CN108970405A - A kind of reverse osmosis composite membrane of the silver nano-grain of in-situ reducing containing graphene oxide quantum dot - Google Patents
A kind of reverse osmosis composite membrane of the silver nano-grain of in-situ reducing containing graphene oxide quantum dot Download PDFInfo
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- CN108970405A CN108970405A CN201810688816.6A CN201810688816A CN108970405A CN 108970405 A CN108970405 A CN 108970405A CN 201810688816 A CN201810688816 A CN 201810688816A CN 108970405 A CN108970405 A CN 108970405A
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- 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
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- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
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- 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
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The present invention relates to a kind of reverse osmosis composite membranes of silver nano-grain of in-situ reducing containing graphene oxide quantum dot, the present invention first will be in silver nano-grain in-situ reducing to graphene oxide quantum dot, obtain a kind of antimicrobial composite material, the anti-biotic material is added again in the aramid layer of reverse osmosis membrane, both had high water flux, height cuts salt, there is high resistance tocrocking again, the reverse osmosis composite membrane of high antibiotic property, it is with good stability, in water process, UF membrane field is with a wide range of applications, graphene oxide quantum dot contains numerous oxygen-containing functional groups, a large amount of nucleation sites are provided for the growth of Nano silver grain, effectively prevent the aggregation of silver nano-grain, improve the specific surface area of sterilization composite material, substantially increase germicidal efficiency.
Description
Technical field
The present invention relates to a kind of reverse osmosis composite membranes of silver nano-grain of in-situ reducing containing graphene oxide quantum dot, belong to
Reverse osmosis membrane technology field.
Background technique
Currently, the problems such as pollution and shortage of water resource be increasingly becoming influence Social Stable Development in Economy it is important because
One of element.It is current every country focus of attention that fresh water how is obtained using limited resource, and wherein sea water desalination becomes
Solve the grand strategy means of shortage of water resources.It is reverse osmosis one of as Membrane Separation for Water Treatment, have purifying rate it is high, at
This low advantage plays more and more important in the fields such as bitter and sea water desalination, ultrapure water preparation and Industrial Waste Water Treatments
Effect.
Reverse osmosis membrane has become the mainstream in Membrane Separation for Water Treatment, but the upper limit of water flux and rejection balance with
And poor antifouling property etc. is still an important factor for restricting reverse osmosis technology development.Fouling membrane can cause water flux and cut
Stay rate rapid decrease.Fouling membrane be broadly divided into inorganic pollution, organic contamination, colloid substances dye and microbial contamination four in type.Its
Middle microbial contamination is most common pollution type.The performance for generally keeping film, needs higher operating pressure micro- to overcome
On the one hand the gel layer bring additional friction that biology is formed influences the service life of film, on the other hand also increases energy consumption significantly
Add, increases equipment operating cost.The bacterial clump that film surface is formed in some cases also will cause water pollution, greatly prestige
Coerce the safe drinking water of the masses.
Microbial contamination has seriously affected the application and popularization of reverse osmosis composite membrane.Therefore high-throughput, highly selective, low dirt
Dye and high antibiotic property are the main developing direction of reverse osmosis membrane technology, are to improve reverse osmosis composite membrane operational efficiency, extend it and make
With the key in service life.Although having made great progress at present, it is still hymenology that preparing, which has the composite membrane of antibacterial functions,
One of the target that art circle and film industry are pursued.Nano material with antibiotic property is introduced into polyam ide TLC formed it is novel
Laminated film come improve water flux, cut salt effect, resistance tocrocking, and assign reverse osmosis membrane anti-microbial property become people research weight
The nano material of antibiotic property is introduced into polyam ide TLC by point, still, current means, is easily caused blocking ultrafiltration membrane, is led
Water flux is caused to substantially reduce, thus sterilization and high water flux cannot get both.
