CN105692608B - A kind of method for preparing graphene using the step of redox one - Google Patents
A kind of method for preparing graphene using the step of redox one Download PDFInfo
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- CN105692608B CN105692608B CN201610256022.3A CN201610256022A CN105692608B CN 105692608 B CN105692608 B CN 105692608B CN 201610256022 A CN201610256022 A CN 201610256022A CN 105692608 B CN105692608 B CN 105692608B
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a kind of method for preparing graphene using the step of redox one, described preparation method comprises the following steps：The graphite oxide obtained after being aoxidized with graphite powder is dissolved in the mixed solution for including organic solvent and water under predetermined temperature, while adds reducing agent and it is ultrasonically treated to obtain graphene dispersing solution；Gained graphene dispersing solution is subjected to vacuum filtration cleaning, gained filtrate is dried and obtains graphene.In the present invention, oxidation, stripping, reduction three phases in traditional oxidation-reduction method for preparing graphene are reduced to two stages, that is oxidation stage and stripping reduction phase, especially, stripping bench and reduction phase are reduced to a step so that peel off reduction phase and carry out simultaneously, both shorten the reaction time, production efficiency is also improved, new method is provided for the industrialized production of graphene.
Description
Technical field
The present invention relates to technical field prepared by graphene, more particularly, is related to one kind and utilizes the step system of redox one
The method of standby graphene.
Background technology
Graphene be one kind by single layer of carbon atom through SP2The carbon material for the honeycomb hexatomic ring two-dimensional structure that hydridization is formed.
Graphene has high-specific surface area, than the small resistivity of silver, high electron mobility, high heat-conduction coefficient, good mechanical flexible
Property and the excellent performance such as mechanical strength, high sensitivity low noise, its attracted large quantities of researchers be applied to carry out it is extensive
Research, its application have had been directed to the fields such as physics, chemistry, environment, biology, medical science, material.But controllable, high-volume life
It is still the problem for perplexing vast researcher to produce graphene, also allows the development of graphene industry to stagnate.
Emerged in an endless stream based on the tempting application prospect of graphene on the report of graphene preparation method.These methods can divide
For " from top to bottom " and " from bottom to top " two class method.It is one that graphene is separated from graphite, expanded graphite from top to bottom
Class method, such as mechanical stripping method, oxidation-reduction method, liquid phase stripping method, electrochemical stripping method, arc discharge method, nanotube cutting
The methods of method；It is a kind of method of the carbon atom in Grown into graphene from bottom to top, such as chemical vapour deposition technique, extension
Growth method, organic synthesis method, solvent-thermal method etc..Wherein oxidation-reduction method is so that its technique is simple, cost is cheap, production equipment is simple
Easily, yield highest advantage, the method for most potential large-scale production graphene is turned into.
, it is necessary to undergo the oxidation degree by graphite oxidation for graphite oxide in traditional oxidation-reduction method prepares graphene
Section, graphite oxide is peeled off into the stripping bench for graphene oxide, graphene oxide is reduced to the reduction phase of graphene.This
Problems be present in technique：(1) there is the factor for influenceing reaction product performance in each stage of reaction, and the superposition of influence factor is led
Cause the unstable of final product；(2) cumbersome time-consuming for technique.In oxidation stage, the cleaning of oxidation reaction and graphite oxide need to disappear
Consume the plenty of time；The consumption of indefinite time is had according to product requirements in stripping bench；In reduction phase according to different reduction
Method also has the consumption of indefinite time.
The content of the invention
In order to solve such as to prepare the oxidation-reduction method of graphene present in prior art, time-consuming, efficiency is low, it is difficult to
The problems such as large-scale industrial production, graphene is prepared using the step of redox one it is an object of the invention to provide one kind
Method.
The invention provides a kind of method for preparing graphene using the step of redox one, the preparation method includes following
Step：The graphite oxide obtained after being aoxidized with graphite powder is dissolved in the mixed solution for including organic solvent and water under predetermined temperature
In, while add reducing agent and it is ultrasonically treated to obtain graphene dispersing solution；Gained graphene dispersing solution is carried out true
Sky filters cleaning, dries gained filtrate and obtains graphene.
