CN109794175A - Graphene oxide composite membrane and its preparation method and application with pH responsiveness - Google Patents
Graphene oxide composite membrane and its preparation method and application with pH responsiveness Download PDFInfo
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Abstract
The invention discloses a kind of graphene oxide composite membrane and its preparation method and application with pH responsiveness.Graphene oxide layer is cross-linked into graphene network by polycation electrolyte, and uniform fold adjusts the form and performance of graphene oxide composite membrane on the surface of matrix membrane.Film chemical stability with higher, while infiltration with higher and strainability.This graphene oxide composite membrane has excellent pH response performance, and thickness, surface hydrophilic and hydrophobic and pore size are realized with the regulation of extraneous pH and adjusted.According to above-mentioned property, which can show the selectivity to different pollutants under condition of different pH, the separation and recycling to different component pollutant may be implemented, while multiple continuous filtration cycles may be implemented.The pH responsiveness graphene oxide composite membrane has high stability, excellent pH responsiveness and recycling property, can be used for the removal of actual water pollutant and the fields such as separates with multicomponent pollutant.
Description
Technical field
The present invention relates to novel environmental responsive materials technical field more particularly to a kind of graphite oxides with pH responsiveness
Alkene composite membrane and its preparation method and application.
Technical background
The membrane material of environment-responsive can be applied to the fields such as separation, drug controlled release and the wastewater treatment of substance.With
In the porous film material of the environment-responsive of separation process, permeability can change with external environmental condition and be changed, thus by
To the extensive concern of people.For example, can prepare has by assembling poly(N-isopropylacrylamide) and graphene oxide
The membrane material of thermo-responsive, membrane aperture can be controlled by extraneous temperature.However, if will water inlet in wastewater treatment process
Or membrane module is heated to 50 DEG C from 25 DEG C, then can consume very huge energy.On the contrary, adjusting solution in water treatment procedure
PH it is comparatively more simple.Therefore, the film with pH responsiveness is more suitable for actual water treatment procedure.
PH responsiveness film, which mainly passes through for the polyelectrolyte containing weak acid or alkalescent functional group to be introduced into matrix membrane, to be obtained,
Preparation method includes blending, grafting and surface coating etc..Due to introducing the dissociation degree of electrolyte in membrane matrix by solution
The influence of pH value, therefore the conformation of polymer chain will be influenced by extraneous pH, corresponding change occur, to further influence
The channel size and surface texture of film.Such as application No. is 201810977977.7 patent by by anionic polymer and sun from
Sub- polymer layers self assembly obtains the polymer coating with pH responsiveness, and pH responsiveness cross-linking multilayer film, Ke Yishi is made
Existing water-oil separating.Application No. is 201610548449.0 patent by by two-dimentional membrane material dip-coating in being total to containing pH responsiveness
In copolymer solution, it is prepared for the two-dimensional film material of pH responsiveness.The material shows to completely contradict at different pH close and distant
It is aqueous, it can be used for the separation of oil hydrosol.However, degree of swelling of the polymer introduced in above-mentioned patent under condition of different pH
It is uncontrollable, therefore the pH responsiveness film and unstable prepared, pH responsiveness is uncontrollable.Polymer chain is carried out
Its stability can be improved in crosslinking, but since crosslinking post-consumer polymer chain is in state that is unordered and mutually tangling, pH
Response effect is limited.
Graphene oxide is one of important derivatives of graphene.It not only has the thickness, excellent of graphene atomic layer
Chemistry and mechanical stability, while oxygen-containing functional group also rich in can be repaired such as hydroxyl, epoxy group and carboxyl
It adorns and modified, expands its application range.Method by suction filtration, LBL self-assembly or knifing etc. can be by graphene oxide layer
It is assembled into graphene oxide composite membrane.Compared to other preparation methods, LBL self-assembly not only can control the thickness of the film of preparation
Degree can also control its interlayer structure and interaction between layers.By being introduced not between graphene oxide layer
With the substance of size, the graphene oxide composite membrane of available difference nanochannel, and it is applied to gas, organic solvent
Separation and the processes such as water body purification.However, the channel sized of existing graphene oxide composite membrane is constant, and not with outer
The change of boundary's environment and change, be not able to satisfy the demand of practical application.The existing patent about response type graphene oxide membrane
Only application No. is 201710846147.6 patents, and the patent is using graphene oxide as basic material, by introducing temperature
Response polymer is spent to prepare the graphene oxide membrane with temperature-responsive.As previously mentioned, in water treatment procedure, adjustment
The temperature of water inlet needs to consume significant energy, is unable to satisfy the requirement of low consumption.Therefore, as based on how graphene oxide
Material, preparing, there is the graphene oxide membrane material of pH responsiveness to have great importance in practical water treatment procedure.
