CN109433030A - A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification - Google Patents
A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of graphene oxide quantum dot-silver orthophosphate composite modification reverse osmosis composite membrane, composite material is dispersed in the aqueous phase solution of polyamine by this method, and the dissolution of polynary acyl chlorides is prepared into oil-phase solution in organic solvent, using PS membrane as basement membrane, utilize interfacial polymerization, graphene oxide quantum dot-silver orthophosphate composite modification reverse osmosis composite membrane has been prepared using the electrostatic drive being simple and efficient, reverse osmosis composite membrane prepared by the present invention has high water flux, and keep good section of salt level, the limitation of " upper limit balance " is broken, outstanding bactericidal property is shown simultaneously, in sea water desalination, bitter processing and UF membrane field are with a wide range of applications.
Description
Technical field
The present invention relates to a kind of preparations of graphene oxide quantum dot-silver orthophosphate composite modification reverse osmosis composite membrane
Method belongs to technical field of membrane separation.
Background technique
With the sharp increase of economic fast development and population, global water resources shortage problem is got worse.Seawater is light
Change is considered as the new way for solving water resources crisis, developing freshwater resources.Reverse osmosis membrane separation technology due to it is technically simple, at
The advantages that this is low, effluent quality is good is widely used in sea water desalination and bitter is handled.Although reverse osmosis membrane has become film point
Mainstream from technology, but in practical applications, there is " upper limit balance " between water flux and rejection in film, serious to restrict
The development of reverse osmosis membrane technology.In addition, film is easily contaminated in the process of running, under causing flux and rejection rapid
Drop, wherein microbial contamination is the most common fouling membrane type.Microorganism easily deposits and breeds in film surface, on the one hand blocks film
Membrane lifetime is shortened in hole, on the other hand, can generate high economy and Environmental costs to film surface cleaning.Therefore high-throughput, high selection
Property, low pollution and good tolerance are the main developing direction of reverse osmosis membrane technology.
In recent years, many scholars are dedicated to nanotechnology and develop high performance reverse osmosis membrane in conjunction with reverse osmosis technology.It receives
Rice corpuscles is mounted in separating layer, can significantly improve separating layer under the premise of not damaging interfacial polymerization membrane separating property
Characteristic, such as: resistance tocrocking, tolerance and mechanical stability can largely solve what conventional reverse osmosis film surface faced
Problem.Nano material with antibiotic property is introduced into polyam ide TLC and forms Novel compound film and improves resistance tocrocking,
And the emphasis that reverse osmosis membrane anti-microbial property becomes people's research is assigned, still, current means draw the nano material of antibiotic property
Enter into polyam ide TLC, easily causes ultrafiltration membrane blocking, water flux is caused to substantially reduce, thus sterilizing cannot with high water flux
It gets both, in addition, the load of most of current film is Nano silver grain, germicidal efficiency is low, and effect is less desirable.
Graphene oxide quantum dot ties up carbon nanomaterial as one kind 0, because of its super-small, good electric conductivity and biology
The properties such as compatibility are widely used in every field.Graphene oxide quantum dot, which also has, be used to prepare nanofiltration membrane or reverse osmosis
Film, although a large amount of hydrophilic functional group in its surface can enhance the hydrophily of film and improve membrane flux, film was being run
It is easily contaminated in journey, microorganism easily deposits and breeds in film surface, blocks fenestra, shortens membrane lifetime.
Summary of the invention
The problem of for above-mentioned background technique, it is multiple that the present invention provides a kind of graphene oxide quantum dot-silver orthophosphate
The preparation method of the modified reverse osmosis composite membrane of condensation material.
Technical scheme is as follows:
A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification, including
Steps are as follows:
(1) graphene oxide quantum dot-phosphoric acid silver composite material preparation: by graphene oxide quantum dot suspension and nitre
Sour silver aqueous solution is mixed evenly, and phosphate is then added into mixed liquor, is vigorously stirred under dark, will mix after mixing evenly
Close object centrifugation, deionized water washing centrifugation product, dry graphene oxide quantum dot-phosphoric acid silver composite material；
(2) preparation of aqueous phase solution: graphene oxide quantum dot-silver orthophosphate compound material ultrasound is dispersed in water, is added
Add polyamine ultrasound to mix, adds surfactant, be configured to aqueous phase solution；
(3) preparation of oil-phase solution: in organic solvent by polynary acyl chlorides ultrasonic dissolution, it is configured to oil-phase solution；
(4) interface polymerization reaction: being upside down in membrane surface for aqueous phase solution, after contact, outwells extra liquid, dries in the air naturally
It is dry, oil-phase solution reaction a period of time is then poured into again, is removed extra oil-phase solution, is dried, obtain graphene oxide quantum
Point-silver orthophosphate composite modification reverse osmosis composite membrane.
