CN105214511B - A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof - Google Patents
A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof Download PDFInfo
- Publication number
- CN105214511B CN105214511B CN201510595471.6A CN201510595471A CN105214511B CN 105214511 B CN105214511 B CN 105214511B CN 201510595471 A CN201510595471 A CN 201510595471A CN 105214511 B CN105214511 B CN 105214511B
- Authority
- CN
- China
- Prior art keywords
- solution
- graphene
- nano silver
- kynoar
- volume
- 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
Abstract
The invention discloses a kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof, comprise the following steps：(1) graphene oxide, polyethylene glycol ultrasonic disperse are obtained into solution A in N, N dimethyl acetamides；By AgNO3, polyethylene glycol be dissolved in N, N dimethyl acetamides to obtain solution B；(2) resulting solution A and solution B are mixed in proportion into obtain Nano Silver/graphene complex solution；(3) Kynoar is dissolved in gained Nano Silver/graphene complex solution, casting solution is obtained after standing and defoaming；(4) gained casting solution is prepared into Nano Silver/graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.Preparation method of the present invention can make nano silver particles are more uniform to be supported on graphene, and Nano Silver/graphene complex may be homogenously dispersed in Kynoar hybrid membranes, and obtained hybrid membranes have good antibacterial and antifouling property.
Description
Technical field
The invention belongs to nano composite material and ultrafiltration membrane technique neck city, and in particular to one kind has antibacterial and resistance tocrocking
The preparation method of Nano Silver/graphene/Kynoar hybrid membranes of energy.
Background technology
Kynoar is current most widely used ultrafiltration membrane material.Due to the hydrophobicity of polyvinylidene fluoride film, make
Easily absorption is deposited on film surface to pollutant during, blocks fenestra, causes the pollution of film, wherein especially with the pollution of microorganism
It is the most serious.Fouling membrane can cause the decay of membrane flux, so as to need to carry out clearly polluted membrane using methods such as physics, chemistry
Wash；In addition, some pollutions will cause the irreversible decay of membrane flux to a certain extent.Fouling membrane will greatly increase operation operation
Cost, shortens the service life of film.Therefore, the antifouling property for improving polyvinylidene fluoride (PVDF) ultrafiltration membrane is enhancing polyvinylidene fluoride film
One of important measures applied in the industry, and improve the antibiotic property of polyvinylidene fluoride (PVDF) ultrafiltration membrane, it is to improve Kynoar again
One of effective means of milipore filter antifouling property.
Silver has efficient antibacterial activity, is widely used in water body filtration film.For example, Application No.
201410168475.1 Chinese invention patent application document disclose a kind of phosphoric acid modified by silver nanometer anion powder modified polyvinilidene
The preparation method of fluoride film.Nano silver is obtained using ion-exchange, and is modified negative ion powder acquisition load silver
Negative ion powder.The appropriate silver negative ion powder that carries is added in Kynoar casting solution again, is prepared for by phase inversion containing load
The modified polyvinilidene fluoride film of silver-colored negative ion powder.By the silver-colored distinctive nanometer size effect of negative ion powder and surface energy is carried, assign
Polyvinylidene fluoride film effective stable against biological contamination ability, improves its hydrophily and flux recovery rate.
The Chinese invention patent application document of Application No. 201210541062.4 discloses a kind of Ag/TiO2Modified polyvinilidene
Fluoride ultrafiltration membrane and preparation method thereof.By Kynoar, pore creating material, TiO2Nano particle, silver ion salt, solvent are made
The casting solution homogeneously disperseed；Casting solution is cast in mould again, the uniform film of a layer thickness is scratched into scraper, steaming is placed in
In distilled water, after drying after continuation dipping after film separation, taking-up film to Ag/TiO2Modified polyvinylidene fluoride ultrafiltration membrane.
The Chinese invention patent application document of Application No. 201410384455.8 discloses a kind of fabricated in situ Nano Silver
The preparation method of modified polyvinylidene fluoride ultrafiltration membrane.Including：1. Kynoar solution is prepared；2. prepare mixed containing Nano Silver
Close liquid；3. casting solution is prepared；4. casting, film forming；5. clean, obtain fabricated in situ Nano Silver modified polyvinylidene fluoride ultrafiltration membrane.
Graphene is with sp2The single carbon atom lamella of hydridization constitutes a kind of Novel Carbon Nanomaterials.Its piece of graphene oxide
Having on layer edge has epoxide group and hydroxyl on oxy radical, such as carboxylic acid group and carbonyl, base plane, therefore graphene oxide energy
It is well dispersed into polar solvent.Graphene also has certain antibacterial action, the two dimensional surface of graphene when being contacted with bacterium
Structure can cut the cell membrane of bacterium, while drawing the phospholipid molecule on cell membrane.Graphene unique structure and property, note
Fixed this new material will be gathered around in ultra-filtration and separation film field to have broad application prospects.