As typical faintly acid group, carboxyl is largely present in the edge and defective locations of graphene oxide layer, because
This, should have pH response characteristic using the graphene oxide composite membrane that graphene oxide layer is prepared as predecessor.However, with pure
The problem of graphene oxide composite membrane of graphene oxide layer preparation equally exists stability.Therefore, research usually by sun from
Sub- polymer carries out the graphene oxide composite membrane compound, preparation is stablized and interlamellar spacing is controllable with graphene oxide layer.It is existing
By LBL self-assembly response film is prepared in graphene oxide layer and poly- (allylamine hydrochloride) assembling by research report, by
In the ionization of graphene oxide layer at different conditions, what is be prepared can show different holes under condition of different pH
Road size.But since the content of carboxyl on graphene oxide layer lamella is less, responsiveness is very limited.Poly- second
Alkene imines contains highdensity alkalescent amino group, it not only can react to form stable amido bond with carboxyl, while can
Change the molecular conformation of its own with the variation according to extraneous pH condition.Polyethyleneimine is introduced in graphene oxide composite membrane
The stability of graphene oxide layer can not only be improved, while the surface charge of graphene oxide layer can be become from negative
Just.Therefore polycation graphene oxide layer preparation graphene oxide layer is introduced to have very important significance.However,
The pH response characteristic of polyethyleneimine is introduced into graphene oxide layer currently without research and is studied.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of systems of graphene oxide composite membrane with pH responsiveness
Preparation Method.The present invention is to prepare a kind of graphene oxide membrane with pH response performance using layer-by-layer and answered
Separation for different sized contaminants.Graphene oxide uniform fold provides a kind of with stratiform on the surface of matrix membrane
Structure, the graphene film of high pH responsiveness, while providing a kind of graphene oxide membrane with pH responsiveness and its preparation side
Method is applied to the separation and recovery of one pack system or multicomponent organic matter, has excellent cycle performance.Due to above-mentioned oxidation stone
The duct of black alkene film is different under condition of different pH, therefore can use a various sizes of pollutant of UF membrane, in pollutant
Separation and recycling field be with a wide range of applications.
The present invention is realized particular by following technical scheme:
A kind of preparation method of the graphene oxide composite membrane with pH responsiveness, comprising the following steps:
1) matrix membrane containing graphene oxide is immersed in polycation electrolyte solution, then washing and drying,
Surface forms polycation layer；
2) it is immersed in graphene solution again, then washing and drying, forms graphite oxide in polycation layer surface
Alkene lamella；
3) step 1) and step 2) are repeated several times to same matrix membrane, so that polycation and graphene oxide are in matrix
It is crosslinked by LBL self-assembly compound on film, finally obtains the graphene oxide composite membrane with pH responsiveness.
In the graphene oxide composite membrane, graphene oxide layer is cross-linked into graphene mesh by polycation electrolyte
Network, and uniform fold adjusts the form and performance of graphene oxide composite membrane on the surface of matrix membrane.Film with higherization
Learn stability, while infiltration with higher and strainability.This graphene oxide composite membrane has excellent pH responsiveness
Can, thickness, surface hydrophilic and hydrophobic and pore size are realized with the regulation of extraneous pH and are adjusted.According to above-mentioned property, which rings
Answering property graphene oxide composite membrane can show (such as polyethylene pyrrole network alkanone, poly- to different pollutants under condition of different pH
Ethylene oxide and silver nano-grain) selectivity, may be implemented to different component pollutant (such as polyethylene pyrrole network alkanone, polyoxy
Change two or three in ethylene and silver nano-grain) separation and recycling, while multiple continuous filtration cycles may be implemented.
Preferably, the polycation electrolyte be the polymer with pH response performance, including polyethyleneimine,
Poly- (4- vinyl pyridine) or poly- (2- vinyl pyridine), the preferably polyethyleneimine (Linear of straight-chain
Polyethylenimine) or the polyethyleneimine of branched, the further preferably polyethyleneimine of straight-chain.Lower part
Other preferred embodiments and effect are introduced by taking polyethyleneimine as an example, but remaining polycation electrolyte actually also may be implemented
Similar effect.
Preferably, the concentration of the polycation electrolyte solution and graphene oxide solution is 0.1mg/mL-
10mg/mL, preferably 1mg/mL.
Preferably, the pH of the polycation electrolyte solution and graphene oxide solution is 2-12.
The change of polycation electrolyte solution (by taking polyethyleneimine as an example) and graphene oxide solution pH in the present invention
Can bring following effect: 1. with polyethylenimine solution pH reduction, the dissociation degree enhancing of polyethyleneimine, layer by layer
During self assembly, it is only necessary to which a small amount of polyethyleneimine can meet the charge balance requirements of basilar memebrane.2. with oxidation
The dissociation degree of the increase of graphene solution pH, graphene oxide layer gradually weakens, therefore, during LBL self-assembly
A large amount of graphene oxide is needed just to be able to satisfy the needs of charge balance.3. the number of graphene oxide, which directly affects, prepares film
Complete and compactness extent, in order to prepare more complete and fine and close graphene oxide composite membrane, the polyethyleneimine and oxygen
The pH of graphite alkene solution can be more preferably 3.5.
Preferably, step 1) and 2) in, each Immersion time be 5-30min.
Further, the straight-chain polyethyleneimine the preparation method comprises the following steps: polyethylene glycol oxide (PEOX) is added to HCl
In solution, micro-wave digestion reaction is carried out；It cools down after reaction, collecting reaction product is purified and is freeze-dried, and is obtained straight
Chain polyethyleneimine.Further, the detailed process of micro-wave digestion reaction are as follows: heat mixture in microwave eliminating device
It to 100 DEG C, is kept for 4 hours, completes reaction.The purifying of reaction product can be purified by dialysis procedure.
Preferably, the matrix membrane containing graphene oxide the preparation method comprises the following steps: graphene oxide is fully dispersed
In organic solvent, high molecular polymer is then added and is uniformly mixed, obtains casting solution；Casting solution is carried out by scraping film device
Knifing obtains the matrix membrane containing graphene oxide after dry.
Further, in the casting solution, the mass fraction that graphene oxide and high molecular polymer account for casting solution is
10%~30%；It is 0.5%~20% that wherein graphene oxide, which accounts for the mass fraction of casting solution, preferably 0.5%-5%.
Further, the high molecular polymer is preferably Kynoar, polysulfones, polyether sulfone, polyacrylonitrile, cellulose
Any one in ester and polytetrafluoroethylene (PTFE).
