CN103539106A - Preparation method of carbon material - Google Patents
Preparation method of carbon material Download PDFInfo
- Publication number
- CN103539106A CN103539106A CN201310511411.2A CN201310511411A CN103539106A CN 103539106 A CN103539106 A CN 103539106A CN 201310511411 A CN201310511411 A CN 201310511411A CN 103539106 A CN103539106 A CN 103539106A
- Authority
- CN
- China
- Prior art keywords
- preparation
- carbon material
- graphene
- graphene oxide
- material according
- 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 provides a preparation method of a carbon material. The carbon material is graphene oxide or graphene. The preparation method comprises the following steps: selecting phosphoric acid or phosphate as an intercalator under the condition of room temperature; adding graphite to the intercalator, leading in ozone as an oxidant under irradiation of ultraviolet light after carrying out ultrasonic treatment for a period of time; continuing to carry out ultrasonic treatment after reaction is finished, and then obtaining the graphene oxide; adding a solvent to the prepared graphene oxide to dilute and filter, and then transferring to a reducing furnace to reduce, so as to obtain the graphene oxide. By adopting the preparation method, the phosphoric acid or phosphate is selected as the intercalator; the ozone is taken as the oxidant; the process is short in time, low in energy consumption, simple and easy to control an operate, environment-friendly and free of pollution in the preparation process.
Description
Technical field
The invention belongs to carbon material technical field, especially relate to a kind of preparation method of graphene oxide of simple environment protection.
Background technology
2004, Geim etc. utilized micromechanics stripping method successfully to obtain single-layer graphene, therefore in 2010, obtained the Nobel prize.Graphene has very high chemical stability, and there is under high thermal conductivity, normal temperature electronic mobility higher than CNT (carbon nano-tube) or silicon crystal, lower than the physical propertys such as resistivity of copper or silver, basic structural unit is carbon six-ring the most stable in organic materials.The theoretical specific surface area of Graphene is up to 2600m
2/ g, has outstanding heat conductivility (3000W/ (mK)) and mechanical property (1060GPa), and electronic mobility (15000cm2/ (Vs)) at a high speed under room temperature.Due to the special property of Graphene, Graphene Application Areas is extensive.
Graphene is the carbonaceous material that the cellular lattice structure of a kind of two-dimension periodic being comprised of carbon six-ring forms.At present, the method for preparing Graphene mainly contains mechanically peel method, epitaxial growth method, chemical Vapor deposition process (CVD method), chemical stripping method etc.Wherein chemical stripping method is the most frequently used method of preparing magnanimity Graphene of generally acknowledging at present, the main preparation process of the method is: graphite oxidation is peeled off as having the graphene oxide of the oxygen-containing functional groups such as carboxyl, aldehyde radical, carbonyl, epoxy, and graphene oxide obtains Graphene after reduction.But this method is mainly used KMnO
4, HNO
3, HClO
4, H
2sO
4, strong oxidizer, the strong acid such as HCl, as being 201010514807.9 at application number, name is called in the Chinese invention patent application of " a kind of preparation method of Graphene ", the intercalator adopting is exactly a kind of in the vitriol oil, concentrated nitric acid, Glacial acetic acid, diacetyl oxide, oxygenant adopts is a kind of in the vitriol oil, hydrogen peroxide, potassium permanganate, concentrated nitric acid, this strong oxidizer, strong acid easily cause environmental pollution, clean difficulty, expend great lot of water resources.
Graphene oxide is peeled off and is obtained through chemical oxidation by Graphite Powder 99, is to prepare intermediate product important in Graphene process, have the abundant functional group of higher specific surface area and surface, but the preparation method of graphene oxide exists problems at present.Therefore, for traditional preparation method's defect, explore a kind of simple applicable, economical and efficient, the preparation in macroscopic quantity graphene oxide of environmental protection and the method for grapheme material, significant for the widespread use of graphene oxide and Graphene.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the method for the preparation in macroscopic quantity graphene oxide material of a kind of simple applicable, economical and efficient and environmental protection, and the method is to take chemical oxidation to peel off ratio juris as basis, selects oxidation capacity to compare KMnO
4, H
28O
4, HClO
4, HNO
3deng stronger, to prepare simple ozone be oxygenant, described ozone, by ultraviolet excitation, not only can improve oxidation capacity under photochemical catalytic oxidation synergy, and has increased free OH, can reduce the consumption of ozone simultaneously; Select phosphoric acid or the phosphoric acid salt of easy removal to prepare graphene oxide and Graphene as intercalator.The method process time is short, energy consumption is low, easy control simple to operate, environment friendly and pollution-free.
