CN109433030B - Preparation method of graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane - Google Patents
Preparation method of graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane Download PDFInfo
- Publication number
- CN109433030B CN109433030B CN201811409377.7A CN201811409377A CN109433030B CN 109433030 B CN109433030 B CN 109433030B CN 201811409377 A CN201811409377 A CN 201811409377A CN 109433030 B CN109433030 B CN 109433030B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- quantum dot
- oxide quantum
- phase solution
- reverse osmosis
- 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.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/26—Polyalkenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a preparation method of a graphene oxide quantum dot-silver phosphate composite modified reverse osmosis composite membrane, which is characterized in that a composite material is dispersed in a polyamine aqueous phase solution, polybasic acyl chloride is dissolved in an organic solvent to prepare an oil phase solution, a polysulfone membrane is taken as a base membrane, and a simple and efficient electrostatic driving method is adopted to prepare the graphene oxide quantum dot-silver phosphate composite modified reverse osmosis composite membrane by utilizing an interfacial polymerization method.
Description
Technical Field
The invention relates to a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane, and belongs to the technical field of membrane separation.
Background
With the rapid development of economy and the rapid growth of population, the problem of global water resource shortage is becoming more serious. Seawater desalination is considered as a new way to solve the water resource crisis and develop fresh water resources. The reverse osmosis membrane separation technology is widely applied to seawater desalination and brackish water treatment due to the advantages of simple technology, low cost, good effluent quality and the like. Although reverse osmosis membranes have become the mainstream of membrane separation technology, in practical application, the membrane has the problem of "upper limit balance" between water flux and rejection rate, and the development of reverse osmosis membrane technology is severely restricted. Furthermore, membranes are susceptible to fouling during operation, resulting in rapid flux and rejection rate reductions, with microbial fouling being the most common type of membrane fouling. Microorganisms are easily deposited and propagated on the membrane surface, which, on the one hand, blocks the membrane pores and shortens the membrane life, and, on the other hand, brings about high economic and environmental costs for cleaning the membrane surface. Therefore, high flux, high selectivity, low pollution and good tolerance are the main development directions of reverse osmosis membrane technology.
In recent years, many researchers have been working on the combination of nanotechnology and reverse osmosis technology to develop high performance reverse osmosis membranes. The nano particles are embedded into the separation layer, so that the characteristics of the separation layer can be obviously improved on the premise of not damaging the separation performance of the interfacial polymerization membrane, such as: the pollution resistance, the tolerance and the mechanical stability can solve the problems of the traditional reverse osmosis membrane to a great extent. The method is characterized in that a nano material with antibacterial property is introduced into a polyamide thin layer to form a novel composite film to improve the pollution resistance, and the antibacterial property of a reverse osmosis membrane is endowed, so that the research is focused on the research of people.
The graphene oxide quantum dots serving as a 0-dimensional carbon nanomaterial are widely applied to various fields due to the properties of ultra-small size, good conductivity, biocompatibility and the like. The graphene oxide quantum dots are also used for preparing a nanofiltration membrane or a reverse osmosis membrane, and although a large number of hydrophilic functional groups on the surface of the graphene oxide quantum dots can enhance the hydrophilicity of the membrane and improve the membrane flux, the membrane is easily polluted in the operation process, microorganisms are easily deposited and propagated on the surface of the membrane, membrane pores are blocked, and the service life of the membrane is shortened.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane.