Further, the organic solvent is preferably dimethylformamide, dimethyl acetamide, methyl pyrrole network alkanone and third
Any one in ketone.
Further, the casting solution the preparation method comprises the following steps: by graphene oxide and high molecular polymer in 30-100
It is stirred 4-24 hours at DEG C, forms uniform casting solution.It is still more preferably to be stirred 24 hours at 70 DEG C.
Another object of the present invention is to provide the oxidations made from a kind of any of the above-described preparation method with pH responsiveness
Graphene composite film, which is layer structure, including hypothallus and multilayer oxygen containing graphene oxide
Graphite alkene lamella；It is electrolysed between hypothallus and graphene oxide layer and adjacent graphene oxide layer by polycation
The crosslinking of matter layer.
Preferably, the thickness of graphene oxide composite membrane, surface hydrophilic and hydrophobic and pore size change with extraneous pH；
Water flux in pH=3 is 30-48LMH, and contact angle is 39-50 °, with a thickness of 25-33nm；Water flux in pH=11 is
6-8LMH, contact angle is 41-50 °, with a thickness of 20-23nm.
Another object of the present invention is to a kind of purposes of above-mentioned graphene oxide composite membrane with pH responsiveness, the use
Way is the separation for one-component or multicomponent mixing organic pollutant.The graphene oxide composite membrane is under different pH environment
With different stalling characteristics, can method by simply adjusting the pH value of water inlet, will be multi-component using same film
Separated from contaminants comes out.Wherein, pollutant can be polyethylene pyrrole network alkanone (PVP), and (PEO, molecular weight are polyethylene glycol oxide
150-750kDa) and one of nano silver (50nm) or a variety of, it is also possible to other contaminant components.
In the present invention, so-called pH responsiveness refers in different pH solution, inside the graphene oxide composite membrane
The trend or degree of amino or carboxyl dissociation are different, and polyethyleneimine shows certain charging property.Due to polyethyleneimine band
Electricity, adjacent amino is mutually exclusive or attracts, and ethylene imine chain is made to show the state for stretching or shrinking.Due to polyethyleneimine
The adjacent graphene oxide layer of amine chain link, therefore the metamorphosis of ethylene imine chain can cause between graphene oxide layer
Away from variation, therefore the pore size of the graphene oxide composite membrane can also change.And experiment shows that the graphene oxide is compound
The pore size of film, which changes, has preferable cyclicity, and change repeatedly can be made with pH value.Duct size determines point of film
From performance.Graphene oxide composite membrane becomes smaller in duct in pH=11, the lesser separated from contaminants of size can be come out；PH=
Duct becomes larger when 3, larger-size separated from contaminants can be come out.It therefore can be by simply adjusting the pH value of water inlet
Method is come out multi-component separated from contaminants using same film.In addition, the change of duct size also results in water flux
Variation, shows higher water flux under conditions of pH=3, and it is logical that lower water is then shown under conditions of pH=11
Amount.
The above-mentioned graphene oxide composite membrane being prepared can pass through thickness, the measurement experiment of contact angle and water flux
Characterize the responsiveness of the pH of graphene oxide composite membrane.The pH responsiveness of contact angle experiments characterization graphene oxide composite membrane: point
The water for not taking pH=3, pH=6, pH=11 is contacted using the water of contact angle measurement measurement graphene oxide composite membrane film surface
Angle.Heights Experiment characterization graphene oxide composite membrane pH responsiveness: by graphene oxide composite membrane be placed in pH=3,5,7,9,
In 11 aqueous solution, thickness change of the graphene oxide composite membrane at different pH is measured by AFM.Water flux measurement experiment table
Levy the pH responsiveness of graphene oxide composite membrane: aqueous solution of the measurement graphene oxide composite membrane in filtering pH=3,5,7,9,11
When water flux.
The present invention provides a kind of method for preparing pH response type graphene oxide membrane using layer-by-layer, the systems
Preparation Method is simple, and the polycation electrolyte by assembling different chain forms, can change the internal junction of graphene oxide membrane
But its pH response condition of structure.The graphene oxide membrane has excellent pH response performance, and four times circulation is still able to maintain original sound
Performance is answered, while the film has excellent separating property to the organic matter of different molecular weight, can carry out multicomponent with same film
The separation of pollutant.
In actual use, which has the advantage that
1. the composite membrane has excellent pH responsiveness, and four circulations are still able to maintain original response performance.
2. the selective removal to different molecular size pollutant may be implemented in the composite membrane, wherein pollutant includes poly- second
Alkene pyrrole network alkanone, polyethylene glycol oxide and silver nano-grain.
3. the film has excellent cycle performance, the same multi-component mixed pollutants of UF membrane can be used.
Since the removal of the pollutant of different molecular weight may be implemented in the graphene oxide composite membrane, and can be at 15 times
Retention property is stablized in circulation, so having very big application potential in actual waste water processing.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the graphene oxide composite membrane with pH responsiveness；
Fig. 2 is that the surface chemistry of the graphene oxide composite membrane with pH responsiveness forms；
Fig. 3 is the Stability Determination figure of the resulting graphene oxide composite membrane of embodiment；
Fig. 4 is the shape appearance figure that the resulting pH of embodiment responds graphene oxide composite membrane, wherein (a) (b) is respectively MB's
SEM and AFM figure, (c) SEM and AFM that (d) is ML scheme；
Fig. 5 is the surface potential that the resulting pH of embodiment responds graphene oxide composite membrane；
Fig. 6 is the thickness change figure that the resulting pH of embodiment responds graphene oxide composite membrane；
Fig. 7 is that the resulting pH of embodiment responds contact angle of the graphene oxide composite membrane at different pH；
Fig. 8 is that the resulting pH of embodiment responds variations of flux figure of the graphene oxide composite membrane at different pH, wherein (a)
For MB and ML flux with pH variation, (b) be MB and ML flux loop condition, (c) be MB and ML schematic diagram of structural changes；
Fig. 9 is that the resulting pH of embodiment responds graphene oxide composite membrane at different pH to the retention feelings of different pollutants
Condition, wherein (a) (b) is respectively the retention of MB and ML to pollutant；
Figure 10 is that the resulting pH of embodiment responds graphene oxide composite membrane to the separation situation of mixed pollutants；
Figure 11 is the separating mechanism that the resulting pH of embodiment responds graphene oxide composite membrane.