It is multiple that the Chinese invention application documents of Application No. 201410383815.2 disclose a kind of polymer/graphene oxide
Close the preparation method of seperation film.This method will aoxidize stone using the aqueous solution of graphene oxide as coagulating bath by inversion of phases process
Black alkene is assembled into the method that separation membrane surface prepares polymer/graphene oxide composite separating film.
The Chinese invention application documents of Application No. 201210557266.7 disclose a kind of polymer/graphene hydridization and received
Filter composite membrane and preparation method thereof.The Nano filtering composite membrane is that one layer is formed in polysulfone porous support membrane by interfacial polymerization process
Include the polymers function cortex of graphene.
The Chinese invention application documents of Application No. 201310014691.6 disclose a kind of hydrophilicity kynoar and changed
Property seperation film and preparation method thereof.This method on the one hand by the oxygen-containing functional group in oxide/carbon nanometer tube and graphene oxide come
Strengthen the hydrophily of seperation film, on the other hand enter the oxide/carbon nanometer tube of tubular structure using the graphene oxide of laminated structure
In network and mutual intercalation, forms relatively stable sandwich hierarchy, thus can effectively suppress identical nanostructure it
Between reunion, and be conducive to migration and assembling of the graphene oxide to composite film surface, and significantly improve in composite membrane and aoxidize
The contact area of CNT and graphene oxide and macromolecule matrix, so that the hydrophily and contamination resistance of film are enhanced,
So that the effluent flux of film is greatly enhanced.
The Chinese invention application documents of Application No. 201510012953.4 disclose a kind of Kynoar-graphite oxide
The preparation method of alkene composite hollow fiber membrane, by Kynoar, pore former, solvent, water is uniformly mixing to obtain PVDF solution.
GO-DMAC mixed liquors are added in Kynoar solution and obtain casting solution；Casting solution is filtered, standing and defoaming.By casting solution
Extruded simultaneously by spinning nozzle with core liquid, obtain the hollow fiber ultrafiltration membrane of graphene oxide doped Kynoar.
The Chinese invention application documents of Application No. 201410241195.9 disclose a kind of carboxylated graphene oxide/poly- inclined
PVF composite hyperfiltration membrane and preparation method.First by carboxylated graphene oxide in dimethyl acetamide and triethyl phosphate group
Into solvent pairs in ultrasonic disperse, then mixed with Kynoar, mechanical agitation dissolving, knifing on glass plate, then spend from
Dried naturally in sub- water immersion, air and obtain carboxylated graphene oxide/Kynoar composite hyperfiltration membrane.The carboxyl of the present invention
Changing graphene oxide/polyvinylidenefluoride fluoride composite ultrafiltration membrane has preferable hydrophily and mechanical strength.
The Chinese invention application documents of Application No. 201210521585.2 disclose one kind using modified graphene enhancing
The preparation method of the milipore filter of antibiotic property and resistance tocrocking.First by graphene modification, drying, then in modified graphene plus
Enter organic solvent, additive, membrane material, casting solution is obtained after being well mixed, after casting solution vacuum defoamation, be poured over to dry and put down
Whole planar surface, knifing is put into coagulant liquid, obtains milipore filter.
The content of the invention
The invention provides a kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof, the preparation
Method can make nano silver particles are more uniform to be supported on graphene, and Nano Silver/graphene complex may be homogenously dispersed in it is poly-
In vinylidene hybrid membranes, and obtained hybrid membranes have good antibacterial and antifouling property.
A kind of preparation method of Nano Silver/graphene/Kynoar hybrid membranes, comprises the following steps：
(1) graphene oxide, polyethylene glycol ultrasonic disperse are obtained into solution A in DMA；By AgNO3、
Polyethylene glycol, which is dissolved in DMA, obtains solution B；
(2) resulting solution A and solution B are well mixed to obtain Nano Silver/graphene complex solution in equal volume；
(3) Kynoar is dissolved in gained Nano Silver/graphene complex solution, casting film is obtained after standing and defoaming
Liquid；
(4) gained casting solution is prepared into Nano Silver/graphene/Kynoar hydridization ultrafiltration by immersion precipitation phase inversion process
Film.
