CN108328612A - A kind of method of quaternary ammonium salt collaboration separation graphene oxide - Google Patents
A kind of method of quaternary ammonium salt collaboration separation graphene oxide Download PDFInfo
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- CN108328612A CN108328612A CN201810212183.1A CN201810212183A CN108328612A CN 108328612 A CN108328612 A CN 108328612A CN 201810212183 A CN201810212183 A CN 201810212183A CN 108328612 A CN108328612 A CN 108328612A
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Abstract
The present invention is a kind of method of quaternary ammonium salt collaboration separation graphene oxide, and technical problems to be solved are the quick separatings of graphene oxide, in favor of industrialization large-scale production.The method of the present invention：Freshly prepd graphene oxide mixed solution first is added in quaternary ammonium salt, it is then allowed to stand 1 hour, it is limpid to obtain upper layer, the heterogeneous system of lower layer's brown precipitate, then pass through any one of filtering, centrifugation, liquid separation operating method method, separating, washing precipitates, and removes metal impurities and other impurities, obtains the graphene oxide of higher degree.After reduction process, final products graphene surface is adsorbed without quaternary ammonium salt.Compared with prior art, the present invention by the flocculation of quaternary ammonium salt, the water-soluble of graphene oxide reduces, and filtering and washing speed are greatly accelerated, and can operate continuously, the large-scale production of appropriate oxidation graphene and graphene.
Description
Technical field
The present invention relates to a kind of methods of graphene oxide separation, especially cooperate with separation graphene oxide with quaternary ammonium salt
Method.
Background technology
Graphene (Graphene, also known as mono-layer graphite or two-dimentional graphite), is the Two-dimensional Carbon atomic crystal of monoatomic thickness.
Since single-layer graphene in 2004 is successfully obtained by the Geim groups of graceful Chester university of Britain, graphene is just with its uniqueness
Physicochemical properties and be concerned, its finder in 2010 also therefore obtain the Nobel Prize.Graphene has high ratio table
A series of excellent properties such as area, heat conductivility outstanding and mechanical property and its outstanding electron transmission performance, make its
There are great application prospect and the market demand in the fields such as the energy, material, medicine.In recent years, about the extensive system of graphene
Standby work has become the hot spot in new material research field.
Hummers methods are to prepare the most common chemical method of graphene at this stage, and typical preparation process is in Strong oxdiative
Under the oxidation of agent, graphite is by oxidation stripping at graphene oxide；Filtration washing falls foreign ion (such as Mn4+、SO4 2-、Na+、
NO3-Deng), isolated graphene oxide；Then reducing agent is added to restore oxygen-containing functional group, finally obtains graphene.
Because the method raw material is extensive, the reaction time is short, obtained graphene stable quality, so Hummers methods and its changing in recent years
It is increasingly subject to favor into method.
However, during Hummers methods prepare graphene, intermediate product-graphene oxide is due to carrying a large amount of carboxylics
The hydrophilic radicals such as base and hydroxyl cause the Zeta potential of graphene oxide to be in aqueous solution up to -40mV, are formed sufficiently stable
Dispersion.According to traditional filtration washing method, even with the oil pump filtering and washing of condition of high vacuum degree, graphene oxide
It also is difficult to quickly separate from the water phase containing impurity, leads to low production efficiency.It, will if reducing filtering and washing number
There is the problem of graphene oxide residual impurity, especially metal ions M n4+、Na+Etc. will necessarily be to final graphene product
It can make a big impact.Centrifugation is another separation method, but only rotating speed is more than 10000 revs/min of high speed centrifugation
Captain's temporal separation could precipitate graphene oxide, not only cumbersome in this way, also improve cost, be unfavorable for advising greatly
Mould produces.Since foreign ion molecular weight is all smaller, and the molecular weight of graphene oxide is more than 10,000, the two mass difference
Great disparity, so the method that can use dialysis removes foreign ion, but bag filter is expensive, and the time of dialysis procedure also tends to
Up to one week, current this method was only applicable to the micro production of use for laboratory graphene.It can be seen that the height of graphene oxide
Effect separation is the committed step for preparing graphene, it has also become solves the key problem of graphene large-scale production.
Invention content
It is an object of the invention to develop a kind of graphene oxide separating technology efficiently, inexpensive.System of the present invention is first
Using quaternary ammonium salt as " flocculant ", the principle of hydrophobic ion pair is formed with carboxyl in graphene oxide using it, for aoxidizing stone
The purification that efficiently separates of black alkene and water phase is studied, to develop a kind of efficient, quick and inexpensive graphene oxide separation
Technique.