MB refers to that polyethyleneimine is the graphene oxide composite membrane of branch in figure, and ML refers to that polyethyleneimine is the oxidation of straight chain
Graphene composite film.
Specific embodiment
Invention is further elaborated with reference to the accompanying drawings and examples, must be understood so that those skilled in the art is more preferable
Essence of the invention.Reagent or material in the present invention, if being commercial product without specified otherwise.
Embodiment 1 (MB)
PH responsiveness graphene oxide composite membrane is by substrate surface self assembly graphene oxide layer and poly- layer by layer
What aziridine was realized, specific structure is as shown in Figure 1.It is specific the preparation method is as follows:
(1) a certain amount of graphene oxide (GO) and Kynoar (PVDF) are added to dimethyl acetamide (DMAc)
In, the mass fraction that the mass fraction control of graphene oxide is 0.2%, PVDF is 16%, and ultrasound makes its dispersion in one hour.
(2) said mixture is stirred under the conditions of 70 DEG C and obtains uniformly mixed casting solution for 24 hours.
(3) above-mentioned casting solution is centrifuged to 5min deaeration under the conditions of 3000rpm, then fills above-mentioned casting solution by knifing
Preparation is set with a thickness of 200 μm of graphene oxide composite membrane.
(4) film prepared by step (3) is placed in water, is then dried to obtain graphene oxide basilar memebrane.
(5) film prepared by step (4) is placed in 1mg/mL, 10min in the branched polyethylenimine solution of pH=3.5, so
After be rinsed with water film surface, after extra polyethyleneimine is rinsed well, with being dried with nitrogen.
(6) film prepared by step (5) is placed in 1mg/mL, then 10min in the graphene oxide solution of pH=3.5 is used
Water rinses film surface, after extra graphene oxide layer is rinsed well, with being dried with nitrogen.
(7) by step (5) and (6) as a circulation, repetitive cycling seven times altogether, obtain having seven strata aziridines/
The graphene oxide composite membrane of graphene oxide layer.
(8) film that step (7) obtains is placed in drying in 60 DEG C of baking ovens, obtains having the graphene oxide of pH responsiveness multiple
It closes film (being denoted as MB).
Embodiment 2 (ML)
Compared with Example 1, difference is only that changes the branched polyethylenimine in step (5) and (7) to the present embodiment
For straight linear polyethylene imines, remaining is all the same, and is the graphene oxide composite membrane of straight chain by finally obtained polyethyleneimine,
It is denoted as ML.
Straight linear polyethylene imines the preparation method is as follows: polyethylene glycol oxide is added in HCl solution, in microwave eliminating device
In heat the mixture to 100 DEG C, kept for 4 hours.After mixture is cooled to room temperature, collecting reaction product and by dialysing
Journey purifies product, finally, product after purification is freeze-dried to obtain straight-chain polyethyleneimine.
Infrared spectroscopy is carried out to the resulting graphene oxide composite membrane of above-described embodiment 1 and 2 and XPS map detects its surface
Chemical composition, as a result as shown in Figure 2.By infrared spectroscopy (Fig. 2 a), it can be observed that the main oxygen-containing official of graphene oxide
It can group.Wherein in 1720,1400,1223 and 1051cm-1Corresponding absorption peak respectively indicates the C=O in carboxyl, in carboxyl
The vibration of C-O in C-O and hydroxyl in C-O, epoxy group.After LBL self-assembly, in graphene oxide composite membrane
1720cm-1The carboxyl peak at place completely disappears, while in 1654,1572 and 1433cm-1There is new absorption peak in place, respectively corresponds
The stretching vibration of HNC=O and N-H key in amido bond, it was confirmed that the generation of amido bond, i.e. graphene oxide layer lamella and poly- second
Alkene imines is successfully crosslinked.It is further disclosed in graphene oxide and is deposited by the XPS map (Fig. 2 b) of graphene oxide composite membrane
In oxygen-containing functional group abundant, after LBL self-assembly, the oxygen-containing functional group of graphene oxide composite membrane disappears, while
There is apparent amido bond peak in MB and ML.XPS map can be seen that the graphene oxide composite membrane chemical composition in MB and ML
It is almost the same.Therefore, infrared spectroscopy and XPS directly confirm graphene oxide layer lamella in graphene oxide composite membrane and gather
The crosslinking of aziridine, while the chemical crosslinking of amino and carboxyl can promote the stability of film.
