CN106245232A - Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application - Google Patents
Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application Download PDFInfo
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- CN106245232A CN106245232A CN201610601138.6A CN201610601138A CN106245232A CN 106245232 A CN106245232 A CN 106245232A CN 201610601138 A CN201610601138 A CN 201610601138A CN 106245232 A CN106245232 A CN 106245232A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
- B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Abstract
The invention discloses graphene oxide@high polymer nano fiber multilayer film and its preparation method and application, the present invention prepares a floor height polymers nano fibrous membrane by method of electrostatic spinning, by electrostatic spraying, graphene oxide is uniformly sprayed on high polymer nano fiber membrane again, then, on graphene oxide membrane layer, a floor height polymers nano fibrous membrane is prepared again by electrostatic spinning, the most repeatedly, multilayer oxygen functionalized graphene@high polymer nano fibrous membrane is prepared.Multi-layer film structure of the present invention, GO load capacity height, mechanical strength height, good stability and pure water flux and nanofiltration are functional, can be applicable to the membrance separation fields such as air filtration, sewage disposal, desalination.
Description
Technical field
The invention belongs to technology of composite film preparation field, relate to graphene oxide@high polymer nano fiber multilayer film and
Preparation method and application, are specifically related to a kind of graphene oxide@high polymer nano fiber multi-layer film structure material, and use quiet
Electrospun combines the method that this material is prepared in electrostatic spraying, and this material is at membrance separation such as air filtration, sewage disposal, desalinations
The application in field.
Background technology
Graphene (Graphene) is that one is passed through sp by carbon atom with hexagonal structure2The monoatomic layer two dimension of hydridization
Material, in recent years, due to the structure of its uniqueness, causes research interest achieve notable widely penetrating filter membrane field
Progress.Perfect single-layer graphene can stop the infiltration of any atom and molecule, only allow proton and isotopic quickly
Selectivity transmits, and can introduce size, the nano-pore of controlled shape at graphenic surface by High energy particles Radiation, it is achieved select
Property mass transfer accuracy controlling, for sewage disposal, gas separates, the field such as desalinization and bio-sensing, but has been constrained to
The preparation of U.S. single-layer graphene and nanometer cheesing techniques, its large-scale application is restricted.
As the derivant of Graphene, graphene oxide (GO, Graphene Oxide) can be by the Hummers improved
Method realizes extensive mass and prepares, and substantial amounts of oxygen-containing functional group is contained on its surface, such as hydroxyl, carboxyl and epoxy radicals, at water and
Dispersibility in some organic solvents is preferable, can obtain graphene oxide membrane by a series of liquid-phase Forming Process.
Nair et al. uses spin-coating method to be prepared for the graphene oxide membrane of micron order thickness, and research shows that this film is only capable of allowing water
Steam passes through, and intercepts any gas and liquid.Tsing-Hua University, Zhu seminar is by dropping solwution method, prepared by vacuum filtration method
Graphene oxide membrane, and have studied its to different metal ion in water and the mechanism of mass transmission of organic dyestuff, but use above-mentioned
Simple graphene oxide membrane application in the solution prepared by method can have that some problems, such as its high-hydrophilic cause molten
In liquid, mechanical strength is the highest, long-time application easily dispersion, strengthens the spacing between its graphene oxide lamella, causes a huge sum of money
The rejection belonging to salt ion reduces.Therefore, a kind of mechanical strength of preparation is high, good stability, the graphene oxide mistake that rejection is high
Filter membrane is for realizing sewage purification, and seawater desalination has important science and industrialization meaning.
Gao seminar passes through graphene oxide lamella intermediate loads CNT, effectively increases pure water flux, the most right
Organic dyestuff keeps higher stop rate, but its mechanical strength is the highest.
Electrostatic spinning is to overcome surface tension to form injection stream by electric field driven polymer solution, and makes solvent quickly wave
Send out and form fiber and be deposited on a kind of technology received on plate, be prepare nanometer or sub-micron fibers material maximally effective
Method, its nano fibrous membrane prepared has the advantages that specific surface area is big and porosity is high, can be applicable to sewage disposal and air
Field of purification.
