CN109264704A - Improve redox graphene preparation method - Google Patents
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- CN109264704A CN109264704A CN201811504084.7A CN201811504084A CN109264704A CN 109264704 A CN109264704 A CN 109264704A CN 201811504084 A CN201811504084 A CN 201811504084A CN 109264704 A CN109264704 A CN 109264704A
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- C01—INORGANIC CHEMISTRY
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
Abstract
The invention discloses redox graphene preparation method is improved, improvement preparation and Vitamin C method redox graphene including graphene oxide prepare graphene；Graphene oxide preparation method operating safety factor of the present invention is high, and preparation time is short, required temperature is low, reactant nonhazardous effect, environmental pollution are small；It is smaller to graphite linings structural damage after oxidation, it can shorten and prepare the time of graphene oxide and improve its yield；Entire reaction does not need addition stabilizer；It is advantageously implemented the precise controlling of graphene preparation, graphene-structured obtained is more complete, and performance is more excellent.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials more particularly to a kind of improvement graphene oxide and preparation sides
Method.
Background technique
Graphene is considered as substitution silicon materials, causes the core material of the next-generation industrial revolution, in recent years because its is superior
Electrical properties, thermal property and quantum hall effect etc. become research hotspot, in sensor, transparence display touch screen, partly lead
The various aspects such as body and biological medicine are applied.Common graphene preparation method has hydrazine hydrate reduction, Vitamin C, and (L- is anti-bad
Hematic acid) reduction, raw material are all graphene oxides.Preparing graphene oxide mainly has Brodie method, Staudenmaider method
With Hummers method, it is to be added in graphite raw material using inorganic acid (such as concentrated sulfuric acid, concentrated nitric acid), is inserted into strong acid small molecule
To graphite layers, preliminary oxidation is carried out to graphite with the use of sodium nitrate；Mixing is added with strong oxidizer (such as potassium permanganate) again
Graphite is further aoxidized in object.The degree of graphite oxidation depends primarily on reaction condition and method.
It is existing prepare graphene oxide during, the graphite of use: 98% concentrated sulfuric acid: potassium permanganate: sodium nitrate=1:23:
3:0.5 efficiency is general.
The method that the reducing agents such as existing hydrazine hydrate, ethylene glycol, hydroquinone prepare graphene, although their simple processes,
But stabilizer, the reducing agent used is more toxic, and endangers environment.It is no longer complete through graphene crystal structure made from the above method
Whole, randomness increase keeps its resistivity higher.Currently, scientist more pays close attention to graphene oxide its structure in reduction process
The research of controllable aspect, domestic and international enterprise has carried out a large amount of research work to this, but result is all not fully up to expectations.
Summary of the invention
The object of the invention is that provide to solve the above-mentioned problems and improve redox graphene preparation method, packet
Include following steps:
S1: it prepares graphene oxide: S11: taking graphite powder and sodium nitrate in reactor, the concentrated sulfuric acid is added and sets reactor
It stirs in ice water bath apparatus to abundant reaction；
S12: 10-20 DEG C is adjusted the temperature to, reactor is added with stirring potassium permanganate reaction；
S13: the temperature was then adjusted to 30-40 DEG C, distilled water dilution is sufficiently added in isothermal reaction afterwards；
S14: diluting and after reacting, and adds potassium permanganate and is reacted, the temperature was then adjusted to 95-98 DEG C of progress after reaction
Isothermal reaction；
S15: hydrogen peroxide is added after being cooled to room temperature and is reacted；
S16: until centrifugate PH is in neutrality, taking-up sediment, drying obtains graphene oxide for centrifugation.
S2: redox graphene prepares graphene:
S21: taking graphene oxide to be stirred with distilled water, ultrasonic treatment；
S22: Vitamin C powder, ultrasonic treatment is added；
S23: above-mentioned solution is placed in closing water-bath, carries out isothermal reaction；
S24: using dehydrated alcohol eccentric cleaning, then after being repeatedly centrifuged with distilled water taking precipitate it is dry graphene.
Further, the graphite, the concentrated sulfuric acid, potassium permanganate, sodium nitrate usage amount ratio are as follows: 1:35:5:0.5.
Further, the ice water bath apparatus is the electric-heated thermostatic water bath for being placed with a large amount of ice cubes.
Further, the reactor is magnetic stirring apparatus.
Further, redox graphene preparation method, which is characterized in that the concentration of the concentrated sulfuric acid is 98%.
Further, the detailed process of potassium permanganate is added in the S2 step are as follows: potassium permanganate is divided into 3 parts of interval stirrings
It is added, interval time 15min.
Further, the hydrogen peroxide concentration is 30%.
Further, water bath temperature is 80 degrees Celsius in the S23 step.
The present invention through the following technical solutions to achieve the above objectives:
The beneficial effects of the present invention are: graphene oxide preparation method operating safety factor of the present invention is high, preparation time
It is short, required temperature is low, reactant nonhazardous effect, environmental pollution are small；It is smaller to graphite linings structural damage after oxidation, it can
Shortening prepares the time of graphene oxide and improves its yield；Entire reaction does not need addition stabilizer；It is advantageously implemented graphite
The precise controlling of alkene preparation, graphene-structured obtained is more complete, and performance is more excellent.
Detailed description of the invention
Fig. 1 is the flow chart of graphene oxide preparation process；
Fig. 2 is the process that Vitamin C reduction method prepares graphene；
Fig. 3 is four probe method measuring resistance rate tables of data.
In figure: GO- graphene oxide；VC-RGO- is using graphene made from Vitamin C；NH-RGO- uses hydrazine hydrate method
Graphene obtained.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings:
As shown in Figure 1, improving redox graphene preparation method, include the following steps:
S1: it prepares graphene oxide: S11: taking graphite powder and sodium nitrate in reactor, the concentrated sulfuric acid is added and sets reactor
It stirs in ice water bath apparatus to abundant reaction；
S12: 10-20 DEG C is adjusted the temperature to, reactor is added with stirring potassium permanganate reaction；
S13: the temperature was then adjusted to 30-40 DEG C, distilled water dilution is sufficiently added in isothermal reaction afterwards；
S14: diluting and after reacting, and adds potassium permanganate and is reacted, the temperature was then adjusted to 95-98 DEG C of progress after reaction
Isothermal reaction；
S15: hydrogen peroxide is added after being cooled to room temperature and is reacted；
S16: until centrifugate PH is in neutrality, taking-up sediment, drying obtains graphene oxide for centrifugation.
S2: redox graphene prepares graphene:
S21: taking graphene oxide to be stirred with distilled water, ultrasonic treatment；
S22: Vitamin C powder, ultrasonic treatment is added；
S23: above-mentioned solution is placed in closing water-bath, carries out isothermal reaction；
S24: using dehydrated alcohol eccentric cleaning, then after being repeatedly centrifuged with distilled water taking precipitate it is dry graphene.
Further, the graphite, the concentrated sulfuric acid, potassium permanganate, sodium nitrate usage amount ratio are as follows: 1:35:5:0.5.
Further, the ice water bath apparatus is the electric-heated thermostatic water bath for being placed with a large amount of ice cubes.
Further, the reactor is magnetic stirring apparatus.
Further, redox graphene preparation method, which is characterized in that the concentration of the concentrated sulfuric acid is 98%.
Further, the detailed process of potassium permanganate is added in the S2 step are as follows: potassium permanganate is divided into 3 parts of interval stirrings
It is added, interval time 15min.
Further, the hydrogen peroxide concentration is 30%.
Further, water bath temperature is 80 degrees Celsius in the S23 step.
Prepare the specific steps of graphene oxide are as follows: first weigh 2g graphite powder and 1g sodium nitrate with electronic balance, be put into
It in 500ml beaker, then takes the 50ml concentrated sulfuric acid to pour into beaker and places it in the electric-heated thermostatic water bath for being placed with a large amount of ice cubes, make
30min is stirred at low speed with magnetic stirring apparatus；Water temperature is adjusted to 15 DEG C, 6g potassium permanganate is added three times, each 2g adds every time
The time interval entered is 15min；Then 35 DEG C, isothermal reaction 2h are adjusted the temperature to by electric hot water bath, slowly added under stirring
Enter 300ml distilled water to dilute solution, a large amount of heat of concentrated sulfuric acid release in dilution, so needing that magnetic agitation is suitably turned up
Device revolving speed is simultaneously stirred with glass bar against magnetic agitation direction；30min is reacted after adding distilled water, it is anti-to be slowly added to 2g potassium permanganate
15min is answered, then water-bath is made to be warming up to 98 DEG C of isothermal reaction 30min；It is dense that 50ml is added after beaker taking-up is cooled to room temperature
The hydrogen peroxide that degree is 30%, observes color change, and Success in Experiment can be observed solution and quickly become golden yellow and companion by brownish black
There are a large amount of bubbles；Be then placed in ultrasound 30min in ultrasonic cleaner, obtained dispersion liquid pour into batches centrifuge tube carry out from
The heart.Revolving speed is first adjusted to 4000r/min centrifugation 10min to go out large granular impurity, be then adjusted to 5000r/min carry out repeatedly from
The heart, each 10min are taken out precipitating in centrifuge tube with key until being in neutrality using PH test paper detection centrifugate；Finally, will
Sediment is placed in drying in baking oven, and dry duration is greater than 36h, and obtained solid is graphene oxide, and sample is ground with mortar
At powder and save.
It prepares the experimental phenomena of graphene oxide: after graphite powder and sodium nitrate, concentrated sulfuric acid addition, being acted in magnetic stirring apparatus
Lower releasing heat, after water-bath medium floe is slowly dissolved full marks batch addition potassium permanganate, the beaker solution wall for containing reactor is in
Dark green illustrates that graphite has been initially oxidised.After rectification water is added, the concentrated sulfuric acid is diluted a large amount of heat of releasing, so solution
There are a large amount of bubbles, need to stir rapidly, slowly fills the water.Adding water to finish solution is yellow-brown suspension；It is cooled to room temperature to solution
After add 30% hydrogenperoxide steam generator still and there are a large amount of bubbles to emerge, solution quickly becomes golden yellow.
Graphene oxide is obtained by above-mentioned steps, stone can be prepared using Vitamin C (L-AA) reduction method
Black alkene, experiments have shown that it is more preferable to prepare graphene effect using Vitamin C reduction method.Vitamin C (L-AA) reduction method, phase
Compared with the reducing agents such as hydrazine hydrate, ethylene glycol, hydroquinone are used, although their simple processes, reducing agent are more toxic, danger
Evil environment；And ascorbic acid reducing power is strong, and mild harmless, can be used as green reducing agent.
Redox graphene prepares the specific steps of graphene are as follows: the graphene oxide and 250ml for taking 1g to prepare steam
Distilled water mixing after stirring 30 minutes at room temperature, is ultrasonically treated 2 hours；It is molten after weighing 4g Vitamin C powder addition ultrasonic treatment
In liquid, it is ultrasonically treated 0.5 hour；The solution that joined Vitamin C is placed in 80 DEG C of water-bath, covers water-bath pot cover, keep away
Exempt from a large amount of evaporations of moisture, isothermal reaction 8 hours；Primary with dehydrated alcohol eccentric cleaning, revolving speed 5000r/min is centrifuged 10 points
Clock, then be centrifuged 7 times with distilled water, centrifuge tube lower part sediment is obtained, sediment is transferred in drying box under the conditions of 60 DEG C dry 24
Hour, obtained solid is graphene；Obtained graphene is crushed into powder with mortar, and is saved.
Redox graphene prepares the experimental phenomena of graphene: can by graphene oxide obtained progress ultrasonic disperse
Filemot suspension is obtained, Vitamin C is added to this solution, originally solution without significant change, does not have substantially after reaction
Agglomeration, solution is relatively uniform, is in dark gray；If hydrazine hydrate is added, it then will appear agglomeration after reaction, solution occurs
Clarification has a large amount of little particle of black to suspend in the solution.To the end of the reaction time, cooling and standings to room temperature, under two kinds of reducing agents
Solution will appear separation of solid and liquid phenomenon, but the supernatant clarification of hydrazine hydrate reduction, transparent, the supernatant of Vitamin C reduction
For dirty-green, bottom solid is in soft fluffy state.
Since in entire reaction process, L-AA plays a part of reducing agent, oxidation product plays stabilizer
Effect, therefore entire reaction does not need addition stabilizer.
The resistivity of graphene oxide (GO) is apparently higher than graphene, this is the process that graphite is slowly aoxidized through strong oxidizer
In, oxygen atom, which is integrated to graphite layers, which seizes moveable pi-electron, is broken the pi bond in level, forms C-O, and C=O etc. is oxygen-containing
Functional group destroys caused by the original crystal structure of graphite.Degree of oxidation is higher, and resistivity is bigger.In fig. 3, in figure:
GO- graphene oxide；VC-RGO- is using graphene made from Vitamin C；NH-RGO- is using graphene made from hydrazine hydrate method.
It can be found that GO variance is 35.58, it was demonstrated that its resistivity fluctuation is larger, this shows not to be uniform inside graphene oxide
Stable, there are more defects.In comparison, NH-RGO and VC-RGO resistivity is all very small, but is still higher than graphene resistance
Rate theory value, although this is because its interior oxygen-containing functional group large area reduction, does not completely remove, in addition graphite is gone back through oxidation
Crystal structure is no longer complete after original, and it is also to cause the higher reason of its resistivity that randomness, which increases,.But it can be sent out in attached drawing 3
Existing, the resistivity of VC-RGO is also somewhat below NH-RGO.Its variance is 4.47x10-7 ratio NH-RGO (variance are as follows: 6.95x10-7)
It is also smaller, it can be seen that, the GO restored using Vitamin C is more thorough, and structure is more complete, and performance is more excellent.
The GO restored using Vitamin C, preparation time is short, required temperature is low, environmental pollution is small.Four probe resistances are surveyed
It takes temperature bright, the VC-RGO piece layer resistivity of 1mm thickness is about 0.01638 Ω .m, more smaller than the 0.01710 Ω .m of NH-RGO.SEM electricity
Mirror photo shows that the surface topography of VC-RGO is relatively more smooth；It is more stable that TG curve then demonstrates VC-RGO；Its XRD's
Characteristic peak ratio NH-RGO also becomes apparent from, defect is less.Raman spectrum analysis prove obtain VC-RGO the peak G it is narrower, the peak D compared with
Weak, ID/IG intensity ratio is smaller, and structural behaviour is more excellent.The graphene quality that this method obtains is higher, is substitution hydrazine hydrate production stone
The ideal method of black alkene.
Graphene oxide preparation method operating safety factor of the present invention is high, reactant nonhazardous effect；To graphite after oxidation
Layer structural damage is smaller and easy to operate, can shorten the time for preparing graphene oxide and improve its yield；Entire reaction
Addition stabilizer is not needed；It is advantageously implemented the precise controlling of graphene preparation, graphene-structured obtained is more complete, and performance is more
It is excellent.
The limitation that technical solution of the present invention is not limited to the above specific embodiments, it is all to do according to the technique and scheme of the present invention
Technology deformation out, falls within the scope of protection of the present invention.
Claims (8)
1. improving redox graphene preparation method, which comprises the steps of:
S1: it prepares graphene oxide: S11: taking graphite powder and sodium nitrate in reactor, the concentrated sulfuric acid is added and reactor is placed in ice
Water bath device is stirred to abundant reaction；
S12: 10-20 DEG C is adjusted the temperature to, reactor is added with stirring potassium permanganate reaction；
S13: the temperature was then adjusted to 30-40 DEG C, distilled water dilution is sufficiently added in isothermal reaction afterwards；
S14: diluting and after reacting, and adds potassium permanganate and is reacted, the temperature was then adjusted to 95-98 DEG C of progress constant temperature after reaction
Reaction；
S15: hydrogen peroxide is added after being cooled to room temperature and is reacted；
S16: until centrifugate PH is in neutrality, taking-up sediment, drying obtains graphene oxide for centrifugation.
S2: redox graphene prepares graphene:
S21: taking graphene oxide to be stirred with distilled water, ultrasonic treatment；
S22: Vitamin C powder, ultrasonic treatment is added；
S23: above-mentioned solution is placed in closing water-bath, carries out isothermal reaction；
S24: using dehydrated alcohol eccentric cleaning, then after being repeatedly centrifuged with distilled water taking precipitate it is dry graphene.
2. according to claim 1 improve redox graphene preparation method, which is characterized in that the graphite, the concentrated sulfuric acid,
The ratio of potassium permanganate, sodium nitrate usage amount are as follows: 1:35:5:0.5.
3. improving redox graphene preparation method according to claim 1, which is characterized in that the ice water bath apparatus is
It is placed with the electric-heated thermostatic water bath of a large amount of ice cubes.
4. improving redox graphene preparation method according to claim 1, which is characterized in that the reactor is magnetic force
Blender.
5. improving redox graphene preparation method according to claim 1, which is characterized in that the concentration of the concentrated sulfuric acid
It is 98%.
6. improving redox graphene preparation method according to claim 1, which is characterized in that the S2 step is added high
The detailed process of potassium manganate are as follows: potassium permanganate is divided into 3 parts of interval stirrings and is added, interval time 15min.
7. improving redox graphene preparation method according to claim 1, which is characterized in that the hydrogen peroxide concentration is
30%.
8. improving redox graphene preparation method according to claim 1, which is characterized in that water in the S23 step
Bath temperature is 80 degrees Celsius.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624546A (en) * | 2019-10-22 | 2019-12-31 | 特烯（厦门）科技有限公司 | Preparation method of copper/graphene catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602504A (en) * | 2009-07-16 | 2009-12-16 | 上海交通大学 | Graphene preparation method based on xitix |
| CN107879329A (en) * | 2017-12-06 | 2018-04-06 | 成都理工大学 | Nitrogen-doped graphene and preparation method thereof |
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- 2018-12-10 CN CN201811504084.7A patent/CN109264704A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602504A (en) * | 2009-07-16 | 2009-12-16 | 上海交通大学 | Graphene preparation method based on xitix |
| CN107879329A (en) * | 2017-12-06 | 2018-04-06 | 成都理工大学 | Nitrogen-doped graphene and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110624546A (en) * | 2019-10-22 | 2019-12-31 | 特烯（厦门）科技有限公司 | Preparation method of copper/graphene catalyst |
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