First with AgNO3For presoma, DMA is solvent, and polyethylene glycol is reducing agent and nano-particle
Dispersant, the DMA solution of Nano Silver/graphene complex is prepared using ultrasonic wave added solvent-thermal process method；
Then added into this solution and uniform, stable casting solution is formed after Kynoar, agitated dissolving, standing and defoaming；Finally
This casting solution is prepared into Nano Silver/graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.Present invention system
Standby Nano Silver/graphene/Kynoar hybrid membranes have preferable antibacterial, antifouling property.
The present invention takes full advantage of a variety of properties and function of polyethylene glycol, and DMA solvent borne
Matter, in the synthesis of Nano Silver/graphene complex, polyethylene glycol has played reducing agent, the work of nano-particle dispersion stabilizer
With；And in the preparation of hybrid membranes, polyethylene glycol serves as pore-foaming agent and used again, DMA is in nanometer
All it is reused in the synthesis of silver/graphite alkene compound and the preparation of hybrid membranes as solvent.The present invention is a kind of green
Colour circle is protected, the fast and convenient method for preparing Nano Silver/graphene/Kynoar hybrid membranes.
Preferably, the ratio between graphene oxide quality and DMA volume are 5~15g/L in the solution A,
The ratio between polyethylene glycol quality and DMA volume are 5~30g/L.
It is further preferred that in the solution A the ratio between graphene oxide quality and DMA volume for 5~
The ratio between 10g/L, polyethylene glycol quality and DMA volume are 10~20g/L.
Preferably, AgNO in the solution B3The ratio between quality and DMA volume are 10~50g/L, poly- second
The ratio between glycol quality and DMA volume are 5~30g/L.
It is further preferred that AgNO in the solution B3The ratio between quality and DMA volume are 10~25g/
The ratio between L, polyethylene glycol quality and DMA volume are 10~20g/L.
The oxygen content of the graphene oxide is 10~30wt%, it is preferable that graphene oxide can select Aladdin
Industrial Cooperation 800 mesh graphite powders obtain (Zhao Li, Chen Yufei, Wang Ting, Wu by the self-control of Hummers methods
The in-situ polymerization of gift light graphene oxides/polyurethane hybrid film is built and gas permeability composite journals, and 2015,
32,673-682)。
The molecular weight of the polyethylene glycol is 800~20000.
Preferably, the ratio between quality volume of the dosage of Kynoar and Nano Silver/graphene complex solution is 150
~250g/L.More preferably 190~230g/L.
Preferably, solution A and solution B are prepared at 50~70 DEG C in step (1).Further preferably made at 60 DEG C
It is standby.
Preferably, solution A and solution B were mixed equal in ultrasonically treated 2.5~3.5 hours at 50~70 DEG C in step (2)
It is even.It is further preferred that ultrasonically treated 3 hours at 60 DEG C.
Preferably, the immersion precipitation phase inversion process is：Casting solution is immersed 25 on cleaned glass plate after overlay film, overlay film
In~35 DEG C of pure water, after film is from glass plate Automatic-falling, it is dipped in distilled water 20~24 hours, pulls nature out and dry
Nano Silver/graphene/Kynoar hybrid membranes are obtained afterwards.
It is further preferred that overlay film thickness of the casting solution on cleaned glass plate is 200~300 μm.Further, cover
Film thickness is 250 μm.
It is further preferred that being immersed after overlay film in 30 DEG C of pure water, after film is from glass plate Automatic-falling, steaming is dipped in
24 hours in distilled water.
Most preferably, the preparation method of Nano Silver/graphene/Kynoar hybrid membranes, comprises the following steps：
Step (1)：At 60 DEG C ultrasound by graphene oxide, polyethylene glycol ultrasonic disperse in DMA,
The ratio between graphene oxide quality and DMA volume are 6g/L, polyethylene glycol quality and DMA
The ratio between volume is 18g/L, and the graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol used is 4000；
Step (2)：By AgNO at 60 DEG C3, polyethylene glycol be dissolved in DMA, AgNO3Quality and N, N-
The ratio between dimethyl acetamide volume is 17g/L, and the ratio between polyethylene glycol quality and DMA volume are 18g/L.Make
Graphene oxide oxygen content is 19.2wt%, and the molecular weight polyethylene glycol used is 4000；
Step (3)：The solution that step (1) is prepared is mixed in equal volume with the solution that step (2) is prepared, at 60 DEG C at ultrasound
Reason 3 hours, is made Nano Silver/graphene complex solution.
