiltration membrane.
Further, the concentrated acid is any one or combination of concentrated sulfuric acid, concentrated nitric acid and concentrated phosphoric acid.
The base membrane material is any one of polyether sulfone, mixed cellulose, cellulose acetate and polycarbonate.
The reaction time of the graphene oxide dispersion liquid and the concentrated acid mixture under the ultrasonic condition is preferably 2 h.
The porous graphene oxide nanofiltration membrane prepared by the invention has pure water permeation flux of 30.5-120.9Lm-2h- 1bar-1And the retention rate of the dye to methyl blue, chrome black T, Congo red and Alxin blue is more than 95 percent.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the porous graphene oxide nanofiltration membrane is simple, convenient and easy to operate, and compared with a pure graphene oxide nanofiltration membrane, the prepared nanofiltration membrane has the advantages that the permeation flux is remarkably improved; and compare in traditional polymer nanofiltration membrane, porous oxidation graphite alkene nanofiltration membrane has overcome the big, water transfer channel irregularity scheduling problem of membrane thickness of traditional polymer nanofiltration membrane. The nanofiltration membrane prepared by the method can be used in the field of dye separation and has wide water treatment application prospect.
Drawings
FIG. 1 is a graph of the separation performance of the p-GO-1 membrane and graphene oxide membrane GO prepared in example 1;
FIG. 2 is a graph of the separation performance of the p-GO-2 membrane and graphene oxide membrane GO prepared in example 2;
FIG. 3 is a graph of the separation performance of the p-GO-3 membrane and graphene oxide membrane GO prepared in example 3;
FIG. 4 is a graph of the separation performance of the p-GO-4 membrane and graphene oxide membrane GO prepared in example 4.
FIG. 5 is a graph of the separation performance of the p-GO-5 membrane and graphene oxide membrane GO prepared in example 5.
Detailed Description
The design idea of the invention is as follows: graphene oxide is used as a material, in-plane pore forming is realized on graphene oxide nanosheets by concentrated acid under the assistance of ultrasound, and the porous graphene oxide membrane with different permeation fluxes is prepared by changing the addition amount of the concentrated acid. The porous graphene oxide membrane prepared by the invention can be widely used for dye separation, and the preparation method is convenient and simple.
The technical solution of the present invention is further described in detail with reference to the following specific embodiments, which are only illustrative and not intended to limit the present invention.
Comparative example, a graphene oxide film was prepared by the following steps:
preparing the graphene oxide into an aqueous solution with the concentration of 0.5mg/mL, taking 40 mu L of graphene oxide solution, carrying out vacuum filtration on the mixed cellulose microfiltration membrane through a vacuum-assisted self-assembly process, and then placing the mixed cellulose microfiltration membrane in an oven for drying for 12 hours at the temperature of 60 ℃ to prepare the graphene oxide nanofiltration membrane. For convenience in subsequent performance evaluation, the graphene oxide nanofiltration membrane is referred to as GO.
The graphene oxide membrane obtained in the comparative example has a relatively flat surface, and the permeation flux of the membrane is 20.0Lm-2h- 1bar-1。
step one, mixing concentrated nitric acid and graphene oxide dispersion liquid with the concentration of 0.5mg/mL under the stirring condition according to the volume ratio of 1:1 (concentrated nitric acid: graphene oxide) by a chemical concentrated acid etching method, and carrying out ultrasonic reaction on the mixture at room temperature for 2 hours. After the ultrasonic reaction, standing the mixture at room temperature, removing concentrated acid from the obtained product in a centrifugal separation mode to prepare a porous graphene oxide nanosheet, and drying the porous graphene oxide nanosheet for later use;
step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking 40 mu L of the dispersion, performing suction filtration on the mixed cellulose microfiltration membrane through a vacuum-assisted self-assembly process, and placing the mixed cellulose microfiltration membrane in an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the porous graphene oxide nanofiltration membrane. For convenience in subsequent performance evaluation, the porous graphene oxide nanofiltration membrane is referred to as p-GO-1.
