CN106564881A - Preparation of reduced graphene oxide by one-step method - Google Patents
Preparation of reduced graphene oxide by one-step method Download PDFInfo
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- CN106564881A CN106564881A CN201610599766.5A CN201610599766A CN106564881A CN 106564881 A CN106564881 A CN 106564881A CN 201610599766 A CN201610599766 A CN 201610599766A CN 106564881 A CN106564881 A CN 106564881A
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Abstract
The invention discloses preparation of reduced graphene oxide by a one-step method, and belongs to the technical field of graphene. Flake graphite is used as a raw material, and the reduced graphene oxide with excellent dispersibility is prepared by the one-step method. The preparation of the reduced graphene oxide by the one-step method comprises the following steps: (1) placing 0.1-5 g of the flake graphite in concentrated H2SO4, respectively adding NaNO3 and KMnO4 solid in the concentrated H2SO4 in ice bath, and enabling the temperature of a system not to exceed 10 DEG C; (2) reacting the mixed system in water bath at the temperature of 30-50 DEG C, transferring the mixed system into oil bath at the temperature of 60-100 DEG C and then adding an H2O2 solution in the mixed system; and (3) adding a metal reducing agent in the mixed system so that the system is gradually changed into a black system from a luminous yellow system, cleaning and filtering the system with diluted hydrochloric acid and deionized water respectively until the system is neutral, finally carrying out ultrasonic treatment on filtrate, then centrifuging the filtrate at low speed, and drying and dispersing the filtrate to obtain the reduced graphene oxide by the one-step method. The method is simple and convenient to operate; large-scale continuous industrial production is facilitated; and the prepared reduced graphene oxide has good dispersing performance in different solvents.
Description
Technical field：
The invention belongs to technical field of graphene, and in particular to one-step method prepares redox graphene.
Background technology：
Graphene is the New Two Dimensional with honeycomb crystal lattice network with monoatomic layer thickness being made up of carbon atom
Crystal, the physicochemical properties with many protrusions, so as to range of application widely.
Preparing the main method of Graphene at present includes mechanical stripping method, epitaxial growth method, chemical vapour deposition technique, colloid
The methods such as solwution method.Wherein, using technology and the finished product Graphene aspect of performance for preparing there is certain office in first three methods
It is sex-limited, its more massive application is limited then；Colloidal solution method is the colloid point that Graphene is prepared using means such as chemistry
Scattered solution, has the advantages that yield is high, can amplify production, be easy to following process, mainly includes redox graphene method and stone
The solution stripping method of ink and its derivative.
At present, redox graphene is the generally acknowledged important channel that can in a large number obtain Graphene at a low price.Scientific research at this stage
Personnel developed it is various prepare redox graphene method (ACS Nano, 2011,5 (1)：191.,
J.Mater.Chem., 2012,22,13064., CN201010610179, CN201310186059, CN201410370975,
CN201410756703).But big multi-method is two step reduction method, the i.e. first step and first graphite powder is oxidized to into graphite oxide, then
Graphene oxide dispersion is obtained by ultrasound；Second step is obtained redox graphene Jing after different method of reducing reactions.
And the method for reducing of graphene oxide mainly includes chemical reduction method, high-energy ray radiation method, solvothermal in prior art
Method etc..Wherein, solvothermal and high-energy ray radiation are stricter to experiment condition, and can limit the size of sample and uniform
Property；Chemical reduction method applies in general to prepare Graphene on a large scale, and conventional reducing agent has hydrazine hydrate, sodium borohydride etc., but this
The shortcomings of a little methods have high energy consumption, high pollution, high toxicity, long preparation period, it is therefore desirable to which a kind of easy, friendly method is come
Successfully prepare redox graphene.
The content of the invention：
With crystalline flake graphite as raw material, with metal simple-substance as reducing agent, the prepared dispersive property of one-step method is excellent to be gone back the present invention
Former graphene oxide, to overcome existing reduction technique in the high energy consumption that occurs, high pollution, high toxicity, the problems such as long preparation period.
The method is simple to operation, with short production cycle and energy consumption is relatively low, it is easy to fairly large continuous industry production, it is prepared also
Former graphene oxide is respectively provided with good dispersive property in different solvents.