Stability test is carried out to the resulting graphene oxide composite membrane of above-described embodiment, as a result as shown in Figure 3.With above-mentioned
The resulting graphene oxide composite membrane of embodiment filters the aqueous solution of different pH, detects oxidation stone by the TOC of measurement water outlet
Whether black alkene lamella and polyethyleneimine dissolve out, further to assess the stability of graphene oxide composite membrane.As shown in figure 3,
In the range of pH is from 3-9, the TOC value of the very close deionized water of the value of TOC of yielding water；When the pH of water inlet rises to 11, water outlet
TOC value still be below 1.5mg/L, show that graphene oxide layer and polyethyleneimine are hardly molten under the conditions of above-mentioned pH
Out.Under conditions of high pH, due to the ionization of carboxyl, the graphene oxide layer not being crosslinked is extremely unstable, is easily operating
When be lost.By being crosslinked for polyethyleneimine, MB and ML show high stability in the range of pH is from 3-11.Together
When, its crosslinking degree and further can be improved by controlling the amount of every layer of graphene oxide layer and polyethyleneimine
Improve the stability of film.
Electron-microscope scanning is carried out to the resulting graphene oxide composite membrane of above-described embodiment, as a result as shown in Figure 4.Graphite oxide
Alkene lamella is uniformly covered on the surface of matrix membrane, and the hole of matrix film surface and defect are oxidized graphene sheet layer/polyethyleneimine
Amine uniformly covers, simultaneously because the stacking of graphene oxide layer, apparent pleated structure is presented in film surface.Above-mentioned fold knot
Structure can be used as the entrance and cushion space of substance during the filtration process, to further enhance the permeance property of matrix membrane.Together
Sample, the afm image of Examples 1 and 2 also show that MB and ML has smooth surface, have lower roughness, respectively
4.8 and 5.2nm.Therefore, SEM and AFM, which is directly confirmed, is deposited on matrix membrane table in graphene oxide layer and polyethyleneimine
Behind face, film surface becomes smooth and pleated structure occurs.
Surface potential detection is carried out to the resulting graphene oxide composite membrane of above-described embodiment, measuring method is by MB and ML
It is cut into 1 × 2cm, is then attached on sample stage, using the KCl solution of 0.01M as background solution, measurement MB and ML is in pH from 2.0-
Zeta potential in 10.0 ranges, as a result as shown in Figure 5.Since during the preparation process, the last layer of MB and ML are all graphite oxides
Alkene lamella, therefore MB and ML is negatively charged in the range of pH is from 3-11.
The measurement of thickness and interlamellar spacing is carried out to the resulting graphene oxide composite membrane of above-described embodiment: first using silicon wafer
Oxygen gas plasma is handled 2 minutes at 80W, obtains the negatively charged silicon wafer in surface.Then according to described in embodiment 1 layer by layer from
The preparation condition of assembling obtains GPM in silicon chip surface alternating deposit GO and PEI.Then it is drawn with sharp blade in silicon chip surface
Scratch out passes through the difference in height between the scanning surface GPM and scratch, the thickness of available GPM.Silicon wafer is placed in sample cell
In, and the aqueous solution of different pH is added in sample cell, then in the height on the same position scanning surface GPM and scratch
With the variation of environment pH, as a result as shown in Figure 6 difference obtains GPM thickness by the method for in-situ monitoring.MB and ML are in drying condition
Under thickness be respectively 16.1 and 20.4nm.Due to above-mentioned graphene oxide composite membrane be by seven layers graphene oxide layer and
Polyethyleneimine composition, therefore every layer of graphene oxide layer/polyethyleneimine thickness is respectively 2.3 and 2.9nm.Pass through list
In 1nm or so, therefore in MB and ML, the spacing of adjacent graphene oxide layer lamella is respectively the thickness of layer graphene oxide
1.3 and 1.9nm.Fig. 6 a discloses MB, and at 9.92 °, there are wider peaks, and the peak is related with the diffraction maximum of graphene oxide layer,
It is 0.89nm according to the interlamellar spacing that MB is calculated in Bragg equation.Meanwhile ML at 9.49 ° there are wider peak, be calculated
The interlamellar spacing of ML is 0.94nm.Although the data that the interlamellar spacing numeric ratio AFM obtained by Fig. 6 a is obtained are smaller, above-mentioned number
The interlamellar spacing of polyethyleneimine amine molecule generation of branch shape is inserted into graphene oxide layer lamella according to equal surface than straight-chain
The interlamellar spacing that polyethyleneimine amine molecule generates is small.In addition, further determining MB and ML thickness at various ph values by AFM
Variation.As shown in Figure 6 b, when the pH value of solution increases to 11 from 3, the thickness of graphene oxide composite membrane is gradually reduced；Work as pH
When being reduced to 3 from 11 again, the thickness of graphene oxide composite membrane increases to initial value again.Under the conditions of above-mentioned pH (3-11),
The thickness of MB is reduced to 20.3nm from 25.6nm, and the thickness of ML changes to 22.7nm from 32.2nm.Due to polyethyleneimine
Chain structure is influenced by solution ph, while the variation of its structure influences the interior spatial structure of graphene oxide composite membrane,
Therefore the variation of above-mentioned graphene oxide composite film thickness is consistent with the degree of protonated amino in polyethyleneimine.Graphite oxide
Alkene composite membrane is made of graphene oxide layer and polyethyleneimine two parts, and polyethyleneimine amine molecule is not only to enhance film
The crosslinking agent of stability, while can control movement of the graphene oxide layer under condition of different pH.At low ph conditions, by
In the protonated amino of polyethyleneimine, and the amino protonated can be mutually exclusive, makes polyethyleneimine amine molecule in low ph condition
It is in the state of chain-unfolding down, so that the distance between adjacent graphene oxide layer lamella increases.On the contrary, in high pH condition
Under, ethylene imine chain is in contraction state, reduces the distance between adjacent graphene oxide layer lamella.Due to polyethylene
The protonation of the amino of imines or deprotonation process are reversible, therefore change the graphene oxide caused by extraneous pH condition
The change procedure of composite film thickness is also reversible.Structure change of the polyethyleneimine under condition of different pH makes graphite oxide
The internal structure of alkene composite membrane changes, in addition, what is formed between polyethyleneimine and graphene oxide layer is stable
Amido bond ensures that graphene oxide layer lamella is limited in certain range in the movement in graphene oxide composite membrane.