The porous graphene oxide nanofiltration membrane prepared in the embodiment 1 has good film-forming property. Compared with the graphene oxide membrane prepared by the comparative example, the permeation flux of the membrane is improved from 20.0 to 30.5Lm-2h-1bar-1And the retention rates of the dye to methyl blue, chrome black T, Congo red, Alxin blue and the like are all more than 95%, and the performances are shown in figure 1 and table 1.
step one, mixing concentrated nitric acid and graphene oxide dispersion liquid with the concentration of 1mg/mL under the stirring condition according to the volume ratio of 4:1 (concentrated nitric acid: graphene oxide) by a chemical concentrated acid etching method, and carrying out ultrasonic reaction on the mixture at room temperature for 2 hours. After the ultrasonic reaction, standing the mixture at room temperature, removing concentrated acid from the obtained product in a centrifugal separation mode to prepare a porous graphene oxide nanosheet, and drying the porous graphene oxide nanosheet for later use;
step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking 40 mu L of the dispersion, performing suction filtration on the mixed cellulose microfiltration membrane through a vacuum-assisted self-assembly process, and placing the mixed cellulose microfiltration membrane in an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the porous graphene oxide nanofiltration membrane. For convenience in subsequent performance evaluation, the porous graphene oxide nanofiltration membrane is referred to as p-GO-2.
Example 2 preparation of the porous graphene oxide nanofiltration membraneThe membrane performance is good and the porosity of the membrane is further increased. Compared with the graphene oxide membrane prepared by the comparative example, the permeation flux of the membrane is improved from 20.0 to 47.4Lm-2h- 1bar-1And the retention rates of the dye to methyl blue, chrome black T, Congo red, Alxin blue and the like are all more than 95%, and the performances are shown in figure 2 and table 1.
step one, mixing concentrated nitric acid and graphene oxide dispersion liquid with the concentration of 1.5mg/mL under the stirring condition according to the volume ratio of 6:1 (concentrated nitric acid: graphene oxide) by a chemical concentrated acid etching method, and carrying out ultrasonic reaction on the mixture at room temperature for 2 hours. After the ultrasonic reaction, standing the mixture at room temperature, removing concentrated acid from the obtained product in a centrifugal separation mode to prepare a porous graphene oxide nanosheet, and drying the porous graphene oxide nanosheet for later use;
step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking 40 mu L of the dispersion, performing suction filtration on the mixed cellulose microfiltration membrane through a vacuum-assisted self-assembly process, and placing the mixed cellulose microfiltration membrane in an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the porous graphene oxide nanofiltration membrane. For convenience in subsequent performance evaluation, the porous graphene oxide nanofiltration membrane is referred to as p-GO-3.
The porous graphene oxide nanofiltration membrane prepared in the embodiment 3 has good film-forming performance, and the porosity of the membrane is further increased. Compared with the graphene oxide membrane prepared by the comparative example, the permeation flux of the membrane is improved from 20.0 to 84.4Lm-2h- 1bar-1And the retention rates of the dye to methyl blue, chrome black T, Congo red, Alxin blue and the like are all more than 95%, and the performances are shown in figure 3 and table 1.
step one, mixing concentrated nitric acid and graphene oxide dispersion liquid with the concentration of 2mg/mL under the stirring condition according to the volume ratio of 8:1 (concentrated nitric acid: graphene oxide) by a chemical concentrated acid etching method, and reacting the mixture for 2 hours under the room temperature ultrasonic condition. After the ultrasonic reaction, standing the mixture at room temperature, removing concentrated acid from the obtained product in a centrifugal separation mode to prepare a porous graphene oxide nanosheet, and drying the porous graphene oxide nanosheet for later use;
step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking 40 mu L of the dispersion, performing suction filtration on the mixed cellulose microfiltration membrane through a vacuum-assisted self-assembly process, and placing the mixed cellulose microfiltration membrane in an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the porous graphene oxide nanofiltration membrane. For convenience in subsequent performance evaluation, the porous graphene oxide nanofiltration membrane is referred to as p-GO-4.
The porous graphene oxide nanofiltration membrane prepared in the embodiment 4 has good film-forming performance and higher membrane porosity. Compared with the graphene oxide membrane prepared by the comparative example, the permeation flux of the membrane is improved from 20.0 to 93.3Lm-2h-1bar-1And the retention rates of the dye to methyl blue, chrome black T, Congo red, Alxin blue and the like are all more than 95%, and the performances are shown in figure 4 and table 1.
step one, mixing concentrated nitric acid and graphene oxide dispersion liquid with the concentration of 2.5mg/mL under the stirring condition according to the volume ratio of 10:1 (concentrated nitric acid: graphene oxide) by a chemical concentrated acid etching method, and reacting the mixture for 2 hours under the room temperature ultrasonic condition. After the ultrasonic reaction, standing the mixture at room temperature, removing concentrated acid from the obtained product in a centrifugal separation mode to prepare a porous graphene oxide nanosheet, and drying the porous graphene oxide nanosheet for later use;
step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking 40 mu L of the dispersion, performing suction filtration on the mixed cellulose microfiltration membrane through a vacuum-assisted self-assembly process, and placing the mixed cellulose microfiltration membrane in an oven to dry for 12 hours at the temperature of 60 ℃ to obtain the porous graphene oxide nanofiltration membrane. For convenience in subsequent performance evaluation, the porous graphene oxide nanofiltration membrane is referred to as p-GO-5.