Technical program of the present invention lies in：One-step method prepares redox graphene, comprises the following steps：
1) 0.1-5g crystalline flake graphites are placed in into a certain amount of dense H2SO4In, and add 0-3g NaNO3, constantly stir in ice-water bath
Mix down and be slowly added to 1-20g KMnO4Solid, makes system temperature be less than 10 DEG C；
2) mixed system is placed in stirring reaction 20min in 30-50 DEG C of water-bath；Add 50-400mL deionized water to mix
In closing solution, continue to be transferred in 60-100 DEG C of oil bath after stirring 20min, add the H that mass fraction is 30%2O2Solution
2-20mL, now system is glassy yellow by brown stain；
3) above-mentioned mixed solution is slowly added to into 0.1-5g metallic reducing agents under stirring, system is gradually become by glassy yellow
Black.Mixed solution is stood into 12-24h, with HCl and deionized water that mass fraction is 5% filtration is cleaned respectively after filtration, will
Low-speed centrifugal 30-180min takes supernatant after the ultrasonically treated 0.5-4h of filtrate, and clear liquid is finally placed in 60 DEG C of vacuum drying chamber
In be dried 24h, by dry sample ultrasonic disperse in different solvents, one-step method obtains final product redox graphene.
Preferably, step 1) described in the concentrated sulfuric acid amount be 10-100mL；
Preferably, step 3) described in metallic reducing agent be magnesium metal, aluminium, iron, zinc at least one；
Preferably, step 3) described in low-speed centrifugal speed be 1000-4000r/min；
Preferably, step 4) described in solvent be ultra-pure water, ethanol, isopropanol, DMF (DMF),
At least one in 1-METHYLPYRROLIDONE (NMP), tetrahydrofuran (THF).
Compared with prior art, the present invention has the advantages that：
The present invention needs not move through graphite oxide from crystalline flake graphite raw material, and direct one-step method obtains reduction-oxidation graphite
Alkene material, effectively alleviates prior art high energy consumption, cycle long characteristic of experiment；
The metal simple-substance reducing agent that the present invention is used is cheap, and nontoxic, contaminative is low, while its also proper energy can be effectively improved
Power, benefits the grapheme material of the high-quality of acquisition；
The redox graphene that the present invention is obtained is soluble in multi-solvents, and for subsequent experimental more possibility are provided；
The method of the invention is simple to operate, efficiently, and without the need for expensive main equipment.
Description of the drawings：
It is main below to wanting accompanying drawing to be briefly described needed for embodiment in order to clearly illustrate the present invention
To be the comparison between embodiment and comparative example, so as to further embody the feasibility of experimental program.
Fig. 1 is the XPS contrast spectrograms of embodiment 1 and prepared sample in comparative example 1；
Fig. 2 is audio-visual picture of the sample dispersion prepared in embodiment in different solvents.
Specific embodiment：
The result in the embodiment of the present invention will more clearly and completely be described below, also, described example
Only it is a part of embodiment of the invention, and it is not all.The embodiment understands the present invention for help, should not be considered as to the present invention
Concrete restriction.
Embodiment 1
2g crystalline flake graphites are placed in into the dense H of 50mL2SO4In, and add 2g NaNO3, be stirred continuously in ice-water bath it is lower slow plus
Enter the KMnO of 10g4Solid；Mixed system is transferred to into stirring reaction 20min in 35 DEG C of water-bath；Add 300mL go from
Sub- water continues to be transferred in 95 DEG C of oil bath after stirring 20min in mixed solution, stirs 20min, and adding mass fraction is
30% H2O2Solution 4mL, now system is glassy yellow by brown stain；The above-mentioned solution of 100mL is taken, by system in stirring
Under be slowly added to 0.8g Fe powder, system gradually becomes black by glassy yellow.Mixed solution is stood and filter after 12h, matter is used respectively
Amount fraction is 5% HCl and deionized water cleaning is filtered to neutrality, is processed with the low-speed centrifugal of 3000r/min after ultrasonic 1.5h,
Supernatant and suction filtration are extracted, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is dried 24h, be precisely weighed and disperse after being dried
Redox graphene is obtained final product into solvent.Jing is tested, and redox graphene C/O obtained in this method is 2.43 (Fig. 1), and
Good dispersiveness (Fig. 2) is presented in pure water, ethanol and acetone solvent.
Embodiment 2
1g crystalline flake graphites are placed in into the dense H of 50mL2SO4In, and add 1g NaNO3, be stirred continuously in ice-water bath it is lower slow plus
Enter the KMnO of 8g4Solid, makes system temperature be less than 10 DEG C；Mixed system is placed in into stirring reaction in 35 DEG C of water-bath
20min；The deionized water of 200mL is added in mixed solution, continues to be transferred in 95 DEG C of oil bath after stirring 20min, stirred
20min, adds the H that mass fraction is 30%2O2Solution 3mL, now system is glassy yellow by brown stain；Take 100mL above-mentioned
Solution, by system 0.4g Mg powder is slowly added under stirring, and system gradually becomes black by glassy yellow.By mixed solution
Stand and filtered after 16h, clean with HCl and deionized water that mass fraction is 5% filter to neutrality respectively, after ultrasonic 2h with
The low-speed centrifugal of 4000r/min is processed, and extracts supernatant and suction filtration, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is dried
24h, is precisely weighed and is dispersed in solvent and obtain final product redox graphene after being dried.Jing is tested, oxygen reduction obtained in this method
Graphite alkene C/O is 2.71, and is opened up in pure water, 1-METHYLPYRROLIDONE (NMP) and DMF (DMF) solvent
Good dispersiveness (Fig. 2) is showed.
Embodiment 3
3g crystalline flake graphites are placed in into the dense H of 75mL2SO4In, and add 2g NaNO3, be stirred continuously in ice-water bath it is lower slow plus
Enter the KMnO of 15g4Solid, makes system temperature be less than 10 DEG C；Mixed system is placed in into stirring reaction in 35 DEG C of water-bath
20min；The deionized water of 350mL is added in mixed solution, continues to be transferred in 95 DEG C of oil bath after stirring 20min, stirred
20min, adds the H that mass fraction is 30%2O2Solution 5mL, now system is glassy yellow by brown stain；Take 100mL above-mentioned
Solution, by system 0.5g Fe powder is slowly added under stirring, and system gradually becomes black by glassy yellow.By mixed solution
Stand and filtered after 8h, clean with HCl and deionized water that mass fraction is 5% filter to neutrality respectively, after ultrasonic 2h with
The low-speed centrifugal of 4000r/min is processed, and extracts supernatant and suction filtration, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is dried
24h, is precisely weighed and is dispersed in solvent and obtain final product redox graphene after being dried.Jing is tested, oxygen reduction obtained in this method
Graphite alkene C/O is 2.48, and good dispersiveness (figure is presented in pure water, isopropanol and tetrahydrofuran (THF) solvent
2)。
Comparative example 1
This comparative example is the experiment flow for preparing graphene oxide, is comprised the following steps：
2g crystalline flake graphites are placed in into the dense H of 50mL2SO4In, and add 2g NaNO3, be stirred continuously in ice-water bath it is lower slow plus
Enter the KMnO of 10g4Solid；Mixed system is transferred to into stirring reaction 20min in 35 DEG C of water-bath；Add 300mL go from
Sub- water continues to be transferred in 95 DEG C of oil bath after stirring 20min in mixed solution, stirs 20min, and adding mass fraction is
30% H2O2Solution 4mL, now system is glassy yellow by brown stain.Mixed solution is stood and filter after 12h, matter is used respectively
Amount fraction is 5% HCl and deionized water cleaning is filtered to neutrality, is processed with the low-speed centrifugal of 3000r/min after ultrasonic 1.5h,
Supernatant and suction filtration are extracted, finally filter cake is placed in 60 DEG C of vacuum drying chamber and is dried 24h, be precisely weighed and disperse after being dried
Graphene oxide is obtained final product into solvent.Jing is tested, and graphene oxide C/O obtained in this method is 2.01 (Fig. 1).
Comparative example 1 do not add in comparative example any reducing agent with differing only in for embodiment 1, directly purifies after reaction
To graphene oxide, and the C/O of the product for finally giving differs 0.42 (Fig. 1), and this shows that this method can obtain function admirable
Redox graphene, and the method is simple to operate, and energy consumption is relatively low, and reduction effect is preferable.
Claims (5)
1. one-step method prepares redox graphene, it is characterised in that：Using metal simple-substance as reducing agent, by one-step method by squama
The reaction of piece graphite is obtained redox graphene, and specific experiment flow process is followed the steps below：
1) 0.1-5g crystalline flake graphites are placed in into a certain amount of dense H2SO4In, and add 0-3g NaNO3, constantly stir in ice-water bath
Mix down the KMnO for being slowly added to 1-20g4Solid, makes system temperature stable within 10 DEG C；
2) mixed system is placed in stirring reaction 20min in 30-50 DEG C of water-bath, 50-400mL deionized waters is added to mixing
In solution, continue to be transferred in 60-100 DEG C of oil bath after stirring 20min, add the H that mass fraction is 30%2O2Solution 2-
20mL, now system is glassy yellow by brown stain；
3) above-mentioned mixed solution is slowly added to into 0.1-5g metallic reducing agents under stirring, system is gradually become by glassy yellow
Black, by mixed solution 12-24h is stood, and is cleaned with HCl and deionized water that mass fraction is 5% respectively after filtration and is filtered extremely
Neutrality, by low-speed centrifugal 30-180min after the ultrasonically treated 0.5-4h of filtrate supernatant is taken, and clear liquid is finally placed in 60 DEG C of vacuum
24h is dried in drying box, by dry sample ultrasonic disperse in different solvents, one-step method obtains final product redox graphene.
2. one-step method as claimed in claim 1 prepares redox graphene, it is characterised in that：Step 1) described in dense sulphur
The amount of acid is 10-100mL.
3. one-step method as claimed in claim 1 prepares redox graphene, it is characterised in that：Step 3) described in metal
Reducing agent is at least one in magnesium metal, aluminium, iron, zinc.
4. one-step method as claimed in claim 1 prepares redox graphene, it is characterised in that：Step 3) described in low speed
Centrifugal speed is 1000-4000r/min.
5. one-step method as claimed in claim 1 prepares redox graphene, it is characterised in that：Step 3) described in solvent
For ultra-pure water, ethanol, isopropanol, DMF (DMF), 1-METHYLPYRROLIDONE (NMP), tetrahydrofuran (THF)
In at least one.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111446022A (en) * | 2020-02-11 | 2020-07-24 | 任国峰 | Graphene conductive slurry for battery and preparation method thereof |
| CN112391664A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院上海硅酸盐研究所 | Method for preparing reduced graphene oxide coating on surface of magnesium alloy |
| WO2021128808A1 (en) * | 2019-12-27 | 2021-07-01 | 福州大学 | High barrier rgo-sio2/pet protective film and preparation method therefor |
| CN113092537A (en) * | 2021-03-30 | 2021-07-09 | 海南聚能科技创新研究院有限公司 | Quadrupole type conductivity electrode capable of improving seawater conductivity measurement accuracy and preparation method and application thereof |
| CN115285977A (en) * | 2022-06-24 | 2022-11-04 | 深圳材启新材料有限公司 | Method for preparing graphene from graphene oxide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112391664A (en) * | 2019-08-16 | 2021-02-23 | 中国科学院上海硅酸盐研究所 | Method for preparing reduced graphene oxide coating on surface of magnesium alloy |
| CN112391664B (en) * | 2019-08-16 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | Method for preparing reduced graphene oxide coating on surface of magnesium alloy |
| WO2021128808A1 (en) * | 2019-12-27 | 2021-07-01 | 福州大学 | High barrier rgo-sio2/pet protective film and preparation method therefor |
| CN111446022A (en) * | 2020-02-11 | 2020-07-24 | 任国峰 | Graphene conductive slurry for battery and preparation method thereof |
| CN113092537A (en) * | 2021-03-30 | 2021-07-09 | 海南聚能科技创新研究院有限公司 | Quadrupole type conductivity electrode capable of improving seawater conductivity measurement accuracy and preparation method and application thereof |
| CN115285977A (en) * | 2022-06-24 | 2022-11-04 | 深圳材启新材料有限公司 | Method for preparing graphene from graphene oxide |
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Application publication date: 20170419 |