Graphene oxide quantum dot is as a kind of carbon nanomaterial, because of its excellent chemical property, high-hydrophilic and good
Dispersibility be widely used every field, while silver nano-grain is anti-because its excellent anti-microbial property is widely used
Among mycoderm field.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of silver nano-grain of in-situ reducing containing graphene oxide quantum dot
Reverse osmosis composite membrane.
The present invention is achieved through the following technical solutions:
A kind of reverse osmosis composite membrane containing in-situ reducing silver nano-grain on graphene oxide quantum dot, including basement membrane and position
Antibacterial agent is uniformly mixed in epilamellar polyamide film layer, polyamide film layer, the antibacterial agent is graphene oxide amount
Son puts the composite material of upper uniform in-situ reducing silver nano-grain.
Preferred according to the present invention, the graphene oxide is two-dimensional slice structure, and the partial size of graphene oxide is 7-
20nm
Preferred according to the present invention, the partial size of silver nano-grain is 2-10nm.
According to the present invention, the preparation containing the reverse osmosis composite membrane of in-situ reducing silver nano-grain on graphene oxide quantum dot
Method comprises the following steps that
1) on graphene oxide quantum dot in-situ reducing silver nano-grain composite material preparation: by graphene oxide quantum
Point solution is mixed with silver nitrate solution, after ultrasound is uniform, alkaline solution is added, and be stirred continuously in water-bath, is aoxidized
In-situ reducing silver nano-grain composite material on graphene quantum dot；
2) preparation of aqueous phase solution: in-situ reducing silver nano-grain composite material on graphene oxide quantum dot is dispersed in
In water, polyamine is added and is made into aqueous phase solution；
3) preparation of oil-phase solution: in organic solvent by the dissolution of polynary acyl chlorides, oil-phase solution is made；
4) aqueous phase solution is poured on basement membrane, after contact, removes extra aqueous phase solution, naturally dry is subsequently poured into oil
Phase solution removes extra oil-phase solution after interface polymerization reaction, dries, and obtains containing in-situ reducing on graphene oxide quantum dot
The reverse osmosis composite membrane of silver nano-grain.
Preferred according to the present invention, the concentration of graphene oxide quantum dot solution is 0.1-0.3mg/ml.
Highly preferred, the concentration of graphene oxide quantum dot solution is 0.25mg/ml.
Preferred according to the present invention, the concentration of silver nitrate solution is 0.1-0.3mg/ml.
Highly preferred, the concentration of silver nitrate solution is 0.25mg/ml.
It is preferred according to the present invention, the volume ratio of graphene oxide quantum dot solution and silver nitrate solution are as follows: (1-3): (1-
3)。
It is preferred according to the present invention, in step 1), the alkaline solution be sodium hydroxide, potassium hydroxide, calcium hydroxide or
One of barium hydroxide；The concentration of alkaline solution is 0.1-6mol/L.
Preferred according to the present invention, in step 1), reaction temperature is 20-90 DEG C in water-bath；Reaction time is 5-60 points
Clock.
It is preferred according to the present invention, in step 1), in-situ reducing silver nano-grain on obtained graphene oxide quantum dot
Silver nano-grain partial size is 2-10nm in composite material.
Preferred according to the present invention, the additional amount of alkaline solution and the volume ratio of graphene oxide quantum dot solution are (5-
8): 30.
It is preferred according to the present invention, in step 2), in-situ reducing silver nanoparticle on graphene oxide quantum dot in aqueous phase solution
The mass concentration of particulate composite is 0.001~0.04% (w/v), and the mass concentration of polyamine is 0.5~3% (w/v).
Preferred according to the present invention, in step 2), polyamine is selected from o-phenylenediamine, p-phenylenediamine, m-phenylene diamine (MPD), second two
One of amine, propane diamine or hexamethylene diamine.