Preferred according to the present invention, in step (1), the concentration of graphene oxide quantum dot suspension is 2-6mg/ml.
Preferred according to the present invention, in step (1), the concentration of silver nitrate solution is 8-12mM.
It is preferred according to the present invention, in step (1), the volume ratio of graphene oxide quantum dot solution and silver nitrate solution
Are as follows: (1-3): (1-3).
Preferred according to the present invention, in step (1), the phosphate is disodium hydrogen phosphate dodecahydrate, biphosphate
One of sodium, sodium phosphate, phosphatic additional amount are that phosphate is added in every milliliter of graphene oxide quantum dot suspension
0.36-3.35mg。
Preferred according to the present invention, in step (1), mixing time is 0.5 to 1h after silver nitrate is added, and centrifugation rate is
6000 to 10000rpm.
It is preferred according to the present invention, in step (2), oxygen graphene oxide quantum dot-silver orthophosphate composite wood in aqueous phase solution
The mass concentration of material is 0.001~0.02% (w/v), and the mass concentration of polyamine is 0.5~3% (w/v).
It is preferred according to the present invention, in step (2), oxygen graphene oxide quantum dot-silver orthophosphate composite wood in aqueous phase solution
The mass concentration of material is 0.003~0.005% (w/v).
It is preferred according to the present invention, in step (2), in aqueous phase solution the mass concentration of surfactant be 0.1~
0.25w% (w/v).
Preferred according to the present invention, in step (2), the polyamine is o-phenylenediamine, p-phenylenediamine, m-phenylene diamine (MPD), second
One of diamines, propane diamine, hexamethylene diamine.
It is currently preferred, in step (2), the surfactant be lauryl sodium sulfate, dodecyl sodium sulfate,
One of fatty alcohol polyoxyethylene ether or α-sodium olefin sulfonate.
Currently preferred, in step (3), the polynary acyl chlorides is pyromellitic trimethylsilyl chloride, three formyl chloride of isophthalic, hexamethylene
Three acyl chlorides, three acyl chlorides of pentamethylene, the third three one of acyl chlorides and penta 3 acyl chlorides；The organic solvent is n-hexane, normal heptane, ten
One of dioxane, tetradecane.
Currently preferred, in step (3), the mass concentration of polynary acyl chlorides is 0.05~0.2% (w/ in oil-phase solution
v)。
Currently preferred, in step (4), the basement membrane is polysulfones, polyether sulfone, polyphenylsulfone, polyacrylonitrile or gathers inclined fluorine
One of ethylene.
Currently preferred, in step (4), drying temperature is 50~120 DEG C, and drying time is 5~10min.
The present invention is modified reverse osmosis composite membrane by graphene oxide quantum dot-phosphoric acid silver composite material, graphite oxide
Alkene quantum dot contains a large amount of electronegative functional group, can combine under electrostatic drive with positively charged silver ion, to system
After middle addition phosphate, electronegative phosphate anion is in conjunction with the silver ion of positive electricity, thus in graphene oxide quantum dot table
Face generates silver orthophosphate.Use graphene oxide quantum dot as the matrix of silver ion, since silver ion passes through charge and oxidation stone
Electronegative oxygen-containing functional group combines on black alkene quantum dot, so silver ion is evenly distributed on graphene oxide quantum dot surface.
Graphene oxide quantum dot surface has a large amount of negative electrical charge, and more reaction positions can be provided for positively charged silver ion
Point effectively controls the nucleation and form of silver orthophosphate, improves dispersion and solubility property of the silver orthophosphate in reverse osmosis membrane, while oxygen
The cooperation of graphite alkene quantum dot and phosphate radical can be such that more silver ions are embedded by m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride
It reacts in the aramid layer generated, based on the insertion of a large amount of silver ions, imparts the efficient bactericidal property of reverse osmosis composite membrane.
In addition, the nanochannel on graphene oxide quantum dot assigns the higher water flux of film, simultaneous oxidation graphene amount
Son point has good hydrophily, improves composite material hydrophily, this hydrophilic composite material is easier to be distributed to water
Xiang Zhong provides advantage to subsequent film-forming process.