Step (4)：It is that Kynoar is added to step (3) by 190g/L by mass volume ratio：Obtained Nano Silver/stone
In black alkene complex solution, stirring and dissolving forms uniform, stable casting solution after standing and defoaming；
Step (5)：On the glass plate that casting solution is poured over to cleaning, the film for spreading to 250 μm of thickness, 1 point are applied with coating device
The glass plate that painting has been scraped into film after clock is immersed in 30 DEG C of pure water, after film is from glass plate Automatic-falling, is put it into and is filled greatly
Soaked 24 hours in the bucket of the distilled water of amount, pull that Nano Silver/graphene/Kynoar is obtained after nature dries is compound super out
Filter membrane.
The present invention also provides Nano Silver/graphene/Kynoar hydridization that a kind of preparation method as described is prepared
Milipore filter.
Compared with prior art, the present invention has the advantages that：
Preparation method of the present invention can make nano silver particles are more uniform to be supported on graphene, and Nano Silver/graphene is compound
Thing may be homogenously dispersed in Kynoar hybrid membranes again, and obtained hybrid membranes have good antibacterial and anti-
Pollutant performance.
Brief description of the drawings
Fig. 1 is the Electronic Speculum that Nano Silver/graphene/Kynoar composite hyperfiltration membrane film surface is prepared in embodiment 3
Photo.
Fig. 2 is the Electronic Speculum that Nano Silver/graphene/Kynoar composite hyperfiltration membrane film section is prepared in embodiment 3
Photo.
Embodiment
Further illustrated below by way of specific embodiment using how the present invention prepares Nano Silver/graphene/poly- inclined fluorine
Ethene hybrid membranes, and its prepared milipore filter performance.
It is raw materials used in following examples to use commercial goods unless otherwise specified.
Embodiment 1
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in DMA at 60 DEG C,
The ratio between graphene oxide quality and DMA volume are 10g/L, polyethylene glycol quality and N, N- dimethylacetamide
The ratio between amine volume is 12g/L.The graphene oxide oxygen content used is 14.6wt%, and the molecular weight polyethylene glycol used is 800.
2. by AgNO at 60 DEG C3, polyethylene glycol be dissolved in DMA, AgNO3Quality and N, N- dimethyl
The ratio between acetamide volume is 25g/L, and the ratio between polyethylene glycol quality and DMA volume are 12g/L.The oxygen used
Graphite alkene oxygen content is 14.6wt%, and the molecular weight polyethylene glycol used is 800.
3. the solution 1. step prepared is mixed in equal volume with the solution that 2. step is prepared, ultrasonic (frequency at 60 DEG C
100Hz) handle 3 hours, Nano Silver/graphene complex solution is made.
4. Kynoar being added into step for 230g/L by mass volume ratio, 3. obtained Nano Silver/graphene is combined
In thing solution, stirring and dissolving forms uniform, stable casting solution after standing and defoaming.
5. casting solution is poured on the glass plate of cleaning, the film for spreading to 250 μm of thickness is applied with coating device, will after 1 minute
Apply in the glass plate 30 DEG C of pure water of immersion for having scraped film, after film is from glass plate Automatic-falling, puts it into and fill substantial amounts of steaming
Soaked 24 hours in the bucket of distilled water, pull out and Nano Silver/graphene/Kynoar composite hyperfiltration membrane is obtained after nature dries.
Embodiment 2
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in DMA at 60 DEG C,
The ratio between graphene oxide quality and DMA volume are 8g/L, polyethylene glycol quality and DMA
The ratio between volume is 15g/L.The graphene oxide oxygen content used is 16.3wt%, and the molecular weight polyethylene glycol used is 2000.
2. by AgNO at 60 DEG C3, polyethylene glycol be dissolved in DMA, AgNO3Quality and N, N- dimethyl
The ratio between acetamide volume is 20g/L, and the ratio between polyethylene glycol quality and DMA volume are 15g/L.The oxygen used
Graphite alkene oxygen content is 14.6wt%, and the molecular weight polyethylene glycol used is 2000.
3. the solution 1. step prepared is mixed in equal volume with the solution that 2. step is prepared, ultrasonic (frequency at 60 DEG C
100Hz) handle 3 hours, Nano Silver/graphene complex solution is made.
4. Kynoar being added into step for 210g/L by mass volume ratio, 3. obtained Nano Silver/graphene is combined
In thing solution, stirring and dissolving forms uniform, stable casting solution after standing and defoaming.
5. casting solution is poured on the glass plate of cleaning, the film for spreading to 250 μm of thickness is applied with coating device, will after 1 minute
Apply in the glass plate 30 DEG C of pure water of immersion for having scraped film, after film is from glass plate Automatic-falling, puts it into and fill substantial amounts of steaming
Soaked 24 hours in the bucket of distilled water, pull out and Nano Silver/graphene/Kynoar composite hyperfiltration membrane is obtained after nature dries.