Preferred according to the present invention, in step 3), the mass concentration of polynary acyl chlorides is 0.05~0.2% in oil-phase solution
(w/v)。
It is preferred according to the present invention, in step 3), the polynary acyl chlorides be pyromellitic trimethylsilyl chloride, three formyl chloride of isophthalic,
Three acyl chlorides of hexamethylene, three acyl chlorides of pentamethylene, the third three one of acyl chlorides or penta 3 acyl chlorides；The organic solvent is n-hexane, just
One of heptane, dodecane or four alkane.
Preferred according to the present invention, in step 4), basement membrane is polysulfones, polyether sulfone, polyethylene, polyamide-imide, polypropylene
Or one of polyacrylonitrile
Preferred according to the present invention, in step 4), aqueous phase solution time of contact is 1-10min, pours into boundary after oil-phase solution
Face polymerization reaction time is 1-10min.
Preferred according to the present invention, in step 4), drying temperature is 50~120 DEG C, and drying time is 5~10min.
The present invention in silver nano-grain in-situ reducing to graphene oxide quantum dot, will first obtain a kind of antibacterial composite wood
Material, then the anti-biotic material is added in the aramid layer of reverse osmosis membrane, not only had high water flux, high section of salt, but also there is highly resistance
Pollution, the reverse osmosis composite membrane of high antibiotic property；
The anti-biotic material of the invention in-situ reducing in graphene oxide quantum dot nanometer sheet grows Nano silver grain, Yin Na
Rice grain partial size is 3 to 20nm.Use graphene oxide quantum dot as the matrix of growth silver nano-grain, it can be largely effective
The aggregation for preventing silver nano-grain, so that silver nano-grain is realized uniform point in graphene oxide quantum dot nanometer sheet
Cloth, and greatly reduce the partial size of silver nano-grain.The reduction of silver nano-grain partial size so that silver nano-grain specific surface
Product substantially increase, may be implemented more efficiently in conjunction with bacterium and kill bacterium, the bactericidal property of composite material is mentioned significantly
It is high.
Contain a large amount of oxygen-containing functional group in graphene oxide quantum dot nanometer sheet, these oxygen-containing functional groups can be silver-colored
Growth provides nucleation site.After graphene oxide quantum dot and silver nitrate are mixed in a certain ratio, on graphene oxide quantum dot
Electronegative oxygen-containing functional group and positively charged silver ion electrostatical binding, by the way that strong base solution is added, silver ion is quickly oxidized
Oxygen-containing functional group on graphene quantum dot is reduced into elemental silver and is attached to graphene oxide quantum dot surface, which can claim
For nucleation；Then the silver ion in solution is grown on core, ultimately forms silver nano-grain；By controlling graphene oxide quantum
The concentration and dosage of point and silver nitrate, obtained silver nano-grain partial size is 3 to 20nm；Since silver ion passes through charge and oxidation
Electronegative oxygen-containing functional group combines on graphene quantum dot, so silver nano-grain is distributed on graphene oxide quantum dot surface
Uniformly.
In addition, the oxygen-containing functional group on graphene oxide quantum dot is partially removed in oxidation-reduction process, final oxygen
Graphite alkene quantum dot is partially reduced.Since graphene oxide quantum dot is not completely reduced, remaining oxygen-containing functional group
Composite material hydrophily is imparted, this hydrophilic composite material is easier to be distributed in water phase, mention to subsequent patternmaking process
Advantage has been supplied, and has assigned reverse osmosis membrane better hydrophily, the hydrophily of film then can be in the feelings for not influencing high rejection
Under condition, the higher water flux of film is assigned.
Technical characterstic and advantage of the invention:
1, the present invention in silver nano-grain in-situ reducing to graphene oxide quantum dot, will first obtain a kind of antibacterial composite wood
Material, then the anti-biotic material is added in the aramid layer of reverse osmosis membrane, not only had high water flux, high section of salt, but also there is highly resistance
Pollution, the reverse osmosis composite membrane of high antibiotic property is with good stability, has in water process, UF membrane field extensive
Application prospect.
2, first by silver nano-grain in-situ reducing to graphene oxide quantum dot, graphene oxide quantum dot contains the present invention
There are numerous oxygen-containing functional groups, provide a large amount of nucleation sites for the growth of Nano silver grain, effectively prevents the poly- of silver nano-grain
Collection improves the specific surface area of sterilization composite material, substantially increases germicidal efficiency.
3, the antimicrobial composite material that the present invention in silver nano-grain in-situ reducing to graphene oxide quantum dot, will first obtain
With good hydrophily, composite film surface hydrophily is enhanced, reverse osmosis composite membrane is made to possess higher water flux.
4, raw material of the invention is to be easily obtained, cheap, to reduce the production cost of reverse osmosis composite membrane.
5, the present invention is compound by in-situ reducing silver nano-grain on graphene oxide quantum dot in specific aqueous phase solution
The mass concentration of material so that water flux and rejection greatly improve, while being provided with excellent antifouling property and antibiotic property
Energy.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram on reverse osmosis composite membrane surface 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 2,4 Yu comparative example 1；
In-situ reducing silver nano-grain composite material on the graphene oxide quantum dot that Fig. 3 obtains for 4 step 1) of embodiment
TEM figure, upper right side illustration is HRTEM image in figure, and lower right illustration is silver nano-grain size distribution histogram；
Fig. 4 is in experimental example with the change of in-situ reducing silver nano-grain composite material concentration on graphene oxide quantum dot
Change, the water flux of composite membrane and the change curve of salt-stopping rate；
Fig. 5 is to have carried out film up in the reverse osmosis test process of 50 hours in experimental example, the water flux of film and is cut
Salt 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.
Embodiment 1
Preparation method containing the reverse osmosis composite membrane of in-situ reducing silver nano-grain on graphene oxide quantum dot, step is such as
Under:
1) on graphene oxide quantum dot in-situ reducing silver nano-grain composite material preparation: 30 milliliters of graphene oxides
Quantum dot (0.25mg/ml) solution is mixed with 30 milliliters of silver nitrate solutions (0.25mg/ml).Ultrasonic treatment is hanged after 30 minutes
The NaOH solution of 7 milliliters of 4M is instilled in suspension, stirs 20 minutes at 80 DEG C, be cooled to room temperature suspension, mistake by supernatant liquid
Filter washing obtains in-situ reducing silver nano-grain composite material on graphene oxide quantum dot；
2) preparation of aqueous phase solution: in-situ reducing silver nano-grain composite material on graphene oxide quantum dot is added to
In deionized water, concentration 0.0025w/v% is stirred by ultrasonic 1h, a certain amount of m-phenylene diamine (MPD) is added into above-mentioned solution, makes isophthalic
Two amine concentrations are 2w/v%, to obtain aqueous phase solution after completely dissolution；
3) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride being added into n-hexane, makes its concentration 0.1w/v%, to abundant
Oil-phase solution is obtained after dissolution；
4) aqueous phase solution is poured on basement membrane, after contacting 1min, removes extra aqueous phase solution, then naturally dry is fallen
Enter oil-phase solution, extra oil-phase solution is removed after interface polymerization reaction 1min, is put into 80 DEG C of drying 5min drying in baking oven, obtains
The reverse osmosis composite membrane of in-situ reducing silver nano-grain on containing graphene oxide quantum dot.
Embodiment 2
Preparation method containing the reverse osmosis composite membrane of in-situ reducing silver nano-grain on graphene oxide quantum dot, step is such as
Under:
1) on graphene oxide quantum dot in-situ reducing silver nano-grain composite material preparation: 30 milliliters of graphene oxides
Quantum dot (0.25mg/ml) solution is mixed with 30 milliliters of silver nitrate solutions (0.25mg/ml).Ultrasonic treatment is hanged after 30 minutes
The NaOH solution of 7 milliliters of 4M is instilled in suspension, stirs 20 minutes at 80 DEG C, be cooled to room temperature suspension, mistake by supernatant liquid
Filter washing obtains in-situ reducing silver nano-grain composite material on graphene oxide quantum dot；
2) preparation of aqueous phase solution: in-situ reducing silver nano-grain composite material on graphene oxide quantum dot is added to
Concentration is 0.005w/v% in deionized water, and 1h is stirred by ultrasonic, a certain amount of m-phenylene diamine (MPD) is added into above-mentioned solution, makes isophthalic two
Amine concentration is 2w/v%, to obtain aqueous phase solution after completely dissolution；
3) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride being added into n-hexane, makes its concentration 0.1w/v%, to abundant
Oil-phase solution is obtained after dissolution；
4) aqueous phase solution is poured on basement membrane, after contacting 1min, removes extra aqueous phase solution, then naturally dry is fallen
Enter oil-phase solution, extra oil-phase solution is removed after interface polymerization reaction 1min, is put into 80 DEG C of drying 5min drying in baking oven, obtains
The reverse osmosis composite membrane of in-situ reducing silver nano-grain on containing graphene oxide quantum dot.
Embodiment 3
Preparation method containing the reverse osmosis composite membrane of in-situ reducing silver nano-grain on graphene oxide quantum dot, step is such as
Under:
1) on graphene oxide quantum dot in-situ reducing silver nano-grain composite material preparation: 30 milliliters of graphene oxides
Quantum dot (0.25mg/ml) solution is mixed with 30 milliliters of silver nitrate solutions (0.25mg/ml).Ultrasonic treatment is hanged after 30 minutes
The NaOH solution of 7 milliliters of 4M is instilled in suspension, stirs 20 minutes at 80 DEG C, be cooled to room temperature suspension, mistake by supernatant liquid
Filter washing obtains in-situ reducing silver nano-grain composite material on graphene oxide quantum dot；
2) preparation of aqueous phase solution: in-situ reducing silver nano-grain composite material on graphene oxide quantum dot is added to
In deionized water, concentration 0.0075w/v% is stirred by ultrasonic 1h, a certain amount of o-phenylenediamine is added into above-mentioned solution, makes adjacent benzene
Two amine concentrations are 2w/v%, to obtain aqueous phase solution after completely dissolution；
3) preparation of oil-phase solution: three formyl chloride of isophthalic is added into normal heptane, makes its concentration 0.05w/v%, wait fill
Oil-phase solution is obtained after dividing dissolution；
4) aqueous phase solution is poured on basement membrane, after contacting 1min, removes extra aqueous phase solution, then naturally dry is fallen
Enter oil-phase solution, extra oil-phase solution is removed after interface polymerization reaction 1min, is put into 80 DEG C of drying 5min drying in baking oven, obtains
The reverse osmosis composite membrane of in-situ reducing silver nano-grain on containing graphene oxide quantum dot.
Embodiment 4
Preparation method containing the reverse osmosis composite membrane of in-situ reducing silver nano-grain on graphene oxide quantum dot, step is such as
Under:
1) on graphene oxide quantum dot in-situ reducing silver nano-grain composite material preparation: 30 milliliters of graphene oxides
Quantum dot (0.25mg/ml) solution is mixed with 30 milliliters of silver nitrate solutions (0.25mg/ml).Ultrasonic treatment is hanged after 30 minutes
The NaOH solution of 7 milliliters of 4M is instilled in suspension, stirs 20 minutes at 80 DEG C, be cooled to room temperature suspension, mistake by supernatant liquid
Filter washing obtains in-situ reducing silver nano-grain composite material on graphene oxide quantum dot；
2) preparation of aqueous phase solution: in-situ reducing silver nano-grain composite material on graphene oxide quantum dot is added to
In deionized water, concentration 0.01w/v% is stirred by ultrasonic 1h, a certain amount of m-phenylene diamine (MPD) is added into above-mentioned solution, makes isophthalic two
Amine concentration is 2w/v%, to obtain aqueous phase solution after completely dissolution；
3) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride being added into n-hexane, makes its concentration 0.1w/v%, to abundant
Oil-phase solution is obtained after dissolution；
4) aqueous phase solution is poured on basement membrane, after contacting 1min, removes extra aqueous phase solution, then naturally dry is fallen
Enter oil-phase solution, extra oil-phase solution is removed after interface polymerization reaction 1min, is put into 80 DEG C of drying 5min drying in baking oven, obtains
The reverse osmosis composite membrane of in-situ reducing silver nano-grain on containing graphene oxide quantum dot.
Comparative example 1
A kind of preparation method of reverse osmosis composite membrane, steps are as follows:
A certain amount of m-phenylene diamine (MPD) is add to deionized water, makes m-phenylene diamine (MPD) concentration 2w/v%, to after completely dissolution
Obtain aqueous phase solution；Pyromellitic trimethylsilyl chloride is added into n-hexane, makes its concentration 0.1w/v%, to after completely dissolution to obtain the final product
To oil-phase solution.Aqueous phase solution is poured on basement membrane, is poured out aqueous phase solution after 1min, oil-phase solution is added, instead in naturally dry
1min is answered, oil-phase solution is poured out, reverse osmosis composite membrane semi-finished product are made.Reverse osmosis composite membrane semi-finished product are put into baking oven 80 DEG C
Drying 5min obtains common reverse osmosis composite membrane (being denoted as TFC film).
Comparative example 2
A kind of preparation method of reverse osmosis composite membrane, steps are as follows:
1) preparation of aqueous phase solution: it is 0.005w/v% that graphene oxide quantum dot, which is add to deionized water concentration,
1h is stirred by ultrasonic, a certain amount of m-phenylene diamine (MPD) is added into above-mentioned solution, makes m-phenylene diamine (MPD) concentration 2w/v%, to after completely dissolution
Obtain aqueous phase solution；
2) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride being added into n-hexane, makes its concentration 0.1w/v%, to abundant
Oil-phase solution is obtained after dissolution；
3) aqueous phase solution is poured on basement membrane, after contacting 1min, removes extra aqueous phase solution, then naturally dry is fallen
Enter oil-phase solution, extra oil-phase solution is removed after interface polymerization reaction 1min, is put into 80 DEG C of drying 5min drying in baking oven, obtains
To reverse osmosis composite membrane.
Comparative example 3
A kind of preparation method of reverse osmosis composite membrane, steps are as follows:
1) preparation of aqueous phase solution: it is 0.005w/v% that silver nitrate, which is add to deionized water concentration, and 1h is stirred by ultrasonic,
A certain amount of m-phenylene diamine (MPD) is added into above-mentioned solution, makes m-phenylene diamine (MPD) concentration 2w/v%, to obtain water phase after completely dissolution
Solution；
2) preparation of oil-phase solution: pyromellitic trimethylsilyl chloride being added into n-hexane, makes its concentration 0.1w/v%, to abundant
Oil-phase solution is obtained after dissolution；
3) aqueous phase solution is poured on basement membrane, after contacting 1min, removes extra aqueous phase solution, then naturally dry is fallen
Enter oil-phase solution, extra oil-phase solution is removed after interface polymerization reaction 1min, is put into 80 DEG C of drying 5min drying in baking oven, obtains
To reverse osmosis composite membrane.
Experimental example
Film properties test:
1, water flux and section salt test:
Water flux and salt-stopping rate are two important parameters for evaluating reverse osmosis membrane separation performance.Reverse osmosis composite membrane is outside
It is tested under pressure, the mode of cross-flow.The NaCl solution of 2g/L is prepared, test pressure is 1.6MPa, and it is steady to be depressed into flux in advance first
It is fixed, the then separating property of testing example 1-4 and comparative example 1-3 reverse osmosis composite membrane, including water flux and rejection.
Rejection (R) is defined as: under certain operating conditions, salinity in feeding liquid salinity (Cf) and penetrating fluid
(Cp) difference, then divided by feeding liquid salinity.
Water flux: under certain operating conditions, through the volume of the water of per membrane area in the unit time, unit is
L/m2/h(LMH)。
2, antibacterial test:
Taking 1mL cell age with liquid-transfering gun is the escherichia coli suspension or golden yellow grape ball that concentration is 106CFU/mL after diluting for 24 hours
Bacteria suspension is dissolved in the sterile saline of 50mL, and the reverse osmosis composite membrane of 4cm × 4cm is immersed in 50mL physiological saline respectively
In, it is fixed on oscillation shaking table, is swayed 2 hours with 120r/min, embodiment 1-4 and comparative example 1-3 reverse osmosis composite membrane are used
Normal saline flushing film surface, the liquid after taking 0.1mL to rinse are placed in solid medium, it is uniformly spreadable, then by it
30 DEG C of constant temperature incubation 12h in constant incubator are placed on, sterilizing rate are calculated by solid medium clump count, as a result such as Fig. 2 institute
Show.Common reverse osmosis composite membrane piece (being free of antibacterial surface material) is tested simultaneously.Sterilizing rate calculates as follows:
Sterilizing rate (%)=((A-B)/A) × 100%
In formula: A-ordinary RO membrane sample clump count；
B-antibacterial reverse osmosis composite membrane sample clump count.
3, influence of the in-situ reducing silver nano-grain composite material concentration to water flux on graphene oxide quantum dot
4, the stability test of reverse osmosis composite membrane separation.
Experimental result:
One, using method described above respectively to embodiment 1-4 and comparative example 1-3 reverse osmosis composite membrane carry out water flux,
Rejection test and anti-microbial property test, test result is as follows table 1:
Water flux, rejection and the antibiotic property of the different reverse osmosis composite membranes of table 1
It can be seen from the data in Table 1 that the water flux of embodiment 1-4 is all more logical than the water of ordinary RO membrane in comparative example 1
Amount (27.128LMH) is significantly improved, and there is no lose very big rejection.Also, from sterilizing rate can be seen that with
The increase of graphene oxide quantum dot/silver nano-grain composite material content, the bactericidal properties of reverse osmosis composite membrane of the invention
It can be gradually increased, and either to gram-positive bacteria (Staphylococcus aureus) or Gram-negative bacteria (large intestine bar
Bacterium) there is very high bactericidal effect.Although comparative example 2 has high water flux and rejection, there is no bactericidal effect, comparative example
Although 3 have bactericidal effect, water flux and rejection are greatly reduced, and therefore, antibacterial reverse osmosis composite membrane film of the invention both had
There are high water flux and salt-stopping rate, and there is good bactericidal property.
Two, with the variation of in-situ reducing silver nano-grain composite material concentration on graphene oxide quantum dot, composite membrane
The variation of water flux and salt-stopping rate is as shown in figure 4, it can be seen from the figure that with in-situ reducing silver on graphene oxide quantum dot
The increase of nano particle composite material concentration, the water flux of composite membrane are also to be gradually increased, but increase to after a certain concentration it
Salt-stopping rate starts in downward trend.
Three, it has carried out in the film to embodiment 2 up in the reverse osmosis test process of 50 hours, the water flux of film and has cut
Salt rate still keeps more stable state, as shown in Figure 5.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 (9)
1. a kind of reverse osmosis composite membrane of the silver nano-grain of in-situ reducing containing graphene oxide quantum dot, including basement membrane and it is located at base
Polyamide film layer on film, antibacterial agent is uniformly mixed in polyamide film layer, and the antibacterial agent is graphene oxide quantum dot
The composite material of upper uniform in-situ reducing silver nano-grain.
2. the reverse osmosis composite membrane of the silver nano-grain of in-situ reducing containing graphene oxide quantum dot according to claim 1,
It is characterized in that, the graphene oxide is two-dimensional slice structure, the partial size of graphene oxide is 7-20nm, silver nano-grain
Partial size be 2-10nm.
3. the preparation method of the reverse osmosis composite membrane of the silver nano-grain of in-situ reducing containing graphene oxide quantum dot, including step is such as
Under:
1) on graphene oxide quantum dot in-situ reducing silver nano-grain composite material preparation: graphene oxide quantum dot is molten
Liquid is mixed with silver nitrate solution, after ultrasound is uniform, alkaline solution is added, and be stirred continuously in water-bath, is obtained graphite oxide
In-situ reducing silver nano-grain composite material on alkene quantum dot；
2) in-situ reducing silver nano-grain composite material on graphene oxide quantum dot the preparation of aqueous phase solution: is dispersed in water
In, polyamine is added and is made into aqueous phase solution；
3) preparation of oil-phase solution: in organic solvent by the dissolution of polynary acyl chlorides, oil-phase solution is made；
4) aqueous phase solution is poured on basement membrane, after contact, removes extra aqueous phase solution, naturally dry is subsequently poured into oil and mixes
Liquid removes extra oil-phase solution after interface polymerization reaction, dries, and obtains receiving containing in-situ reducing silver on graphene oxide quantum dot
The reverse osmosis composite membrane of rice grain.
4. preparation method according to claim 3, which is characterized in that the concentration of graphene oxide quantum dot solution is 0.1-
0.3mg/ml；Preferably, the concentration of graphene oxide quantum dot solution is 0.25mg/ml；The concentration of silver nitrate solution is 0.1-
0.3mg/ml；Preferably, the concentration of silver nitrate solution is 0.25mg/ml.
5. preparation method according to claim 3, which is characterized in that graphene oxide quantum dot solution and silver nitrate solution
Volume ratio are as follows: (1-3): (1-3).
6. preparation method according to claim 3, which is characterized in that in step 1), the alkaline solution be sodium hydroxide,
One of potassium hydroxide, calcium hydroxide or barium hydroxide；The concentration of alkaline solution is 0.1-6mol/L；Temperature is reacted in water-bath
Degree is 20-90 DEG C；Reaction time is 5-60 minutes；In-situ reducing silver nano-grain is compound on obtained graphene oxide quantum dot
Silver nano-grain partial size is 3-20nm in material；The additional amount of alkaline solution and the volume ratio of graphene oxide quantum dot solution are
(5-8): 30.
7. preparation method according to claim 3, which is characterized in that in step 2), graphene oxide amount in aqueous phase solution
The mass concentration that son puts upper in-situ reducing silver nano-grain composite material is 0.001~0.04% (w/v), and the quality of polyamine is dense
Degree is 0.5~3% (w/v)；Polyamine is selected from o-phenylenediamine, p-phenylenediamine, m-phenylene diamine (MPD), ethylenediamine, propane diamine or hexamethylene diamine
One of.
8. preparation method according to claim 3, which is characterized in that in step 3), polynary acyl chlorides in oil-phase solution
Mass concentration is 0.05~0.2% (w/v)；In step 3), the polynary acyl chlorides is pyromellitic trimethylsilyl chloride, three formyl of isophthalic
Chlorine, three acyl chlorides of hexamethylene, three acyl chlorides of pentamethylene, the third three one of acyl chlorides or penta 3 acyl chlorides；The organic solvent be n-hexane,
One of normal heptane, dodecane or four alkane.
9. preparation method according to claim 3, which is characterized in that in step 4), basement membrane is polysulfones, polyether sulfone, poly- second
One of alkene, polyamide-imide, polypropylene or polyacrylonitrile；Aqueous phase solution time of contact is 1-10min, pours into oil-phase solution
The interface polymerization reaction time is 1-10min afterwards；Drying temperature is 50~120 DEG C, and drying time is 5~10min.
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