The porous graphene oxide nanofiltration membrane prepared in the embodiment 5 is good in membrane forming performance and high in membrane porosity. Compared with the graphene oxide membrane prepared by a comparative example, the permeation flux of the porous graphene oxide nanofiltration membrane is improved from 20.0 to 120.9Lm-2h-1bar-1And the retention rates of the dye to methyl blue, chrome black T, Congo red, Alxin blue and the like are all more than 95%, and the performances are shown in figure 5 and table 1.
The flux and separation performance of the porous graphene oxide membranes prepared in the examples of the present invention and the graphene oxide membranes prepared in the comparative examples are compared as shown in table 1:
TABLE 1
In conclusion, the preparation method of the porous graphene oxide nanofiltration membrane provided by the invention has the advantages that the preparation conditions are mild, the preparation process is simple and feasible, and the preparation of the high-flux porous graphene oxide membrane can be realized by utilizing a concentrated acid etching mode under the assistance of ultrasound. According to the preparation method, the in-plane pore channels of the graphene oxide nanosheets are introduced, so that the permeation flux of the membrane is improved, meanwhile, the retention rate of the membrane on dye molecules is ensured by the interlayer spacing of the porous graphene oxide membrane, and finally, the synergistic optimization of the separation performance of the porous graphene oxide nanofiltration membrane is realized.
While the invention has been described in connection with the drawings and tables, the present invention is not limited to the embodiments described above, which are intended to be illustrative rather than restrictive, and many modifications may be made by those skilled in the art without departing from the spirit of the invention within the scope of the appended claims.
Claims (7)
1. PorousThe preparation method of the graphene oxide nanofiltration membrane is characterized in that in-plane pore-forming of the graphene oxide nanosheets is realized by chemically etching the graphene oxide nanosheets with concentrated acid, so that porous graphene oxide nanosheets are prepared; performing suction filtration on the obtained porous graphene oxide nanosheet to a base membrane through a vacuum-assisted self-assembly process to obtain a porous graphene oxide nanofiltration membrane; the pure water permeation flux of the membrane is 30.5-120.9Lm-2h-1bar-1And the retention rate of the dye to methyl blue, chrome black T, Congo red and Alxin blue is more than 95 percent.
2. The preparation method according to claim 1, wherein the in-plane pore-forming of the graphene oxide nanoplatelets by the concentrated acid chemical etching of the graphene oxide nanoplatelets is: the method is characterized in that concentrated acid and graphene oxide are used as basic materials, and the concentrated acid reacts with unsaturated carbon atoms existing in the graphene oxide under the action of ultrasonic crushing force, so that part of the carbon atoms are separated from graphene oxide sheets, and finally, in-plane pore forming of graphene oxide nanosheets is realized.
3. The method of claim 1, comprising the steps of:
step one, mixing concentrated acid and graphene oxide dispersion liquid with the concentration of 0.5-2.5 mg/mL by a chemical concentrated acid etching method under stirring, wherein the volume ratio of the graphene oxide dispersion liquid to the concentrated acid is 1: 1-1: 10; carrying out ultrasonic reaction on the mixture for 0.5-2h, standing at room temperature, removing concentrated acid in the mixture in a centrifugal separation mode to obtain porous graphene oxide nanosheets, and drying for later use;
and step two, preparing the porous graphene oxide nanosheet obtained in the step one into a porous graphene oxide nanosheet aqueous dispersion with the concentration of 0.5mg/mL, taking a certain amount of porous graphene oxide nanosheet aqueous dispersion, performing suction filtration on the base membrane through a vacuum-assisted self-assembly process, and placing the base membrane in an oven for drying to obtain the porous graphene oxide nanofiltration membrane.
4. The preparation method according to claim 1, wherein the concentrated acid is any one or combination of concentrated sulfuric acid, concentrated nitric acid and concentrated phosphoric acid.