Compared with prior art, excellent results of the invention are:
(1) the raw material graphene oxide quantum dot for preparing of the invention is nano-carbon material, from a wealth of sources, cheap,
To reduce the preparation cost of novel reverse osmosis composite membrane.
(2) the phosphoric acid silver nano material that the present invention selects has excellent bactericidal property, with graphene oxide quantum dot
In conjunction with the bactericidal property that can cooperate with enhancing reverse osmosis membrane.
(3) graphene oxide quantum dot has a large amount of oxygen-containing functional group in raw material of the invention, can be Ag+It provides more
More reaction sites effectively controls the nucleation and form of silver orthophosphate, improves dispersion and dissolution of the silver orthophosphate in reverse osmosis membrane
Performance.
(4) graphene oxide quantum dot prepared by the present invention/phosphoric acid silver composite material has excellent hydrophily, will be compound
Material, which is introduced into film, can improve film surface hydrophily, greatly improve the water flux of film, and keep good section of salt level,
Water process and UF membrane field are with a wide range of applications.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of reverse osmosis composite membrane prepared by the embodiment of the present invention 4.
Fig. 2 is the reverse osmosis composite membrane anti-microbial property result schematic diagram of the embodiment of the present invention 4 Yu comparative example 1；
Fig. 3 is with the variation of graphene oxide quantum dot-phosphoric acid silver composite material concentration in experimental example, and the water of composite membrane is logical
The change curve of amount and salt-stopping rate；
Fig. 4 is to have carried out the film of embodiment 4 up in the reverse osmosis test process of 50 hours in experimental example, the water of film
Flux and salt-stopping rate change curve.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The preparation of 1 graphene oxide quantum dot of embodiment-phosphoric acid silver composite material
10 milliliters of graphene oxide quantum dot (4mg/ml) suspension are mixed with 12 milliliters of silver nitrate (10mM) aqueous solutions, magnetic
Power stirs 30 minutes, and 0.0144g disodium hydrogen phosphate dodecahydrate is then added into mixed liquor, is vigorously stirred 1 hour under dark,
Mixture is centrifugated with 8000rpm after uniformly, deionized water is washed three times, and vacuum freeze drying obtains graphene oxide amount
Sub- point-phosphoric acid silver composite material.
Embodiment 2:
A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification, including
Steps are as follows:
(1) graphene oxide quantum dot of embodiment 1-phosphoric acid silver composite material is add to deionized water, ultrasound is stirred
It mixes 1 hour,
(2) m-phenylene diamine (MPD) is added into step (1), adds a certain amount of dodecyl sodium sulfate after mixing evenly, ultrasound
Aqueous phase solution is obtained after dissolution；Graphene oxide quantum dot-phosphoric acid silver composite material mass concentration is in aqueous phase solution
0.001% (w/v), the mass concentration of m-phenylene diamine (MPD) are 2% (w/v), and the mass concentration of dodecyl sodium sulfate is 0.15w%
(w/v)。
(3) a certain amount of pyromellitic trimethylsilyl chloride is added in n-hexane, after keeping its concentration 0.1w/v%, ultrasound uniform
Obtain oil-phase solution；
(4) aqueous phase solution is upside down in membrane surface, extra liquid is outwelled in contact after 2 minutes, naturally dry, then again
It pours into oil-phase solution to react 1 minute, pours out oil-phase solution, reverse osmosis membrane semi-finished product are made；
(5) reverse osmosis membrane semi-finished product are put and is dried 5 minutes for 80 DEG C in an oven, obtain graphene oxide quantum dot-phosphoric acid
The modified reverse osmosis composite membrane of silver composite material.
Embodiment 3:
A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification, including
Steps are as follows:
(1) graphene oxide quantum dot of embodiment 1-phosphoric acid silver composite material is add to deionized water, ultrasound is stirred
It mixes 1 hour,
(2) m-phenylene diamine (MPD) is added into step (1), adds a certain amount of dodecyl sodium sulfate after mixing evenly, ultrasound
Aqueous phase solution is obtained after dissolution；Graphene oxide quantum dot-phosphoric acid silver composite material mass concentration is in aqueous phase solution
0.002% (w/v), the mass concentration of m-phenylene diamine (MPD) are 2% (w/v), and the mass concentration of dodecyl sodium sulfate is 0.15w%
(w/v)。
(3) a certain amount of pyromellitic trimethylsilyl chloride is added in n-hexane, after keeping its concentration 0.1w/v%, ultrasound uniform
Obtain oil-phase solution；
(4) aqueous phase solution is upside down in membrane surface, extra liquid is outwelled in contact after 2 minutes, naturally dry, then again
It pours into oil-phase solution to react 1 minute, pours out oil-phase solution, reverse osmosis membrane semi-finished product are made；
(5) reverse osmosis membrane semi-finished product are put and is dried 5 minutes for 80 DEG C in an oven, obtain graphene oxide quantum dot-phosphoric acid
The modified reverse osmosis composite membrane of silver composite material.
