CN102701199A - Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method - Google Patents
Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method Download PDFInfo
- Publication number
- CN102701199A CN102701199A CN2012102429101A CN201210242910A CN102701199A CN 102701199 A CN102701199 A CN 102701199A CN 2012102429101 A CN2012102429101 A CN 2012102429101A CN 201210242910 A CN201210242910 A CN 201210242910A CN 102701199 A CN102701199 A CN 102701199A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- preparing
- oxide precursor
- ultrapure water
- grapheme
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a method for preparing graphene oxide by dispersed emulsion assisted with a Hummers method. The method comprises the following steps of: firstly preparing graphene oxide precursor suspending liquid by adopting the Hummers method, repeatedly washing the graphene oxide precursor suspending liquid with ultrapure water and centrifuging at a low speed to obtain neutral graphene oxide precursor, finally dispersing the neutral graphene oxide precursor into the ultrapure water, and dispersing the neutral graphene oxide precursor by a laboratory dispersed emulsifying machine at a high speed so as to improve the interlamellar spacing of grapheme, thus finally obtaining monolayer graphene oxide by low-speed centrifugation. The process is simple, fast, safe and environment-friendly and is conducive to large-scale industrial production, and the number of layers of the graphene oxide can be effectively reduced. The prepared graphene oxide can be used as a drug carrier and mechanics enhancement phase of a composite material and can be used for preparing high drug carrying or high mechanical property miniature oxidation graphite-base composite materials. A reduction product of the grapheme can be widely used for preparing grapheme-base complex materials of energy storage materials, chemical/ biologic sensors, conductive materials, and the like.
Description
Technical field
The present invention relates to quick, simple and direct, the cheap method for preparing graphene oxide of the auxiliary Hummers method of dispersion and emulsion.
Background technology
Graphene is a kind of novel material of the laminate structure that is made up of carbon atom, wherein between the carbon atom with sp
2Hybridized orbital is connected to form the two-dimensional material that is hexangle type honeycomb lattice.Before 2004, Graphene is considered to always can't exist singly, through experiment it has been become the fact until the An Deliehaimu and the Constantine Nuo Woxiaoluofu of Univ Manchester UK
[1](KS Novoselov, AK Geim, SV Morozov, et al. Electric field effect in atomically thin carbon films [J] .Science, 2004 (306): 666-669.).Because Graphene has many excellent photoelectric, machinery and chemical property, come out from Graphene, just caused global research boom.At present, preparation method of graphene mainly contains mechanical means and two kinds of methods of chemical process.Wherein mechanical means comprises that mainly micromechanics peels off method, carbon nanotube patterning method, directly ultrasonic method, epitaxy method and heating SiC method etc.; Chemical process then mainly includes machine synthesis method, chemical reduction method and chemical Vapor deposition process etc.
[2](Wan Wubo, Zhao Zongbin, Hu Han etc. the green reduction preparation of Trisodium Citrate Graphene [J]. novel charcoal material, 2011,26 (1): 16-20).Wherein chemical reduction method mainly is meant to be graphite oxide with graphite oxidation at first, again graphite oxide is prepared into graphene oxide through certain means, through chemical reduction graphene oxide is prepared into Graphene at last.Chemical reduction method is with simple, with low cost industrial preparation Graphene one of the most attractive approach that becomes of its technology
[3](D Li, MB Muller, et al. Processable aqueous dispersions of graphene nanosheets [J]. Nature Nanotechnology, 2008 (3): 101-105.).In numerous methods that prepare graphite oxide, the technical process of Hummers method is simple, green, safety, thereby becomes present one of the most frequently used method of graphite oxide for preparing
[4](WS Hummers, RE Offeman. Preparation of graphitic oxide [J]. Journal of the American Chemical Society, 1958 (80): 1339.).The treatment process for preparing graphene oxide from graphite oxide then mainly is the ultrasonic method of peeling off
[5](Zhao Qian, Qiu Dongfang, WANG XIAOYAN etc. the form of chitosan/oxidized graphene nano matrix material and mechanical property research [J]. chemical journal, 2011,69 (10): 1260-1263).Yet supersound process method operating equipment is complicated, and noise pollution is big, unsuitable industrial applications.
Summary of the invention
The objective of the invention is to the ultrasonic shortcoming of peeling off method, provide a kind of operating equipment simple, quick, green, the safe method for preparing graphene oxide.