The technical scheme of the invention is as follows:
a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane comprises the following steps:
(1) preparing a graphene oxide quantum dot-silver phosphate composite material: mixing and stirring the graphene oxide quantum dot suspension liquid and a silver nitrate aqueous solution uniformly, then adding phosphate into the mixed solution, stirring vigorously in the dark, centrifuging the mixture after stirring uniformly, washing a centrifugal product with deionized water, and drying to obtain the graphene oxide quantum dot-silver phosphate composite material;
(2) preparing an aqueous phase solution: ultrasonically dispersing a graphene oxide quantum dot-silver phosphate composite material in water, adding polyamine, ultrasonically mixing uniformly, and then adding a surfactant to prepare an aqueous phase solution;
(3) preparing an oil phase solution: ultrasonically dissolving polyacyl chloride in an organic solvent to prepare an oil phase solution;
(4) interfacial polymerization reaction: and inverting the water phase solution on the surface of the base film, pouring out excessive liquid after the water phase solution is contacted with the base film, naturally drying the liquid, pouring the oil phase solution again for reaction for a period of time, removing the excessive oil phase solution, and drying the solution to obtain the graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite film.
Preferably, in the step (1), the concentration of the graphene oxide quantum dot suspension is 2-6 mg/ml.
Preferably, according to the invention, in step (1), the concentration of the silver nitrate solution is between 8 and 12 mM.
Preferably, in step (1), the volume ratio of the graphene oxide quantum dot solution to the silver nitrate solution is: (1-3): (1-3).
Preferably, in the step (1), the phosphate is one of disodium hydrogen phosphate dodecahydrate, sodium dihydrogen phosphate and sodium phosphate, and the amount of the phosphate added is 0.36-3.35mg per ml of the graphene oxide quantum dot suspension.
Preferably, in step (1), the stirring time is 0.5 to 1 hour after adding the silver nitrate, and the centrifugation rate is 6000 to 10000 rpm.
According to the invention, in the step (2), the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.001-0.02% (w/v), and the mass concentration of the polyamine is 0.5-3% (w/v).
According to the invention, in the step (2), the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is preferably 0.003-0.005% (w/v).
Preferably, in the step (2), the mass concentration of the surfactant in the aqueous solution is 0.1-0.25 w% (w/v).
Preferably, in step (2), the polyamine is one of o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, ethylenediamine, propylenediamine and hexamethylenediamine.
Preferably, in the step (2), the surfactant is one of sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether or sodium alpha-alkenyl sulfonate.
Preferably, in the step (3), the polyacyl chloride is one of trimesoyl chloride, m-trimesoyl chloride, cyclohexanetriyl chloride, cyclopentanetriyl chloride, propanetriacyl chloride and pentatriacyl chloride; the organic solvent is one of n-hexane, n-heptane, dodecane and tetradecane.
In the present invention, preferably, in the step (3), the mass concentration of the polybasic acyl chloride in the oil phase solution is 0.05 to 0.2% (w/v).
Preferably, in step (4), the base membrane is one of polysulfone, polyethersulfone, polyphenylsulfone, polyacrylonitrile or polyvinylidene fluoride.
Preferably, in the step (4), the drying temperature is 50-120 ℃, and the drying time is 5-10 min.
According to the invention, the reverse osmosis composite membrane is modified by the graphene oxide quantum dot-silver phosphate composite material, the graphene oxide quantum dot contains a large number of negatively charged functional groups, and can be combined with positively charged silver ions under electrostatic driving, and after phosphate is added into the system, the negatively charged phosphate ions are combined with the positively charged silver ions, so that silver phosphate is generated on the surface of the graphene oxide quantum dot. The graphene oxide quantum dots are used as the matrix of silver ions, and the silver ions are combined with the oxygen-containing functional groups with negative charges on the graphene oxide quantum dots through charges, so that the silver ions are uniformly distributed on the surfaces of the graphene oxide quantum dots. The surface of the graphene oxide quantum dot is provided with a large amount of negative charges, so that more reaction sites can be provided for silver ions with positive charges, the nucleation and the form of silver phosphate are effectively controlled, the dispersion and the dissolution performance of the silver phosphate in a reverse osmosis membrane are improved, meanwhile, the graphene oxide quantum dot is matched with phosphate radicals, so that more silver ions can be embedded into a polyamide layer generated by the reaction of m-phenylenediamine and trimesoyl chloride, and the reverse osmosis composite membrane is endowed with high-efficiency bactericidal performance based on the embedding of a large amount of silver ions.