5. The preparation method according to claim 1, wherein in the first step, the ultrasonic reaction time is 2 h.
6. The preparation method according to claim 1, wherein the base film material is any one of polyethersulfone, mixed cellulose, cellulose acetate and polycarbonate.
7. The preparation method according to claim 1, wherein in the second step, the temperature of the oven drying is 60 ℃ and the time is 12 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110183596.3A CN112915787A (en) | 2021-02-08 | 2021-02-08 | Preparation method of porous graphene oxide nanofiltration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110183596.3A CN112915787A (en) | 2021-02-08 | 2021-02-08 | Preparation method of porous graphene oxide nanofiltration membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112915787A true CN112915787A (en) | 2021-06-08 |
Family
ID=76171517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110183596.3A Pending CN112915787A (en) | 2021-02-08 | 2021-02-08 | Preparation method of porous graphene oxide nanofiltration membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112915787A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522059A (en) * | 2021-07-02 | 2021-10-22 | 五邑大学 | Folded graphene oxide film and preparation method thereof |
| CN113648850A (en) * | 2021-09-01 | 2021-11-16 | 北京理工大学 | Preparation method of MXene/reduced porous graphene oxide (r-HGO) composite membrane with high flux and high removal rate |
| CN115121125A (en) * | 2022-06-28 | 2022-09-30 | 天津工业大学 | Preparation method for assembling and film-forming graphene oxide by gamma ray irradiation etching |
| CN115888432A (en) * | 2023-02-20 | 2023-04-04 | 浙江国辐环保科技有限公司 | Carbon-based nanofiltration membrane and preparation method and application thereof |
| CN116586054A (en) * | 2023-07-17 | 2023-08-15 | 中国科学院理化技术研究所 | Membrane catalytic material for rapid high-yield synthesis of aspirin at room temperature |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706264A (en) * | 2014-01-14 | 2014-04-09 | 中国海洋大学 | Layer-by-layer self-assembling oxidized graphene nano-filtration membrane and preparation method thereof |
| CN104874301A (en) * | 2014-02-28 | 2015-09-02 | 中国科学院上海高等研究院 | Graphene oxide film, preparation method and applications thereof |
| US20170144107A1 (en) * | 2015-11-24 | 2017-05-25 | National University Of Singapore | Graphene-based membrane and method of preparation thereof |
| CN107720886A (en) * | 2017-10-17 | 2018-02-23 | 山东大学 | A kind of nano-particle intercalation graphene oxide film and preparation method and application |
| CN108584938A (en) * | 2018-06-11 | 2018-09-28 | 中国科学院高能物理研究所 | A kind of preparation method of porous oxidation graphene |
| US20190314770A1 (en) * | 2016-12-20 | 2019-10-17 | Monash University | Reverse osmosis membrane and method of use |
| EP3772086A1 (en) * | 2019-08-01 | 2021-02-03 | Fundació Institut Català de Nanociència i Nanotecnologia (ICN2) | Method to form a laser-scribed rgo pattern on a substrate |
| CN113457470A (en) * | 2021-06-21 | 2021-10-01 | 清华大学 | Graphene oxide nanofiltration membrane and preparation method thereof |
-
2021
- 2021-02-08 CN CN202110183596.3A patent/CN112915787A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706264A (en) * | 2014-01-14 | 2014-04-09 | 中国海洋大学 | Layer-by-layer self-assembling oxidized graphene nano-filtration membrane and preparation method thereof |
| CN104874301A (en) * | 2014-02-28 | 2015-09-02 | 中国科学院上海高等研究院 | Graphene oxide film, preparation method and applications thereof |
| US20170144107A1 (en) * | 2015-11-24 | 2017-05-25 | National University Of Singapore | Graphene-based membrane and method of preparation thereof |
| US20190314770A1 (en) * | 2016-12-20 | 2019-10-17 | Monash University | Reverse osmosis membrane and method of use |
| CN107720886A (en) * | 2017-10-17 | 2018-02-23 | 山东大学 | A kind of nano-particle intercalation graphene oxide film and preparation method and application |
| CN108584938A (en) * | 2018-06-11 | 2018-09-28 | 中国科学院高能物理研究所 | A kind of preparation method of porous oxidation graphene |
| EP3772086A1 (en) * | 2019-08-01 | 2021-02-03 | Fundació Institut Català de Nanociència i Nanotecnologia (ICN2) | Method to form a laser-scribed rgo pattern on a substrate |