By the variation of AFM thickness data, it can be concluded that, under dry and wet condition, MB is thinner than ML, and the change of MB thickness
It is small to change range ratio ML.Above-mentioned phenomenon is mainly as caused by the different molecular structure of polyethyleneimine (branch and straight chain).
The XPS spectrum of MB and ML shows the polyethyleneimine compared to straight-chain, due to branch polyethyleneimine amino group to
Different direction stretching, extensions, therefore the amino of branched ethylene imine is reacted with the carboxyl of graphene oxide layer and is easier, instead
It is more amido bond should to be formed by.Compared to ML, in MB, polyethyleneimine is opposite to form more " anchor points ", and therefore, MB is not
The membrane structure of more consolidation is only shown, and its degrees of expansion ratio ML is smaller.
Contact angle of the MB and ML under condition of different pH is measured by bubble method, the specific operation method is as follows: GPM is fixed
It on glass slide, then places it in the sample cell containing different pH aqueous solutions, places 30 minutes, by the note for having crochet hook
Bubble is discharged into film surface by emitter, obtains bubble and the contact image of GPM.By software Surface Meter to the water of GPM
Contact angle is analyzed, as a result as shown in Figure 7.For MB under conditions of pH is 3,6 and 11, water contact angle is respectively 48.3 °,
56.0 ° and 49.8 °.For ML under conditions of pH is 3,6 and 11, water contact angle is respectively 39.5 °, 44.6 ° and 41.2 °.It is above-mentioned
The result shows that graphene oxide composite membrane when pH is 6 with highest water contact angle or minimum hydrophily, but sourer and
More hydrophilic surface is showed in the case where compared with alkali.The amino of polyethyleneimine protonates in acid condition, so that poly- second
More hydrophilic state is presented in alkene imines；Simultaneously because the deprotonation under alkaline condition of the carboxyl of graphene oxide layer, makes
It obtains graphene oxide layer and shows more hydrophilic state, therefore under conditions of acid or alkali, graphene oxide composite membrane is in
Reveal more hydrophilic surface.Further, since the crosslinking degree of ML is lower, therefore contain more hydrophily function compared to MB
Group, ML shows the surface more more hydrophilic than MB under the test conditions above, while hydrophilic surface can further increase
The permeation flux of film.
As previously mentioned, the graphene oxide composite membrane of preparation should have good pH response performance.In order to evaluate oxidation stone
The pH response performance of black alkene composite membrane, determine MB and ML under condition of different pH (3-11) water flux.As shown in Fig. 8 (a),
In the range of pH is from 3 to 11, the flux of MB and ML with the increase of the pH of solution and linear reduction.When pH is 3, MB's is logical
Amount is 30.9L m-2h-1bar-1, be under the conditions of pH=11 under four times (in pH=11, flux is 7.5L m-2h-1bar-1).When the pH of solution is adjusted to 11 from 3, the flux of ML is from 47.5L m-2h-1bar-1Drop to 6.2L m-2h-1bar-1.It is above-mentioned
Embodiment shows variation of the permeation flux in response to extraneous pH of graphene oxide composite membrane.
In order to study the invertibity of graphene oxide composite membrane pH response performance, to 3, then the pH of water inlet is adjusted from 11
11 carry out four circulations are recalled to from 3, the flux of the MB and ML under above-mentioned cycling condition are measured, as shown in Fig. 8 (b).Above-mentioned four
In a cyclic process, the flux of MB and ML under the conditions of pH is 3 and 11 is consistent with unitary determination result.The above results surface
The film of MB and ML preparation has stable structure and reversible pH response performance.
Embodiment 3: the retention of one-component organic pollutant
In order to evaluate screening effect of the graphene oxide composite membrane under condition of different pH, it is organic to have chosen several representativenesses
Pollutant carries out separating experiment, including polyethylene pyrrole network alkanone (PVP, molecular weight 58K), polyethylene glycol oxide (PEO, molecular weight
For 300K and 600K) and nano-Ag particles (Ag NP, having a size of 50nm), above-mentioned four kinds of pollutants are in the range of pH is from 3 to 11
It keeps stablizing.As shown in figure 9, MB and ML increases the rejection of above-mentioned four kinds of pollutants with the increase of pH.Work as solution
When pH becomes 11 from 3, MB and ML increase to 45.5% from < 1% respectively to the rejection of PVP and increase to 26.4% from 1.5%；
MB and ML becomes 88.7% from 29.6% respectively to the rejection of PEO1 (300K) and increases to 81.7% from 32.6%；MB and ML
96.6% is increased to from 56.7% respectively to the retention of PEO2 (600K) and increases to 97.4% from 53.9%.For size maximum
Ag NP, MB and ML can achieve in the range of pH is from 3 to 11 90% or more rejection.Above-mentioned one-component pollutant
Filtration experiment show that the duct size of MB and ML reduces with the increase of pH, it is consistent with the variation tendency of water flux.In mistake
During filter, the gap between adjacent two dimensional oxidation graphene sheet layer edge and lamella edge forms three-dimensional duct, is filtering
Sieving actoion is played to pollutant in the process.But between graphene oxide layer and lamella, the gap at edge and edge all may be used
To be convenient for passing through for hydrone during the filtration process as aquaporin.In pH change procedure, graphene oxide layer and lamella
The distance between, the gap at edge and edge is all reduced with the increase of pH, and identical variation tendency is presented.Although MB's and ML
The water flux of graphene oxide composite membrane has larger difference, but they are closely similar to the cutoff performance of pollutant.In addition, MB
It can be continuously adjusted, can be used for more within the scope of certain pH with the molecular cut off of the graphene oxide composite membrane of ML
The separation process of component molecular.