In addition, the nano-channel on the graphene oxide quantum dot endows the membrane with higher water flux, and meanwhile, the graphene oxide quantum dot has good hydrophilicity, so that the hydrophilicity of the composite material is improved, the hydrophilic composite material is easier to disperse into a water phase, and favorable conditions are provided for the subsequent membrane preparation process.
Compared with the prior art, the invention has the following excellent effects:
(1) the graphene oxide quantum dots serving as the raw material for preparing the novel reverse osmosis composite membrane are nano carbon materials, and are wide in source and low in price, so that the preparation cost of the novel reverse osmosis composite membrane is reduced.
(2) The silver phosphate nano material selected by the invention has excellent bactericidal performance, and the bactericidal performance of the reverse osmosis membrane can be synergistically enhanced by combining the silver phosphate nano material with the graphene oxide quantum dots.
(3) The graphene oxide quantum dots in the raw material have a large number of oxygen-containing functional groups, and can be Ag+More reaction sites are provided, the nucleation and the form of the silver phosphate are effectively controlled, and the dispersion and the dissolution performance of the silver phosphate in the reverse osmosis membrane are improved.
(4) The graphene oxide quantum dot/silver phosphate composite material prepared by the invention has excellent hydrophilicity, and the composite material is introduced into a membrane, so that the hydrophilicity of the surface of the membrane can be improved, the water flux of the membrane is greatly improved, and a good salt cut level is kept.
Drawings
FIG. 1 is a scanning electron microscope photograph of a reverse osmosis composite membrane prepared in example 4 of the present invention.
FIG. 2 is a graph showing the results of the antibacterial performance of the reverse osmosis composite membranes of example 4 of the present invention and comparative example 1;
FIG. 3 is a graph showing the variation of water flux and salt rejection of the composite membrane with the variation of the concentration of the graphene oxide quantum dot-silver phosphate composite material in the experimental example;
fig. 4 is a graph showing the change in water flux and salt rejection of the membrane of example 4 during reverse osmosis testing for 50 hours in the experimental example.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 preparation of graphene oxide quantum dot-silver phosphate composite
Mixing 10 ml of graphene oxide quantum dot (4mg/ml) suspension with 12 ml of silver nitrate (10mM) aqueous solution, magnetically stirring for 30 minutes, then adding 0.0144g of disodium hydrogen phosphate dodecahydrate into the mixed solution, vigorously stirring for 1 hour in the dark, centrifuging the mixture at 8000rpm after the mixture is uniform, washing the mixture for three times by using deionized water, and carrying out vacuum freeze drying to obtain the graphene oxide quantum dot-silver phosphate composite material.
Example 2:
a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane comprises the following steps:
(1) adding the graphene oxide quantum dot-silver phosphate composite material obtained in the example 1 into deionized water, ultrasonically stirring for 1 hour,
(2) adding m-phenylenediamine into the step (1), uniformly stirring, adding a certain amount of sodium dodecyl sulfate, and performing ultrasonic dissolution to obtain an aqueous phase solution; the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.001% (w/v), the mass concentration of m-phenylenediamine is 2% (w/v), and the mass concentration of sodium dodecyl sulfate is 0.15 w% (w/v).
(3) Adding a certain amount of trimesoyl chloride into normal hexane to enable the concentration of the trimesoyl chloride to be 0.1 w/v%, and performing ultrasonic homogenization to obtain an oil phase solution;
(4) inverting the water phase solution on the surface of the base membrane, pouring out the redundant liquid after contacting for 2 minutes, naturally drying, then pouring the oil phase solution for reacting for 1 minute, and pouring out the oil phase solution to obtain a semi-finished product of the reverse osmosis membrane;
(5) and (3) drying the semi-finished reverse osmosis membrane in an oven at 80 ℃ for 5 minutes to obtain the graphene oxide quantum dot-silver phosphate composite modified reverse osmosis composite membrane.