The invention has the advantages that：
1, hydrophobic ion pair, the Zeta potential of surface of graphene oxide are formed by carboxyl in quaternary ammonium salt and graphene oxide
Zero is can reach, to make graphene oxide rapid precipitation, larger precipitation particle is formed, is easy to centrifuge or be separated by filtration.
2, the cationic competitive Adsorption such as quaternary ammonium salt and manganese ion is effectively reduced in surface of graphene oxide in graphene oxide
The residual volume of manganese ion.
3, above-mentioned gained graphene oxide can obtain the reduced graphene of high-purity by conventional reduction technique.
The present invention forms hydrophobic ion pair by the way that quaternary ammonium salt to be used as to " flocculant ", using itself and carboxyl in graphene oxide
Principle, efficiently separate research for graphene oxide and water phase, develop a kind of efficient, quick and inexpensive oxidation stone
Black alkene separating technology.Metal impurities ion is low in the graphene oxide being prepared, purity is high, using conventional reduction technique, such as
Hydrazine hydrate reduction etc. can eliminate the oxygen-containing functional group of surface of graphene oxide, prepare high-quality graphene on a large scale.
Description of the drawings
Fig. 1 is UV-Vis figures prepared by the embodiment of the present invention 1.
Fig. 2 is FT-IR figures prepared by the embodiment of the present invention 1.
Fig. 3 is XRD diagram prepared by the embodiment of the present invention 1.
Fig. 4 is TEM figures prepared by the embodiment of the present invention 1.
Specific implementation mode
The graphene oxide process for separation and purification of the present invention, includes the following steps：
One, the preparation of graphene oxide mixed solution
The preparation of graphene oxide uses document (Hummers S；Offeman R.Preparation of graphitic
Oxide.J.Am.Chem.Soc., 1958,80：Hummers methods 1339-1339) obtain graphite oxide and carry potassium permanganate
The mixed solution of equal impurity.This process can make graphite layers distance be expanded to 0.78nm from 0.34nm, but also make graphite oxide
The a large amount of carboxyls of alkene Surface Creation, hydroxyl and epoxy group etc..Graphene oxide is resulted in disperse in aqueous solution so very steady
It is fixed, it is unfavorable for filtering and centrifuges.In addition, beavy metal impurity Mn2+Deng due to electrostatic attraction, easily adsorb on the surface of graphene,
The electrical and optical properties of follow-up graphene product are impacted.
Two, the precipitation of graphene oxide and purification
Graphene mixed solution obtained above is diluted, under stiring, is slowly added to surfactant, quaternary ammonium salt dosage
About 0.5-5 times of graphene quality.Then, it was stood by 0.5-5 hours, partly becomes limpid on solution, lower layer is precipitation
Layer.By any one of filtering, centrifugation, liquid separation operating method method, separating, washing precipitation removes metal impurities and other
Impurity.
Three, the reduction of graphene oxide
Graphene oxide obtained above is diluted to the water concentration of 1-1000mg/L, is added in the solution containing reducing agent,
Heating stirring for a period of time after, graphene oxide is gradually reduced into graphene, finally centrifugation, liquid separation or filtering, using dry
Dry processing obtains reduced graphene powder, the presence without quaternary ammonium salt substantially of final products graphene surface.
Embodiment 1
Impure graphite oxide mixed solution is prepared using the method for Hummers, according to graphite oxide in solution
Quality, be added twice of mass cetyl trimethylammonium bromide, stir 0.5 hour, be then allowed to stand 1 hour, centrifugation,
It is washed three times, then is washed with distilled water three times with dilute hydrochloric acid, freeze-drying finally obtains the graphene oxide powder of brown.
Above-mentioned gained graphene oxide is made into the solution of 2mg/L again, the hydrazine hydrate and ammonia spirit of quality such as is added,
After 2 hours, then filtration washing is freeze-dried 90 degree of water-baths, obtain the graphene powder of black.
Embodiment 2
Impure graphite oxide mixed solution is prepared using the method for Hummers, according to graphite oxide in solution
Quality, be added one times of quality cationic polyacrylamide, stir 1 hour, be then allowed to stand 2 hours, filtering precipitation, with dilute salt
Acid elution three times, then is washed with distilled water three times, and freeze-drying finally obtains the graphene oxide powder of brown.
Above-mentioned gained graphene oxide is made into the solution of 10mg/L, the sodium borohydride of the quality such as addition, 100 degree of water again
After bath reaction 1 hour, then filtration washing is freeze-dried, obtain the graphene powder of black.
Embodiment 3
Impure graphite oxide mixed solution is prepared using the method for Hummers, according to graphite oxide in solution
Quality, be added three times quality dodecyl trimethyl ammonium bromide, stir 1 hour, stand 3 hours after, it is molten that liquid separation obtains lower layer
Liquid is washed three times with dilute hydrochloric acid, then is washed with distilled water three times, and freeze-drying finally obtains the graphene oxide powder of brown.
Above-mentioned gained graphene oxide is made into the solution of 20mg/L again, the hydrazine hydrate and ammonium hydroxide of the quality such as addition are molten
Liquid, after 4 hours, then filtration washing is freeze-dried 90 degree of water-baths, obtain the graphene powder of black.
Embodiment 4
Impure graphite oxide mixed solution is prepared using the method for Hummers, according to graphite oxide in solution
Quality, be added two times of quality 4 bromide, stir 0.5 hour, stand 2 hours after, centrifugation is washed with dilute hydrochloric acid
It washs precipitation three times, then is washed with distilled water three times, freeze-drying finally obtains the graphene oxide powder of brown.
Above-mentioned gained graphene oxide is made into the solution of 5mg/L again, the hydrazine hydrate and ammonia spirit of quality such as is added,
After 3 hours, then filtration washing is freeze-dried 100 degree of water-baths, obtain the graphene powder of black.
Embodiment 5
Impure graphite oxide mixed solution is prepared using the method for Hummers, according to graphite oxide in solution
Quality, be added two times of quality tetrabutylammonium bromide, stir 0.5 hour, stand 5 hours after, centrifugation is washed with dilute hydrochloric acid
It washs precipitation three times, then is washed with distilled water three times, freeze-drying finally obtains the graphene oxide powder of brown.
Above-mentioned gained graphene oxide is made into the solution of 30mg/L again, the hydrazine hydrate and ammonium hydroxide of the quality such as addition are molten
Liquid, after 4 hours, then filtration washing is freeze-dried 100 degree of water-baths, obtain the graphene powder of black.
Claims (5)
1. a kind of graphene oxide process for separation and purification, includes the following steps：In whipping process, quaternary ammonium salt is added freshly prepared
Graphene oxide mixed solution, be then allowed to stand 0.5-5 hours, obtain that upper layer is limpid, the heterogeneous system of lower layer's brown precipitate,
Then by any one of filtering, centrifugation, liquid separation operating method method, separating, washing precipitation, remove metal ion etc. its
His impurity, obtains the graphene oxide of higher degree；After reduction process, final products graphene surface is substantially without season
Ammonium salt adsorbs.
2. graphene oxide process for separation and purification according to claim 1, which is characterized in that the graphene oxide is by existing
There are chemical oxidization method or Hummers methods to be prepared.
3. graphene oxide process for separation and purification according to claim 1, it is characterized in that quaternary ammonium salt is ammonium chloride, bromination
The compound that ammonium and logical formula (I) and (II) are indicated,
Wherein：
R1、R2、R3And R4It is the alkyl containing 1~16 carbon atom,
Polymer is polymer segment,
X-For halide anion.
4. graphene oxide process for separation and purification according to claim 1, it is characterized in that being grasped by filtering, centrifugation, liquid separation
Make any one of method method, separating, washing precipitation removes metal impurities and other impurities, obtains the oxidation of higher degree
Graphene.
5. graphene oxide process for separation and purification according to claim 1, characterized in that obtained higher degree oxidation stone
Black alkene can pass through conventional reduction process, generate reduced graphene, and surface is adsorbed without quaternary ammonium salt.
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| CN109231194A (en) * | 2018-09-05 | 2019-01-18 | 七台河宝泰隆石墨烯新材料有限公司 | A kind of device of microporous silica membrane separation graphene oxide |
| CN109553093A (en) * | 2018-12-29 | 2019-04-02 | 厦门十维科技有限公司 | Electrochemistry swelling prepares the preparation method of graphene dispersing solution |
| CN110078063A (en) * | 2019-04-25 | 2019-08-02 | 广东博智林机器人有限公司 | The preparation method of redox graphene dispersion liquid and the device with graphite ene coatings |
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Application publication date: 20180727 |