Wu Qingzhi et al. has invented a kind of electrostatic spinning and has prepared the side of collagen protein/stannic oxide/graphene nano composite fiber membrane
Method, is placed in deionized water ultrasonic by graphene oxide, and being allowed to is uniformly dispersed obtains the water solution A of graphene oxide；Collagen egg
It is dissolved in vain in hexafluoroisopropanol and obtains solution B；Solution A being added in solution B and be sufficiently mixed uniformly, standing and defoaming obtains collagen
The composite spinning liquid of albumen/graphene oxide, then prepares composite cellulosic membrane by electrostatic spinning, finally by crosslinking Treatment,
Natural drying obtains collagen protein/stannic oxide/graphene nano composite fiber membrane.By the composite membrane that the method obtains aoxidizes stone
The content of ink alkene is the lowest, and graphene oxide accounts for the mass fraction of collagen protein and is only 0.03% 1.25%.Further, oxidation stone
Ink alkene lamella can fractional load in nanofiber, limit it and preferably play a role.
Summary of the invention
For the shortcoming overcoming above-mentioned prior art to exist, the present invention uses electrostatic spinning to prepare high polymer nano fiber
Film, then loads graphene oxide membrane, the most repeatedly, it is thus achieved that can not only by electrostatic spraying on high polymer nano fibrous membrane
Strengthen its mechanical strength, moreover it is possible to be effectively increased pure water flux and organic dye solution is kept the multilayer complex films of higher rejection
Material.
An object of the present invention is to provide a kind of novel graphene oxide@high polymer nano fiber multilayer film material
Material.
Another object of the present invention is to provide the preparation method of graphene oxide@high polymer nano fiber multilayer film.
The purpose of the present invention also includes the application of graphene oxide@high polymer nano fiber multilayer film.
Concrete, the present invention relates to techniques below scheme:
First, the invention discloses a kind of graphene oxide@high polymer nano fiber multi-layer film material, this film is by high polymer
Nano fibrous membrane, graphene oxide membrane alternately composition, the mass fraction of graphene oxide is about 50 80%, high polymer nano
All at least 2 layers of fibrous membrane, graphene oxide layer.Wherein graphene oxide lamella is mutually packed together, and by high polymer
Nanofiber fetters, fixing.
Graphene oxide@high polymer nano fiber multi-layer film structure schematic diagram of the present invention is as it is shown in figure 1, pass through electrostatic
Spin processes prepares a floor height polymers nano fibrous membrane, then by electrostatic spraying, graphene oxide is uniformly sprayed high polymer and receive
On rice fiber membrane, then, then in graphene oxide membrane, a floor height polymers nano fibrous membrane is prepared, so by electrostatic spinning
Repeatedly, multilayer oxygen functionalized graphene@high polymer nano fibrous membrane is prepared；Or directly use existing microporous filter membrane, pass through electrostatic
Graphene oxide is uniformly sprayed on microporous filter membrane by spraying, loads microporous filter membrane and electrostatic spraying graphite oxide the most again
Alkene, the most repeatedly, prepares multilayer oxygen functionalized graphene@high polymer nano fibrous membrane.
Inventor finds in the preparation process of graphene oxide@high polymer nano composite fiber membrane, by aoxidizing stone
Ink alkene is when being supported on high polymer the structure of composite membrane forming two membranes, can improve the water flux of composite membrane, but answering of being formed
Film combining machine tool limited strength, pressure performance is bad；Secondly, in the structure of composite membrane of two membranes, GO load capacity is limited, although permissible
Improve GO load capacity by increasing the thickness of graphene oxide membrane, but after GO thickness increases, its mass transfer pressure increases, and leads
The water flux causing composite membrane declines rapidly.Inventor is prepared a floor height polymers nano fibrous membrane by method of electrostatic spinning, is passed through
After graphene oxide is uniformly sprayed the structure of composite membrane forming two membranes on high polymer nano fiber membrane by electrostatic spraying,
In graphene oxide membrane, a floor height polymers nano fibrous membrane is prepared and by electrostatic spraying by oxygen further by electrostatic spinning
Functionalized graphene uniformly sprays the alternately design of high polymer nano fiber membrane, obtains a kind of graphene oxide@high polymer and receives
Rice fiber multi-layer film material.Wherein, graphene oxide lamella can be implemented on high polymer nano fibrous membrane regularly arranged, simultaneously
Due to the constraint of high polymer nano fiber, improve the mechanical strength of composite multilayer membrane, and due to the alternately design of multilamellar, multiple
Closing the operation pressure that bears of multilayer film to strengthen, compaction effect is alleviated, and both can effectively promote its pure water flux, to organic dyestuff and
The rejection of heavy metallic salt ion also greatly improves；Multilayer film stability in the solution promotes, owing to multilamellar high polymer nano is fine
The constraint of dimension, composite membrane is difficult to dispersion；By alternately design, while substantially increasing GO load capacity, it is effectively increased pure water and leads to
Measure and organic dyestuff is retained efficiency.