Embodiment 3
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in DMA at 60 DEG C,
The ratio between graphene oxide quality and DMA volume are 6g/L, polyethylene glycol quality and DMA
The ratio between volume is 18g/L.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol used is 4000.
2. by AgNO at 60 DEG C3, polyethylene glycol be dissolved in DMA, AgNO3Quality and N, N- dimethyl
The ratio between acetamide volume is 17g/L, and the ratio between polyethylene glycol quality and DMA volume are 18g/L.The oxygen used
Graphite alkene oxygen content is 19.2wt%, and the molecular weight polyethylene glycol used is 4000.
3. the solution 1. step prepared is mixed in equal volume with the solution that 2. step is prepared, ultrasonic (frequency at 60 DEG C
100Hz) handle 3 hours, Nano Silver/graphene complex solution is made.
4. Kynoar being added into step for 190g/L by mass volume ratio, 3. obtained Nano Silver/graphene is combined
In thing solution, stirring and dissolving forms uniform, stable casting solution after standing and defoaming.
5. casting solution is poured on the glass plate of cleaning, the film for spreading to 250 μm of thickness is applied with coating device, will after 1 minute
Apply in the glass plate 30 DEG C of pure water of immersion for having scraped film, after film is from glass plate Automatic-falling, puts it into and fill substantial amounts of steaming
Soaked 24 hours in the bucket of distilled water, pull out and Nano Silver/graphene/Kynoar composite hyperfiltration membrane is obtained after nature dries.
Embodiment 4
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in DMA at 60 DEG C,
The ratio between graphene oxide quality and DMA volume are 6g/L, polyethylene glycol quality and DMA
The ratio between volume is 20g/L.The graphene oxide oxygen content used is 19.2wt%, and the molecular weight polyethylene glycol used is 6000.
2. by AgNO at 60 DEG C3, polyethylene glycol be dissolved in DMA, AgNO3Quality and N, N- dimethyl
The ratio between acetamide volume is 15g/L, and the ratio between polyethylene glycol quality and DMA volume are 20g/L.The oxygen used
Graphite alkene oxygen content is 19.2wt%, and the molecular weight polyethylene glycol used is 6000.
3. the solution 1. step prepared is mixed in equal volume with the solution that 2. step is prepared, ultrasonic (frequency at 60 DEG C
100Hz) handle 3 hours, Nano Silver/graphene complex solution is made.
4. Kynoar being added into step for 200g/L by mass volume ratio, 3. obtained Nano Silver/graphene is combined
In thing solution, stirring and dissolving forms uniform, stable casting solution after standing and defoaming.
5. casting solution is poured on the glass plate of cleaning, the film for spreading to 250 μm of thickness is applied with coating device, will after 1 minute
Apply in the glass plate 30 DEG C of pure water of immersion for having scraped film, after film is from glass plate Automatic-falling, puts it into and fill substantial amounts of steaming
Soaked 24 hours in the bucket of distilled water, pull out and Nano Silver/graphene/Kynoar composite hyperfiltration membrane is obtained after nature dries.
Embodiment 5
1. graphene oxide, polyethylene glycol ultrasonic (frequency 100Hz) are scattered in DMA at 60 DEG C,
The ratio between graphene oxide quality and DMA volume are 8g/L, polyethylene glycol quality and DMA
The ratio between volume is 22g/L.The graphene oxide oxygen content used is 22.4wt%, and the molecular weight polyethylene glycol used is 20000.
2. by AgNO at 60 DEG C3, polyethylene glycol be dissolved in DMA, AgNO3Quality and N, N- dimethyl
The ratio between acetamide volume is 10g/L, and the ratio between polyethylene glycol quality and DMA volume are 22g/L.The oxygen used
Graphite alkene oxygen content is 22.4wt%, and the molecular weight polyethylene glycol used is 20000.
3. the solution 1. step prepared is mixed in equal volume with the solution that 2. step is prepared, ultrasonic (frequency at 60 DEG C
100Hz) handle 3 hours, Nano Silver/graphene complex solution is made.
4. Kynoar being added into step for 220g/L by mass volume ratio, 3. obtained Nano Silver/graphene is combined
In thing solution, stirring and dissolving forms uniform, stable casting solution after standing and defoaming.
5. casting solution is poured on the glass plate of cleaning, the film for spreading to 250 μm of thickness is applied with coating device, will after 1 minute
Apply in the glass plate 30 DEG C of pure water of immersion for having scraped film, after film is from glass plate Automatic-falling, puts it into and fill substantial amounts of steaming
Soaked 24 hours in the bucket of distilled water, pull out and Nano Silver/graphene/Kynoar hybrid membranes are obtained after nature dries.