Embodiment 4:
A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification, including
Steps are as follows:
(1) graphene oxide quantum dot of embodiment 1-phosphoric acid silver composite material is add to deionized water, ultrasound is stirred
It mixes 1 hour,
(2) o-phenylenediamine is added into step (1), adds a certain amount of dodecyl sodium sulfate after mixing evenly, ultrasound
Aqueous phase solution is obtained after dissolution；Graphene oxide quantum dot-phosphoric acid silver composite material mass concentration is in aqueous phase solution
0.005% (w/v), the mass concentration of o-phenylenediamine are 2% (w/v), and the mass concentration of dodecyl sodium sulfate is 0.15w%
(w/v)。
(3) a certain amount of pyromellitic trimethylsilyl chloride is added in n-hexane, after keeping its concentration 0.1w/v%, ultrasound uniform
Obtain oil-phase solution；
(4) aqueous phase solution is upside down in membrane surface, extra liquid is outwelled in contact after 2 minutes, naturally dry, then again
It pours into oil-phase solution to react 1 minute, pours out oil-phase solution, reverse osmosis membrane semi-finished product are made；
(5) reverse osmosis membrane semi-finished product are put and is dried 5 minutes for 80 DEG C in an oven, obtain graphene oxide quantum dot-phosphoric acid
The modified reverse osmosis composite membrane of silver composite material.
Embodiment 5:
A kind of preparation method of the reverse osmosis composite membrane of graphene oxide quantum dot-silver orthophosphate composite modification, including
Steps are as follows:
(1) graphene oxide quantum dot of embodiment 1-phosphoric acid silver composite material is add to deionized water, ultrasound is stirred
It mixes 1 hour,
(2) m-phenylene diamine (MPD) is added into step (1), adds a certain amount of dodecyl sodium sulfate after mixing evenly, ultrasound
Aqueous phase solution is obtained after dissolution；Graphene oxide quantum dot-phosphoric acid silver composite material mass concentration is in aqueous phase solution
0.01% (w/v), the mass concentration of m-phenylene diamine (MPD) are 2% (w/v), and the mass concentration of dodecyl sodium sulfate is 0.15w% (w/
v)。
(3) a certain amount of pyromellitic trimethylsilyl chloride is added in n-hexane, after keeping its concentration 0.1w/v%, ultrasound uniform
Obtain oil-phase solution；
(4) aqueous phase solution is upside down in membrane surface, extra liquid is outwelled in contact after 2 minutes, naturally dry, then again
It pours into oil-phase solution to react 1 minute, pours out oil-phase solution, reverse osmosis membrane semi-finished product are made；
(5) reverse osmosis membrane semi-finished product are put and is dried 5 minutes for 80 DEG C in an oven, obtain graphene oxide quantum dot-phosphoric acid
The modified reverse osmosis composite membrane of silver composite material.
Comparative example 1:
A kind of preparation method of reverse osmosis composite membrane, steps are as follows:
(1) a certain amount of m-phenylene diamine (MPD) is added to deionized water, makes its concentration 2w/v%, add after mixing evenly certain
Dodecyl sodium sulfate is measured, makes its concentration 0.15w/v%, obtains aqueous phase solution after ultrasonic dissolution；
(2) a certain amount of pyromellitic trimethylsilyl chloride is added in n-hexane, after keeping its concentration 0.1w/v%, ultrasound uniform
Obtain oil-phase solution；
(3) aqueous phase solution is upside down in membrane surface, extra liquid is outwelled in contact after 2 minutes, naturally dry, then again
It pours into oil-phase solution to react 1 minute, pours out oil-phase solution, reverse osmosis membrane semi-finished product are made；
(4) reverse osmosis membrane semi-finished product are put and is dried 5 minutes for 80 DEG C in an oven, obtained reverse osmosis composite membrane and (be denoted as TFC
Film).