For achieving the above object, technical scheme of the present invention is: a kind of carbon material preparation method, described carbon material is graphene oxide, the preparation method of described graphene oxide comprises: under room temperature condition, in intercalator, add graphite, after ultrasonic for some time, pass into oxygenant, continue ultrasonic to the graphene oxide described in obtaining after react.
Preferably, described intercalator is phosphoric acid or phosphoric acid salt.
Preferably, the concentration of described intercalator is 70%-98%, is greater than 5: 1 with the mol ratio of carbon.
Preferably, described graphite in intercalator ultrasonic time between 0.5h-10h.
Preferably, described oxygenant is the ozone under ozone or UV-irradiation.
Preferably, described oxidant concentration is greater than 5mg/m
3, flow is higher than 1L/min, and described graphite ultrasonic time in oxygenant is more than 2h.
Preferably, described ultraviolet wavelength should be at 185-280nm, more than the UV-irradiation time should be 2h.
Preferably, by filtering after the graphene oxide solubilizing agent dilution preparing, be then transferred to after reduction furnace reduction, obtain Graphene.
Preferably, described graphene oxide, under hydrogen atmosphere, is obtaining Graphene dry powder after thermal reduction in reduction furnace.
Preferably, described graphene oxide and LiOH solution reaction, obtain dispersibling the Graphene in water.
Preferably, described Graphite Powder 99 selects particle diameter to be less than 50 μ m.
Compared with prior art, advantage of the present invention is: preparation method's material therefor kind of the present invention is few, preparation technology's time is shorter, and the intercalator of selecting in preparation process and comparatively environmental protection of oxygenant.Meanwhile, because the present invention selects ozone as oxygenant, its oxidation capacity is stronger than oxygenant of the prior art, and oxygenant and intercalator can not meet environmental protection needs to environment in process of production, has reduced production cost simultaneously.
Graphene oxide obtains Graphene through reduction, but the impact that the difference of method of reducing used can be certain on the structure generation of Graphene.At present, conventional method of reducing mainly contains: hot reducing method, chemical reduction method and multistep reduction method.The invention provides two kinds of methods that graphene oxide are reduced to Graphene: (one) is under hydrogen atmosphere, graphene oxide in reduction furnace through thermal reduction, obtain the Graphene that lipophilicity is good, the cellular lattice structure of two-dimension periodic that described Graphene is comprised of carbon six-ring forms, and selects H with hydrogen atmosphere
2/ N
2or H
2a kind of in/Ar, the shared volume ratio of hydrogen is that 1-10% is excellent; (2) graphene oxide and LiOH solution reaction, obtain the Graphene of good hydrophilic property, contains the hydrophilic oxygen-containing functional group of part in described Graphene.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the graphite oxide for preparing in the embodiment of the present invention 1;
Fig. 2 is the X-ray diffractogram of the Graphene for preparing in the embodiment of the present invention 2;
Fig. 3 is the X-ray diffractogram of the Graphene for preparing in the embodiment of the present invention 3.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is for further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The preparation method of a kind of carbon material that the present invention proposes, carbon material wherein comprises graphene oxide and Graphene, it comprises and is prepared as follows step:
First, at ambient temperature, select phosphoric acid, phosphoric acid salt as a kind of as intercalator in primary ammonium phosphate or monometallic, in intercalator, add Graphite Powder 99 to carry out supersound process, wherein ultrasonic time is 0.5h-10h, Graphite Powder 99 selects particle diameter to be less than 50 μ m, and the concentration of intercalator is 70%-98%, is greater than 5: 1 with the mol ratio of carbon.
Then, in completing the solution of supersound process, pass into the ozone as oxygenant, or under UV-irradiation condition, pass into the ozone as oxygenant, continue the ultrasonic 2h of oxidation above to reacting completely.Wherein, the concentration of oxygenant is greater than 5mg/m
3, flow is higher than 1L/min, and described ultraviolet wavelength should be at 185-280nm, and the intermediate product that now obtains preparing Graphene is graphene oxide.
Subsequently, by washing filtering in above-mentioned graphene oxide, be transferred to reduction furnace reduction, reducing atmosphere can adopt H
2/ N
2or H
2/ Ar, temperature is controlled at 500-1050 ℃, more than lasting 2h, obtains Graphene dry powder; By above-mentioned graphene oxide and LiOH solution reaction, must dispersible the Graphene in water.
It should be noted that, the characteristic of the Graphene that graphene oxide is prepared by different approaches is slightly different, and the Graphene that high temperature reduction obtains does not have oxygen-containing functional group substantially, is difficult for disperseing in solvent; The Graphene that liquid-phase reduction obtains retains small part oxygen-containing functional group, is convenient to it and disperses in solvent.
Below in conjunction with specific embodiment, such scheme is described further, the implementation condition adopting in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment.
Embodiment 1
It is in 85% strong phosphoric acid that 6g Graphite Powder 99 is added to 150mL concentration, supersound process 1.0h, and then passing into continuously concentration is 20g/m
3, the flow ozone that is 1L/min, after ultrasonic 2.5h, add 450mL water to continue the ultrasonic 3.5h of oxidation, must be dispersed in the graphene oxide in phosphoric acid.After washing and drying, obtain graphite oxide (GO).
Utilize X-ray diffractometer to analyze graphite oxide, obtain X-ray diffractogram, as shown in Figure 1, graphite oxide is ° obvious 002 diffraction peak of appearance in 2 θ=10.04, by Bragg equation, calculating its spacing is 0.88nm, higher than 002 spacing (0.34nm) of graphite, illustrate that graphite oxide interlayer exists oxide group; By Scherrer formula, calculating known its Lc is 10.29nm.
Embodiment 2
By the method preparation of embodiment 1, be dispersed in the graphene oxide in phosphoric acid, washing, filter, dry after at hydrogen nitrogen mixed gas (V
nitrogen: V
hydrogen=9: 1) under atmosphere, in atmosphere furnace, reduce, with the speed of 10 ° of C/min, be warming up to 550 ℃, insulation 3.0h, is cooled to room temperature subsequently.Through ethanol, disperse ultrasonic 4.0h, 120 ℃ of oven dry obtain Graphene.
Utilize X-ray diffractometer to analyze Graphene, obtain X-ray diffractogram, as shown in Figure 2,002 diffraction peak that graphite oxide is reduced rear oxidation graphite disappears, 002 diffraction peak of graphite, 101 diffraction peaks occur, illustrate that graphite oxide is reduced to Graphene, and Graphene do not have other functional groups substantially, easily in the solvent of non-water, disperse.
Method preparation by embodiment 1 is dispersed in the graphene oxide in phosphoric acid, after washing, filter, being dried, get 0.3g and be distributed in 600mL water, be heated to 80 ℃, obtain being dispersed in the Graphene in alkali lye after adding the ultrasonic 0.5h of LiOH (8M) solution of 8mL.After washing, filter, being dried, obtain Graphene.
Utilize X-ray diffractometer to analyze Graphene, obtain X-ray diffractogram, as shown in Figure 3,002 diffraction peak intensity that graphite oxide is reduced rear graphite increases, and illustrates that graphite oxide is reduced to Graphene; But in collection of illustrative plates, still there is 002 diffraction peak of graphite oxide, show that liquid-phase reduction obtains having part oxygen-containing functional group in Graphene, increased the wetting ability of Graphene, be convenient to it and disperse in water.
Technology contents of the present invention and technical characterictic have disclosed as above; yet those of ordinary skill in the art still may be based on teaching of the present invention and announcements and are done all replacement and modifications that does not deviate from spirit of the present invention; therefore; protection domain of the present invention should be not limited to the content that embodiment discloses; and should comprise various do not deviate from replacement of the present invention and modifications, and contained by present patent application claim.
Claims (10)
1. a preparation method for carbon material, described carbon material is graphene oxide, it is characterized in that preparing according to the following steps:
Under room temperature condition, in intercalator, add graphite, after ultrasonic for some time, pass into oxygenant, continue ultrasonic to react, the graphene oxide described in obtaining.
2. the preparation method of carbon material according to claim 1, is characterized in that, described intercalator is phosphoric acid or phosphoric acid salt.
3. the preparation method of carbon material according to claim 1 and 2, is characterized in that, the concentration of described intercalator is 70%-98%, is greater than 5: 1 with the mol ratio of carbon.
4. the preparation method of carbon material according to claim 1, is characterized in that, described graphite ultrasonic time in intercalator is between 0.5h-10h.
5. the preparation method of carbon material according to claim 1, is characterized in that, described oxygenant is the ozone under ozone or UV-irradiation.
6. the preparation method of carbon material according to claim 1 or 5, is characterized in that, described oxidant concentration is greater than 5mg/m
3, flow is higher than 1L/min; Described graphite ultrasonic time in oxygenant is more than 2h.
7. the preparation method of carbon material according to claim 1 or 5, is characterized in that, more than the described UV-irradiation time should be 2h, ultraviolet wavelength is between 185-280nm.
8. the preparation method of carbon material according to claim 1, is characterized in that, by the graphene oxide solubilizing agent dilute filtration preparing, is then transferred to after reduction furnace reduction, obtains Graphene.
9. the preparation method of carbon material according to claim 8, is characterized in that, described graphene oxide, under hydrogen atmosphere, is obtaining Graphene dry powder after thermal reduction in reduction furnace.
10. the preparation method of carbon material according to claim 8, is characterized in that, described graphene oxide and LiOH solution reaction, obtain dispersibling the Graphene in water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511411.2A CN103539106A (en) | 2013-10-25 | 2013-10-25 | Preparation method of carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511411.2A CN103539106A (en) | 2013-10-25 | 2013-10-25 | Preparation method of carbon material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103539106A true CN103539106A (en) | 2014-01-29 |
Family
ID=49963029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310511411.2A Pending CN103539106A (en) | 2013-10-25 | 2013-10-25 | Preparation method of carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103539106A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445164A (en) * | 2014-11-18 | 2015-03-25 | 扬州大学 | Universal method for controllable growth of nano structure on single-layer graphene film |
| CN104876219A (en) * | 2015-06-19 | 2015-09-02 | 湖南农业大学 | Method for synthesizing oxidized graphene simply and conveniently at normal temperature |
| CN106587045A (en) * | 2017-01-23 | 2017-04-26 | 宣城亨旺新材料有限公司 | Production process of graphene oxide |
| CN109321096A (en) * | 2018-10-09 | 2019-02-12 | 湘潭大学 | A kind of UV modified graphite alkene polymer and preparation method thereof |
| CN109928388A (en) * | 2019-04-28 | 2019-06-25 | 电子科技大学 | A kind of graphene oxide preparation method of ultraviolet light enhancing oxidation |
| 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 |
| CN111463028A (en) * | 2020-04-09 | 2020-07-28 | 陕西科技大学 | rGO-L iOH micro-spring/wood composite electrode material, and preparation method and application thereof |
| CN112002885A (en) * | 2020-09-10 | 2020-11-27 | 中国空间技术研究院 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN112048147A (en) * | 2020-09-18 | 2020-12-08 | 高碑店市安普光电材料科技有限公司 | Antibacterial and deodorant plastic master batch taking elastomer as carrier and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| CN102781830A (en) * | 2009-11-03 | 2012-11-14 | 维尔萨利斯股份公司 | Process for the preparation of nano-scaled graphene platelets with a high dispersibility in low-polarity polymeric matrixes and relative polymeric compositions |
| WO2012166001A1 (en) * | 2011-07-21 | 2012-12-06 | Общество С Ограниченной Ответственностью "Акколаб" (Ооо "Акколаб") | Process for producing graphene |
| CN103332670A (en) * | 2013-06-21 | 2013-10-02 | 重庆交通大学 | Method for preparing graphene oxide |
-
2013
- 2013-10-25 CN CN201310511411.2A patent/CN103539106A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102781830A (en) * | 2009-11-03 | 2012-11-14 | 维尔萨利斯股份公司 | Process for the preparation of nano-scaled graphene platelets with a high dispersibility in low-polarity polymeric matrixes and relative polymeric compositions |
| CN102153075A (en) * | 2011-03-22 | 2011-08-17 | 桂林理工大学 | Method for synthesizing graphene oxide by ultrasonic assistance Hummers method |
| WO2012166001A1 (en) * | 2011-07-21 | 2012-12-06 | Общество С Ограниченной Ответственностью "Акколаб" (Ооо "Акколаб") | Process for producing graphene |
| CN103332670A (en) * | 2013-06-21 | 2013-10-02 | 重庆交通大学 | Method for preparing graphene oxide |
Non-Patent Citations (2)
| Title |
|---|
| QING TANG，ET AL.: "Graphene-related nanomaterials：tuning properties by functionalization", 《NANOSCALE》 * |
| ZHEN YUAN XIA，ET AL.: "The Exfoliation of Graphene in liquids by Electrochemical，Chemical，and Sonication-Assisted Techniques：A Nanoscale Study", 《ADVANCED FUNCTIONAL MATERIALS》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445164B (en) * | 2014-11-18 | 2016-09-14 | 扬州大学 | A kind of method of controllable growth nanostructured in single layer graphene film |
| CN104445164A (en) * | 2014-11-18 | 2015-03-25 | 扬州大学 | Universal method for controllable growth of nano structure on single-layer graphene film |
| CN104876219A (en) * | 2015-06-19 | 2015-09-02 | 湖南农业大学 | Method for synthesizing oxidized graphene simply and conveniently at normal temperature |
| CN104876219B (en) * | 2015-06-19 | 2017-03-15 | 湖南农业大学 | A kind of method of easy synthesis graphene oxide under room temperature |
| CN106587045B (en) * | 2017-01-23 | 2021-08-17 | 宣城亨旺新材料有限公司 | Production process of graphene oxide |
| CN106587045A (en) * | 2017-01-23 | 2017-04-26 | 宣城亨旺新材料有限公司 | Production process of graphene oxide |
| CN109321096A (en) * | 2018-10-09 | 2019-02-12 | 湘潭大学 | A kind of UV modified graphite alkene polymer 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 |
| CN109928388A (en) * | 2019-04-28 | 2019-06-25 | 电子科技大学 | A kind of graphene oxide preparation method of ultraviolet light enhancing oxidation |
| CN111463028B (en) * | 2020-04-09 | 2021-06-29 | 陕西科技大学 | rGO-LiOH micro-spring/wood composite electrode material and preparation method and application thereof |
| CN111463028A (en) * | 2020-04-09 | 2020-07-28 | 陕西科技大学 | rGO-L iOH micro-spring/wood composite electrode material, and preparation method and application thereof |
| CN112002885A (en) * | 2020-09-10 | 2020-11-27 | 中国空间技术研究院 | Silicon-carbon composite material, preparation method thereof and lithium ion battery |
| CN112048147A (en) * | 2020-09-18 | 2020-12-08 | 高碑店市安普光电材料科技有限公司 | Antibacterial and deodorant plastic master batch taking elastomer as carrier and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103539106A (en) | Preparation method of carbon material | |
| Li et al. | Photocatalyst design based on two-dimensional materials | |
| Kim et al. | Simple and cost-effective reduction of graphite oxide by sulfuric acid | |
| Feng et al. | Improvement of g-C3N4 photocatalytic properties using the Hummers method | |
| Wei et al. | Graphene quantum dots prepared from chemical exfoliation of multiwall carbon nanotubes: An efficient photocatalyst promoter | |
| CN102568641B (en) | Preparation method for graphene composite material loaded with nano metal particles | |
| CN102126720B (en) | Method for synthesizing graphene | |
| CN103145120B (en) | A kind of preparation method of porous graphene | |
| CN104150471B (en) | A kind of method of redox graphene | |
| CN104401977A (en) | Preparation method of graphene aerogel and graphene-carbon nanotube aerogel | |
| CN104174422B (en) | High nitrogen doped Graphene and fullerene selenizing molybdenum hollow ball nano composite material and preparation method thereof | |
| CN103570012B (en) | A kind of preparation method of Graphene | |
| CN103769187A (en) | Preparation method of graphene/g-C3N4 compound photocatalyst | |
| CN103390509B (en) | A kind of electrode material for super capacitor and preparation method thereof | |
| WO2015081663A1 (en) | Method for preparing aza graphene and nanometer metal graphene by using solid phase cracking method | |
| CN103950923A (en) | New method for preparing high-quality graphene | |
| CN106185902A (en) | A kind of method that clean oxidation technology prepares the controlled graphene oxide of size | |
| CN102070142A (en) | Method for preparing graphene by chemical oxidation reduction | |
| CN102942177A (en) | Method for preparing graphene sheet | |
| CN104787751A (en) | Graphene powder and preparation method thereof | |
| Sun et al. | Controlled synthesis of Sn doped ZnO microspheres stringed on carbon fibers with enhanced visible-light photocatalytic activities | |
| CN104556016A (en) | Low-temperature environment-friendly preparation method of graphene | |
| CN106744859A (en) | Graphene three-dimensional multistage pore structure powder prepared by a kind of low temperature polymer cracking | |
| CN104386676A (en) | Preparation method of graphene | |
| Shanmugam et al. | Photocatalytic properties of graphene-SnO2-PMMA nanocomposite in the degradation of methylene blue dye under direct sunlight irradiation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for 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: 20140129 |