Concrete steps are:
Under (1) 0 ℃ 2 ~ 5 g Graphite Powder 99s and 1 ~ 3 g SODIUMNITRATE slowly being joined 60 mL mass percent concentrations is in 98% the sulfuric acid, continues mechanical stirring, add fully after, slowly add 8 ~ 15g potassium permanganate, kept the constant temperature sustained reaction 1 ~ 2 hour; Reaction is accomplished post-heating and is warming up to 35 ~ 55 ℃; Slowly add 150 ~ 200 ml ultrapure waters, continue to be warming up to 98 ℃, this moment, solution colour changed glassy yellow into by brown; Adding 500 mL ultrapure waters and 40 mL mass percent concentrations again is 30 % H
2O
2, remove unreacted potassium permanganate; Filter, using mass percent concentration is that 10 ~ 15% hydrochloric acid flush cake detects until the filtrating sulfate radical-free, and the ultrapure water flushing is neutral until filtrating then, makes the graphene oxide filter cake;
(2) the graphene oxide filter cake that step (1) is made is put in the 200mL ultrapure water, uses dispersion emulsifying machine with 3000 ~ 5000 rotating speeds/divisional processing 20 ~ 30 minutes, promptly gets graphene oxide colloidal sol; Place-20 ~ 0 ℃ of vacuum lyophilizations promptly to get graphene oxide the graphene oxide colloidal sol that obtains.
Technology of the present invention is simple, quick, safety, environmental protection, helps large-scale commercial prodn, and can more effectively reduce the number of plies of graphene oxide; Prepared graphene oxide can be used as the mechanics wild phase of pharmaceutical carrier, matrix material, can prepare the miniature graphite oxide based composites of high medicine carrying or strong mechanical performance; Its reduzate Graphene can be widely used in graphene-based matrix materials such as preparation energy storage material, chemical/biological sensors, electro-conductive material.
Description of drawings
Fig. 1 is a synthesis process flow diagram of the present invention.
Fig. 2 is the transmission electron microscope photo of the graphene oxide of embodiment of the invention preparation.
Fig. 3 be a raw material through the infrared absorpting light spectra of the Graphene of reduction preparation (line a: reduce the Graphene that forms by graphene oxide for the graphene oxide of embodiment of the invention preparation and with it; Line b: the graphene oxide of present embodiment preparation; The graphite oxide of line c:Hummers method preparation).
Embodiment
Embodiment:
1. adopt the Hummers legal system to be equipped with graphite oxide:
Measure the 60mL mass percent concentration and be 98% sulfuric acid and pour beaker into; Beaker places freezer compartment of refrigerator to be cooled to 0 ℃; Take by weighing 2.5 g Graphite Powder 99s and 1.3 g SODIUMNITRATE slowly add in this beaker, continue mechanical stirring, add fully after; Slowly add 8g potassium permanganate, kept 4 ℃ of sustained reactions of constant temperature 1 hour; Reaction is accomplished post-heating and is warming up to 35 ℃; Slowly add the 150ml ultrapure water after 30 minutes, continue to be warming up to 98 ℃, this moment, solution colour changed glassy yellow into by brown; Add 500 mL ultrapure waters and 40 mL mass percent concentrations are the H of 30 %
2O
2, remove unreacted potassium permanganate; Then with the 3000 rev/mins of centrifugal removal of impurities of product warp that obtain; At last the product that obtains is filtered; And the functional quality percentage concentration is that 10% hydrochloric acid flush cake detects until the filtrating sulfate radical-free, is neutral with the ultrapure water flushing until filtrating again, makes the graphene oxide filter cake;
2. adopt dispersion emulsifying machine to handle graphite oxide suspension preparation graphene oxide:
The graphene oxide filter cake that step (1) makes is put in the 200mL ultrapure water; Use dispersion emulsifying machine with 300 rotating speeds/divisional processing 20 minutes; This moment, the reactant in the beaker changed the disperse phase dissolved colloidal state of uniform component into by suspension liquid originally, promptly got graphene oxide colloidal sol; With 1.2 ten thousand rev/mins of centrifugal removal of impurities of the graphene oxide colloidal sol that obtains, place-20 ℃ of vacuum lyophilizations promptly to get the sheet graphene oxide at last.
Claims (1)
1. a dispersion and emulsion assists the Hummers legal system to be equipped with the method for graphene oxide, it is characterized in that concrete steps are:
Under (1) 0 ℃ 2 ~ 5 g Graphite Powder 99s and 1 ~ 3 g SODIUMNITRATE slowly being joined 60 mL mass percent concentrations is in 98% the sulfuric acid, continues mechanical stirring, add fully after, slowly add 8 ~ 15g potassium permanganate, kept the constant temperature sustained reaction 1 ~ 2 hour; Reaction is accomplished post-heating and is warming up to 35 ~ 55 ℃; Slowly add 150 ~ 200 ml ultrapure waters, continue to be warming up to 98 ℃, this moment, solution colour changed glassy yellow into by brown; Adding 500 mL ultrapure waters and 40 mL mass percent concentrations again is 30 % H
2O
2, remove unreacted potassium permanganate; Filter, using mass percent concentration is that 10 ~ 15% hydrochloric acid flush cake detects until the filtrating sulfate radical-free, and the ultrapure water flushing is neutral until filtrating then, makes the graphene oxide filter cake;
(2) the graphene oxide filter cake that step (1) is made is put in the 200mL ultrapure water, uses dispersion emulsifying machine with 3000 ~ 5000 rotating speeds/divisional processing 20 ~ 30 minutes, promptly gets graphene oxide colloidal sol; Place-20 ~ 0 ℃ of vacuum lyophilizations promptly to get graphene oxide the graphene oxide colloidal sol that obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102429101A CN102701199A (en) | 2012-07-15 | 2012-07-15 | Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102429101A CN102701199A (en) | 2012-07-15 | 2012-07-15 | Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102701199A true CN102701199A (en) | 2012-10-03 |
Family
ID=46894339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102429101A Pending CN102701199A (en) | 2012-07-15 | 2012-07-15 | Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102701199A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265019A (en) * | 2013-05-25 | 2013-08-28 | 桂林理工大学 | Preparation method for highly-nitrogen-doped graphene light-weight ferromagnetic material |
| CN103318874A (en) * | 2013-05-21 | 2013-09-25 | 宁夏大学 | Temperature-sensitive graphene oxide and temperature-sensitive element preparation method |
| CN103839698A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene composite electrode material and preparation method and application thereof |
| CN104609399A (en) * | 2014-12-29 | 2015-05-13 | 南京大学 | Graphene oxide, preparation method and application thereof |
| CN105271189A (en) * | 2015-09-23 | 2016-01-27 | 东莞市迈科科技有限公司 | Nitrogen doped graphene particle and preparation method thereof |
| CN105967179A (en) * | 2016-06-30 | 2016-09-28 | 常州第六元素材料科技股份有限公司 | Preparation method of easy-dispersible graphene powder and graphene powder prepared by method |
| CN106517175A (en) * | 2016-12-08 | 2017-03-22 | 中国化工集团曙光橡胶工业研究设计院有限公司 | Preparation method of epoxy liquid crystal grafted graphene oxide compound |
| CN106556677A (en) * | 2016-10-27 | 2017-04-05 | 苏州大学 | A kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof |
| CN110104633A (en) * | 2019-04-27 | 2019-08-09 | 北京鼎臣石墨科技有限公司 | A kind of preparation method of graphene oxide and graphene |
| CN110436450A (en) * | 2019-09-04 | 2019-11-12 | 广东石油化工学院 | A method of removing graphite oxide prepares graphene oxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941694A (en) * | 2010-09-07 | 2011-01-12 | 湘潭大学 | Preparation method of high-dispersivity graphene |
| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
| CN102212616A (en) * | 2011-04-27 | 2011-10-12 | 湖北富邦科技股份有限公司 | Preparation method for synthesizing nanocomposite from graphene oxide and organic dye |
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN102534730A (en) * | 2012-02-23 | 2012-07-04 | 南昌航空大学 | Preparation method for flexibly transparent high-conductivity graphene thin film |
-
2012
- 2012-07-15 CN CN2012102429101A patent/CN102701199A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101941694A (en) * | 2010-09-07 | 2011-01-12 | 湘潭大学 | Preparation method of high-dispersivity graphene |
| CN102173414A (en) * | 2011-03-18 | 2011-09-07 | 中国地质大学（武汉） | Method for preparing graphene oxide by chemical peeling |
| CN102212616A (en) * | 2011-04-27 | 2011-10-12 | 湖北富邦科技股份有限公司 | Preparation method for synthesizing nanocomposite from graphene oxide and organic dye |
| CN102491318A (en) * | 2011-12-13 | 2012-06-13 | 河北工业大学 | Method for preparing graphene oxide |
| CN102534730A (en) * | 2012-02-23 | 2012-07-04 | 南昌航空大学 | Preparation method for flexibly transparent high-conductivity graphene thin film |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103839698A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | Graphene composite electrode material and preparation method and application thereof |
| CN103318874A (en) * | 2013-05-21 | 2013-09-25 | 宁夏大学 | Temperature-sensitive graphene oxide and temperature-sensitive element preparation method |
| CN103318874B (en) * | 2013-05-21 | 2014-12-24 | 宁夏大学 | Temperature-sensitive graphene oxide and temperature-sensitive element preparation method |
| CN103265019A (en) * | 2013-05-25 | 2013-08-28 | 桂林理工大学 | Preparation method for highly-nitrogen-doped graphene light-weight ferromagnetic material |
| CN103265019B (en) * | 2013-05-25 | 2015-04-15 | 桂林理工大学 | Preparation method for highly-nitrogen-doped graphene light-weight ferromagnetic material |
| CN104609399A (en) * | 2014-12-29 | 2015-05-13 | 南京大学 | Graphene oxide, preparation method and application thereof |
| CN105271189A (en) * | 2015-09-23 | 2016-01-27 | 东莞市迈科科技有限公司 | Nitrogen doped graphene particle and preparation method thereof |
| CN105967179A (en) * | 2016-06-30 | 2016-09-28 | 常州第六元素材料科技股份有限公司 | Preparation method of easy-dispersible graphene powder and graphene powder prepared by method |
| CN105967179B (en) * | 2016-06-30 | 2018-11-20 | 常州第六元素材料科技股份有限公司 | A kind of easy dispersed graphite alkene raw powder's production technology and the graphene powder using this method preparation |
| CN106556677A (en) * | 2016-10-27 | 2017-04-05 | 苏州大学 | A kind of three-dimensional porous graphene extra-thin film gas sensor and preparation method thereof |
| CN106517175A (en) * | 2016-12-08 | 2017-03-22 | 中国化工集团曙光橡胶工业研究设计院有限公司 | Preparation method of epoxy liquid crystal grafted graphene oxide compound |
| CN110104633A (en) * | 2019-04-27 | 2019-08-09 | 北京鼎臣石墨科技有限公司 | A kind of preparation method of graphene oxide and graphene |
| CN110436450A (en) * | 2019-09-04 | 2019-11-12 | 广东石油化工学院 | A method of removing graphite oxide prepares graphene oxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102701199A (en) | Method for preparing graphene oxide by dispersed emulsion assisted with Hummers method | |
| Ikram et al. | Advances in synthesis of graphene derivatives using industrial wastes precursors; prospects and challenges | |
| Ding et al. | Controlled intercalation and chemical exfoliation of layered metal–organic frameworks using a chemically labile intercalating agent | |
| CN102145887B (en) | Method for preparing and purifying graphene oxide | |
| CN101875491B (en) | Green preparation method of graphene based on tea polyphenol/green tea juice | |
| Zhang et al. | Graphene nanosheets synthesis via chemical reduction of graphene oxide using sodium acetate trihydrate solution | |
| Pan et al. | A rapid low-temperature synthetic method leading to large-scale carboxyl graphene | |
| WO2015109916A1 (en) | Method for preparing graphene | |
| US10472243B2 (en) | Industrial method for preparing large-sized graphene | |
| Moosa et al. | Green reduction of graphene oxide using tea leaves extract with applications to lead ions removal from water | |
| Zhang et al. | Dipotassium hydrogen phosphate as reducing agent for the efficient reduction of graphene oxide nanosheets | |
| CN103613095B (en) | A kind of method of purifying and classifying Graphene | |
| KR20180068954A (en) | Methods for cost-effective industrial production of graphite oxides, graphene oxides and graphene | |
| CN102976320A (en) | Method using carbon dioxide as raw material to prepare high-quality graphene | |
| Park et al. | Facile synthesis of graphene oxide in a Couette–Taylor flow reactor | |
| CN101591014A (en) | A kind of method of realizing large-scale preparation of monolayer oxidized graphene | |
| Varela-Rizo et al. | Highly crystalline graphene oxide nano-platelets produced from helical-ribbon carbon nanofibers | |
| CN104556016B (en) | A kind of low-temperature environment-friendly preparation method of Graphene | |
| Mohd Firdaus et al. | From 2D graphene nanosheets to 3D graphene‐based macrostructures | |
| CN103896240B (en) | A kind of preparation method of Graphene/carbon nanotube composite material | |
| Ankamwar et al. | Water soluble graphene synthesis | |
| CN105502373B (en) | A kind of environment-friendly preparation method thereof of graphene | |
| Abdel-Motagaly et al. | Fast technique for the purification of as-prepared graphene oxide suspension | |
| Sumdani et al. | Recent advances of the graphite exfoliation processes and structural modification of graphene: a review | |
| CN107324319B (en) | A kind of big lamella graphene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121003 |