CN106006609A - Method for preparing graphene with step-by-step purification method - Google Patents
Method for preparing graphene with step-by-step purification method Download PDFInfo
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- CN106006609A CN106006609A CN201610323376.5A CN201610323376A CN106006609A CN 106006609 A CN106006609 A CN 106006609A CN 201610323376 A CN201610323376 A CN 201610323376A CN 106006609 A CN106006609 A CN 106006609A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a method for preparing graphene with a step-by-step purification method to achieve the technical purposes that an intermediate product graphene oxide can be quickly separated and purified, and thus industrial large-scale production can be easier. Compared with the prior art, impurities can be completely removed with ammonium hydroxide and acid liquor in two steps; due to the fact that the solubility of products and the solubility of impurities in the process have a large difference all the time, the filtering and washing speed is greatly increased, continuous operation can be achieved, and the method is suitable for large-scale production of high-quality graphene.
Description
Technical field
The present invention relates to field of graphene, specifically process, in order to ammonia and acid solution, the graphite oxide that Hummers method obtains respectively
Alkene mixture, goes the removal of impurity by simple sucking filtration or low-speed centrifugal, and finally reduction prepares high-quality graphene.
Technical background
Graphene (Graphene, also known as mono-layer graphite or two dimension graphite), is the Two-dimensional Carbon atomic crystal of monoatomic thickness.From
Since single-layer graphene in 2004 is successfully obtained by the Geim group of graceful Chester university of Britain, Graphene is just unique with it
Physicochemical properties and receive much concern, have fabulous light transmission and heat conductivity, be the thinnest, the hardest known, resistivity
Minimum material, within 2010, the most therefore its finder obtains Nobel Prize.Graphene has high specific surface area, prominent leading
Hot property and the character of a series of excellences such as mechanical property and outstanding electron transmission performance thereof, at new forms of energy, new material, energy
The various fields such as source chemical industry, electronic information, Aero-Space and defence and military realize extensively application.In recent years, about Graphene
Extensive preparation work have become as the focus in new material research field.
At present, Hummers method is to prepare the chemical method that Graphene is the most frequently used present stage, and typical preparation process is at strong oxygen
Under the Oxidation of agent, graphite is oxidized peels off into graphene oxide；Filtration washing falls foreign ion (such as Mn4+、SO4 2-、
Na+、NO3-Deng), isolated graphene oxide；It is subsequently adding reducing agent oxygen-containing functional group is reduced, finally gives
Graphene.Because the method raw material is extensive, the response time is short, the Graphene steady quality obtained, so Hummer in recent years
S method and improved method thereof are increasingly subject to favor.The patent of such as Publication No. CN200910187298 is namely based on the H of modification
Ummers method, to stripping ultrasonic after graphite oxidation, i.e. obtains high-quality graphene after reduction.
But, during Hummers method prepares Graphene, intermediate product-graphene oxide is due to a large amount of carboxyls
With the hydrophilic radical such as hydroxyl, cause graphene oxide Zeta potential to be in aqueous up to-40mV, formed sufficiently stable
Dispersion.Impurity Mn in solution simultaneously4+、SO4 2-、Na+、NO3-Deng being also the ion that water solublity is the best.Therefore need
Water miscible graphene oxide and water-solubility impurity separated, to be the most difficult thing.Traditional filter method, it is necessary to
Using the oil pump filtering and washing of condition of high vacuum degree, separating rate is slow, causes production efficiency low.Centrifugation is another kind of separation side
Method, but only the rotating speed Ultracentrifuge more than 10000 revs/min separate for a long time could by graphene oxide precipitate under
Come, the most not only complex operation, also improve cost, be unfavorable for large-scale production.Additionally, use the method for dialysis to go
Removal of impurity ion, but bag filter is expensive, and the time of dialysis procedure also tends to up to one week, and current this method is only suitable for
Trace in use for laboratory Graphene produces.As can be seen here, the high efficiency separation of graphene oxide is to prepare the key step of Graphene
Suddenly, it has also become the key problem of restriction Graphene large-scale production.
Summary of the invention
It is an object of the invention to develop a kind of efficient, graphene preparation method of low cost, solve prior art exists
Cost height, the problem such as low, the purification difficult of efficiency.
The technical scheme is that
A kind of efficiently, quickly and the method preparing Graphene of low cost, process Hummers method respectively with ammonia and acid solution and obtain
The graphene oxide mixture arrived, after going the removal of impurity by simple sucking filtration or low-speed centrifugal, prepares height through reduction step
Quality Graphene.Concrete scheme is as follows: first pass through the graphene oxide mixture that traditional Hummers method obtains.Then
Add ammonia, regulation system pH to more than 7, fully react 0.5～10 hour under conditions of 0～100 DEG C, now solution
In main there are two kinds of reactions: under the conditions of (1) Low acid, Mn4+Mn (OH) can be generated4Precipitation；(2) graphene oxide exists
Under the reduction of ammonia, water-insoluble partial reduction Graphene precipitation can be generated.By the two of previous step kinds of precipitation simple filtration
Or low-speed centrifugal (less than 5000 revs/min) washing, remove water soluble ion.Next adds acid solution, and regulation system pH is extremely
Less than 7, make Mn (OH)4Precipitation regenerates water miscible Mn4+, filter and remove Mn4+Pure partial reduction stone can be obtained
Ink alkene.Partial reduction Graphene, through reduction and drying steps, i.e. can get high-quality graphene powder.
In the present invention, regulation the used ammonia spirit of alkalescence.
The acid solution used, one or more the mixing aqueous acids including hydrochloric acid, sulphuric acid or nitric acid etc..
Advantages of the present invention:
Compared with conventional purge process, the present invention is directed to graphene oxide and separate the deficiency that difficulty is time-consuming with purification, it is proposed that
The substep purification schemes of high efficiency separation, utilizes condition of different pH to remove different impurities ion, then carries out reduction step, only need
Low-speed centrifugal or simple filtration, it is expected to for fast purifying and the efficient preparation research of Graphene of graphene oxide,
Significantly reduce production cycle and the cost of Graphene.This be only Graphene accomplish scale production offer innovative technology prop up
Support, is also that the Graphene scale application in fields such as the energy, material, medical science creates advantage.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the embodiment of the present invention 1 gained Graphene.
Fig. 2 is the atomic force microscope figure of the embodiment of the present invention 1 gained Graphene.
Fig. 3 is the transmission electron microscope figure of the embodiment of the present invention 1 gained Graphene.
Detailed description of the invention
The graphene preparation method of the present invention, comprises the following steps:
One, the preparation of graphene oxide mixture
The preparation of graphene oxide uses document (Hummers S；Offeman R.Preparation of graphitic
Oxide.J.Am.Chem.Soc., Hummers method 1958,80:1339-1339) obtains with Mn4+、SO4 2-、
Na+、NO3-Graphene oxide mixed solution Deng impurity.This process can make graphite layers distance expand to from 0.34nm
0.78nm, but also make surface of graphene oxide generate a large amount of carboxyls, hydroxyl and epoxy radicals etc..Thus cause aoxidizing stone
Ink alkene disperses sufficiently stable in aqueous, is unfavorable for filtering and centrifugal.
Two, ammonia treatment
Being diluted by Graphene mixed solution obtained above, under agitation, the pH being slowly added to ammonia regulation mixture is more than 7,
The consumption of ammonia is about 0.5～5 times of Graphene quality, abundant reaction 0.5～10 hour under conditions of 0～100 DEG C, then,
Standing through 0.5～5 hour, solution upper part becomes limpid, and lower floor is the beds of precipitation.By filtering, being centrifuged, separatory operates
Any one of method method, separating, washing precipitates, and removes water-solubility impurity ion.
Three, acid solution processes
Precipitation obtained above is placed in water ultrasonic, makes the suspension that solid content is 0.01～500%, add acid solution, ammonia
The consumption of water is about 0.5～5 times of Graphene quality, regulation system pH to less than 7, heated and stirred 0.5～after 5 hours, makes
Mn(OH)4Precipitation regenerates water miscible Mn4+, remove Mn by centrifugal, separatory or filter method4+, can obtain pure
Partial reduction Graphene.
Four, the reduction of Graphene
The partial reduction Graphene that upper step is obtained, ultrasonic disperse is in water again, adds reducing agent and reduces further and be dried,
I.e. can get high-quality graphene powder.
Embodiment 1:
The method utilizing Hummers prepares impure graphite oxide mixed solution, according to the matter of graphite oxide in solution
Amount, adds the ammonia spirit of one times of quality, and regulation pH is 10, stirs 0.5 hour in the temperature of 100 DEG C, the most quiet
Put 1 hour, 3000 revs/min of centrifugations, wash three times with dilute hydrochloric acid, then with distilled water wash three times, oven drying,
Finally obtain graphene oxide and the Mn (OH) of black4Mixed precipitation.
By ultrasonic for mixed precipitation be again dispersed in water be configured to 1% suspension, the hydrochloric acid of the quality such as addition, be heated to
100 DEG C are reacted 2 hours, make manganese ion dissolution, filtration washing obtain pure partial reduction Graphene.
Above-mentioned gained partial reduction Graphene is dispersed in water again, the hydrazine hydrate of the quality such as addition, 90 DEG C of water-baths 2
After hour, filtration washing, then lyophilization, obtain the graphene powder of black.
Embodiment 2
The method utilizing Hummers prepares impure graphite oxide mixed solution, according to the matter of graphite oxide in solution
Amount, adds the ammonia of twice quality, and regulation pH is 13, stirs 1 hour, then stands 2 hours, filter precipitation, uses
Dilute hydrochloric acid washs three times, then with distilled water wash three times, lyophilization, finally obtains graphene oxide and the Mn (OH) of black4
Mixed precipitation.
By ultrasonic for mixed precipitation be again dispersed in water be configured to 5% suspension, add two times of quality sulphuric acid, be heated to
100 DEG C are reacted 2 hours, make manganese ion dissolution, filtration washing obtain pure partial reduction Graphene.
Above-mentioned gained partial reduction Graphene is dispersed in water again, the hydrazine hydrate of the quality such as addition, 90 DEG C of water-baths 2
After hour, filtration washing, then lyophilization, obtain the graphene powder of black.
Embodiment 3
The method utilizing Hummers prepares impure graphite oxide mixed solution, according to the matter of graphite oxide in solution
Amount, adds the ammonia of three times of quality, stirs 1 hour, and after standing 3 hours, separatory obtains lower floor's solution, washs with dilute hydrochloric acid
Three times, then with distilled water wash three times, lyophilization, finally obtain graphene oxide and the Mn (OH) of black4Mixed precipitation.
By ultrasonic for mixed precipitation be again dispersed in water be configured to 1% suspension, add three times of quality nitric acid, be heated to
100 DEG C are reacted 2 hours, make manganese ion dissolution, filtration washing obtain pure partial reduction Graphene.
Above-mentioned gained partial reduction Graphene is dispersed in water again, the hydrazine hydrate of the quality such as addition, 90 DEG C of water-baths 2
After hour, filtration washing, then lyophilization, obtain the graphene powder of black.
Embodiment 4
The method utilizing Hummers prepares impure graphite oxide mixed solution, according to the matter of graphite oxide in solution
Amount, adds the ammonia of five times of quality, stirs 0.5 hour, after standing 0.5 hour, coarse vacuum sucking filtration, washs two with dilute hydrochloric acid
Secondary, then by distilled water wash twice, 110 degree of oven for drying, finally obtain graphene oxide and the manganous hydroxide mixing of black
Precipitation.
By ultrasonic for mixed precipitation be again dispersed in water be configured to 1% suspension, add one times of quality nitric acid, be heated to
100 DEG C are reacted 15 minutes, make manganese ion dissolution, filtration washing obtain pure partial reduction Graphene.
Above-mentioned gained partial reduction Graphene is dispersed in water again, the hydrazine hydrate of the quality such as addition, 90 DEG C of water-baths 5
After hour, filtration washing, then lyophilization, obtain the graphene powder of black.
Claims (5)
1. the method that a substep method of purification prepares Graphene, it is characterised in that: comprise the following steps:
Ammonia is added in the graphene oxide mixture solution with a large amount of impurity prepared by Hummers method,
Regulation system pH, to more than 7, is fully reacted 0.5～10 hour under conditions of 0～100 DEG C, is then led to
Filter, any one of centrifugal, separatory operational approach method, separating, washing precipitates, and removes and dissolves
The foreign ion of property, obtains the mixed precipitation of partial reduction Graphene and manganous hydroxide；Again to mixed precipitation
Middle addition acid solution, regulation system pH to less than 7, make Mn (OH)4Precipitation regenerates water miscible
Mn4+, filter and remove Mn4+Pure partial reduction Graphene can be obtained；Partial reduction Graphene is through entering
One step reduction and drying steps, i.e. can get high-quality graphene powder.
The method that substep method of purification the most according to claim 1 prepares Graphene, it is characterised in that:
Described graphene oxide mixture is prepared by existing chemical oxidization method or Hummers method.
The method that substep method of purification the most according to claim 1 prepares Graphene, is characterized in that making
Processing graphene oxide mixture in two steps by ammonia and acid solution, wherein acid solution is hydrochloric acid, nitric acid or sulphuric acid
In one or more.
The method that substep method of purification the most according to claim 1 prepares Graphene, is characterized in that leading to
Filter, any one of centrifugal, separatory operational approach method, separating, washing precipitates, and removes metal
Impurity and other impurity, obtain the graphene oxide of higher degree.
The method that substep method of purification the most according to claim 1 prepares Graphene, is characterized in that
The high-purity partial reduction Graphene arrived can generate high-quality graphite through further conventional reduction process
Alkene product.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106587042A (en) * | 2016-12-19 | 2017-04-26 | 上海交通大学 | Rapid purifying method for crude graphene oxide liquid |
| CN108328612A (en) * | 2018-03-15 | 2018-07-27 | 成都科中云方科技有限公司 | A kind of method of quaternary ammonium salt collaboration separation graphene oxide |
| CN110559873A (en) * | 2019-09-23 | 2019-12-13 | 景德镇陶瓷大学 | Preparation method of graphene oxide separation membrane with adsorption function and product prepared by preparation method |
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| CN108328612A (en) * | 2018-03-15 | 2018-07-27 | 成都科中云方科技有限公司 | A kind of method of quaternary ammonium salt collaboration separation graphene oxide |
| CN110559873A (en) * | 2019-09-23 | 2019-12-13 | 景德镇陶瓷大学 | Preparation method of graphene oxide separation membrane with adsorption function and product prepared by preparation method |
| CN110559873B (en) * | 2019-09-23 | 2021-08-13 | 景德镇陶瓷大学 | Preparation method of graphene oxide separation membrane with adsorption function and product prepared by preparation method |
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