Inventor finds in process of the test, and in composite membrane, GO layer is supported on high polymer nano fiber by vacuum filtration method
Time on film, the impact being limited by GO thicknesses of layers is more obvious, and when needing to prepare thicker GO layer, mass transfer pressure increases, because of
This vacuum filtration pressure needed is bigger, and the time is more long, and electrostatic spraying is the most affected by these factors, can lead to well
The time crossing control electrostatic spraying controls the thickness of GO layer, it is achieved batch preparation, and meanwhile, the height prepared by electrostatic spinning is gathered
Thing nano fibrous membrane thickness is less, can be effectively improved the stability of multilayer film, also will not even if soaking in aqueous many days
Cause the dispersion of GO, and high polymer nano fibrous membrane and the separation of GO layer, and, high polymer nano fibrous membrane is present in oxidation
Its nanochannel can be effectively increased between graphene sheet layer, improve pure water flux.
Secondly, the present invention provides the preparation method of a kind of graphene oxide@high polymer nano fiber multilayer film, described method
Including:
(1) a floor height polymers nano fibrous membrane is prepared by method of electrostatic spinning；
(2) by electrostatic spraying, graphene oxide is uniformly sprayed previous step and obtain the high polymer nano fiber of film
On thin film；
(3) on the graphene oxide layer that previous step obtains film, a floor height polymers Nanowire is prepared by method of electrostatic spinning
Dimension film；
(4) repeat step (2) (3) and obtain the multilayer film of graphene oxide@high polymer nano fibrous membrane alternately design.
In order to realize the alternately design of multilayer film, the present invention uses method of electrostatic spinning to prepare high polymer nano fiber membrane layer
With the engagement means that electrostatic spray prepares graphene oxide membrane layer.The technology of preparing of nanofiber includes electrostatic spinning, from group
Dress, phase detachment technique and template, the present invention is in view of for the system meeting graphene oxide@high polymer nano fiber multilayer film
Standby, need to realize considering of the control of nanofibrous structures and preparation cost and commercial production application, Static Spinning is selected in screening
Silk method prepares high polymer nano fiber membrane layer；Graphene oxide-loaded to time on polymer film, need to consider its method
Simplicity and the reliability of load, existing have multiple load means, such as, spin-coating method and solution suction method, but the film after load
Poor stability, generally requires and cross-links further, and the present invention passes through electrostatic spraying means effectively by graphene oxide-loaded
On high polymer layer, the film of formation is uniformly and excellent stability；And both means effectively coordinate, and pass through Static Spinning
High polymer nano fiber membrane layer prepared by silk and electrostatic spray prepares being used alternatingly of graphene oxide layer, is effectively prepared for
GO load capacity height, mechanical strength height, good stability and water flux and nanofiltration composite multilayer membrane of good performance.
It should be understood by those skilled in the art that high polymer is passed through covalent bond by many construction units identical, simple
Repeating the high-molecular weight compounds being formed by connecting, in preferred embodiments, high polymer of the present invention is for being appropriate to
The high polymer of electrostatic spinning, it is further preferred that high polymer is selected from nylon 6 (Nylon6), polyacrylonitrile (PAN), polystyrene
(PS), one or more of polypropylene (PP) etc..