Example 3:
a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane comprises the following steps:
(1) adding the graphene oxide quantum dot-silver phosphate composite material obtained in the example 1 into deionized water, ultrasonically stirring for 1 hour,
(2) adding m-phenylenediamine into the step (1), uniformly stirring, adding a certain amount of sodium dodecyl sulfate, and performing ultrasonic dissolution to obtain an aqueous phase solution; the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.002% (w/v), the mass concentration of m-phenylenediamine is 2% (w/v), and the mass concentration of sodium dodecyl sulfate is 0.15 w% (w/v).
(3) Adding a certain amount of trimesoyl chloride into normal hexane to enable the concentration of the trimesoyl chloride to be 0.1 w/v%, and performing ultrasonic homogenization to obtain an oil phase solution;
(4) inverting the water phase solution on the surface of the base membrane, pouring out the redundant liquid after contacting for 2 minutes, naturally drying, then pouring the oil phase solution for reacting for 1 minute, and pouring out the oil phase solution to obtain a semi-finished product of the reverse osmosis membrane;
(5) and (3) drying the semi-finished reverse osmosis membrane in an oven at 80 ℃ for 5 minutes to obtain the graphene oxide quantum dot-silver phosphate composite modified reverse osmosis composite membrane.
Example 4:
a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane comprises the following steps:
(1) adding the graphene oxide quantum dot-silver phosphate composite material obtained in the example 1 into deionized water, ultrasonically stirring for 1 hour,
(2) adding o-phenylenediamine into the step (1), uniformly stirring, adding a certain amount of sodium dodecyl sulfate, and performing ultrasonic dissolution to obtain an aqueous phase solution; the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.005% (w/v), the mass concentration of o-phenylenediamine is 2% (w/v), and the mass concentration of sodium dodecyl sulfate is 0.15 w% (w/v).
(3) Adding a certain amount of trimesoyl chloride into normal hexane to enable the concentration of the trimesoyl chloride to be 0.1 w/v%, and performing ultrasonic homogenization to obtain an oil phase solution;
(4) inverting the water phase solution on the surface of the base membrane, pouring out the redundant liquid after contacting for 2 minutes, naturally drying, then pouring the oil phase solution for reacting for 1 minute, and pouring out the oil phase solution to obtain a semi-finished product of the reverse osmosis membrane;
(5) and (3) drying the semi-finished reverse osmosis membrane in an oven at 80 ℃ for 5 minutes to obtain the graphene oxide quantum dot-silver phosphate composite modified reverse osmosis composite membrane.
Example 5:
a preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane comprises the following steps:
(1) adding the graphene oxide quantum dot-silver phosphate composite material obtained in the example 1 into deionized water, ultrasonically stirring for 1 hour,
(2) adding m-phenylenediamine into the step (1), uniformly stirring, adding a certain amount of sodium dodecyl sulfate, and performing ultrasonic dissolution to obtain an aqueous phase solution; the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.01% (w/v), the mass concentration of m-phenylenediamine is 2% (w/v), and the mass concentration of sodium dodecyl sulfate is 0.15 w% (w/v).
(3) Adding a certain amount of trimesoyl chloride into normal hexane to enable the concentration of the trimesoyl chloride to be 0.1 w/v%, and performing ultrasonic homogenization to obtain an oil phase solution;
(4) inverting the water phase solution on the surface of the base membrane, pouring out the redundant liquid after contacting for 2 minutes, naturally drying, then pouring the oil phase solution for reacting for 1 minute, and pouring out the oil phase solution to obtain a semi-finished product of the reverse osmosis membrane;
(5) and (3) drying the semi-finished reverse osmosis membrane in an oven at 80 ℃ for 5 minutes to obtain the graphene oxide quantum dot-silver phosphate composite modified reverse osmosis composite membrane.