According to one embodiment of the method that graphene is prepared using the step of redox one of the present invention, the graphite oxide
Preparation method it is more, such as Brodie methods, Staudenmaier methods and Hummers methods, the present invention not to graphite oxide powder
Method carries out excessive limitation.But present invention preferably uses the oxidation that a kind of improved Hummers methods carry out graphite powder,
So as to provide more excellent material condition for follow-up preparation.
Improved Hummers methods comprise the following steps:
Graphite powder is added in the concentrated sulfuric acid and stirred under condition of ice bath, potassium permanganate is added after room temperature to be restored and is continued
Stirring reaction, then distilled water diluting is used under condition of ice bath, obtain dilution；Hydrogen peroxide is slowly added in the dilution simultaneously
Lasting stirring, eccentric cleaning obtains graphite oxide to neutrality after placing a night.
Wherein, the particle diameter of the graphite powder is 0.42~150um；The mass concentration of the concentrated sulfuric acid is 96~98%, institute
The mass concentration for stating hydrogen peroxide is 0.1~30%, and the mass volume ratio of the graphite powder and the concentrated sulfuric acid is 0.1:100~1:10,
The mass ratio of the graphite powder and potassium permanganate is 0.1:6~1:0.6, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 1:1~
1:50。
According to one embodiment of the simplification preparation method that graphene is prepared using oxidation-reduction method of the present invention, the oxygen
The concentration of graphite is 0.02~10g/L, and the volume ratio of organic solvent and water is 1 in the mixed solution:0.01~1:100.
According to one embodiment of the method that graphene is prepared using the step of redox one of the present invention, the organic solvent
For chitin, DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), N- methyl
One kind or at least two combination in pyrrolidones (NMP), the wherein deacetylation of chitin are 50%~90%.
According to one embodiment of the method that graphene is prepared using the step of redox one of the present invention, the predetermined temperature
For 5~90 DEG C, preferably 40~60 DEG C.
According to one embodiment of the method that graphene is prepared using the step of redox one of the present invention, the supersound process
Condition be 42~80kHz with working frequency and ultrasonication that ultrasonic power is 300~1200W 10~180 minutes.
According to the present invention the method that graphene is prepared using the step of redox one one embodiment, the reducing agent
Concentration is 0.01~10g/L.
According to one embodiment of the method that graphene is prepared using the step of redox one of the present invention, the reducing agent is
One kind or at least two combination in Tea Polyphenols, rhodioloside, anthocyanidin, ellagic acid, amino acid.
According to one embodiment of the method that graphene is prepared using the step of redox one of the present invention, the vacuum filtration
Filter sizes used are 0.1~10 μm.
Compared with prior art, the present invention has following features：
(1) in the present invention, tradition is prepared to oxidation in the oxidation-reduction method of graphene, peeled off, reduction three phases letter
Two stages, i.e. oxidation stage and stripping reduction phase are turned to, especially, stripping bench and reduction phase are reduced to a step, make
Reduction phase must be peeled off while carried out, the reaction time is both shortened, also improve production efficiency, be the industrialized production of graphene
Provide new method.
(2) the grapheme material size that the present invention is prepared is because the difference of raw material graphite powder mesh number makes its lateral dimension
In the range of 0.02~3um, thickness is in the range of 0.8~2.4nm；Due to being related to oxidation in whole preparation process, it is made
Graphene layer on carry part oxygen-containing functional group, by XPS test graphene C/O ratios be 8.1~20.7；Reduction process
Deoxidation the defects of inevitably causing graphene layer, obtain I by carrying out Raman spectrum analysis to grapheneD/IGValue
For 0.02~1.18；The defects of graphenic surface is present makes its specific surface area in 78.9~240.1.
Brief description of the drawings
Fig. 1, which is shown, is scanned what electron microscope (SEM) observation obtained to obtained graphene in example 1 of the present invention
Surface topography map.
Fig. 2, which is shown, carries out the table that AFM (AFM) observation obtains to obtained graphene in example 1 of the present invention
Face shape appearance figure.
Fig. 3 shows the infrared spectrogram of obtained graphene and graphite powder and graphite oxide in example 3 of the present invention.
Fig. 4 shows the x-ray photoelectron spectroscopy analysis chart of obtained graphene and graphite oxide in example 3 of the present invention.
Fig. 5 shows the Raman spectrogram of obtained graphene in example 5 of the present invention.
Embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine in any way.
Any feature disclosed in this specification (including any accessory claim, summary and accompanying drawing), except non-specifically chatting
State, can alternative features equivalent by other or with similar purpose replaced.I.e., unless specifically stated otherwise, each feature
It is an example in a series of equivalent or similar characteristics.
The method for being prepared graphene using the step of redox one to the present invention is described in detail below.
It is described to prepare the method for graphene including following using the step of redox one according to the exemplary embodiment of the present invention
Multiple steps.
Step 1：
Graphite powder is oxidized to graphite oxide.
Wherein, the present invention does not carry out excessive limitation to the method for graphite oxide powder, for example, it is also possible to using Brodie
Method, Staudenmaier methods and Hummers methods etc..
But present invention preferably uses the oxidation that a kind of improved Hummers methods carry out graphite powder, so as to for
Follow-up ultrasound peels off reduction and provides more excellent material condition.
Specifically, the improved Hummers methods comprise the following steps:
First, graphite powder is added in the concentrated sulfuric acid and stirred under condition of ice bath, potassium permanganate is added after room temperature to be restored
And continue stirring reaction, then distilled water diluting is used under condition of ice bath, obtain dilution；
Then, hydrogen peroxide is slowly added in the dilution and continues to stir, after placing a night eccentric cleaning to neutrality,
Obtain graphite oxide.
In above-mentioned steps, specific experiment parameter condition includes：The mass concentration of the concentrated sulfuric acid is 96~98%, hydrogen peroxide
Mass concentration be 0.1~30%, the mass volume ratio of graphite powder and the concentrated sulfuric acid is 0.1:100~1:10, graphite powder and Gao Meng
The mass ratio of sour potassium is 0.1:6~1:0.6, the volume ratio of the concentrated sulfuric acid and hydrogen peroxide is 1:1~1:50.Wherein, the present invention uses
The particle diameter of graphite powder be preferably 0.42~150um.
Step 2：
Graphite oxide made from step 1 is dissolved in the mixed solution for including organic solvent and water of predetermined temperature, simultaneously
Add reducing agent and it is ultrasonically treated to obtain graphene dispersing solution.Wherein, it is ultrasonically treated and not only passes through Accelerating reduction agent
The motion of molecule improves the speed of reduction reaction, also as a kind of mode for peeling off graphene；And the mixing of organic solvent and water
Liquid is then used as dispersant, while controlling suitable graphite layers away from assisting ultrasound to overcome Van der Waals force to peel off, also prevents
To graphene reunite, be to peel off and reduction process is able to the key factor that carries out simultaneously, because partial reduction agent may
It is immiscible with part organic solvent, so water is also necessary exist.
According to a preferred embodiment of the invention, the concentration for controlling graphite oxide is 0.02~10g/L, and controls mixed solution
The volume ratio of middle organic solvent and water is 1:0.01~1:100.Wherein, organic solvent can be chitin (the de- second of chitin
Acyl degree is preferably 50%~90%, such as 50%, 60%, 70%, 80%, 90%), DMA (DMAc), N, N-
Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), one kind or at least two group in 1-METHYLPYRROLIDONE (NMP)
Close；Such as DMAc/DMF, DMAc/DMSO, chitin/NMP, chitin/DMSO, the combined volume ratio is 1 for the combination:
10~10:1, the preferably best organic solvent of dispersion effect or its combination.
Meanwhile it is 0.01~10g/L to control the concentration of reducing agent, and reducing agent can be Tea Polyphenols, rhodioloside, flower
Blue or green element, ellagic acid, one kind in amino acid or at least two combination, combination such as Tea Polyphenols/anthocyanidin, the rhodiola root
Glucoside/amino acid, ellagic acid/Tea Polyphenols etc., the combination quality ratio are 1:10~10:1, the preferably best reducing agent of reduction effect
And combinations thereof.
For reaction condition, heating water bath can be utilized to control the temperature of mixed solution as 5~90 DEG C and preferably controlled
For 40~60 DEG C to reach optimal reaction effect.Control be ultrasonically treated condition be：In order to super suitable for industrial production, control
Acoustic frequency is in conventional 25~130kHz of industrial frequency, and because supersonic frequency is higher, cavitation effect is weaker, and caused bubble is close
Degree is denser, and the probability for promoting reducing agent to be contacted with oxygenated functional group is higher, and reduction is more complete；And supersonic frequency is higher, ultrasound
Wave impact power is smaller, can just play a part of stripping when impulsive force is more than the Van der Waals force of graphite layers.Therefore, ultrasonic work
Working frequency should not it is too high also should not be too low, preferably in the range of 42~80kHz.In addition, ultrasonic power and sonication treatment time
It is respectively set to 300~1200W and 10~180 minute, so as to realize optimal stripping reduction effect.Wherein it is possible to using super
The instruments such as sound wave cleaning machine are ultrasonically treated.
Also, this step is actually stripping and two stages of reduction in the oxidation-reduction method for prepare tradition graphene
The step for being reduced to carry out simultaneously peels off reduction phase, shortens the reaction time and improves production efficiency, is the work of graphene
The production of industry metaplasia provides new method.
Step 3：
Step 2 gained graphene dispersing solution is subjected to vacuum filtration cleaning, gained filtrate is dried and obtains graphene.Its
In, it is preferably 0.1~10 μm to be filtered by vacuum filter sizes used.
On the whole, the present invention is using graphite powder as raw material, graphite oxide is obtained using improved Hummers legal systems, by oxygen
Graphite is dissolved in the organic solvent of certain temperature and the mixed solution of water, while adds reducing agent and in certain frequency, power
The lower ultrasound that carries out peels off reduction treatment, then filters product vacuum and is cleaned and dried to obtain grapheme material.Wherein it is possible to using
The modes such as vacuum freeze drying.
It is as follows according to the specific embodiment of the present invention, specific preparation method：
(1) according to improved Hummers methods, 1.5g graphite powders are added in the 100mL concentrated sulfuric acids, ice bath adds after 1 hour
KMnO45.0g, 6 hours are then reacted at normal temperatures, then diluted with 200mL distilled water under conditions of ice bath；Treat dilute
Release liquid cooling after, be added dropwise 120mL mass concentrations be 5% hydrogenperoxide steam generator, place a night after with distilled water from
The heart is cleaned to neutrality.Wherein, the particle diameter of graphite powder is 6.5 μm~0.15mm.
(2) by organic solvent and distilled water according to 1:0.01~1:100 proportional arrangement is into mixed solution, wherein organic molten
Agent be chitin (deacetylation of chitin be 50%~90%, such as 50%, 60%, 70%, 80%, 90%), N, N- diformazans
In yl acetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), 1-METHYLPYRROLIDONE (NMP)
It is a kind of or at least two combination.
(3) toward the mixed solution water-bath (or ice bath) prepared to 5~90 DEG C, 0.02~10g/L oxidation is then added
The reducing agent of graphite and 0.01~10g/L, wherein, reducing agent is in Tea Polyphenols, rhodioloside, anthocyanidin, ellagic acid, amino acid
One kind or at least two combination.
(4) mixed solution in (3) is placed in supersonic wave cleaning machine with 42~80kHz working frequency and 300~1200W
Power ultrasonic handle 10~180 minutes.Then obtained graphene dispersing solution is filtered by vacuum, the filter membrane of filtering is
0.1~10um.
It should be understood that above-mentioned embodiment and the example below that the present invention is described in detail are merely to illustrate the present invention rather than limitation
The scope of the present invention, some nonessential modifications and adaptations that those skilled in the art makes according to the above of the present invention
Belong to protection scope of the present invention.Following specific parameters of example etc. are also only an example in OK range, i.e. ability
Field technique personnel can be done in suitable scope by this paper explanation and be selected, and not really want to be defined in the specific number of hereafter example
Value.
The method that graphene is prepared using the step of redox one of the present invention is described further with reference to example.