Further, in order to realize preparation method of the present invention, preparation technology is optimized by inventor further,
Preparation technology after optimization includes:
Above-mentioned steps (1), (3) including: a certain amount of high polymer is dissolved in corresponding solvent by (1-1), ultrasonic 1-3h,
Magnetic agitation obtains the high polymeric solution B being completely dissolved；
(1-2) by solution B standing and defoaming, being then transferred in syringe, by electrostatic spinning film forming, spinning voltage is
8 30KV, relative humidity is 20% 50%, and temperature is 15 30 DEG C, and fltting speed is 0.001 0.01mL/min, accepts
Distance is 15 20cm, and spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 800 1000r/min, spinning
Time is 1 5min.
Above-mentioned steps (2) including: a certain amount of graphene oxide at room temperature, is dissolved in water and dimethyl methyl by (2-1)
In the mixed solution of amide (DMF) 1:1, ultrasonic 1-3h, magnetic agitation obtains finely dispersed graphene oxide solution A；
(2-2) solution A is transferred in syringe, by electrostatic spraying, graphene oxide is sprayed to high polymer nano
On fibrous membrane, electrostatic spraying voltage is 25 35KV, and relative humidity is 20% 50%, and temperature is 15 30 DEG C, fltting speed
Being 0.1 0.2mL/min, receiving range is 15 20cm, and spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, drum rotation speed
Being 200 400r/min, the electrostatic spraying time is 10 40min.
Preferably, graphene oxide used in step (2-1) in step (2) is to be prepared by the Hummers method improved,
Its mass fraction is 0.1 1%.
In preferred embodiment, in said method step (1)-(3), can be by controlling electrostatic spinning time, spinning
Voltage, prepares different-thickness, different fibre diameter and the graphene oxide high polymer multilayer film of the different number of plies.
In preferred embodiment, step (4) farther includes: put into by acquisition multilayer film in the baking oven of 45 DEG C dry
Dry, remove remaining solvent.
Furthermore, the invention discloses the graphene oxide@high polymer nano fiber multilamellar that above-mentioned preparation method prepares
Film.
Additionally, the invention also discloses above-mentioned graphene oxide@high polymer nano fiber multilayer film at air filtration, sewage
The application in the membrance separation fields such as process, desalination.
The present invention achieves following beneficial effect:
(1) graphene oxide high polymer nano fiber multilayer film of the present invention, graphene oxide lamella can realize rule
Then arranging, simultaneously because the constraint of multilamellar high polymer fibre, its mechanical strength is higher；Stability is preferable in the solution, does not disperses；
(2) graphene oxide@high polymer nano fiber multilayer film of the present invention, the diameter of high polymer fibre is 90
200nm, and porosity is higher, will not hinder being fully contacted and permeation filtration of graphene oxide and solution, and meanwhile, it can also
Increase the nanochannel between graphene oxide lamella, improve its pure water flux.
(3) multilayer film of the present invention is designed by alternating layer, while substantially increasing GO load capacity, promotes the pure of film
Water flux and retain efficiency.
(4) graphene oxide that the present invention uses is to be prepared by the Hummers method improved, and method is simple, economical and efficient；
And the preparation method of multilayer film uses electrostatic spinning and electrostatic spraying means, integrated artistic is simply efficient, can realize extensive
Industrialized production.
Accompanying drawing explanation
The structural representation of Fig. 1 graphene oxide@high polymer nano fiber multilayer film
The surface scan Electronic Speculum figure of the graphene oxide@nylon 6/nanometer fiber multilayer film that Fig. 2 embodiment 1 prepares
The cross-sectional scans Electronic Speculum figure of the graphene oxide@nylon 6/nanometer fiber multilayer film that Fig. 3 embodiment 1 prepares.
After the graphene oxide@nylon 6/nanometer fiber multilayer film that Fig. 4 embodiment 1 prepares soaks 48h in the solution
Scanning electron microscope (SEM) photograph.
Fig. 5 makes vertical current defecator by oneself.
Detailed description of the invention
Below by being embodied as case, the present invention is done specific description.
Embodiment 1
Prepare graphene oxide@nylon 6/nanometer fiber multilayer film, specifically comprise the following steps that
Step 1: preparation graphene oxide solution: use graphene oxide water solution prepared by the Hummers method improved, so
Rear employing vacuum lyophilization prepares the powder of graphene oxide.A certain amount of graphene oxide is added water and dimethyl formyl
In the mixed solution of amine (DMF) 1:1, ultrasonic 2h, magnetic agitation 5h, obtain finely dispersed graphene oxide solution A.In solution
The mass fraction of graphene oxide is 0.5%.
Step 2: 3g nylon 6 is added 17.64g formic acid is in acetic acid mixed solution (formic acid, quality of acetic acid ratio is for 7:3), super
Sound 2h, magnetic agitation 12h, obtain nylon 6 solution B being completely dissolved.
Step 3: solution B stands 1h deaeration, is then transferred in 20mL syringe, by electrostatic spinning film forming, spinning
Voltage is 27KV, and relative humidity is 35 45%, and temperature is 20 25 DEG C, and fltting speed is 0.01mL/min.Receiving range is
20cm, spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 900r/min.The spinning time is 5min.
Step 4: solution A transferred in syringe, sprays to nylon 6/nanometer by electrostatic spraying fine by graphene oxide
On dimension film, electrostatic spraying voltage is 35KV, and relative humidity is 35 45%, and temperature is 20 25 DEG C, and fltting speed is 0.2mL/
min.Receiving range is 20cm, and spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 300r/min.Electrostatic
The painting time is 30min.
Above-mentioned steps 3,4 the most alternately, it is thus achieved that 6 layers of graphene oxide@nylon 6/nanometer fiber multilayer film.Finally, will
Graphene oxide@nylon 6/nanometer fiber multilayer film is put in the baking oven of 45 DEG C and is dried, and removes remaining solvent.
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphene oxide@nylon 6/nanometer fiber multi-layer film surface that embodiment 1 prepares,
The diameter of nylon 6 fiber, about at 100nm, is attached on graphene oxide lamella, " is pinned " by graphene oxide lamella, increases
Its mechanical strength and stability.
Fig. 2 is the scanning electron microscope (SEM) photograph in the graphene oxide@nylon 6/nanometer fiber multilayer film cross section of preparation in embodiment 1, from
It may be seen that graphene oxide from level to level is separated by nylon 6/nanometer fibrous membrane in figure.
Fig. 3 is the graphene oxide@nylon 6/nanometer fiber multilayer film of preparation scanning after 48h soaks in embodiment 1
Electronic Speculum figure, it can be seen that do not disperse through soaking rear oxidation graphene film, still restrainted by nylon 6/nanometer fiber
Tie up, illustrate that this multilayer film structure stability in the solution is preferable.
Embodiment 2
The preparation method of graphene oxide@polyacrylonitrile nanofiber multilayer film, specifically comprises the following steps that
Step 1: preparation graphene oxide solution: use graphene oxide water solution prepared by the Hummers method improved, so
Rear employing vacuum lyophilization prepares the powder of graphene oxide.A certain amount of graphene oxide is added water and dimethyl formyl
In the mixed solution of amine (DMF) 1:1, ultrasonic 2h, magnetic agitation 5h, obtain finely dispersed graphene oxide solution A.In solution
The mass fraction of graphene oxide is 0.5%.
Step 2: 1g polyacrylonitrile is added in 9g dimethylformamide, ultrasonic 2h, magnetic agitation 12h, obtain the most molten
Polyacrylonitrile solution B solved.
Step 3: solution B stands 1h deaeration, is then transferred in 20mL syringe, by electrostatic spinning film forming, spinning
Voltage is 12KV, and relative humidity is 35 45%, and temperature is 20 25 DEG C, and fltting speed is 0.008mL/min.Receiving range is
15cm, spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 900r/min.The spinning time is 5min.
Step 4: solution A transferred in syringe, sprays to polyacrylonitrile by electrostatic spraying by graphene oxide and receives
On rice fibrous membrane, electrostatic spraying voltage is 35KV, and relative humidity is 35 45%, and temperature is 20 25 DEG C, and fltting speed is
0.2mL/min.Receiving range is 15cm, and spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 300r/min.
The electrostatic spraying time is 30min.
Above-mentioned steps 3,4 the most alternately, it is thus achieved that 8 layers of graphene oxide@polyacrylonitrile nanofiber multilayer film.?