Comparative example 1:
a preparation method of a reverse osmosis composite membrane comprises the following steps:
(1) adding a certain amount of m-phenylenediamine into deionized water to enable the concentration of the m-phenylenediamine to be 2 w/v%, uniformly stirring, adding a certain amount of sodium dodecyl sulfate to enable the concentration of the sodium dodecyl sulfate to be 0.15 w/v%, and performing ultrasonic dissolution to obtain an aqueous phase solution;
(2) adding a certain amount of trimesoyl chloride into normal hexane to enable the concentration of the trimesoyl chloride to be 0.1 w/v%, and performing ultrasonic homogenization to obtain an oil phase solution;
(3) inverting the water phase solution on the surface of the base membrane, pouring out the redundant liquid after contacting for 2 minutes, naturally drying, then pouring the oil phase solution for reacting for 1 minute, and pouring out the oil phase solution to obtain a semi-finished product of the reverse osmosis membrane;
(4) and (3) drying the semi-finished product of the reverse osmosis membrane in an oven at 80 ℃ for 5 minutes to obtain the reverse osmosis composite membrane (recorded as TFC membrane).
Comparative example 2:
a preparation method of a reverse osmosis composite membrane containing graphene oxide quantum dots comprises the following steps:
(1) adding the graphene oxide quantum dots into deionized water, ultrasonically stirring for 1 hour,
(2) adding o-phenylenediamine into the step (1), uniformly stirring, adding a certain amount of sodium dodecyl sulfate, and performing ultrasonic dissolution to obtain an aqueous phase solution; the mass concentration of the graphene oxide quantum dots in the aqueous phase solution is 0.005% (w/v), the mass concentration of the o-phenylenediamine is 2% (w/v), and the mass concentration of the sodium dodecyl sulfate is 0.15 w% (w/v).
(3) Adding a certain amount of trimesoyl chloride into normal hexane to enable the concentration of the trimesoyl chloride to be 0.1 w/v%, and performing ultrasonic homogenization to obtain an oil phase solution;
(4) inverting the water phase solution on the surface of the base membrane, pouring out the redundant liquid after contacting for 2 minutes, naturally drying, then pouring the oil phase solution for reacting for 1 minute, and pouring out the oil phase solution to obtain a semi-finished product of the reverse osmosis membrane;
(5) and (3) drying the semi-finished reverse osmosis membrane in an oven at 80 ℃ for 5 minutes to obtain the reverse osmosis composite membrane containing the graphene oxide quantum dots.
Experimental example:
firstly, membrane performance testing:
1. water flux and salt rejection test: the reverse osmosis composite membranes were tested in a cross-flow filtration apparatus. 2g/L of NaCl solution is prepared as a feeding solution, and the testing pressure is 1.6 MPa. The membranes were first pre-stressed until flux stabilized, and then the reverse osmosis composite membranes of examples 2-5 and comparative example 1 were tested for separation performance, including water flux and salt rejection.
2. And (3) antibacterial testing: escherichia coli cultured for 24 hours was diluted to 106CFU/mL, pipette 1 mL of inoculum into 25 mL of saline. The reverse osmosis membrane is cut into 4cm multiplied by 4cm and soaked in physiological saline, and then cultured for 2 hours under visible light and dark conditions respectively. After the culture is finished, the reverse osmosis membrane is taken out, the surface of the membrane is washed by using normal saline, then 0.1 ml of bacterial suspension is absorbed and uniformly dropped into a culture dish, the bacterial suspension is uniformly coated by using a glass rod, then the culture dish is placed in a constant temperature incubator at 37 ℃ for 48 hours, the bacteriostasis rate of the reverse osmosis membrane is calculated according to the colony count on a culture medium, and the antibacterial performance of the reverse osmosis composite membrane of the embodiment 4 and the comparative example 1 on escherichia coli is shown in figure 2.