| CN113457470A (en) * | 2021-06-21 | 2021-10-01 | 清华大学 | Graphene oxide nanofiltration membrane and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113522059A (en) * | 2021-07-02 | 2021-10-22 | 五邑大学 | Folded graphene oxide film and preparation method thereof |
| CN113522059B (en) * | 2021-07-02 | 2023-02-17 | 五邑大学 | Folded graphene oxide film and preparation method thereof |
| CN113648850A (en) * | 2021-09-01 | 2021-11-16 | 北京理工大学 | Preparation method of MXene/reduced porous graphene oxide (r-HGO) composite membrane with high flux and high removal rate |
| CN115121125A (en) * | 2022-06-28 | 2022-09-30 | 天津工业大学 | Preparation method for assembling and film-forming graphene oxide by gamma ray irradiation etching |
| CN115888432A (en) * | 2023-02-20 | 2023-04-04 | 浙江国辐环保科技有限公司 | Carbon-based nanofiltration membrane and preparation method and application thereof |
| CN116586054A (en) * | 2023-07-17 | 2023-08-15 | 中国科学院理化技术研究所 | Membrane catalytic material for rapid high-yield synthesis of aspirin at room temperature |
| CN116586054B (en) * | 2023-07-17 | 2023-10-13 | 中国科学院理化技术研究所 | Membrane catalytic material for rapid high-yield synthesis of aspirin at room temperature |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112915787A (en) | Preparation method of porous graphene oxide nanofiltration membrane | |
| CN108435002B (en) | Preparation method of functionalized carbon quantum dot modified composite nanofiltration membrane | |
| CN112023732B (en) | Forward osmosis composite membrane and preparation method and application thereof | |
| CN106076132B (en) | A kind of graphene oxide modified polyamide composite nanometer filtering film and preparation method thereof | |
| CN103464004B (en) | high-strength nano modified ultrafiltration membrane and preparation method thereof | |
| CN105540970B (en) | The technique of the integrated processing of Treated sewage reusing reverse osmosis concentrated water near-zero release embrane method | |
| CN105617882B (en) | A kind of compound forward osmosis membrane of chitosan-modified stannic oxide/graphene nano and preparation method thereof | |
| CN109433023A (en) | The graphene oxide nanofiltration membrane and the preparation method and application thereof of one type graphitic nitralloy carbon intercalation | |
| Chu et al. | Bio-enhanced powder-activated carbon dynamic membrane reactor for municipal wastewater treatment | |
| CN103212309B (en) | Preparation method of supportless forward osmosis membrane | |
| CN107530642A (en) | The graphene-based film composite material of functionalized monolayers and its manufacture method | |
| CN109806769B (en) | Preparation method of modified graphite-phase carbon nitride material nanofiltration membrane | |
| CN102219327A (en) | Membrane method treatment process for caprolactam waste water | |
| Chen et al. | PEGylated polyvinylidene fluoride membranes via grafting from a graphene oxide additive for improving permeability and antifouling properties | |
| CN110922300A (en) | Alcohol recovery method and device | |
| CN105582816A (en) | Preparation method of forward osmosis membrane modified with oxidized graphene | |
| CN110152503A (en) | A kind of preparation method for the solvent resistant nanofiltration membrane that graphene oxide is compound with tool microporous polymer certainly | |
| CN113522039A (en) | Preparation method of forward osmosis membrane based on PVA (polyvinyl alcohol) grafting modification | |
| CN110627284B (en) | Method for treating salt-containing wastewater by forward osmosis membrane distillation | |
| CN114130197A (en) | Graphene oxide titanium dioxide-dopamine PEI nanofiltration membrane and preparation method thereof | |
| CN105399270B (en) | A kind of method of chemical-biological combination method processing high-concentration formaldehyde wastewater | |
| CN108211794B (en) | High-selectivity hollow fiber desalting membrane and preparation method thereof | |
| WO2022217906A1 (en) | Modified multi-walled carbon nanotube, low-pressure membrane thereof, preparation method therefor and use thereof | |
| CN102350232A (en) | Hydrophilic stain-resistant PVDF (polyvinylidene fluoride) blended microfiltration flat membrane and preparation method thereof | |
| CN110639366B (en) | Method for preparing Fe-cage intercalated layered double hydroxide nanofiltration membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210608 |
|
| WD01 | Invention patent application deemed withdrawn after publication |