After, graphene oxide@polyacrylonitrile nanofiber multilayer film is put in the baking oven of 45 DEG C and be dried, remove remaining solvent.
Embodiment 3
The preparation method of graphene oxide@polyvinylidene fluoride (PVDF) microporous filter membrane multilayer film, specifically comprises the following steps that
Step 1: preparation graphene oxide solution: use graphene oxide water solution prepared by the Hummers method improved, so
Rear employing vacuum lyophilization prepares the powder of graphene oxide.A certain amount of graphene oxide is added water and dimethyl formyl
In the mixed solution of amine (DMF) 1:1, ultrasonic 2h, magnetic agitation 5h, obtain finely dispersed graphene oxide solution A.In solution
The mass fraction of graphene oxide is 0.5%.
Step 2: solution A transferred in syringe, sprays to gather inclined difluoro second by graphene oxide by electrostatic spraying
On alkene (PVDF) microporous filter membrane, electrostatic spraying voltage is 35KV, and relative humidity is 35 45%, and temperature is 20 25 DEG C, advances
Speed is 0.2mL/min.Receiving range is 15cm, and spinning syringe needle is No. 9, uses polyvinylidene fluoride microporous filter membrane, and cylinder connects
Receiving, drum rotation speed is 300r/min.The electrostatic spraying time is 30min.
Step 3: polyvinylidene fluoride microporous filter membrane is loaded in the graphene oxide membrane that step 2 obtains.
Above-mentioned steps 2,3 the most alternately, it is thus achieved that 6 layers of graphene oxide@vinylidene fluoride microporous filter membrane multilayer film.?
After, graphene oxide@vinylidene fluoride microporous filter membrane multilayer film is put in the baking oven of 45 DEG C and be dried, remove remaining solvent.
Embodiment 4
Prepare graphene oxide@nylon 6/nanometer fiber multilayer film, specifically comprise the following steps that
Step 1: preparation graphene oxide solution: use graphene oxide water solution prepared by the Hummers method improved, so
Rear employing vacuum lyophilization prepares the powder of graphene oxide.A certain amount of graphene oxide is added water and dimethyl formyl
In the mixed solution of amine (DMF) 1:1, ultrasonic 2h, magnetic agitation 5h, obtain finely dispersed graphene oxide solution A.In solution
The mass fraction of graphene oxide is 0.5%.
Step 2: 3g nylon 6 is added 17.64g formic acid is in acetic acid mixed solution (formic acid, quality of acetic acid ratio is for 7:3), super
Sound 2h, magnetic agitation 12h, obtain nylon 6 solution B being completely dissolved.
Step 3: solution B stands 1h deaeration, is then transferred in 20mL syringe, by electrostatic spinning film forming, spinning
Voltage is 27KV, and relative humidity is 35 45%, and temperature is 20 25 DEG C, and fltting speed is 0.01mL/min.Receiving range is
20cm, spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 900r/min.The spinning time is 5min.
Step 4: use the method for vacuum filtration by the solution A sucking filtration of certain capacity to nylon 6/nanometer fibrous membrane.
Above-mentioned steps 3,4 the most alternately, it is thus achieved that 6 layers of graphene oxide@nylon 6/nanometer fiber multilayer film.Finally, will
Graphene oxide@nylon 6/nanometer fiber multilayer film is put in the baking oven of 45 DEG C and is dried, and removes remaining solvent.
Embodiment 5
Use self-control vertical current defecator as shown in Figure 5, injected by water filling port, under same operation pressure (1bar)
Measure embodiment 1 and the pure water flux of embodiment 4 graphene oxide@nylon 6/nanometer fiber multilayer film and molten to methylene blue
The rejection experiment of liquid.Result shows, described in embodiment 1, the pure water flux of multilayer film is up to 7Lm-2h-1bar-1(embodiment 1 institute
State in 6 tunics graphene oxide thickness at 300 400nm), to the rejection that initial methylene blue concentration is 100mg/L solution
Reach 100%, intercept completely；And the pure water flux of multilayer film described in embodiment 4 is 1.12Lm-2h-1bar-1(described in embodiment 46
In tunic, graphene oxide thickness is at 200 300nm), the rejection that initial methylene blue concentration is 100mg/L solution is reached
99.2%, basic realization intercepts completely.
In embodiment 1, the graphene oxide@nylon 6/nanometer fiber multilayer film of preparation is after 48h soaks, graphene oxide
Film does not disperse, and is still fettered by nylon 6/nanometer fiber, and this multilayer film structure stability in the solution is preferable；
And the graphene oxide@nylon 6/nanometer fiber multilayer film of preparation is after 48h soaks in embodiment 4, graphene oxide membrane occurs
Part discongests dispersion, less stable.
Although the detailed description of the invention of the present invention is described by the above-mentioned accompanying drawing that combines, but not the present invention is protected model
The restriction enclosed, on the basis of technical scheme, those skilled in the art need not pay creative work and can do
The various amendments gone out or deformation are still within protection scope of the present invention.
Claims (10)
1. a graphene oxide high polymer nano fiber multilayer film, it is characterised in that this film by high polymer nano fibrous membrane,
Graphene oxide membrane layer alternately composition, the mass fraction of graphene oxide is about 50 80%, high polymer nano fibrous membrane, oxygen
All at least 2 layers of functionalized graphene layer.
2. a preparation method for graphene oxide high polymer nano fiber multilayer film, described method includes:
(1) a floor height polymers nano fibrous membrane is prepared by method of electrostatic spinning；
(2) by electrostatic spraying, graphene oxide is uniformly sprayed previous step and obtain the high polymer nano fiber membrane of film
On；
(3) on the graphene oxide membrane layer that previous step obtains film, a floor height polymers nanofiber is prepared by method of electrostatic spinning
Film；
(4) repeat step (2) (3) and obtain the multilayer film of graphene oxide@high polymer nano fibrous membrane alternately design.
Method the most according to claim 2, it is characterised in that described high polymer is that the height being appropriate to electrostatic spinning gathers
Thing.
Method the most according to claim 3, it is characterised in that high polymer is selected from nylon 6 (Nylon6), polyacrylonitrile
(PAN), polystyrene (PS), polypropylene (PP), polyvinylidene fluoride (PVDF) one or more.
Method the most according to claim 2, it is characterised in that described step (1), the operating procedure of (3) be:
(1-1) being dissolved in corresponding solvent by a certain amount of high polymer, ultrasonic 1-3h, magnetic agitation obtains the height being completely dissolved
Copolymer solution B；
(1-2) by solution B standing and defoaming, being then transferred in syringe, by electrostatic spinning film forming, spinning voltage is 8
30KV, relative humidity is 20% 50%, and temperature is 15 30 DEG C, and fltting speed is 0.001 0.01mL/min, accepts distance
Being 15 20cm, spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is 800 1000r/min, the spinning time
It is 1 5min.
6. according to the method described in claim 2 or 5, it is characterised in that described step (2) including:
(2-1) mixing that at room temperature, a certain amount of graphene oxide is dissolved in water and dimethylformamide (DMF) 1:1 is molten
In liquid, ultrasonic 1-3h, magnetic agitation obtains finely dispersed graphene oxide solution A；
(2-2) solution A is transferred in syringe, by electrostatic spraying, graphene oxide is sprayed to high polymer nano fiber
On film, electrostatic spraying voltage is 25 35KV, and relative humidity is 20% 50%, and temperature is 15 30 DEG C, and fltting speed is
0.1 0.2mL/min, receiving range is 15 20cm, and spinning syringe needle is No. 9, uses aluminium foil, and cylinder receives, and drum rotation speed is
200 400r/min, the electrostatic spraying time is 10 40min.
Method the most according to claim 6, it is characterised in that graphene oxide used in step (2-1) in step (2)
Being to be prepared by the Hummers method improved, its mass fraction is 0.1 1%.
Method the most according to claim 2, it is characterised in that step (4) farther includes: put into by acquisition multilayer film
The baking oven of 45 DEG C is dried, removes remaining solvent.
9. the graphene oxide@high polymer nano fiber multilayer film that any one of claim 2-8 preparation method prepares.
10. the graphene oxide@high polymer nano fiber multilayer film stated described in claim 1 or claim 9 air filtration,
Sewage disposal, the application of desalination membrane separation field.
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