Example 1：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 13um graphite powder, by DMSO
(dimethyl sulfoxide (DMSO)) and distilled water are according to 1:5 volume ratio is configured to mixed solution, and obtained solution is heated under water-bath
40℃；Then it is 0.55g/L to add in the mixed solution and control the concentration of graphite oxide by graphite oxide, while is added certain
The Tea Polyphenols of quality, the concentration for making Tea Polyphenols are 2.0g/L；Then solution is placed in supersonic wave cleaning machine with 50kHz work
Frequency and 700W supersound process (continuing to be ultrasonically treated after being down to 40 DEG C if temperature is more than 40 DEG C in ultrasonic procedure) are tired
Meter 30 minutes, then obtained graphene dispersing solution is subjected to vacuum filtration with 0.22um filter membrane and cleaned, it is finally cold using vacuum
Freeze desciccate and obtain graphene.Observed, had with the surface topography of graphene of the SEM to being prepared
For body as shown in figure 1, as shown in Figure 1, gained graphene is in the flexible accordion of out-of-flatness, prepared by the different explanations of its transparency
The graphene number of plies is different.Size characteristic analysis is carried out to the graphene being prepared with AFM again, as shown in Fig. 2
The lateral dimension of gained graphene is 2um or so, and thickness is 1.2nm or so, and the graphene theoretic throat according to individual layer is
0.34nm infers that obtained graphene is 3~4 layers or so.
Example 2：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 6.5um graphite powder, by DMAc
With distilled water according to 1:1 volume ratio is configured to mixed solution, and obtained solution is heated into 80 DEG C under water-bath；Then it is oxygen
It is 1.0g/L that graphite, which adds in the mixed solution and controlled the concentration of graphite oxide, while adds the rhodiola root of certain mass
Glucoside, the concentration for making rhodioloside are 4.0g/L；Then solution is placed in supersonic wave cleaning machine with 50kHz working frequency and
1000W power ultrasonic processing (continuing to be ultrasonically treated after being down to 80 DEG C if temperature is more than 80 DEG C in ultrasonic procedure) is accumulative
20 minutes, then obtained graphene dispersing solution is subjected to vacuum filtration with 0.22um filter membrane and cleaned, finally using vacuum refrigeration
Desciccate obtains graphene.Size characteristic analysis, gained graphite are carried out to the graphene being prepared with AFM
The lateral dimension of alkene is about 1.5um, and thickness is 1.2nm or so, and obtained graphene is 3~4 layers or so.
Example 3：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 2.6um graphite powder, will
DMAc, NMP and distilled water are according to 1:1:1 volume ratio is configured to mixed solution, and obtained solution is heated into 60 under water-bath
℃；Then it is 3.0g/L to add in the mixed solution and control the concentration of graphite oxide by graphite oxide, while adds certain matter
The anthocyanidin of amount, the concentration for making anthocyanidin are 2.5g/L；Then solution is placed in supersonic wave cleaning machine with 60kHz work frequency
Rate and 800W power ultrasonic handle (continuing to be ultrasonically treated after being down to 60 DEG C if temperature is more than 60 DEG C in ultrasonic procedure)
It is accumulative 60 minutes, then obtained graphene dispersing solution is subjected to vacuum filtration with 0.22um filter membrane and cleaned, finally using vacuum
Freeze-drying product obtains graphene.Size characteristic analysis, gained are carried out to the graphene being prepared with AFM
The lateral dimension of graphene is about 1.5um, and thickness is 1.8nm or so, is pushed away according to the graphene theoretic throat of individual layer for 0.34nm
Disconnected, obtained graphene is 4~5 layers or so.
Use Fourier infrared spectrograph comparative analysis graphite powder, graphite oxide and graphene function made from this example simultaneously
Unity structure, increases from graphite to graphite oxide oxygen-containing functional group as shown in Figure 3, and the graphene oxygen-containing functional group after reduction subtracts
It is few.
Elementary analysis is carried out to it with x-ray photoelectron spectroscopy again, the C/O ratios of graphene made from this example are by oxygen
The 1.9 of graphite are changed into 10.51；And can be seen that the C=C peaks of graphite oxide become by force after reduction from its energy spectrum diagram Fig. 4, C-O
It is then on the contrary with C=O.It is 150.87m to analyze graphene specific surface area made from this example with N2 adsorption surface analysis instrument2/
g。
Example 4：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 18um graphite powder, by crust
Plain (deacetylation 70%) and distilled water are according to 3:2 volume ratio is configured to mixed solution, by obtained solution under water-bath
It is heated to 25 DEG C；Then it is 5.0g/L to add in the mixed solution and control the concentration of graphite oxide by graphite oxide, is added simultaneously
Enter the ellagic acid of certain mass, the concentration for making ellagic acid is 0.5g/L；Then solution is placed in ultrasound under the ice-water bath of interruption
It is accumulative 80 minutes with the processing of 60kHz working frequency and 400W power ultrasonic in ripple cleaning machine, then obtained graphene is divided
Dispersion liquid carries out vacuum filtration with 0.45um filter membrane and cleaned, and finally obtains graphene using vacuum freeze drying product.Use X ray
Photoelectron spectrograph carries out elementary analysis to it, and its C/O ratio is 9.47；This example is analyzed with N2 adsorption surface analysis instrument
Obtained graphene specific surface area is 160.79m2/g。
Example 5：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 0.64um graphite powder, will
DMF, DMAc and distilled water are according to 1:2:2 volume ratio is configured to mixed solution, and obtained solution is heated into 50 under water-bath
℃；Then it is 4.0g/L to add in the mixed solution and control the concentration of graphite oxide by graphite oxide, while adds certain matter
The amino acid of amount, the concentration for making amino acid are 4.0g/L；Then solution is placed in supersonic wave cleaning machine with 42kHz work frequency
Rate and 900W power ultrasonic handle (continuing to be ultrasonically treated after being down to 50 DEG C if temperature is more than 50 DEG C in ultrasonic procedure)
It is accumulative 40 minutes, then obtained graphene dispersing solution is subjected to vacuum filtration with 0.1um filter membrane and cleaned, it is finally cold using vacuum
Freeze desciccate and obtain graphene.The observation of apparent form is carried out to the graphene being prepared, its lateral dimension is about
0.3um, thickness are 1.2nm or so；And Raman spectrum analysis is carried out to it, as shown in figure 5, measuring its defective value ID/IGFor
0.25。
Example 6：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 0.42um graphite powder, by NMP
With distilled water according to 2:3 volume ratio is configured to mixed solution, and obtained solution is heated into 55 DEG C under water-bath；Then by oxygen
It is 0.8g/L that graphite, which adds in the mixed solution and controlled the concentration of graphite oxide, while according to 1:1 mass ratio adds tea
Polyphenol and anthocyanidin, the concentration for making reducing agent are 1.5g/L；Then solution is placed in supersonic wave cleaning machine with 70kHz work
The processing of frequency and 750W power ultrasonic (continues at ultrasound in ultrasonic procedure after being down to 55 DEG C if temperature is more than 55 DEG C
Reason) it is accumulative 90 minutes, then obtained graphene dispersing solution is subjected to vacuum filtration with 0.1um filter membrane and cleaned, finally using true
Vacuum freecing-dry product obtains graphene.The observation of apparent form is carried out to the graphene being prepared, its lateral dimension is about
0.2um, thickness are 1.2nm or so；Elementary analysis is carried out to it with x-ray photoelectron spectroscopy, its C/O ratio is 17.01.
Example 7：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 25um graphite powder, by crust
Plain (deacetylation 80%) and distilled water are according to 4:1 volume ratio is configured to mixed solution, by obtained solution under water-bath
It is heated to 80 DEG C；Then it is 1.6g/L to add in the mixed solution and control the concentration of graphite oxide by graphite oxide, is pressed simultaneously
According to 2:It is 0.8g/L that 1 mass ratio, which adds amino acid and ellagic acid, the concentration for making reducing agent,；Then it is clear solution to be placed in ultrasonic wave
(dropped in washing machine with the processing of 42kHz working frequency and 1200W power ultrasonic in ultrasonic procedure if temperature is more than 80 DEG C
Continue to be ultrasonically treated after to 80 DEG C) it is accumulative 120 minutes, then obtained graphene dispersing solution is subjected to vacuum with 0.45um filter membrane
Cleaning is filtered, graphene is finally obtained using vacuum freeze drying product.Enter row element point to it with x-ray photoelectron spectroscopy
Analysis, its C/O ratio are 16.71.
Example 8：
Use above-mentioned improved Hummers methods that average grain diameter is oxidized into graphite oxide for 1.6um graphite powder, will
DMAc, DMF, NMP and distilled water are according to 1:1:1:1 volume ratio is configured to mixed solution, by obtained solution in ice bath to 10
℃；Then it is 6.0g/L to add in the mixed solution and control the concentration of graphite oxide by graphite oxide, while according to 2:1:1
It is 5.5g/L that mass ratio, which adds Tea Polyphenols, amino acid and rhodioloside, the concentration for making reducing agent,；Then solution in ice bath state
Under be placed in supersonic wave cleaning machine and handled 180 minutes with 80kHz working frequency and 300W power ultrasonic, then the stone that will be obtained
Black alkene dispersion liquid carries out vacuum filtration with 0.1um filter membrane and cleaned, and finally obtains graphene using vacuum freeze drying product.With
X-ray photoelectron spectroscopy carries out elementary analysis to it, and its C/O ratio is 19.23.
The invention is not limited in foregoing embodiment.The present invention, which expands to, any in this manual to be disclosed
New feature or any new combination, and disclose any new method or process the step of or any new combination.
Claims (7)
- A kind of 1. method for preparing graphene using the step of redox one, it is characterised in that the preparation method includes following step Suddenly：The graphite oxide obtained after being aoxidized with graphite powder is dissolved in the mixed solution for including organic solvent and water under predetermined temperature In, wherein the concentration of the graphite oxide be 0.02~10g/L and the mixed solution in the volume ratio of organic solvent and water be 1:0.01~1:100, while add reducing agent and supersound process is carried out to it and obtain graphene dispersing solution in 10~120 minutes；Will Gained graphene dispersing solution carries out vacuum filtration cleaning, dries gained filtrate and obtains graphene；Wherein, the oxidation of graphite powder is carried out using improved Hummers methods, the improved Hummers methods comprise the following steps:Graphite powder is added in the concentrated sulfuric acid and stirred under condition of ice bath, potassium permanganate is added after room temperature to be restored and continues to stir Reaction, then distilled water diluting is used under condition of ice bath, obtain dilution；Hydrogen peroxide is slowly added in the dilution and continued Stirring, eccentric cleaning obtains graphite oxide to neutrality after placing a night；The organic solvent is chitin, DMAC N,N' dimethyl acetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl Sulfoxide (DMSO) and one kind or the deacetylation of at least two combination, wherein chitin in 1-METHYLPYRROLIDONE (NMP) For 50%~90%；The reducing agent is Tea Polyphenols, rhodioloside, anthocyanidin, ellagic acid, one kind in amino acid or at least two The combination of kind.
- 2. the method according to claim 1 for preparing graphene using the step of redox one, it is characterised in that the graphite The particle diameter of powder is 0.42~150um.
- 3. the method according to claim 1 for preparing graphene using the step of redox one, it is characterised in that described predetermined Temperature is 5~90 DEG C.
- 4. the method for preparing graphene using the step of redox one according to claim 1 or 3, it is characterised in that described Predetermined temperature is 40-60 DEG C.
- 5. the method according to claim 1 for preparing graphene using the step of redox one, it is characterised in that the ultrasound The ultrasonication that it is 42~80kHz with working frequency that the condition of processing, which is, and ultrasonic power is 300~1200W.
- 6. the method according to claim 1 for preparing graphene using the step of redox one, it is characterised in that the reduction The concentration of agent is 0.01~10g/L.
- 7. the method according to claim 1 for preparing graphene using the step of redox one, it is characterised in that the vacuum It is 0.1~10 μm to filter filter sizes used.
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| CN107161984B (en) * | 2017-06-28 | 2019-07-16 | 华南理工大学 | A kind of method that ascorbic acid/tea polyphenols synergistic effect prepares graphene |
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