Comparative example 2:
A kind of preparation method of the reverse osmosis composite membrane containing graphene oxide quantum dot, steps are as follows:
(1) graphene oxide quantum dot is added in deionized water, is stirred by ultrasonic 1 hour,
(2) o-phenylenediamine is added into step (1), adds a certain amount of dodecyl sodium sulfate after mixing evenly, ultrasound
Aqueous phase solution is obtained after dissolution；The mass concentration of graphene oxide quantum dot is 0.005% (w/v), adjacent benzene two in aqueous phase solution
The mass concentration of amine is 2% (w/v), and the mass concentration of dodecyl sodium sulfate is 0.15w% (w/v).
(3) a certain amount of pyromellitic trimethylsilyl chloride is added in n-hexane, after keeping its concentration 0.1w/v%, ultrasound uniform
Obtain oil-phase solution；
(4) aqueous phase solution is upside down in membrane surface, extra liquid is outwelled in contact after 2 minutes, naturally dry, then again
It pours into oil-phase solution to react 1 minute, pours out oil-phase solution, reverse osmosis membrane semi-finished product are made；
(5) reverse osmosis membrane semi-finished product are put and is dried 5 minutes for 80 DEG C in an oven, obtained containing the anti-of graphene oxide quantum dot
Osmosis composite membrane.
Experimental example:
One, film properties test:
1, water flux and section salt test: reverse osmosis composite membrane is tested in cross-flow filtration device.Prepare 2g/L's
NaCl solution is feedstock solution, and test pressure is 1.6MPa.Precompressed is carried out until flux stabilized to film first, then test implementation
The separating property of example 2-5 and the reverse osmosis composite membrane of comparative example 1, including water flux and salt-stopping rate.
2, the Escherichia coli for having cultivated 24 hours antibacterial test: are diluted to 106CFU/mL draws 1 milliliter with liquid-transfering gun
Bacterium solution is added in 25 milliliters of physiological saline.Reverse osmosis membrane is cut into 4cm × 4cm and is immersed in physiological saline, being individually placed to can
It is cultivated 2 hours under light-exposed and dark condition.After culture, by reverse osmosis membrane taking-up normal saline flushing film surface, then
0.1 milliliter of bacterial suspension is drawn equably to drip in culture dish, it is uniformly spreadable with glass bar, it is subsequently placed in constant incubator
37 DEG C of culture 48h, the bacteriostasis rate of reverse osmosis membrane is calculated by the clump count on culture medium, and embodiment 4 is reverse osmosis with comparative example 1
Composite membrane is as shown in Figure 2 to the anti-microbial property of Escherichia coli.
Experimental result:
Water is carried out to the reverse osmosis composite membrane of embodiment 2-5 and comparative example 1, comparative example 2 respectively using method described above
Flux, rejection test and anti-microbial property test, test result is as follows table 1:
Table 1
It can be seen from the data in Table 1 that embodiment 2 is into embodiment 5 as graphene oxide quantum dot-silver orthophosphate is compound
The bactericidal property of the increase of material content, reverse osmosis composite membrane of the invention is gradually increased, it is seen that the bactericidal property under light
The sterilizing rate being better than under dark, this may be because graphene oxide quantum dot-phosphoric acid silver composite material has photocatalysis raising
Caused by bactericidal effect, no matter embodiment 4 all has superelevation under dark condition or under radiation of visible light to Escherichia coli
Sterilizing rate, that is, graphene oxide quantum dot-phosphoric acid silver composite material mass concentration is 0.005% (w/v) in aqueous phase solution
Effect is optimal, and the blank membrane flux and sterilizing rate of comparative example 1 be far smaller than it is of the invention, although comparative example 2 is in certain journey
Water flux is improved on degree, but does not have bactericidal effect, therefore, graphene oxide quantum dot of the present invention-phosphoric acid silver composite material
Modified reverse osmosis composite membrane has both with high water flux and salt-stopping rate, can break " upper limit balance " limit of conventional reverse osmosis film
System, while also there is excellent bactericidal property, therefore can be widely applied in sea water desalination and bitter processing.
Two, with the variation of graphene oxide quantum dot-phosphoric acid silver composite material concentration, the water flux and salt-stopping rate of composite membrane
Variation as shown in figure 3, it can be seen from the figure that with the increase of graphene oxide quantum dot-phosphoric acid silver composite material concentration,
The water flux of composite membrane is also to be gradually increased, but increase to its salt-stopping rate after a certain concentration and start in downward trend.
