CN102992309A - Method for quickly preparing high-quality graphene oxide solids in large scale - Google Patents
Method for quickly preparing high-quality graphene oxide solids in large scale Download PDFInfo
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- CN102992309A CN102992309A CN2012104860296A CN201210486029A CN102992309A CN 102992309 A CN102992309 A CN 102992309A CN 2012104860296 A CN2012104860296 A CN 2012104860296A CN 201210486029 A CN201210486029 A CN 201210486029A CN 102992309 A CN102992309 A CN 102992309A
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Abstract
The invention belongs to the technical field of nano new functional materials, and in particular relates to a method for quickly preparing high-quality graphene oxide solids on large scale. The method comprises the following steps: oxidizing natural graphene by adopting an oxidizing agent to obtain graphene oxide; preparing the graphene oxide into a graphene oxide aqueous solution with low concentration; carrying out ultrasonic treatment and centrifugal filtration to remove the graphene oxide which cannot be stripped completely, so that the graphene oxide aqueous solution is obtained. A separating agent is added into the graphene oxide aqueous solution to generate flocculent precipitate, after standing and filtering, a mixed solvent of tert-butyl alcohol and water is adopted to flush, and freeze drying is carried out after vacuum filtration, so that the graphene oxide solids are greatly prepared. The method is simple, low in equipment requirements, wide in raw material selective scope, low in prices, small in addition amount, good in effect, small in damage of the graphene oxide and high in product quality and large-scale industrial production is carried out.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nanomaterial, the method of the high-quality graphene oxide solid of a kind of efficient extensive preparation specifically, namely with the flocculation sediment of the quick accelerating oxidation Graphene of separating agent, mixing solutions with the trimethyl carbinol and water carries out lyophilize as solvent, thereby obtains high-quality graphene oxide solid.
Background technology
Graphene is the carbon nanomaterial of a new generation, is not only in the known materials the thinnest a kind ofly, also very firmly hard, and as simple substance, it is all faster than known conductor that it at room temperature transmits the speed of electronics.The physicist An Deliehaimu of Univ Manchester UK and Constantine Nuo Woxiaoluofu, successfully in experiment, from graphite, isolate Graphene, two people also serve as reasons because of " in the initiative experiment of two-dimentional grapheme material ", jointly obtain Nobel Prize in physics in 2010, caused the upsurge of global concern Graphene.Chemical reduction method is one of method for preparing Graphene, graphene oxide is as the presoma of preparation Graphene, at chemical synthesis of graphene and mixture field thereof very important meaning is arranged, and the parent that itself special chemical property has also obtained many researchers looks at.Extensive preparation graphene oxide solid runs into following factor restriction: separation difficulty, sample are reunited, output is little.The technique of scale operation graphene oxide solid mainly contains at present: the methods such as graphene oxide solution high speed centrifugation, semi-permeable membranes filtration, adding precipitation agent are separated the graphene oxide solution that obtains high density, and then dry in baking oven.The method of graphene oxide solution that obtains high density by high speed centrifugation is simple, but because the very easily water-soluble very difficult centrifugation of graphene oxide, so poor effect, productive rate is excessively low simultaneously.It is long that semi-permeable membranes filters then the production cycle.The method that adds flocculating settling agent can be separated the graphene oxide solution that obtains a large amount of high densitys, but different flocculation agent effects differs, and can introduce other impurity in sample.Simultaneously, high oxygen concentration functionalized graphene solution adopts the conventional drying mode at present, causes easily the reunion of sample.
Retrieval through existing document is found, the effective ways of an An Effective Method for Bulk Obtaining Graphene Oxide Solids(extensive preparation graphene oxide solid), Chinese Journal of Chemistry, (Chemistry In China (English edition)) 2010,28 (10): 1935-1940. once utilized sodium hydroxide as flocculating settling agent separation of oxygenated graphene solution, obtain the graphene oxide solution of high density, but graphene oxide can be reduced in this process, destroyed sample, introduce simultaneously the impurity such as a large amount of alkaline matters, can't reach the purpose of the high-quality graphene oxide solid of preparation.
Summary of the invention
The object of the invention is according to the deficiencies in the prior art, provide a kind of rapid large-scale to produce the method for high quality graphene oxide solid, by adding separating agent, impel graphene oxide that flocculation sediment occurs in the aqueous solution fast, utilize the mixing solutions of the trimethyl carbinol and water to carry out the repetitive scrubbing precipitation as solvent, carry out at last lyophilize, obtain high-quality graphene oxide solid.
The present invention is achieved by the following technical solutions, and the surface chemical modification that the present invention utilizes separating agent that graphene oxide is carried out has promoted fast the precipitation of graphene oxide in the aqueous solution and separated, and obtains the graphite oxide aqueous solution of high density.Repeatedly wash with the mixed solvent of the trimethyl carbinol and the water graphene oxide solution to high density, then can remove the adding separating agent, guaranteed the purity of sample, and as follow-up cryodesiccated liquid phase solvent.Utilize at last freeze-drying to obtain high quality, the graphene oxide solid that dispersibility can be high.
Below the inventive method is further described, concrete steps are as follows:
(1) adopt oxygenant that natural flake graphite is carried out oxide treatment, obtain oxidation graphite solid, graphite oxide is configured to the graphite oxide aqueous solution, adopt supersound process, the graphite oxide of failing fully to peel off is removed in centrifuging, obtains the aqueous solution of graphene oxide;
(2) utilize separating agent that graphene oxide (GO) is carried out surface modification, the precipitation of accelerating oxidation Graphene in the aqueous solution with separate, obtain the graphene oxide solid; The concentration of control graphene oxide is 1mg/100ml ~ 200mg/100ml;
(3) wash with the mixed solvent of the trimethyl carbinol and the water graphene oxide solution to high density, remove the separating agent that adds, lyophilize is processed, and obtains the graphene oxide solid.
Among the present invention, employed graphene oxide is the graphene oxide sample of mechanically peel method, chemical oxidization method, crystal epitaxy method, chemical Vapor deposition process, organic synthesis method or the preparation of carbon nanotube stripping method method in the step (2).
Among the present invention, in the step (2) employed separating agent be in diallyl dimethyl ammoniumchloride, Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride or the calcium chloride any.Separating agent addition in solution is: 5mg/100ml ~ 30 mg/100ml.
Among the present invention, adopting the volume ratio of the trimethyl carbinol and water in the step (2) is 1:5-2:1.
The present invention adopts diallyl dimethyl ammoniumchloride (PDDA), Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride, a kind of separating agent as the graphite oxide aqueous solution in the calcium chloride etc., only need trace (0.01g) just can well be effective, substitution impurity seldom, and sample do not destroyed, thereby the problem that the extensive preparation of graphene oxide solid separates with aqueous phase solved.While diallyl dimethyl ammoniumchloride (PDDA), Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride, the calcium chloride source is wide, and cheap, need not complex apparatus.
The present invention adopts the mixed solvent of the trimethyl carbinol and water to have the double effects of washing composition and freezing dispersion solvent.The present invention adopts this mixed solvent as washing composition, thereby this is that separating agent can well dissolved flush away because graphene oxide dispersing property in this solvent of high density is bad, the washing that is conducive to sample with separate; The present invention adopts this mixed solvent as lyophilized preparation, although this is because the trimethyl carbinol is solid at normal temperatures, but when the mixed solvent of the trimethyl carbinol and water is in a liquid state at normal temperatures, and the trimethyl carbinol is as the rate of mass transfer in the freeze-dried quickening freezing dry process, save freeze-drying time, product is stable.
Present method adopts freeze-drying to replace common oven for drying, can avoid introducing impurity in the drying process, avoids the phenomenons such as the even and reunion of uneven drying, obtains fast the graphene oxide solid sample of high yield.
Description of drawings
The projection Electronic Speculum picture of the graphene oxide that obtains among Fig. 1 embodiment 1.
The projection Electronic Speculum picture of the graphene oxide that obtains among Fig. 2 embodiment 1.
Embodiment
The below elaborates to embodiments of the invention, and present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
With oxidation graphite solid, be configured to behind the graphite oxide aqueous solution of 1g/L ultrasonic 3 hours, ultrasonic frequency is 60kHz, centrifugal 4000rm/min obtains graphene oxide solution after removing precipitated solid.Then, the neutral GO solution 1g/L of 150ml, the iron nitrate of adding 0.01g stirred 1 minute with glass stick, left standstill behind the generation precipitation separation to take off layer precipitation in 3 hours.Mixed solvent with the trimethyl carbinol and water (2:1) washs the sample after precipitating, cumulative volume is controlled at about 200ml, then taking off layer precipitation after centrifugal 10 minutes with whizzer under 4000rm/min speed puts into freeze drier and carries out drying, sampling after 48 hours, adopt transmission electron microscope that the acquisition graphene oxide is characterized (Fig. 1, Fig. 2), can find that the graphene oxide integrity is better, the number of plies is about 1 ~ 3 layer.
Embodiment 2
With oxidation graphite solid, be configured to behind the graphite oxide aqueous solution of 1g/L ultrasonic 3 hours, ultrasonic frequency is 60kHz, centrifugal 4000rm/min obtains graphene oxide solution after removing precipitated solid.Then, the neutral GO solution 1g/L of 150ml, the calcium chloride of adding 0.01g stirred 1 minute with glass stick, left standstill behind the generation precipitation separation to take off layer precipitation in 3 hours.Mixed solvent with the trimethyl carbinol and water (2:1) washs the sample after precipitating, cumulative volume is controlled at about 200ml, then taking off layer precipitation after centrifugal 10 minutes with whizzer under 4000rm/min speed puts into freeze drier and carries out drying, sampling after 48 hours.Adopt transmission electron microscope that the acquisition graphene oxide is characterized, can find that the graphene oxide integrity is better, the number of plies is about 1 ~ 3 layer.
Embodiment 3
With oxidation graphite solid, be configured to behind the graphite oxide aqueous solution of 1g/L ultrasonic 3 hours, ultrasonic frequency is 60kHz, centrifugal 4000rm/min obtains graphene oxide solution after removing precipitated solid.Then, the neutral GO solution 1g/L of 150ml, the Tai-Ace S 150 of adding 0.01g stirred 1 minute with glass stick, left standstill behind the generation precipitation separation to take off layer precipitation in 3 hours.Mixed solvent with the trimethyl carbinol and water (1:1) washs the sample after precipitating, cumulative volume is controlled at about 200ml, then taking off layer precipitation after centrifugal 10 minutes with whizzer under 4000rm/min speed puts into freeze drier and carries out drying, sampling after 48 hours.Adopt transmission electron microscope that the acquisition graphene oxide is characterized, can find that the graphene oxide integrity is better, the number of plies is about 1 ~ 3 layer.
Embodiment 4
With oxidation graphite solid, be configured to behind the graphite oxide aqueous solution of 1g/L ultrasonic 3 hours, ultrasonic frequency is 60kHz, centrifugal 4000rm/min obtains graphene oxide solution after removing precipitated solid.Then, the neutral GO solution 1g/L of 150ml, the diallyl dimethyl ammoniumchloride (PDDA) of adding 0.01g stirred 1 minute with glass stick, left standstill behind the generation precipitation separation to take off layer precipitation in 3 hours.Mixed solvent with the trimethyl carbinol and water (3:1) washs the sample after precipitating, cumulative volume is controlled at about 200ml, then taking off layer precipitation after centrifugal 10 minutes with whizzer under 4000rm/min speed puts into freeze drier and carries out drying, sampling after 48 hours.Adopt transmission electron microscope that the acquisition graphene oxide is characterized, can find that the graphene oxide integrity is better, the number of plies is about 1 ~ 3 layer.
Claims (4)
1. a rapid large-scale prepares the method for graphene oxide solid, it is characterized in that concrete steps are as follows:
(1) adopt oxygenant that natural flake graphite is carried out oxide treatment, obtain oxidation graphite solid, graphite oxide is configured to the graphite oxide aqueous solution, adopt supersound process, the graphite oxide of failing fully to peel off is removed in centrifuging, obtains the aqueous solution of graphene oxide;
(2) utilize separating agent that graphene oxide is carried out surface modification, the precipitation of accelerating oxidation Graphene in the aqueous solution with separate, obtain the graphene oxide solid; The concentration of control graphene oxide is 1mg/100ml ~ 200mg/100ml;
(3) mixed solvent with the trimethyl carbinol and water washes the graphene oxide solid, removes the separating agent that adds, and lyophilize is processed, and obtains the graphene oxide solid.
2. method according to claim 1 is characterized in that employed graphene oxide is the graphene oxide sample of mechanically peel method, chemical oxidization method, crystal epitaxy method, chemical Vapor deposition process, organic synthesis method or the preparation of carbon nanotube stripping method method in the step (2).
3. method according to claim 1, it is characterized in that in the step (2) employed separating agent be in diallyl dimethyl ammoniumchloride, Tai-Ace S 150, aluminum chloride, ferric sulfate, iron(ic) chloride or the calcium chloride any, separating agent addition in solution is: 5mg/100ml ~ 30 mg/100ml.
4. method according to claim 1 is characterized in that adopting the volume ratio of the trimethyl carbinol and water in the step (2) is 1:5-2:1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303901A (en) * | 2013-06-05 | 2013-09-18 | 山西大同大学 | Method for growing carbon nano tubes on surface of graphene |
| CN103482613A (en) * | 2013-09-03 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | High-efficiency separation and purification method of graphite oxide |
| CN104003376A (en) * | 2014-05-21 | 2014-08-27 | 张家港市东大工业技术研究院 | Method for rapidly preparing high specific surface area graphene oxide |
| 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 |
| CN109224900A (en) * | 2018-10-09 | 2019-01-18 | 柳州蓓蒂芬科技有限公司 | Graphene oxide sucrose fatty ester enriched substance and preparation method |
| CN109317678A (en) * | 2018-11-20 | 2019-02-12 | 贵州大学 | A kind of synthetic method of ultravacuum in-situ hot pressing sintering graphite alkene enhancing stone titanium composite material |
| CN110831896A (en) * | 2017-05-05 | 2020-02-21 | 加利福尼亚大学董事会 | Purification and drying of graphene oxide |
| CN112744811A (en) * | 2021-02-07 | 2021-05-04 | 李永锋 | Large-sheet-diameter graphene oxide and preparation method thereof |
| CN113908807A (en) * | 2021-11-29 | 2022-01-11 | 北京师范大学 | Nitrogen-doped modified graphene electrode material for adsorbing electroreduction radionuclide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101591014A (en) * | 2009-06-30 | 2009-12-02 | 湖北大学 | A kind of method of realizing large-scale preparation of monolayer oxidized graphene |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303901A (en) * | 2013-06-05 | 2013-09-18 | 山西大同大学 | Method for growing carbon nano tubes on surface of graphene |
| CN103482613A (en) * | 2013-09-03 | 2014-01-01 | 中国科学院山西煤炭化学研究所 | High-efficiency separation and purification method of graphite oxide |
| CN104003376A (en) * | 2014-05-21 | 2014-08-27 | 张家港市东大工业技术研究院 | Method for rapidly preparing high specific surface area graphene oxide |
| CN110831896A (en) * | 2017-05-05 | 2020-02-21 | 加利福尼亚大学董事会 | Purification and drying of graphene oxide |
| US11787698B2 (en) | 2017-05-05 | 2023-10-17 | The Regents Of The University Of California | Purification and drying of graphene oxide |
| 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 |
| CN109224900A (en) * | 2018-10-09 | 2019-01-18 | 柳州蓓蒂芬科技有限公司 | Graphene oxide sucrose fatty ester enriched substance and preparation method |
| CN109224900B (en) * | 2018-10-09 | 2021-05-11 | 柳州蓓蒂芬科技有限公司 | Graphene oxide sucrose fatty acid ester enrichment and preparation method thereof |
| CN109317678A (en) * | 2018-11-20 | 2019-02-12 | 贵州大学 | A kind of synthetic method of ultravacuum in-situ hot pressing sintering graphite alkene enhancing stone titanium composite material |
| CN112744811A (en) * | 2021-02-07 | 2021-05-04 | 李永锋 | Large-sheet-diameter graphene oxide and preparation method thereof |
| CN112744811B (en) * | 2021-02-07 | 2023-01-17 | 常州精瑞斯新材料科技有限公司 | Large-sheet-diameter graphene oxide and preparation method thereof |
| CN113908807A (en) * | 2021-11-29 | 2022-01-11 | 北京师范大学 | Nitrogen-doped modified graphene electrode material for adsorbing electroreduction radionuclide |
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Application publication date: 20130327 |