Embodiment 4: the separation of plurality of organic pollutants
Other than filtering the organic pollutant solution of above-mentioned one-component, oxygen is determined with multi-component mixed pollutants
The separating property of graphite alkene composite membrane.Separation process for mixed pollutants passes through graphite oxide prepared by embodiment 2
The mixture of the filtering of alkene composite membrane PVP (58K) and PEO2 (600K).Specific implementation method is as follows: will be mixed containing PVP and PEO2
It closes object to be filtered under conditions of pH=11, after all filtering out PVP, the pH value for solution of intaking is adjusted to 3, then
It is filtered.As Figure 10 shows the concentration variation of PVP during the separation process and PEO.When pH is 11, only PVP molecule can
It is passed through with the film prepared from embodiment 1, after 9 circulations, the PVP in mixture is essentially completely recovered.Then, by the pH of water inlet
3 are adjusted to, with this condition, PEO2 molecule starts gradually to penetrate film, equally, the PEO2 after nine circulations, in mixture
It is essentially completely recovered.The above results are confirmed using graphene oxide composite membrane prepared by embodiment 2, by simply adjusting water inlet
Pollutant can be kept completely separate and successively recycle by the pH value of solution.Theoretically, any can object within the scope of molecular cut off
Matter can be separated and recovered from by way of adjusting pH.
The mechanism of above-mentioned separated from contaminants is as shown in figure 11.In pH=11, the duct of graphene oxide composite membrane is smaller,
Only the lesser PVP molecule of size is allowed to pass through；And when pH is adjusted to 3, the duct of graphene oxide composite membrane becomes larger, and size is larger
PEO molecule can also penetrate through.The mixture of PVP and PEO can be kept completely separate by the method adjusted by simple pH
It comes.
In conclusion the amino of polyethyleneimine can be crosslinked with the carboxyl of graphene oxide, the oxidation stone of preparation is promoted
The stability of black alkene composite membrane；It can use the pH response performance of polyethyleneimine simultaneously, change graphene oxide composite membrane
Interlamellar spacing realizes the pH response performance of graphene oxide composite membrane, to effectively carry out the separation and recycling of pollutant, simultaneously
Graphene oxide composite membrane after crosslinking has very excellent cycle performance.
Comparative example 1: the preparation and evaluation comparison of pure zirconia graphene composite film
Specific preparation method: (1) dispersing graphene oxide powder in deionized water, and ultrasonic disperse prepares graphite oxide
Alkene dispersion liquid.
(2) graphene oxide dispersion that will be prepared, is prepared graphene oxide by way of vacuum filtration
Composite membrane.
Separative efficiency evaluation to organic matter: the graphene oxide composite membrane that above-mentioned vacuum filtration method is prepared carries out
Organic matter separating experiment.During the experiment, graphene oxide composite membrane is to all organic matters substantially without retention.This is because oxygen
Graphite alkene is highly soluble in water, during the filtration process, causes graphene oxide composite membrane broken, loses separating effect.
Comparative example 2: the preparation and evaluation comparison of carbon nano-tube film
Specific preparation method: (1) a certain amount of carbon nanotube (CNT) and Kynoar (PVDF) is added to dimethyl
In acetamide (DMAc), the mass fraction that the mass fraction control of carbon nanotube is 0.2%, PVDF is 16%, ultrasound one hour
Make its dispersion.
(2) said mixture is stirred under the conditions of 70 DEG C and obtains uniformly mixed casting solution for 24 hours.
(3) above-mentioned casting solution is centrifuged to 5min deaeration under the conditions of 3000rpm, then fills above-mentioned casting solution by knifing
Preparation is set with a thickness of 200 μm of graphene oxide composite membrane.
(4) film prepared by step (3) is placed in water, is then dried to obtain carbon nanotube basilar memebrane.
(5) film prepared by step (4) is placed in 1mg/mL, 10min in the branched polyethylenimine solution of pH=3.5, so
After be rinsed with water film surface, after extra polyethyleneimine is rinsed well, with being dried with nitrogen.
(6) film prepared by step (5) is placed in 1mg/mL, then 10min in the carbon nano-tube solution of pH=3.5 uses water
Film surface is rinsed, after extra graphene oxide layer is rinsed well, with being dried with nitrogen.
(7) by step (5) and (6) as a circulation, repetitive cycling seven times altogether, obtain having seven strata aziridines/
The graphene oxide composite membrane of CNT.
(8) film that step (7) obtains is placed in drying in 60 DEG C of baking ovens, obtains carbon nano-tube film.
PH response performance comparison: since graphene oxide stacked in multi-layers itself could be formed with the aquaporin of effect, polyethylene
The metamorphosis of imines can cause the varying aperture of graphene oxide composite membrane aquaporin, so that pH response performance is shown,
By Experimental comparison, the pH response performance of graphene oxide composite membrane prepared by the present invention is 3 times of carbon nano-tube film.
Separative efficiency evaluation: compared with prepared graphene oxide composite membrane, since the stacking of carbon nanotube is unable to shape
At effective aquaporin, therefore during actual separation, carbon nano-tube film is lower to the separative efficiency of different component organic matter,
It is nothing like graphene oxide composite membrane prepared by the present invention.
In conclusion graphene oxide composite membrane prepared by the present invention has both higher stability, excellent pH response
Performance, excellent separating property and cycle performance have extremely strong application prospect in actual environment pollutant process field.
Above-mentioned embodiment is only a preferred solution of the present invention, it however is not intended to limit the invention.Example
Such as, in examples detailed above, ratio of the graphene oxide in film can need to change according to different.Height is only listed in above-described embodiment
Molecularly Imprinted Polymer PVDF is changed to cellulose esters, the film forming matrix such as polytetrafluoroethylene (PTFE) after material adjustment as film forming matrix
Also it can reach same effect.Polycation electrolyte can be other with pH response performance other than polyethyleneimine
Polymer, similar effect may be implemented in such as poly- (4- vinyl pyridine) or poly- (2- vinyl pyridine) etc..
It can be seen that those of ordinary skill in related technical field, the case where not departing from the spirit and scope of the present invention
Under, it can also make a variety of changes and modification.Therefore all to take the mode of equivalent replacement or equivalence replacement technical side obtained
Case is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of preparation method of the graphene oxide composite membrane with pH responsiveness, which comprises the following steps:
1) matrix membrane containing graphene oxide is immersed in polycation electrolyte solution, then washing and drying, on surface
Form polycation layer；
2) it is immersed in graphene solution again, then washing and drying, forms graphene oxide sheet in polycation layer surface
Layer；
3) step 1) and step 2) are repeated several times to same matrix membrane, so that polycation and graphene oxide are on matrix membrane
It is crosslinked by LBL self-assembly compound, finally obtains the graphene oxide composite membrane with pH responsiveness.
2. the preparation method of the graphene oxide composite membrane with pH responsiveness as described in claim 1, which is characterized in that described
Polycation electrolyte be the polymer with pH response performance, including polyethyleneimine, poly- (4- vinyl pyridine) or poly- (2-
Vinyl pyridine), the preferably polyethyleneimine of straight-chain or branched.
3. the preparation method of the graphene oxide composite membrane with pH responsiveness as described in claim 1, which is characterized in that described
Polycation electrolyte solution and graphene oxide solution concentration be 0.1mg/mL-10mg/mL, preferably 1mg/mL；Institute
The polycation electrolyte solution stated and the pH of graphene oxide solution are 2-12, preferably 3.5；Step 1) and 2) in, every time
Immersion time is 5-30min.
4. the preparation method of the graphene oxide composite membrane with pH responsiveness as claimed in claim 2, which is characterized in that described
The polyethyleneimine of straight-chain the preparation method comprises the following steps: polyethylene glycol oxide is added in HCl solution, carry out micro-wave digestion reaction；
It cools down after reaction, collecting reaction product is purified and is freeze-dried, and straight-chain polyethyleneimine is obtained.
5. the preparation method of the graphene oxide composite membrane with pH responsiveness as described in claim 1, which is characterized in that described
Matrix membrane containing graphene oxide the preparation method comprises the following steps: graphene oxide is well-dispersed in organic solvent, be then added
High molecular polymer is uniformly mixed, and obtains casting solution；Casting solution is subjected to knifing by scraping film device, is obtained after dry containing aerobic
The matrix membrane of graphite alkene.
6. the preparation method of the graphene oxide composite membrane with pH responsiveness as claimed in claim 5, which is characterized in that described
In casting solution, the mass fraction that graphene oxide and high molecular polymer account for casting solution is 10%~30%；Wherein graphite oxide
The mass fraction that alkene accounts for casting solution is 0.5%~20%, preferably 0.5%-5%；The high molecular polymer is preferably poly- inclined
Any one in vinyl fluoride, polysulfones, polyether sulfone, polyacrylonitrile, cellulose esters and polytetrafluoroethylene (PTFE)；The organic solvent is preferred
For any one in dimethylformamide, dimethyl acetamide, methyl pyrrole network alkanone and acetone.
7. the preparation method of the graphene oxide composite membrane with pH responsiveness as claimed in claim 5, which is characterized in that described
Casting solution the preparation method comprises the following steps: graphene oxide and high molecular polymer are stirred 4-24 hours at 30-100 DEG C, formed
Uniform casting solution.
8. there is the graphene oxide composite membrane of pH responsiveness made from a kind of preparation method as described in claim 1-7 is any,
It is characterized in that, graphene oxide composite membrane is layer structure, and including the hypothallus containing graphene oxide, the hypothallus table
Face superimposion has multilayer graphene oxide layer；Between hypothallus and graphene oxide layer and adjacent graphene oxide
It is crosslinked between lamella by polycation electrolyte layer.
9. as claimed in claim 8 with the graphene oxide composite membrane of pH responsiveness, which is characterized in that graphene oxide is compound
Thickness, surface hydrophilic and hydrophobic and the pore size of film change with extraneous pH；Water flux in pH=3 is 30-48LMH, is connect
Feeler is 39-50 °, with a thickness of 25-33nm；Water flux in pH=11 is 6-8LMH, and contact angle is 41-50 °, with a thickness of
20-23nm。
10. a kind of purposes of the graphene oxide composite membrane with pH responsiveness as claimed in claim 8, which is characterized in that use
In the removal of one-component organic pollutant or the separation of multicomponent mixing organic pollutant；The organic pollutant includes molecule
Amount is the polyethylene glycol oxide of 150-750kDa, polyethylene pyrrole network alkanone.
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| CN113019151A (en) * | 2021-03-01 | 2021-06-25 | 北京碧水源膜科技有限公司 | Graphene oxide-polyvinylidene fluoride composite hollow fiber membrane, and preparation method and application thereof |
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