Three, it has carried out in the film to embodiment 4 up in the reverse osmosis test process of 35 hours, the water flux of film and has cut
Salt rate still keeps more stable state, as shown in Figure 4.Composite membrane of the present invention is steady in sea water desalination and water treatment procedure
Qualitative, its addition is so that the structure of aramid layer is more firm.
Claims (10)
1. a kind of preparation method of graphene oxide quantum dot-silver orthophosphate composite modification reverse osmosis composite membrane, including step
It is rapid as follows:
(1) graphene oxide quantum dot-phosphoric acid silver composite material preparation: by graphene oxide quantum dot suspension and silver nitrate
Aqueous solution is mixed evenly, and phosphate is then added into mixed liquor, is vigorously stirred under dark, after mixing evenly by mixture
Centrifugation, deionized water washing centrifugation product, dry graphene oxide quantum dot-phosphoric acid silver composite material；
(2) preparation of aqueous phase solution: graphene oxide quantum dot-silver orthophosphate compound material ultrasound is dispersed in water, and is added more
First amine ultrasound mixes, and adds surfactant, is configured to aqueous phase solution；
(3) preparation of oil-phase solution: in organic solvent by polynary acyl chlorides ultrasonic dissolution, it is configured to oil-phase solution；
(4) interface polymerization reaction: being upside down in membrane surface for aqueous phase solution, after contact, outwells extra liquid, naturally dry,
Then oil-phase solution reaction a period of time is poured into again, is removed extra oil-phase solution, is dried, obtain graphene oxide quantum dot-
The reverse osmosis composite membrane of silver orthophosphate composite modification.
2. preparation method according to claim 1, which is characterized in that in step (1), graphene oxide quantum dot suspension
Concentration be 2-6mg/ml, the concentration of silver nitrate solution is 8-12mM.
3. preparation method according to claim 1, which is characterized in that in step (1), in step (1), graphene oxide amount
The volume ratio of son point solution and silver nitrate solution are as follows: (1-3): (1-3).
4. preparation method according to claim 1, which is characterized in that in step (1), in step (1), the phosphate
For one of disodium hydrogen phosphate dodecahydrate, sodium dihydrogen phosphate, sodium phosphate, phosphatic additional amount is every milliliter of graphite oxide
Phosphate 0.36-3.35mg is added in alkene quantum dot suspension, mixing time is 0.5 to 1h after silver nitrate is added, centrifugation rate
It is 6000 to 10000rpm.
5. preparation method according to claim 1, which is characterized in that in step (2), oxygen graphene oxide in aqueous phase solution
Quantum dot-phosphoric acid silver composite material mass concentration is 0.001~0.02% (w/v), the mass concentration of polyamine is 0.5~
3% (w/v), it is preferred that oxygen graphene oxide quantum dot-phosphoric acid silver composite material mass concentration is 0.003 in aqueous phase solution
~0.005% (w/v).
6. preparation method according to claim 1, which is characterized in that in step (2), surfactant in aqueous phase solution
Mass concentration is 0.1~0.25w% (w/v).
7. preparation method according to claim 1, which is characterized in that in step (2), the polyamine be o-phenylenediamine,
One of p-phenylenediamine, m-phenylene diamine (MPD), ethylenediamine, propane diamine, hexamethylene diamine, the surfactant are dodecyl sulphate
One of sodium, dodecyl sodium sulfate, fatty alcohol polyoxyethylene ether or α-sodium olefin sulfonate.
8. preparation method according to claim 1, which is characterized in that in step (3), the polynary acyl chlorides is equal benzene front three
Acyl chlorides, three formyl chloride of isophthalic, three acyl chlorides of hexamethylene, three acyl chlorides of pentamethylene, the third three one of acyl chlorides and penta 3 acyl chlorides；It is described to have
Solvent is one of n-hexane, normal heptane, dodecane, the tetradecane.
9. preparation method according to claim 1, which is characterized in that in step (3), polynary acyl chlorides in oil-phase solution
Mass concentration is 0.05~0.2% (w/v).
10. preparation method according to claim 1, which is characterized in that in step (4), the basement membrane is polysulfones, polyethers
One of sulfone, polyphenylsulfone, polyacrylonitrile or Kynoar, drying temperature be 50~120 DEG C, drying time be 5~
10min。
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