The experimental results are as follows:
the reverse osmosis composite membranes of examples 2-5, comparative example 1 and comparative example 2 were respectively tested for water flux, rejection rate and antibacterial performance by the above-mentioned methods, and the test results are shown in table 1 below:
TABLE 1
As can be seen from the data in table 1, in examples 2 to 5, as the content of the graphene oxide quantum dot-silver phosphate composite material increases, the sterilization performance of the reverse osmosis composite membrane of the present invention is gradually improved, and the sterilization performance under visible light is better than that under dark, which is probably caused by the photocatalytic improvement of the sterilization effect of the graphene oxide quantum dot-silver phosphate composite material, example 4 has an ultrahigh sterilization rate to escherichia coli under dark condition and under visible light irradiation, that is, the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.005% (w/v) optimal, while the blank membrane water flux and sterilization rate of comparative example 1 are far less than those of the present invention, and comparative example 2 improves the water flux to a certain extent but has no sterilization effect, therefore, the graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane has high water flux and salt rejection rate, can break through the limit of 'upper limit balance' of the traditional reverse osmosis membrane, and has excellent bactericidal performance, so that the graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane can be widely applied to seawater desalination and brackish water treatment.
Secondly, the change of the water flux and the salt rejection rate of the composite membrane is shown in fig. 3 along with the change of the concentration of the graphene oxide quantum dot-silver phosphate composite material, and it can be seen from the figure that the water flux of the composite membrane is gradually increased along with the increase of the concentration of the graphene oxide quantum dot-silver phosphate composite material, but the salt rejection rate of the composite membrane starts to be in a descending trend after the concentration is increased to a certain concentration.
Thirdly, the water flux and salt rejection of the membrane of example 4 remained relatively stable during the reverse osmosis test for up to 35 hours, as shown in fig. 4. The composite membrane has stability in the processes of seawater desalination and water treatment, and the structure of the polyamide layer is more stable due to the addition of the composite membrane.
Claims (5)
1. A preparation method of a graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane comprises the following steps:
(1) preparing a graphene oxide quantum dot-silver phosphate composite material: mixing and stirring the graphene oxide quantum dot suspension liquid and a silver nitrate aqueous solution uniformly, then adding phosphate into the mixed solution, stirring vigorously in the dark, centrifuging the mixture after stirring uniformly, washing a centrifugal product with deionized water, and drying to obtain the graphene oxide quantum dot-silver phosphate composite material; the concentration of the graphene oxide quantum dot suspension liquid is 2-6mg/ml, and the concentration of the silver nitrate solution is 8-12 mM; the volume ratio of the graphene oxide quantum dot solution to the silver nitrate solution is as follows: (1-3): (1-3); the phosphate is one of disodium hydrogen phosphate dodecahydrate, sodium dihydrogen phosphate and sodium phosphate, the addition amount of the phosphate is that 0.36-3.35mg of the phosphate is added into each milliliter of graphene oxide quantum dot suspension, the stirring time is 0.5-1 h after the silver nitrate is added, and the centrifugal speed is 6000-10000 rpm;
(2) preparing an aqueous phase solution: ultrasonically dispersing a graphene oxide quantum dot-silver phosphate composite material in water, adding polyamine, ultrasonically mixing uniformly, and then adding a surfactant to prepare an aqueous phase solution; the mass concentration of the graphene oxide quantum dot-silver phosphate composite material in the aqueous phase solution is 0.001-0.02% (w/v), the mass concentration of the polyamine is 0.5-3% (w/v), and the mass concentration of the surfactant in the aqueous phase solution is 0.1-0.25% (w/v);
(3) preparing an oil phase solution: ultrasonically dissolving polyacyl chloride in an organic solvent to prepare an oil phase solution;
(4) interfacial polymerization reaction: and inverting the water phase solution on the surface of the base film, pouring out excessive liquid after the water phase solution is contacted with the base film, naturally drying the liquid, pouring the oil phase solution again for reaction for a period of time, removing the excessive oil phase solution, and drying the solution to obtain the graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite film.
2. The method according to claim 1, wherein in the step (2), the polyamine is one of o-phenylenediamine, p-phenylenediamine, m-phenylenediamine, ethylenediamine, propylenediamine and hexamethylenediamine, and the surfactant is one of sodium dodecyl sulfate, fatty alcohol-polyoxyethylene ether or sodium alpha-olefin sulfonate.
3. The method according to claim 1, wherein in the step (3), the polybasic acid chloride is one of trimesoyl chloride, m-trimesoyl chloride, cyclohexanetriyl chloride, cyclopentanetriyl chloride, propanetriacyl chloride and pentatriacyl chloride; the organic solvent is one of n-hexane, n-heptane, dodecane and tetradecane.
4. The method according to claim 1, wherein in the step (3), the mass concentration of the polybasic acid chloride in the oil phase solution is 0.05-0.2% (w/v).
5. The preparation method according to claim 1, wherein in the step (4), the base film is one of polysulfone, polyethersulfone, polyphenylsulfone, polyacrylonitrile or polyvinylidene fluoride, and the drying temperature is 50-120 ℃ and the drying time is 5-10 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811409377.7A CN109433030B (en) | 2018-11-23 | 2018-11-23 | Preparation method of graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811409377.7A CN109433030B (en) | 2018-11-23 | 2018-11-23 | Preparation method of graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109433030A CN109433030A (en) | 2019-03-08 |
| CN109433030B true CN109433030B (en) | 2021-08-10 |
Family
ID=65554223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811409377.7A Active CN109433030B (en) | 2018-11-23 | 2018-11-23 | Preparation method of graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109433030B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112007520B (en) * | 2019-05-28 | 2023-03-24 | 中国石油化工股份有限公司 | Reverse osmosis membrane resistant to biological pollution and preparation method and application thereof |
| CN111137942B (en) * | 2019-12-11 | 2022-03-15 | 扬州大学 | Flaky porous graphene quantum dot/copper phosphide composite material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102861600A (en) * | 2012-10-10 | 2013-01-09 | 江苏大学 | Graphene oxide/silver phosphate/P25 composite material and preparation method thereof |
| US20130284665A1 (en) * | 2011-06-20 | 2013-10-31 | Lg Chem, Ltd | Reverse osmosis separation membrane having high degree of salt rejection and high permeation flux and method of manufacturing the same |
| CN105771696A (en) * | 2016-04-29 | 2016-07-20 | 中国海洋大学 | Grapheme oxide quantum dot function sphere nanoparticle, polyamide reverse osmosis membrane/nanofiltration membrane modified by nanoparticle and preparation method |
| CN106492654A (en) * | 2015-09-07 | 2017-03-15 | 中山市创思泰新材料科技股份有限公司 | A kind of multifunctional graphite vinyl/polymer composite water permeable membrane and its production and use |
| CN108568217A (en) * | 2018-03-29 | 2018-09-25 | 同济大学 | A kind of modified Wholly aromatic polyamide film and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10953371B2 (en) * | 2017-01-25 | 2021-03-23 | University Of South Carolina | Thin film composites having graphene oxide quantum dots |
-
2018
- 2018-11-23 CN CN201811409377.7A patent/CN109433030B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130284665A1 (en) * | 2011-06-20 | 2013-10-31 | Lg Chem, Ltd | Reverse osmosis separation membrane having high degree of salt rejection and high permeation flux and method of manufacturing the same |
| CN102861600A (en) * | 2012-10-10 | 2013-01-09 | 江苏大学 | Graphene oxide/silver phosphate/P25 composite material and preparation method thereof |
| CN106492654A (en) * | 2015-09-07 | 2017-03-15 | 中山市创思泰新材料科技股份有限公司 | A kind of multifunctional graphite vinyl/polymer composite water permeable membrane and its production and use |
| CN105771696A (en) * | 2016-04-29 | 2016-07-20 | 中国海洋大学 | Grapheme oxide quantum dot function sphere nanoparticle, polyamide reverse osmosis membrane/nanofiltration membrane modified by nanoparticle and preparation method |
| CN108568217A (en) * | 2018-03-29 | 2018-09-25 | 同济大学 | A kind of modified Wholly aromatic polyamide film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Facile synthesis of Ag3PO4 modified with GQDs composites with enhanced visible-light photocatalytic activity;Yafei Wang et al.;《Journal of Materials Science:Materials in Electronics》;20181031;第29卷(第19期);第1节，第2.2节 * |
| Pressure-assisted preparation of graphene oxide quantum dot-incorporated reverse osmosis membranes: antifouling and chlorine resistance potentials;Song Xiangju et al.;《Journal of Materials Chemistry A》;20160912;第4卷(第43期);摘要，第2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109433030A (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108970405B (en) | Reverse osmosis composite membrane containing graphene oxide quantum dots in-situ reduction silver nanoparticles | |
| CN110935322B (en) | High-flux alpha-C-containing3N4/Ag3PO4Forward osmosis membrane of composite material and preparation method thereof | |
| CN106310957A (en) | Nanometer fiber-reinforced hydrogel filter membrane and preparation method thereof | |
| CN109433030B (en) | Preparation method of graphene oxide quantum dot-silver phosphate composite material modified reverse osmosis composite membrane | |
| CN107174950A (en) | The positive osmosis composite membrane of high-performance and preparation method that a kind of graphene oxide is modified | |
| CN113083036A (en) | Two-dimensional layered composite membrane and preparation method and application thereof | |
| CN111420567B (en) | Preparation method of in-situ reduced nano-silver anti-pollution polyamide reverse osmosis membrane | |
| CN109433029A (en) | A kind of preparation method of the reverse osmosis membrane of anti-pollution type doped cerium oxide and silver nano-grain | |
| CN106823865A (en) | A kind of aromatic polyamide composite reverse osmosis membrane and preparation method for being grafted carbon fluorine class material and aminoglycoside antibiotics | |
| CN113144919A (en) | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof | |
| Al-Araji et al. | The permeation and separation characteristics of polymeric membranes incorporated with nanoparticles for dye removal and interaction mechanisms between polymer and nanoparticles: A mini review | |
| US11925905B2 (en) | Forward osmosis membrane and method of preparing same | |
| CN114870641B (en) | Piperazinyl primary positively charged nanofiltration membrane and preparation method thereof | |
| CN114016285B (en) | Preparation method of functional nanofiber membrane for sea water desalination | |
| CN108479396A (en) | Based on nano zinc oxide modified positive osmosis composite membrane and preparation method | |
| CN104107641B (en) | Forward osmosis organic-inorganic composite membrane and preparation method thereof | |
| CN112370976B (en) | Interface enhanced composite nanofiltration membrane and preparation method thereof | |
| CN111888943B (en) | Preparation method of reverse osmosis membrane containing buffer layer free interface polymerization | |
| CN110743383B (en) | Modification method for improving permeation flux of polyamide composite membrane | |
| CN108854587A (en) | A kind of high-throughput, antibacterial type doping hectorite-metal ion reverse osmosis composite membrane preparation method | |
| CN113797774B (en) | Antibacterial reverse osmosis composite membrane and preparation method thereof | |
| KR101076221B1 (en) | Method for fabricating of reverse osmosis membrane from polyelectrolyte multilayers and reverse osmosis membrane of fabricated using the same | |
| Salim et al. | Graphene oxide incorporated polyether sulfone nanocomposite antifouling ultrafiltration membranes with enhanced hydrophilicity | |
| CN115624869A (en) | Graphene quantum dot antibacterial adsorption electrostatic spinning nanofiltration membrane and preparation method thereof | |
| CN104548966A (en) | Antibacterial polyamide nanofiltration composite membrane and preparation method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |