CN110040731A - A method of based on ion regulation graphene film interlamellar spacing - Google Patents
A method of based on ion regulation graphene film interlamellar spacing Download PDFInfo
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Abstract
The invention discloses a kind of methods based on ion regulation graphene film interlamellar spacing.This method includes the following steps: to infiltrate graphene oxide membrane into 0.2-1h in the aqueous solution of inorganic salt solution or inorganic base；The concentration of the anion of the aqueous solution of inorganic salt solution or inorganic base is 0.10-1.0mol/L.The interlamellar spacing that method of the invention accurately controls the graphene oxide membrane under drying regime existsIn range, withAmplitude carries out accurate change in size；The interlamellar spacing of graphene oxide membrane exists under moisture stateIn range, with
Description
Technical field
The present invention relates to a kind of methods based on ion regulation graphene film interlamellar spacing.
Background technique
Graphene oxide membrane (graphene oxide/GO membrane) has special ultra-thin lamellar structure, thus has
There is the filter membrane feature that high flow capacity, energy conservation etc. are excellent, is the ideal filter membrane (Science 2011,333,712- of filter ions, molecule
717), in sea water desalination (Science 2011,332,674-676；Science 2012,335,442-444；Adv Funct
Mater 2013,23,3693-3700), gas separate (ACS Nano 2016,10,3398-3409), lithium battery
(J.Am.Chem.Soc.2012,134,8646-54) and super capacitor (ACS Nano 2011,5,5463-5471) and biology
The fields such as sensing (Nano Lett.2010,10,3163) are with a wide range of applications.
Inter-layer passages in graphene oxide membrane are shape by the interaction superposition of group between graphene oxide layer
At, interlamellar spacing is difficult to fix, this becomes the critical issue that limitation graphene oxide is used as membrane material.Especially exist
In solution in use, due to solution swelling effect, the interlamellar spacing of graphene oxide membrane is difficult to reduce and fix, this extreme influence
Application of the graphene oxide membrane in water process, ion/molecular separation and battery capacitor design etc..
The method of the inter-layer passages of existing control graphene film includes: to be increased using biggish rigid chemical group crosslinking
Inter-layer passages (Science 2014,343,740-742；Environ.Sci.Technol.2013,47,3715-3723)；Pass through
(inter-layer passages of graphene oxide membrane are made of oxygen-containing group graphene oxide layer, lamella on partial reduction graphene sheet layer
The content of upper oxygen-containing group influences channel sized), group is reduced with this, the effect for reducing inter-layer passages is realized, although this method
Reduce oxygen-containing group, but the swelling effect after impregnating due to solution, layer channel size can be big by support again
(Adv.Mater.2016,28,2287-231).These methods all increase inter-layer passages, but the film layer spacing of its control is equal
In 2nmMore than, can only separating and filtering 2nm or more molecular cluster, graphene film can not be accurately controlled in more
Small size.In addition, generally existing Na in actual environment such as seawater+、Mg2+、Ca2+、K+And Li+The hydration radius of plasma is small
In this critical value.Therefore, the layer channel of graphene oxide how is accurately reduced, while in the filtering screening of solution soaking state
In the process, continue to stablize the size in retaining layer channel, to realize lesser ion (such as Na of graphene oxide membrane pair radius+、Mg2+、
Ca2+、K+And Li+) filtering or screening, be graphene oxide membrane be applied to sea water desalination, sewage purification, gas separation and electricity
Urgent problem to be solved (Science 2014,343,740-742 in pond, capacitor area；Nano Lett.2014,14,
1234-1241；Adv.Mater.2016,28,2287-2310).
Summary of the invention
Technical problem solved by the invention be in order to overcome the interlamellar spacing of graphene oxide membrane in the prior art it is larger,
It is difficult to control accurately and then is difficult to meet answering in sea water desalination, sewage purification, gas separation and battery, capacitor area
With the defect of demand, to provide a kind of method based on ion regulation graphene film interlamellar spacing.Processing method of the invention has
Effect controls the interlamellar spacing of graphene oxide membrane: interlamellar spacing is under moisture stateAnd the interlamellar spacing under drying regime
ForIn addition the difference of different ions isIt is precisely controlled to realize.
The present invention is to solve above-mentioned technical problem by the following technical programs:
The present invention provides a kind of processing methods of the controllable graphene oxide membrane of the interlamellar spacing of wetting comprising Xia Shubu
It is rapid:
Graphene oxide membrane is infiltrated into 0.2-1h in the aqueous solution of inorganic salt solution or inorganic base；
Wherein, the concentration of the anion of the aqueous solution of the inorganic salt solution or the inorganic base is 0.10-1.0mol/
L。
In the present invention, as known to those skilled in the art, in raw material, the graphene oxide membrane should be intact smooth, and
And do not have crack, hole the defects of, preferably, the graphene oxide membrane with a thickness of 10-200 μm.
In the present invention, in raw material, it can be oxygen that the graphene oxide membrane, which is graphene oxide membrane commonly used in the art,
The independent film or support membrane of graphite alkene.
In the present invention, in raw material, the graphene oxide membrane can be made by conventional method in that art, for example, method 1 is dripped
Build 2 suction method of method or method.
Wherein, the drop that the drop builds that method is this field routine builds method.Preferably, building method (method 1) preparation using the drop
The method of graphene oxide membrane includes the following steps: to drip graphene oxide solution in smooth paper surface, is drying to obtain oxidation
The independent film of graphene.
Wherein, the suction method is the suction method of this field routine.Preferably, being prepared using the suction method (method 2)
The method of graphene oxide membrane includes the following steps: to filter graphene oxide solution, and filter membrane is drying to obtain graphene oxide
Support membrane；Wherein, described filter is that filter membrane filters.
In method 1 or method 2, the graphene oxide solution is graphene oxide solution commonly used in the art, institute
The concentration for stating graphene oxide solution is preferably 3-5mg/mL.The graphene oxide solution can remove graphite method by oxidation
(i.e. Hummers method) is made comprising following step:
(1) graphite pre-oxidizes: potassium peroxydisulfate, phosphorus pentoxide and the concentrated sulfuric acid being mixed, are heated to 78-82 DEG C, Zhi Houyu
Natural graphite mixing, is cooled to room temperature after heat preservation, after being diluted with deionized water, stands 12-18h, filtration drying must pre-oxidize object；
(2) it aoxidizes: step (1) pre-oxidation object obtained is mixed under the conditions of 0-5 DEG C with the concentrated sulfuric acid, later and permanganic acid
Potassium is in 34-36 DEG C of reaction 1.5-2.5h, then mixture is reacted to obtain with hydrogen peroxide；
(3) it post-processes: up to graphene oxide solution after mixture washing that step (2) is obtained, filtering, ultrasound.
Wherein, the potassium peroxydisulfate, phosphorus pentoxide, the concentrated sulfuric acid in step (1), the natural graphite, described
Deionized water, the concentrated sulfuric acid in step (2), the potassium permanganate and the hydrogen peroxide amount ratio can be to be conventional, preferably
(2.3-2.7g): (2.3-2.7g): (100-150mL): (2-4g): (1-1.1L): (120-130mL): (14-16g): (18-
It 22mL), is more preferably 2.5g:2.5g:100mL:3g:1L:120mL:15g:20mL；Wherein, the potassium peroxydisulfate and described five
The amount ratio for aoxidizing two phosphorus is preferably 1:1.
In step (1), the concentrated sulfuric acid is the concentrated sulfuric acid commonly used in the art, and the mass concentration of the concentrated sulfuric acid is preferable
Ground is 98%.
In step (1), the operation of the filtering and condition are the operation and condition of the filtering of this field routine, the purpose is to
In order to remove residual acid.
In step (1), the operation of the heat preservation and condition can be to be conventional, for example, the process of the heat preservation is at 78-82 DEG C
Under the conditions of with temperature constant magnetic stirring stir to solution present it is thick.
In step (2), the concentrated sulfuric acid is the concentrated sulfuric acid commonly used in the art, and the mass concentration of the concentrated sulfuric acid is preferable
Ground is 98%.
In step (2), the dosage of the hydrogen peroxide is can be routine, for example, the mass concentration of the hydrogen peroxide is preferably
It is 30%.
In step (3), the operation of the ultrasound and condition are the conventional ultrasonic operation and condition in this field, preferably,
The ultrasound carries out in deionized water.
In method 1 or in method 2, the operation of the drying and condition are the operation and condition of the drying of this field routine,
Preferably, the process of the drying are as follows: after first time is dry, eluted repeatedly with deionized water, impregnate half in deionized water
It is taken out after hour, it is dry through second.Wherein, first time dry temperature is preferably 55-65 DEG C, more preferably for
60℃；The time of the first time drying is preferably 5-7h, is more preferably 6h；Second of dry temperature is preferably
55-65 DEG C, be more preferably 60 DEG C；Second of the dry time is preferably 11-13h, is more preferably 12h.
In method 2, the filter membrane is filter membrane commonly used in the art, preferably water phase filter membrane, the hole of the filter membrane
Diameter is preferably 0.22 μm.
In the present invention, also contain in the aqueous solution of the inorganic salt solution or the inorganic base as known to those skilled in the art
There is cation, " cation of the aqueous solution of inorganic salt solution or inorganic base " this concept those skilled in the art know its culvert
The type of the cation of lid, such as Na+、Mg2+、Ca2+、K+Or Li+。
In the present invention, preferably, the size of the hydrated anions of the anion of the inorganic salt solution is less than the sun
The size of the hydrated cation of ion, such as F-、Cl-、Br-、I-、SO4 2-、CO3 2-Or NO3 -。
In the present invention, the cation and the anion form as known to those skilled in the art inorganic salts or inorganic base
It should be water-soluble inorganic salts or inorganic base.
In the present invention, preferably, the cation is K in the inorganic salt solution+, the anion is F-、Cl-、
Br-、I-、CO3 2-Or NO3 -。
In the present invention, preferably, the cation is Na in the inorganic salt solution+, the anion is F-、Cl-、
Br-、I-、CO3 2-Or NO3 -。
In the present invention, preferably, the cation is Li in the inorganic salt solution+, the anion is F-、Cl-、
Br-、I-Or NO3 -。
In the present invention, preferably, the cation is Ca in the inorganic salt solution2+, the anion is F-、
Cl-、Br-、I-Or NO3 -。
In the present invention, preferably, the cation is Mg in the inorganic salt solution2+, the anion is F-、
Cl-、Br-、I-、SO4 2-Or NO3 -。
In the present invention, in the inorganic salt solution, the concentration of anion has biggish control effect to layer channel, if
The concentration of anion is lower than 0.10mol/L, then is unfavorable for the stability in control layer channel, is also unfavorable for practical application, such as sea
Water desalination application.If anion concentration is higher than 1.0mol/L, excessively high ion concentration can cause layer logical because of ion enrichment in film
Salt obstruction occurs for road, influences water flux.
In the present invention, the pH value of the inorganic salt solution is that this field is conventional, preferably 7-13.
In the present invention, for the accurate amplitude of further control interlamellar spacing, the temperature of the infiltration is preferably 17-23 DEG C,
It is more preferably 20 DEG C.
The present invention also provides a kind of controllable graphene oxide membranes of the interlamellar spacing of wetting obtained by above-mentioned processing method.
Wherein, the interlamellar spacing of the graphene oxide membrane existsIn range, withAmplitude carries out accurate
Change in size.
The present invention also provides the controllable graphene oxide membrane of the interlamellar spacing of the wetting sea water desalination, sewage purification,
Application in gas separation.
The present invention also provides a kind of preparation methods of the controllable graphene oxide membrane of the interlamellar spacing of drying, by above-mentioned profit
The controllable graphene oxide membrane of wet interlamellar spacing is dry.
In the present invention, the operation of the drying and condition can be to be conventional, for example, the process of the drying can be centrifugation removal
The surface solution of the graphene oxide membrane, be placed in baking oven it is dry；The temperature of the drying is preferably 65-75 DEG C,
It is more preferably 70 DEG C；The time of the drying is preferably 10-14h, is more preferably 12h.
The present invention also provides a kind of controllable graphene oxide membranes of the interlamellar spacing of drying obtained by above-mentioned processing method.
Wherein, the interlamellar spacing of the graphene oxide membrane existsIn range, withAmplitude carries out accurate ruler
Very little variation.
The present invention also provides the controllable graphene oxide membranes of the interlamellar spacing of the drying in battery, capacitor area
Using.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Apply example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
The interlamellar spacing that method of the invention accurately controls the graphene oxide membrane under drying regime existsRange
It is interior, withAmplitude carries out accurate change in size；The interlamellar spacing of graphene oxide membrane exists under moisture stateModel
In enclosing, withAmplitude carries out accurate change in size, and the graphene oxide membrane is not easily broken；Method system of the invention
Standby process is simple, easily operated, and graphene oxide membrane is made to have the function of screening and filter compared with small ion, in sea water desalination, dirt
Water warfare, gas separation and battery, capacitor area have a good application prospect.
Detailed description of the invention
Fig. 1 is the shape appearance figure of the graphene oxide membrane prepared using method of the invention, wherein A is graphene oxide membrane
Photo in kind, B be graphene oxide membrane scanning electron microscope characterize surface topography map.
Fig. 2 is the interlamellar spacing of graphene oxide membrane products obtained therefrom after various salts impregnate in 1-5 of the embodiment of the present invention
Datagram.
Products obtained therefrom after Fig. 3 is dried after various salts impregnate for graphene oxide membrane in 1-5 of the embodiment of the present invention
Interlamellar spacing datagram.
Fig. 4 is the layer that graphene oxide membrane products obtained therefrom after various salts impregnate is aoxidized in 7-11 of the embodiment of the present invention
Spacing data figure.
Products obtained therefrom after Fig. 5 is dried after various salts impregnate for graphene oxide membrane in 6-11 of the embodiment of the present invention
Interlamellar spacing datagram.
Products obtained therefrom after Fig. 6 is dried after various salts impregnate for graphene oxide membrane in 1-11 of the embodiment of the present invention
Interlamellar spacing datagram.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
Preparing for graphene oxide membrane in following example 1-13 is as follows:
1, the preparation of graphene oxide solution:
(1) graphite pre-oxidizes: by 2.5g potassium peroxydisulfate, 2.5g phosphorus pentoxide, being dissolved in the 100mL concentrated sulfuric acid, (quality is dense
It spends in 98%), is heated to 78-82 DEG C；Then 3g natural graphite is added, (under the conditions of 78-82 DEG C temperature constant magnetic stirring after heat preservation
Presented to solution thick), it is cooled to room temperature, after the dilution of 1L deionized water, stands overnight；Filtering is floating to remove residual acid, dry
Object must be pre-oxidized；
(2) it aoxidizes: by step (1) pre-oxidation object obtained and the 120mL concentrated sulfuric acid (mass concentration 98%) in 0-5 DEG C of condition
Lower mixing, is added 15g potassium permanganate, and it is anti-to add 20mL hydrogen peroxide (mass concentration 30%) by 34-36 DEG C of reaction 1.5-2.5h
It answers, obtains mixture；
(3) post-process: after the mixture washing in step (2), filtering obtains oxidation stone in deionized water after ultrasound
Black alkene solution.
2, drop is taken to build method preparation graphene oxide membrane:
It takes 3-5mg/mL graphene oxide solution (to prepare) 1mL by the above method, drips on the smooth scraps of paper, and at 60 DEG C
Dry 12h, removes independent graphene oxide membrane, is eluted repeatedly with deionized water, and soak in removing a large amount of ionized waters in baking oven
It takes out after bubble half an hour, after 60 DEG C of re-dry dry 6h, is put into drying basin in case using.The thickness of gained graphene oxide membrane
About 30 μm.
Fig. 1 is the shape appearance figure of graphene oxide membrane obtained above, wherein A is regulation interlamellar spacing graphene oxide membrane
Photo in kind, B are the surface topography map that the scanning electron microscope of graphene oxide membrane characterizes.Thus obtained graphene oxide
Film has that ultra-thin, flow is high, the excellent filter membrane feature such as energy saving, has independent unsupported mechanical strength, can be directly used for salt
Water sieve is selected and is separated.
The controllable graphene oxide of interlamellar spacing of the present invention is characterized using XRD (X-ray diffractometer) in following example 1-13
The interlamellar spacing of film.Using D8A A25X x ray diffractometer x (German Bruker), test scope is 5-25 °, 0.15 ° of step-length.
Embodiment 1
Graphene oxide membrane is infiltrated into the K in 0.25mol/L2SO4In solution (pH value 7), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out the wet shape of XRD detection
The interlamellar spacing of state is(referring to fig. 2)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h,
The controllable graphene oxide membrane of corresponding interlamellar spacing is obtained, the interlamellar spacing for carrying out XRD detection drying regime is taken out, is
(referring to Fig. 3).
Embodiment 2
By graphene oxide membrane infiltration in the KCl solution of 0.25mol/L (pH value 7), impregnating 0.5h, (environment temperature is
20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection moisture state
Interlamellar spacing, be(referring to fig. 2)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains
The controllable graphene oxide membrane of corresponding interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is
(referring to Fig. 3).
Embodiment 3
By graphene oxide membrane infiltration in the KBr solution of 0.25mol/L (pH value 7), impregnating 0.5h, (environment temperature is
20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlamellar spacing,
For(referring to fig. 2)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding interlayer
Away from controllable graphene oxide membrane, the interlamellar spacing for carrying out XRD detection drying regime is taken out, is(referring to Fig. 3).
Embodiment 4
Graphene oxide membrane is infiltrated into the K in 0.25mol/L2CO3In solution (pH value 12), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlayer
Away from being(referring to fig. 2)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding
The controllable graphene oxide membrane of interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is(referring to figure
3)。
Embodiment 5
By graphene oxide membrane infiltration in the KOH solution of 0.25mol/L (pH value 13), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlayer
Away from being(referring to fig. 2)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding
The controllable graphene oxide membrane of interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is(referring to figure
3)。
Embodiment 6
By graphene oxide membrane infiltration in the NaF solution of 0.25mol/L (pH value 7), 1h (environment temperature 20 is impregnated
DEG C), it is centrifuged film surface solution after being swollen raw material sufficiently and in 70 DEG C of baking ovens after dry 12h, it is controllable to obtain corresponding interlamellar spacing
Graphene oxide membrane, take out carry out XRD detection drying regime interlamellar spacing, be(referring to Fig. 5).Due to NaF
It is corrosive, does not test the interlamellar spacing of moisture state.
Embodiment 7
Graphene oxide membrane is infiltrated into the Na in 0.25mol/L2SO4In solution (pH value 7), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out the wet shape of XRD detection
The interlamellar spacing of state is(referring to fig. 4)；It is centrifuged film surface solution later and in 7 DEG C of baking ovens after dry 12h, obtains
The controllable graphene oxide membrane of corresponding interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is
(referring to Fig. 5).
Embodiment 8
By graphene oxide membrane infiltration in the NaCl solution of 0.25mol/L (pH value 7), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlayer
Away from being(referring to fig. 4)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding
The controllable graphene oxide membrane of interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is(referring to figure
5)。
Embodiment 9
By graphene oxide membrane infiltration in the NaBr solution of 0.25mol/L (pH value 7), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlayer
Away from being(referring to fig. 4)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding
The controllable graphene oxide membrane of interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is(referring to figure
5)。
Embodiment 10
Graphene oxide membrane is infiltrated into the Na in 0.25mol/L2CO3In solution (pH value 12), 0.5h (environment temperature is impregnated
Degree is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlayer
Away from being(referring to fig. 4)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding
The controllable graphene oxide membrane of interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is(referring to figure
5)。
Embodiment 11
By graphene oxide membrane infiltration in the NaOH solution of 0.25mol/L (pH value 13), 0.5h (environment temperature is impregnated
It is 20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlayer
Away from being(referring to fig. 4)；It is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, obtains corresponding
The controllable graphene oxide membrane of interlamellar spacing takes out the interlamellar spacing for carrying out XRD detection drying regime, is(referring to figure
5)。
Graphene oxide membrane in above-described embodiment 1-11 is shown in Fig. 6, and gained produces after drying after various salts impregnate
The interlamellar spacing datagram of product.
Embodiment 12
By graphene oxide membrane infiltration in the NaCl solution of 1.0mol/L (pH value 7), impregnating 0.2h, (environment temperature is
20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlamellar spacing,
ForIt is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, it is controllable to obtain corresponding interlamellar spacing
Graphene oxide membrane takes out the interlamellar spacing for carrying out XRD detection drying regime, is
Embodiment 13
By graphene oxide membrane infiltration in the NaCl solution of 0.1mol/L (pH value 7), impregnating 0.2h, (environment temperature is
20 DEG C), it is swollen raw material sufficiently, obtains the controllable graphene oxide membrane of corresponding interlamellar spacing；It takes out and carries out XRD detection interlamellar spacing,
ForIt is centrifuged film surface solution later and in 70 DEG C of baking ovens after dry 12h, it is controllable to obtain corresponding interlamellar spacing
Graphene oxide membrane takes out the interlamellar spacing for carrying out XRD detection drying regime, is
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only
For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from
Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and
Modification each falls within protection scope of the present invention.
Claims (10)
1. a kind of processing method for the graphene oxide membrane that the interlamellar spacing of wetting is controllable, which is characterized in that it includes the following steps:
Graphene oxide membrane is infiltrated into 0.2-1h in the aqueous solution of inorganic salt solution or inorganic base；
Wherein, the concentration of the anion of the aqueous solution of the inorganic salt solution or the inorganic base is 0.10-1.0mol/L.
2. processing method as described in claim 1, which is characterized in that in raw material, the graphene oxide membrane with a thickness of 10-
200μm；
In raw material, the graphene oxide membrane is the independent film or support membrane of graphene oxide；
The independent film of the graphene oxide preferably uses method 1 to be prepared, and the method 1 is the following steps are included: by oxygen
Graphite alkene solution drop is dry in smooth paper surface；
And/or the support membrane of the graphene oxide preferably uses method 2 to be prepared, the method 2 includes following step
It is rapid: graphene oxide solution to be filtered, filter membrane is dry；Wherein, described filter is that filter membrane filters.
3. processing method as claimed in claim 2, which is characterized in that
In method 1 or method 2, the concentration of the graphene oxide solution is 3-5mg/mL；The graphene oxide solution uses
Oxidation removing graphite method is made, and the oxidation removing graphite method includes the following steps:
(1) graphite pre-oxidizes: potassium peroxydisulfate, phosphorus pentoxide and the concentrated sulfuric acid being mixed, are heated to 78-82 DEG C, later and naturally
Graphite mixing, is cooled to room temperature after heat preservation, after being diluted with deionized water, stands 12-18h, filtration drying must pre-oxidize object；
(2) it aoxidizes: step (1) pre-oxidation object obtained being mixed under the conditions of 0-5 DEG C with the concentrated sulfuric acid, is existed later with potassium permanganate
34-36 DEG C of reaction 1.5-2.5h, then mixture is reacted to obtain with hydrogen peroxide；
(3) it post-processes: up to graphene oxide solution after mixture washing that step (2) is obtained, filtering, ultrasound；
In method 1 or in method 2, the process of the drying are as follows: after first time is dry, is eluted, gone repeatedly with deionized water
It is taken out after impregnating half an hour in ionized water, it is dry through second；The temperature of the first time drying is 55-65 DEG C, preferably
Ground is 60 DEG C；The time of the first time drying is 5-7h, preferably 6h；Second of dry temperature is 55-65 DEG C,
Preferably 60 DEG C；Second of the dry time is 11-13h, preferably 12h；
In method 2, the filter membrane is water phase filter membrane, and the aperture of the filter membrane is 0.22 μm.
4. processing method as claimed in claim 3, which is characterized in that
The potassium peroxydisulfate, the phosphorus pentoxide, the concentrated sulfuric acid in step (1), the natural graphite, the deionized water,
The amount ratio of the concentrated sulfuric acid, the potassium permanganate and the hydrogen peroxide in step (2) is (2.3-2.7g): (2.3-2.7g):
(100-150mL): (2-4g): (1-1.1L): (120-130mL): (14-16g): (18-22mL), preferably 2.5g:2.5g:
100mL:3g:1L:120mL:15g:20mL；
The amount ratio of the potassium peroxydisulfate and the phosphorus pentoxide is 1:1；
In step (1), the mass concentration of the concentrated sulfuric acid is 98%；
In step (1), the process of the heat preservation is sticky to solution presentation to be stirred under the conditions of 78-82 DEG C with temperature constant magnetic stirring
Shape；
In step (2), the mass concentration of the concentrated sulfuric acid is 98%；
In step (2), the mass concentration of the hydrogen peroxide is 30%；
In step (3), the ultrasound carries out in deionized water.
5. processing method as described in claim 1, which is characterized in that the inorganic salt solution or the inorganic base it is water-soluble
The cation of liquid is Na+、Mg2+、Ca2+、K+Or Li+；
The anion of the inorganic salt solution is F-、Cl-、Br-、I-、SO4 2-、CO3 2-Or NO3 -；
The pH value of the inorganic salt solution is 7-13；
The temperature of the infiltration is 17-23 DEG C, preferably 20 DEG C；
In the inorganic salt solution, the syntagmatic of the anion and the cation is preferably:
The cation is K+, the anion is F-、Cl-、Br-、I-、CO3 2-Or NO3 -；
Alternatively, the cation is Na+, the anion is F-、Cl-、Br-、I-、CO3 2-Or NO3 -；
Alternatively, the cation is Li+, the anion is F-、Cl-、Br-、I-Or NO3 -；
Alternatively, the cation is Ca2+, the anion is F-、Cl-、Br-、I-Or NO3 -；
Alternatively, the cation is Mg2+, the anion is F-、Cl-、Br-、I-、SO4 2-Or NO3 -。
6. a kind of graphite oxide that the interlamellar spacing for the wetting that processing method according to any one of claims 1 to 5 obtains is controllable
Alkene film.
7. the controllable graphene oxide membrane of the interlamellar spacing that one kind soaks as claimed in claim 6 is in sea water desalination, sewage purification
Or the application in gas separation.
8. a kind of preparation method for the graphene oxide membrane that the interlamellar spacing of drying is controllable, which is characterized in that it includes the following steps:
The controllable graphene oxide membrane of the interlamellar spacing soaked as claimed in claim 6 is dry；
The process of the drying is preferably the surface solution for being centrifuged and removing the graphene oxide membrane, be placed in baking oven and do
It is dry；
The temperature of the drying is preferably 65-75 DEG C, is more preferably 70 DEG C；
The time of the drying is preferably 10-14h, is more preferably 12h.
9. a kind of graphene oxide membrane that the interlamellar spacing for the drying that preparation method as claimed in claim 8 obtains is controllable.
10. a kind of graphene oxide membrane that the interlamellar spacing dried as claimed in claim 9 is controllable is in battery or capacitor area
In application.
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| US20150103469A1 (en) * | 2013-10-16 | 2015-04-16 | Research & Business Foundation Sungkyunkwan University | Interlayer distance controlled graphene, supercapacitor and method of producing the same |
| WO2015075451A1 (en) * | 2013-11-21 | 2015-05-28 | The University Of Manchester | Water purification |
| CN105727758A (en) * | 2016-04-13 | 2016-07-06 | 天津大学 | Preparation method and application of graphene oxide composite membrane |
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| US20150103469A1 (en) * | 2013-10-16 | 2015-04-16 | Research & Business Foundation Sungkyunkwan University | Interlayer distance controlled graphene, supercapacitor and method of producing the same |
| WO2015075451A1 (en) * | 2013-11-21 | 2015-05-28 | The University Of Manchester | Water purification |
| CN105727758A (en) * | 2016-04-13 | 2016-07-06 | 天津大学 | Preparation method and application of graphene oxide composite membrane |
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| CN114100570A (en) * | 2020-08-25 | 2022-03-01 | 华东理工大学 | Preparation method and application of lithium ion selective adsorption membrane |
| CN114100570B (en) * | 2020-08-25 | 2023-10-03 | 华东理工大学 | Preparation method and application of lithium ion selective adsorption film |
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