Comparative example
Kynoar 210g, polyethylene glycol (molecular weight is 2000) 30g, DMA 2L are mixed, stirred
Mix and uniform, stable casting solution is formed after dissolving, standing and defoaming.On the glass plate that casting solution is poured over to cleaning, coating device is used
The film for spreading to 250 μm of thickness is applied, the glass plate that painting has been scraped into film after 1 minute is immersed in 30 DEG C of pure water, treat film from glass plate certainly
Move after coming off, put it into the bucket for filling substantial amounts of distilled water and soak 24 hours, pull out and obtain gathering inclined fluorine after nature dries
Ethene milipore filter.
The anti-microbial property experiment of film：
Using the method for plate culture count, Nano Silver/graphene/Kynoar prepared by testing example and comparative example
The antibacterial effect of hybrid membranes and polyvinylidene fluoride (PVDF) ultrafiltration membrane to Escherichia coli.Specific test operating procedure is as follows：
(1) by beef extract 4.5g, peptone 15g, NaCl 7.5g, agar 35g, water 2000mL are configured to LB nutrient solutions
(pH7.0~7.2).
(2) 10 conical flasks are taken, labeled as 1~No. 10,100mL LB nutrient solutions are separately added into every conical flask；So
10 conical flasks and some test tubes bandaged, liquid-transfering gun pipette tips etc. are placed in high-pressure sterilizing pot together afterwards, 121 DEG C damp and hot to go out
Bacterium 20min.
(3) take No. 1 conical flask sterilized to be placed on sterile, ultra-clean workbench, the large intestine activated is accessed into bottle
Bacillus bacterium solution 1mL, appropriate vibration is mixed, and is put into constant temperature oscillator (30 DEG C, 150r/min) and is cultivated 16 hours.
(4) take 2~No. 6 conical flasks sterilized to be placed on sterile, clean workbench, into 2~No. 5 conical flasks respectively
Add Nano Silver/graphene/Kynoar hydridization prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5
Each 0.25g of milipore filter；Polyvinylidene fluoride (PVDF) ultrafiltration membrane 0.25g as a control group 1 prepared by comparative example 1 is added into No. 7 conical flasks；
Any material (blank) as a control group 2 is added without in No. 8 conical flasks.
(5) 0.10mL is respectively taken to be respectively connected to 2~No. 8 cones the Escherichia coli bacteria liquid cultivated 16 hours in No. 1 conical flask
In shape bottle nutrient solution, constant-temperature table culture (150r/min, 30 DEG C) is carried out.
(6) count plate after constant-temperature table culture 24 hours, calculates antibiotic rate.
The antifouling property experiment of film：
1g/L bovine serum albumin(BSA) is used for pollutant, anti-soil is carried out to obtained milipore filter in embodiment and comparative example
Contaminate performance evaluation.
Test process is as follows：At 25 DEG C, milipore filter is placed in cup type ultrafilter under 0.15MPa pressure to precompressed 1 is small
When, the pure water flux J of milipore filter is then determined under 0.1MPa pressurew,1, using 1g/L bovine serum albumin(BSA) as object,
Under 0.1MPa after ultrafiltration 30min, the milipore filter 15 minutes cleaned with deionized water after pollution, then repeatedly above pre-compaction process,
The pure water flux J of milipore filter is determined under 0.1MPa againw,2.And with initial pure water flux Jw,1Contrast obtains pure water flux recovery rate
(FRR)。
Milipore filter antifouling property is generally characterized with the pure water flux recovery rate (FRR) of film.
FRR=Jw,2/Jw,1
FRR is bigger, shows that the antifouling property of film is better.
The anti-microbial property test result of film：
Nano Silver/graphene/Kynoar prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5
Hybrid membranes reach more than 92% to Escherichia coli antibiotic rate.And polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by comparative example is to large intestine
Bacillus does not have antibacterial action.
The antifouling property test result of film：
Nano Silver/graphene/Kynoar prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5
Super pure water flux recovery rate (FRR) rate of hydridization is above 83%.And the pure water of polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by comparative example
Flux recovery rate (FRR) is 60% or so.
In addition, Nano Silver/graphene of embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 preparation/poly- inclined
The super pure water flux of PVF hydridization is up to 200L/m2More than hr, the rejection to bovine serum albumin(BSA) is all higher than 96%,
The polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared also superior to comparative example.
Claims (4)
1. a kind of preparation method of Nano Silver/graphene/Kynoar hybrid membranes, it is characterised in that including following step
Suddenly：
(1) graphene oxide, polyethylene glycol ultrasonic disperse are obtained into solution A in DMA；By AgNO3, poly- second
Glycol, which is dissolved in DMA, obtains solution B；Graphene oxide quality and N, N- dimethylacetamide in the solution A
The ratio between amine volume is 5~15g/L, and the ratio between polyethylene glycol quality and DMA volume are 5~30g/L；It is described molten
AgNO in liquid B3The ratio between quality and DMA volume are 10~50g/L, polyethylene glycol quality and N, N- dimethyl
The ratio between acetamide volume is 5~30g/L；Solution A and solution B are prepared at 50~70 DEG C；
(2) resulting solution A and solution B are mixed in equal volume, obtains Nano Silver/stone within ultrasonically treated 2.5~3.5 hours at 50~70 DEG C
Black alkene complex solution；
(3) Kynoar is dissolved in gained Nano Silver/graphene complex solution, casting solution is obtained after standing and defoaming；It is poly-
The ratio between the dosage of vinylidene and the quality volume of Nano Silver/graphene complex solution are 150~250g/L；
(4) gained casting solution is prepared into Nano Silver/graphene/Kynoar hybrid membranes by immersion precipitation phase inversion process.
2. preparation method according to claim 1, it is characterised in that the immersion precipitation phase inversion process is：Casting solution is existed
Immersed after overlay film on cleaned glass plate, overlay film in 25~35 DEG C of pure water, after film is from glass plate Automatic-falling, be dipped in steaming
20~24 hours in distilled water, pull out and Nano Silver/graphene/Kynoar hybrid membranes are obtained after nature dries.
3. preparation method according to claim 2, it is characterised in that overlay film thickness of the casting solution on cleaned glass plate is
200~300 μm.
4. Nano Silver/graphene that a kind of preparation method as described in claims 1 to 3 any claim is prepared/poly- inclined
PVF hybrid membranes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510595471.6A CN105214511B (en) | 2015-09-18 | 2015-09-18 | A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510595471.6A CN105214511B (en) | 2015-09-18 | 2015-09-18 | A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105214511A CN105214511A (en) | 2016-01-06 |
| CN105214511B true CN105214511B (en) | 2017-11-07 |
Family
ID=54983986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510595471.6A Active CN105214511B (en) | 2015-09-18 | 2015-09-18 | A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105214511B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105797591B (en) * | 2016-03-28 | 2019-01-18 | 上海应用技术学院 | A kind of preparation method of super-hydrophobicity polyvinylidene fluoride microporous film |
| CN105833742A (en) * | 2016-04-26 | 2016-08-10 | 上海应用技术学院 | Preparation method for hydrophilic polyvinylidene fluoride (PVDF) antibacterial ultrafiltration membrane |
| CN105771689A (en) * | 2016-04-26 | 2016-07-20 | 福州大学 | High antimicrobial PVDF/GO/Ag composite membrane and preparation method thereof |
| CN106582327B (en) * | 2016-12-21 | 2019-08-20 | 华南理工大学 | A kind of silver-colored graphene oxide-polyvinyl alcohol ultrafiltration membrane of load and its preparation and application |
| CN107051208B (en) * | 2016-12-22 | 2019-09-10 | 浙江工商大学 | Doping Kynoar mixed-matrix ultrafiltration membrane and its preparation is blended in three-dimensional structure nano-complex |
| CN106807255B (en) * | 2016-12-22 | 2019-03-26 | 浙江工商大学 | Three-dimensional structure TiO2Stannic oxide/graphene nano composite in-situ polymerization doped polyimide film and its preparation |
| KR101986437B1 (en) * | 2017-12-11 | 2019-06-05 | 건국대학교 산학협력단 | Process of membrane fouling resistance based on silver-graphene oxide compounds |
| CN108479424A (en) * | 2018-04-02 | 2018-09-04 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of modified polyvinilidene fluoride film |
| CN109081388A (en) * | 2018-08-30 | 2018-12-25 | 盐城市新能源化学储能与动力电源研究中心 | A kind of method of quickly cleaning water |
| CN110433675A (en) * | 2019-06-28 | 2019-11-12 | 浙江工业大学 | A kind of guanidine radicals functional graphene oxide/polysulfone ultrafiltration membrane and preparation method thereof |
| CN112316726A (en) * | 2020-10-22 | 2021-02-05 | 海瑞膜科技南通有限公司 | Graphene ultrafiltration membrane and preparation method thereof |
| CN113144919A (en) * | 2020-11-23 | 2021-07-23 | 兰州大学 | 3D printing multifunctional filter membrane for sewage treatment and preparation method and application thereof |
| CN113372809B (en) * | 2021-04-23 | 2022-02-18 | 浙江工商大学 | Intelligent heat-insulating coating and preparation and application thereof |
| CN114307691A (en) * | 2021-12-28 | 2022-04-12 | 上海普利特复合材料股份有限公司 | Hollow nano-silver/graphene/PE ultrafiltration membrane and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101118473B1 (en) * | 2009-03-27 | 2012-03-12 | (주)바이오니아 | Nanoporous films and method of manufacturing nanoporous films |
| CN102989330A (en) * | 2012-12-20 | 2013-03-27 | 浙江工商大学 | Hybrid graphene/aromatic polyamide reverse osmosis membrane and preparation method thereof |
| CN103172775B (en) * | 2013-03-19 | 2015-07-15 | 浙江工商大学 | Preparation method and application of antibiosis composite emulsion containing nano silver particles |
| CN104028123B (en) * | 2014-05-14 | 2016-04-20 | 浙江大学 | A kind of preparation method of polymer nanofiber diffusion barrier |
| CN104226127A (en) * | 2014-09-10 | 2014-12-24 | 浙江工商大学 | Preparation method of graphene/polyurethane hybridized gas separation membrane and product of preparation method |
| CN104353366B (en) * | 2014-11-10 | 2016-08-17 | 东华大学 | A kind of polymeric film with antifouling and antibiosis function and preparation method thereof |
| CN104725596B (en) * | 2015-03-26 | 2017-06-20 | 浙江工商大学 | A kind of Nano Silver/carbon nano-tube/poly urethane hybridized film and preparation method thereof |
-
2015
- 2015-09-18 CN CN201510595471.6A patent/CN105214511B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105214511A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105214511B (en) | A kind of Nano Silver/graphene/Kynoar hybrid membranes and preparation method thereof | |
| Cao et al. | Multifunctional nanofibrous membranes with sunlight-driven self-cleaning performance for complex oily wastewater remediation | |
| RU2751513C1 (en) | Method for producing a superhydrophylic ultrafiltration membrane with photocatalytic properties | |
| Zhu et al. | Recent progress in developing advanced membranes for emulsified oil/water separation | |
| CN102580560B (en) | Method for preparing nano-material-doped polymer film | |
| CN106731841B (en) | A kind of supermolecule composite nanometer filtering film and its preparation method and application | |
| CN101890315B (en) | Carbon nano tube-polymer composite nanofiltration membrane and preparation method thereof | |
| CN109224861A (en) | A kind of modified nanofiltration/reverse osmosis membrane of metal organic framework and its application | |
| CN108409981A (en) | A kind of preparation method of modified metal organic frame and composite nanometer filtering film | |
| CN109126463A (en) | A kind of preparation method of the high-flux nanofiltration membrane of middle layer containing micropore | |
| CN107126845B (en) | A kind of composite nanometer filtering film and preparation method thereof containing modified carbon nano-tube | |
| Siddique et al. | Mixed-matrix membrane fabrication for water treatment | |
| CN108126650B (en) | Functional flexible inorganic porous fiber membrane, preparation method and application thereof in simultaneously removing oil stains and heavy metal ions in water | |
| CN104548952B (en) | A kind of preparation method of antibacterial composite nanometer filtering film | |
| Sai et al. | Facile and green route to fabricate bacterial cellulose membrane with superwettability for oil–water separation | |
| CN108187512A (en) | A kind of high throughput compound nanometer filtering membrane of polyamide and preparation method thereof | |
| CN109289550A (en) | A kind of preparation method and application of anti-pollution polyvinylidene fluoride hybrid membranes | |
| Yu et al. | Low cost fabrication of polypropylene fiber composite membrane with excellent mechanical, superhydrophilic, antifouling and antibacterical properties for effective oil-in-water emulsion separation | |
| CN107837690A (en) | Flat mixed-matrix forward osmosis membrane and preparation method based on metal organic framework ZIF 8 | |
| CN105597552A (en) | Forward osmosis membrane with high water flux and high salt rejection rate and method for preparing forward osmosis membrane with one-step method | |
| Barhoum et al. | Nanocelluloses as sustainable membrane materials for separation and filtration technologies: Principles, opportunities, and challenges | |
| CN102626595A (en) | Formula for industrial high-strength anti-pollution ultrafiltration flat plate membrane and preparation method thereof | |
| CN106040014B (en) | A kind of antioxidant nanofiltration membrane and preparation method thereof that nanocrystalline cellulose is compound | |
| CN107899432A (en) | A kind of plate compounding NF membrane for water filter purification and preparation method thereof | |
| CN108014654B (en) | Molecular sieve membrane modification method for dehydration separation of strong polar solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |