CN102225754A - Preparation method of graphene oxide and preparation method of graphene - Google Patents
Preparation method of graphene oxide and preparation method of graphene Download PDFInfo
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- CN102225754A CN102225754A CN 201110121338 CN201110121338A CN102225754A CN 102225754 A CN102225754 A CN 102225754A CN 201110121338 CN201110121338 CN 201110121338 CN 201110121338 A CN201110121338 A CN 201110121338A CN 102225754 A CN102225754 A CN 102225754A
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Abstract
The invention provides a preparation method of graphene oxide, which comprises the following steps of: uniformly mixing graphite, a concentrated acid and a strong oxidant; and carrying out reaction in a sealed environment at 80-130 DEG C to obtain grapheme oxide. The invention also provides a preparation method of graphene, which comprises the following steps of: uniformly mixing graphite, a concentrated acid and a strong oxidant; carrying out reaction in a sealed environment at 80-130 DEG C to obtain grapheme oxide; adding hydrazine hydrate to the grapheme oxide; and carrying out reduction reaction to obtain graphene. The methods provided by the invention do not need step-by-step precise control of reaction temperature and reaction time, and the process is simple and easy to operate. Graphene oxide prepared by the preparation method provided by the invention has multiple oxygen-containing functional groups, facilitates surface modification, and widens the application of graphene oxide.
Description
Technical field
The invention belongs to the Graphene technical field, relate in particular to a kind of preparation method and a kind of preparation method of graphene of graphene oxide.
Background technology
Since (Andre K.Geim) produced Graphene first, as a kind of novel two-dimensional nano carbonaceous material, Graphene has caused in scientific circles to be paid close attention to and deep research widely from peace moral strong K sea nurse in 2004.Graphene be have the monolayer carbon atomic thickness, be a kind of novel carbonaceous material that bi-dimensional cellular shape crystalline network is arranged by carbon atom, the essentially consist unit that is considered to every other dimension carbonaceous material, as can be bundled into the soccerballene of zero dimension, be curled into the unidimensional carbon nanotube, be piled into three-dimensional graphite etc.Graphene is with sp by carbon atom
2The monatomic carbon-coating that hydridization is combined into, structure is highly stable, have excellent mechanical property, peculiar electrical properties and good thermal property, discover, the Graphene Young's modulus can reach 11000GPa, breaking tenacity reaches 125GPa, and thermal conductivity reaches 5000W/ (mK), and theoretical specific surface area is up to 2630m
2/ g, and the character such as specific conductivity (preparation of Graphene and the characterization research that have perfect quantum tunneling effect, half integral quantum hall effect and never disappear, " material Leader ", in August, 2008), have a good application prospect in fields such as aerospace, novel material, electric power, electronics.
Prior art discloses multiple preparation method of graphene, comprise that graphite oxide reduction method, micromechanics peel off method, chemical Vapor deposition process, SiC epitaxial growth method and electrochemical process etc., wherein, micromechanics is peeled off method, chemical Vapor deposition process, SiC epitaxial growth method and electrochemical process and is all had shortcomings such as complex process, cost height, becomes the research focus and have graphite oxide reduction rule with low cost, as can to quantize advantages such as preparing, method is simple.The graphite oxide reduction method at first with graphite oxidation and peel off into graphene oxide, restores and obtains Graphene usually, wherein, and with graphite oxidation and peel off that to obtain graphene oxide be committed step.
The Hummers method is a kind of common method for preparing graphene oxide, mainly be in opening wide system, under the concentrated acid environment with strong oxidizer with graphite oxidation and peel off, generally comprise following steps: in beaker, add the vitriol oil, graphite and SODIUMNITRATE, in ice bath, be cooled to 0 ℃～4 ℃, agitation condition slowly adds potassium permanganate down, makes reacting liquid temperature below 20 ℃ in this process; Then beaker is placed 35 ℃ of waters bath with thermostatic control, continue to stir 0.5h～1h; Under agitation condition, slowly add entry, make reacting liquid temperature reach 98 ℃～100 ℃, continue to stir 15min～60min; Last water adds aqueous hydrogen peroxide solution with reaction solution dilution back, obtains graphene oxide after washing, filtering.This process need substep is control reaction temperature and reaction times accurately, not only complex procedures, complex operation, and be difficult to prepare the big particle diameter graphene oxide that abundant oxidation is peeled off.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method and a kind of preparation method of graphene of graphene oxide, and preparation method's technology provided by the invention is simple, easy and simple to handle, and the reaction conditions control accuracy requires low.
The invention provides a kind of preparation method of graphene oxide, may further comprise the steps:
Graphite, concentrated acid and strong oxidizer are mixed, in 80 ℃～130 ℃ closed environment, react, obtain graphene oxide.
Preferably, described concentrated acid is the vitriol oil, and described strong oxidizer is potassium permanganate and nitrate.
Preferably, the mass ratio of described graphite, the vitriol oil, potassium permanganate and nitrate is 1: (30～90): (3～8): (1～4).
Preferably, described concentrated acid is a concentrated hydrochloric acid, and described strong oxidizer is potassium perchlorate or sodium perchlorate.
Preferably, the mass ratio of described graphite, concentrated hydrochloric acid, strong oxidizer is 1: (10～60): (6～12).
Preferably, before graphite, concentrated acid and strong oxidizer mixing, graphite, concentrated acid and strong oxidizer are carried out cooling process respectively.
Preferably, the temperature of described cooling process is 0 ℃～4 ℃.
Preferably, the time of described reaction is 1h～4h.
The present invention also provides a kind of preparation method of graphene, may further comprise the steps:
Graphite, concentrated acid and strong oxidizer are mixed, in 80 ℃～130 ℃ closed environment, react, obtain graphene oxide;
In described graphene oxide, add hydrazine hydrate, carry out obtaining Graphene after the reduction reaction.
Preferably, the temperature of described reduction reaction is 90 ℃～100 ℃, and the time of described reduction reaction is 12h～100h.
Compared with prior art, the present invention mixes the back with graphite, concentrated acid and strong oxidizer and reacts in 80 ℃～130 ℃ closed environment, obtains graphene oxide.Graphite and strong oxidizer can produce gas and heat release when reacting in the concentrated acid environment, form high-temperature and high-pressure conditions in closed environment, make graphite oxidized and peel off, and generate graphene oxide.Method provided by the invention need not accurate control reaction temperature of substep and reaction times, and technology is simple, easy and simple to handle.Oxygen-containing functional group is more in the graphene oxide of method preparation provided by the invention, helps it is carried out finishing, enlarges the application of graphene oxide.In addition, adopt that method provided by the invention can prepare that particle diameter is big, oxidation peels off comparatively fully, and output is higher, is suitable for scale operation.Experiment shows, adopts the particle diameter of the graphene oxide of method preparation provided by the invention can reach more than the 500 μ m.
Description of drawings
Fig. 1 is the graphene oxide of the embodiment of the invention 1 preparation and the X ray diffracting spectrum of Graphene;
Fig. 2 is the graphene oxide of the embodiment of the invention 1 preparation and the infared spectrum of Graphene;
Fig. 3 is the graphene oxide of the embodiment of the invention 1 preparation and the Raman spectrum of Graphene;
Fig. 4 is the x-ray photoelectron power spectrum of carbon oxygen element in the graphene oxide of the embodiment of the invention 1 preparation;
Fig. 5 is the x-ray photoelectron power spectrum of each functional group in the graphene oxide of the embodiment of the invention 1 preparation;
Fig. 6 is the x-ray photoelectron power spectrum of carbon oxygen element in the Graphene of the embodiment of the invention 1 preparation;
Fig. 7 is the x-ray photoelectron power spectrum of each functional group in the Graphene of the embodiment of the invention 1 preparation;
Fig. 8 is the atomic force micrograph of the graphene oxide of the embodiment of the invention 1 preparation;
Fig. 9 is the light micrograph of the graphene oxide of the embodiment of the invention 1 preparation.
Embodiment
The invention provides a kind of preparation method of graphene oxide, may further comprise the steps:
Graphite, concentrated acid and strong oxidizer are mixed, in 80 ℃～130 ℃ closed environment, react, obtain graphene oxide.
The present invention is raw material with graphite, carries out oxidation and makes graphite peel off into the monolithic layer structure with strong oxidizer under concentrated acid, high temperature, airtight condition, obtains graphene oxide.
The present invention does not have particular restriction to described graphite, can be natural flake graphite or pure Graphite Powder 99; When described graphite was natural flake graphite, the present invention did not have particular restriction to the particle diameter of described natural flake graphite, was preferably 20 orders～800 orders, more preferably 30 orders～200 orders; When described graphite is pure Graphite Powder 99, is preferably the analytical pure Graphite Powder 99 or composes pure Graphite Powder 99.
According to the present invention, described concentrated acid is preferably the vitriol oil or concentrated nitric acid, and the mass concentration of the described vitriol oil is preferably more than 85%, and more preferably 98%; The mass concentration of described concentrated nitric acid is preferably more than 55%, and more preferably 60%～65%.
According to the present invention, when described concentrated acid was the vitriol oil, described strong oxidizer was preferably potassium permanganate and nitrate, and described nitrate is preferably SODIUMNITRATE, saltpetre and lithium nitrate.The mass ratio of described graphite, the vitriol oil, potassium permanganate and nitrate is preferably 1: (30～90): (3～8): (1～4), more preferably 1: (40～80): (4～6): (2～3).
According to the present invention, when described concentrated acid was concentrated hydrochloric acid, described strong oxidizer was preferably sodium perchlorate or potassium perchlorate.The mass ratio of described graphite, concentrated hydrochloric acid and strong oxidizer is preferably 1: (10～60): (6～12), more preferably 1: (20～50): (8～10).
In order to improve the security of preparation process, before graphite, concentrated acid and strong oxidizer were mixed, the present invention preferably carried out cooling process with graphite, concentrated acid and strong oxidizer, and the temperature of described cooling process is preferably 0 ℃～4 ℃, more preferably 1 ℃～3 ℃; The time of described cooling process is preferably 1h～4h, more preferably 2h～3h.
To mix through graphite, concentrated acid and the strong oxidizer of cooling process, the present invention preferably adopts following method to mix:
To in closed environment, mix through graphite, concentrated acid and the strong oxidizer of cooling process, slowly stir 0.5min～1min;
The mixture that obtains is left standstill 0.5h～2h under 0 ℃～4 ℃.
At first will as mixing in the encloses containers such as tetrafluoroethylene reactor, slowly stir 0.5min～1min, graphite, concentrated acid and strong oxidizer are tentatively mixed through graphite, concentrated acid and the strong oxidizer of cooling process at closed environment;
The encloses container that mixture will be housed then leaves standstill 0.5h～2h under 0 ℃～4 ℃, preferred 0.6h～1.5h fully is dissolved in the concentrated acid strong oxidizer.
After graphite, concentrated acid and strong oxidizer mixed in closed environment, described mixture is heated up, be warming up to 80 ℃～130 ℃, be preferably 90 ℃～120 ℃, more preferably 95 ℃～110 ℃, Graphene, concentrated acid and strong oxidizer are reacted and peel off, obtain graphene oxide.
In temperature-rise period, graphite in concentrated acid with strong oxidizer generation redox reaction, generate gas, and discharge big calorimetric.Because graphite and being reflected in the closed environment of strong oxidizer are carried out, along with the carrying out of reaction, the generation of gas and the release of heat, form high-temperature and high-pressure conditions in the closed environment, thereby be beneficial to graphite by abundant oxidation with peel off.
In the present invention, the time that described graphite, concentrated acid and strong oxidizer react is preferably 1h～4h, more preferably 2h～3h.
After reaction finishes, the reaction mixture that obtains is cooled off, described reaction mixture is added to the water obtains suspension liquid, and described suspension liquid suction filtration, washing can be obtained graphene oxide.When the concentrated acid of selecting for use is the vitriol oil, when strong oxidizer is potassium permanganate and nitrate, with the reaction mixture that obtains be added to the water obtain suspension liquid after, in described suspension liquid, add aqueous hydrogen peroxide solution, will obtain graphene oxide after the solution suction filtration that obtain, the washing.In the present invention, the mass ratio of described water and described graphite is preferably (100～400): 1, more preferably (150～350): 1.The mass concentration of described aqueous hydrogen peroxide solution is preferably 20%～30%, and more preferably 25%～30%, the mass ratio of described aqueous hydrogen peroxide solution and described graphite is preferably (1～15): 1, more preferably (3～10): 1.According to the present invention, be 6～7 o'clock preferably with described suspension liquid filtering and washing to pH value, can obtain graphene oxide.
After obtaining graphene oxide, described graphene oxide is carried out Infrared spectroscopy and Raman spectrum analysis, the result shows, the graphene oxide that method provided by the invention prepares has the typical infrared spectra and the Raman spectrum of graphene oxide, illustrates that method provided by the invention can access graphene oxide; Described graphene oxide is carried out X-ray photoelectron spectroscopic analysis, and the result shows that oxy radical is more in the graphene oxide that method provided by the invention prepares, and helps carrying out finishing by the chemical reaction of oxy radical; Described graphene oxide is carried out X-ray diffraction analysis, and the result shows that the graphene oxide that method provided by the invention prepares does not have diffraction peak, and graphite flake layer is fully peeled off; Described graphene oxide is carried out atomic power microscopic examination and optical microscope, and the result shows that the graphene oxide that method provided by the invention prepares is the monolithic layer structure, the big and homogeneous of particle diameter.
After obtaining graphene oxide, described graphene oxide reduction can be obtained Graphene, preferably include following steps:
In the graphene oxide that technique scheme prepares, add hydrazine hydrate, carry out obtaining Graphene after the reduction reaction.
After obtaining graphene oxide, described graphene oxide is scattered in the water, obtains the graphene oxide suspension liquid, then to wherein adding hydrazine hydrate.
The present invention preferably adds hydrazine hydrate aqueous solution in described graphene oxide, the mass concentration of described hydrazine hydrate aqueous solution is preferably 60%～85%, and more preferably 70%～85%.
In the present invention, the mass ratio of described graphene oxide and described hydrazine hydrate is preferably 1: (0.7～4), more preferably 1: (1～2.5).
Graphene oxide and hydrazine hydrate carry out redox reaction, and graphene oxide is reduced into and is Graphene.According to the present invention, the temperature that graphene oxide and hydrazine hydrate react is preferably 90 ℃～100 ℃, more preferably 92 ℃～98 ℃; The time of reacting is preferably 12h～100h, more preferably 24h～48h.
After reaction finishes, will obtain Graphene after reaction mixture cooling, sedimentation, suction filtration, washing, the drying.According to the present invention, behind described reaction mixture cooling, sedimentation, suction filtration, the solid matter that obtains to be washed with deionized water, washing finishes the back 60 ℃ of following vacuum-dryings, obtains Graphene.
After obtaining Graphene, described Graphene is carried out X-ray diffraction analysis, Infrared spectroscopy and Raman spectrum analysis, the result shows, the Graphene that method provided by the invention prepares has exemplary x-ray diffracting spectrum, infrared spectra and the Raman spectrum of Graphene, illustrates that method provided by the invention can access Graphene; Described Graphene is carried out X-ray photoelectron spectroscopic analysis, and the result shows that the graphene oxide that method provided by the invention prepares can be reduced into and be Graphene.
In order to further specify the present invention, the preparation method and the preparation method of graphene of graphene oxide provided by the invention are described in detail below in conjunction with embodiment.
Below among each embodiment raw materials used being from the market buy.
Be that 98% the vitriol oil is respectively at 2 ℃～4 ℃ cooling 1h with 20g 50 purpose natural flake graphites, 50g SODIUMNITRATE, 100g potassium permanganate and 800g mass concentration, join the tetrafluoroethylene reactor that places the stainless steel still shell then, slowly stir 1min, cover tight kettle cover, under 2 ℃～4 ℃, leave standstill 1h, in 100 ℃ of baking ovens, react 1h then; Fully after the cooling, the tetrafluoroethylene reactor is taken out in the stainless steel still shell, with wherein reaction mixture slowly to going in the 6L deionized water, the back adding 90mL mass concentration that stirs is 20% aqueous hydrogen peroxide solution, being stirred to suspension liquid is glassy yellow, with described suspension liquid suction filtration, to wash to the pH value be to obtain graphene oxide after 7;
Described graphene oxide is joined in the 5L deionized water, adding 25g mass concentration is 85% hydrazine hydrate under the stirring condition, being warming up to 95 ℃ of reaction 15h, is to obtain Graphene after the drying in 7,60 ℃ of vacuum drying ovens with the reaction mixture cooling that obtains, sedimentation, suction filtration, with deionized water wash to pH value.
Described natural flake graphite, graphene oxide and Graphene are carried out X-ray diffraction analysis, the result is referring to Fig. 1, Fig. 1 is the graphene oxide of the embodiment of the invention 1 preparation and the X ray diffracting spectrum of Graphene, wherein, curve 11 is the X ray diffracting spectrum of natural flake graphite, curve 12 is the X ray diffracting spectrum of the graphene oxide of embodiment 1 preparation, and curve 13 is the X ray diffracting spectrum of the Graphene of embodiment 1 preparation.As shown in Figure 1, graphite disappears in the X ray diffracting spectrum of graphene oxide and Graphene 26.5 ° strong diffraction peak, and there is no in the X ray diffracting spectrum of graphene oxide and Graphene and other obvious diffraction peaks occur, illustrate that the present invention has prepared graphene oxide and Graphene that lamella is fully peeled off.
Described graphene oxide and Graphene are carried out Infrared spectroscopy, the result is referring to Fig. 2, Fig. 2 is the graphene oxide of the embodiment of the invention 1 preparation and the infared spectrum of Graphene, wherein, curve 21 is the infared spectrum of the graphene oxide of embodiment 1 preparation, have the typical infrared signature of graphene oxide, illustrate that the present invention has prepared graphene oxide; Curve 22 is the infared spectrum of the Graphene of embodiment 1 preparation, has the typical infrared signature of Graphene, compares with the infrared spectrum of graphene oxide, and the peak of its each oxygen-containing functional group is strong significantly to be reduced or disappear, and illustrates that graphene oxide is reduced into to be Graphene.
Described graphene oxide and Graphene are carried out Raman spectrum analysis, the result is referring to Fig. 3, Fig. 3 is the graphene oxide of the embodiment of the invention 1 preparation and the Raman spectrum of Graphene, wherein, curve 31 is the Raman spectrum of the graphene oxide of embodiment 1 preparation, and it has typical peak position of graphene oxide and intensity; Curve 32 is the Raman spectrum of the Graphene of embodiment 1 preparation, and it has typical peak position of Graphene and intensity.
Described graphene oxide and Graphene are carried out X-ray photoelectron spectroscopic analysis, the result is referring to Fig. 4, Fig. 5, Fig. 6 and Fig. 7, Fig. 4 is the x-ray photoelectron power spectrum of carbon in the graphene oxide of the embodiment of the invention 1 preparation, oxygen element, Fig. 5 is the x-ray photoelectron power spectrum of carbon in the graphene oxide of the embodiment of the invention 1 preparation, Fig. 6 is the x-ray photoelectron power spectrum of carbon in the Graphene of the embodiment of the invention 1 preparation, oxygen element, Fig. 7 be in the Graphene for preparing of the embodiment of the invention 1 carbon the x-ray photoelectron power spectrum.By Fig. 4 and Fig. 5 as can be known, the graphene oxide oxygen level height of embodiment 1 preparation, oxidized carbon is more; Fig. 6 and Fig. 7 have the typical carbon-to-oxygen ratio of Graphene and functional group's ratio, illustrate that method provided by the invention can access graphene oxide, and this graphene oxide can be reduced into and is Graphene.
Described graphene oxide is carried out the atomic force microscope analysis, the result is referring to Fig. 8, Fig. 8 is the atomic force micrograph of the graphene oxide of the embodiment of the invention 1 preparation, as shown in Figure 8, the graphene oxide very thin thickness of embodiment 1 preparation, between 1nm～2.5nm, the single-layer oxidized graphite thought of 1nm alkene, 2.5nm a slice single-layer oxidized graphite alkene of can thinking be stacked on another sheet single-layer oxidized graphite alkene, in first figure of Fig. 8, can observe this stacked structure.
Described graphene oxide is carried out the opticmicroscope analysis, the result is referring to Fig. 9, Fig. 9 is the light micrograph of the graphene oxide of the embodiment of the invention 1 preparation, as shown in Figure 9, the graphene oxide particle diameter of the present invention's preparation illustrates that at 100-300 μ m method provided by the invention can effectively prepare the graphene oxide of big particle diameter.
Embodiment 2
Described graphene oxide is joined in the 0.4L deionized water, adding 2.4g mass concentration is 85% hydrazine hydrate under the stirring condition, being warming up to 95 ℃ of reaction 15h, is to obtain Graphene after the drying in 7,60 ℃ of vacuum drying ovens with the reaction mixture cooling that obtains, sedimentation, suction filtration, with deionized water wash to pH value.
Respectively described graphene oxide and Graphene are carried out X-ray diffraction analysis, Infrared spectroscopy, Raman spectrum analysis and X-ray photoelectron spectroscopic analysis, the result shows, has prepared graphene oxide and Graphene respectively by method provided by the invention.
Described graphene oxide and Graphene are carried out atomic force microscope analysis and opticmicroscope analysis, the result shows, obtained single-layer oxidized graphite alkene by method provided by the invention, the particle diameter of described graphene oxide is 50-80 μ m, and particle diameter homogeneous comparatively.
Embodiment 3
10g 38 purpose natural flake graphites, 20g SODIUMNITRATE, 60g potassium permanganate and the 900g vitriol oil are cooled off 1h respectively at 2 ℃～4 ℃, join the tetrafluoroethylene reactor that places the stainless steel still shell then, slowly stir 1min, cover tight kettle cover, under 2 ℃～4 ℃, leave standstill 2h, in 110 ℃ of baking ovens, react 2h then; Fully after the cooling, the tetrafluoroethylene reactor is taken out in the stainless steel still shell, with wherein reaction mixture slowly to going in the 4L deionized water, the back adding 20mL mass concentration that stirs is 30% aqueous hydrogen peroxide solution, being stirred to suspension liquid is glassy yellow, with described suspension liquid suction filtration, to wash to the pH value be to obtain graphene oxide after 7;
Described graphene oxide is joined in the 3.2L deionized water, adding 15g mass concentration is 80% hydrazine hydrate under the stirring condition, being warming up to 95 ℃ of reaction 24h, is to obtain Graphene after the drying in 7,60 ℃ of vacuum drying ovens with the reaction mixture cooling that obtains, sedimentation, suction filtration, with deionized water wash to pH value.
Respectively described graphene oxide and Graphene are carried out X-ray diffraction analysis, Infrared spectroscopy, Raman spectrum analysis and X-ray photoelectron spectroscopic analysis, the result shows, has prepared graphene oxide and Graphene respectively by method provided by the invention.
Described graphene oxide and Graphene are carried out atomic force microscope analysis and opticmicroscope analysis, the result shows, obtained single-layer oxidized graphite alkene by method provided by the invention, the particle diameter of described graphene oxide is 500～600 μ m, and particle diameter homogeneous comparatively.
Embodiment 4
The pure Graphite Powder 99 of 3g, 10g saltpetre, 10g potassium permanganate and the 100g vitriol oil are cooled off 1h respectively at 0 ℃～4 ℃, join the tetrafluoroethylene reactor that places the stainless steel still shell then, slowly stir 1min, cover tight kettle cover, under 0 ℃～4 ℃, leave standstill 1h, in 80 ℃ of baking ovens, react 0.6h then; Fully after the cooling, the tetrafluoroethylene reactor is taken out in the stainless steel still shell, with wherein reaction mixture slowly to going in the 0.5L deionized water, the back adding 10mL mass concentration that stirs is 30% aqueous hydrogen peroxide solution, being stirred to suspension liquid is tawny, with described suspension liquid suction filtration, to wash to the pH value be to obtain graphene oxide after 7;
Described graphene oxide is joined in the 0.8L deionized water, adding 6g mass concentration is 70% hydrazine hydrate under the stirring condition, being warming up to 95 ℃ of reaction 12h, is to obtain Graphene after the drying in 7,60 ℃ of vacuum drying ovens with the reaction mixture cooling that obtains, sedimentation, suction filtration, with deionized water wash to pH value.
Respectively described graphene oxide and Graphene are carried out X-ray diffraction analysis, Infrared spectroscopy, Raman spectrum analysis and X-ray photoelectron spectroscopic analysis, the result shows, has prepared graphene oxide and Graphene respectively by method provided by the invention.
Described graphene oxide and Graphene are carried out atomic force microscope analysis and opticmicroscope analysis, and the result shows, has obtained single-layer oxidized graphite alkene by method provided by the invention, and the particle diameter of described graphene oxide is about 0.5-1 μ m.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. the preparation method of a graphene oxide may further comprise the steps:
Graphite, concentrated acid and strong oxidizer are mixed, in 80 ℃～130 ℃ closed environment, react, obtain graphene oxide.
2. preparation method according to claim 1 is characterized in that, described concentrated acid is the vitriol oil, and described strong oxidizer is potassium permanganate and nitrate.
3. preparation method according to claim 2 is characterized in that, the mass ratio of described graphite, the vitriol oil, potassium permanganate and nitrate is 1: (30～90): (3～8): (1～4).
4. preparation method according to claim 1 is characterized in that, described concentrated acid is a concentrated hydrochloric acid, and described strong oxidizer is potassium perchlorate or sodium perchlorate.
5. preparation method according to claim 4 is characterized in that, the mass ratio of described graphite, concentrated hydrochloric acid, strong oxidizer is 1: (10～60): (6～12).
6. according to any described preparation method of claim 1～5, it is characterized in that, before graphite, concentrated acid and strong oxidizer are mixed, graphite, concentrated acid and strong oxidizer are carried out cooling process respectively.
7. preparation method according to claim 6 is characterized in that, the temperature of described cooling process is 0 ℃～4 ℃.
8. preparation method according to claim 1 is characterized in that, the time of described reaction is 1h～4h.
9. preparation method of graphene may further comprise the steps:
Graphite, concentrated acid and strong oxidizer are mixed, in 80 ℃～130 ℃ closed environment, react, obtain graphene oxide;
In described graphene oxide, add hydrazine hydrate, carry out obtaining Graphene after the reduction reaction.
10. preparation method according to claim 9 is characterized in that, the temperature of described reduction reaction is 90 ℃～100 ℃, and the time of described reduction reaction is 12h～100h.
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| CN111072005A (en) * | 2018-10-22 | 2020-04-28 | 天津工业大学 | Preparation method of carbon material oxide |
| CN112473642A (en) * | 2020-06-11 | 2021-03-12 | 中科远方(北京)科技有限公司 | Graphene oxide modified attapulgite, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559918A (en) * | 2009-04-30 | 2009-10-21 | 上海大学 | Preparation method of graphene/cadmium sulfide quantum dot composite material applied to photoelectric conversion |
| CN101863463A (en) * | 2010-05-18 | 2010-10-20 | 北京化工大学 | Method for preparing water dispersible carbon nano tube |
-
2011
- 2011-05-11 CN CN 201110121338 patent/CN102225754B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559918A (en) * | 2009-04-30 | 2009-10-21 | 上海大学 | Preparation method of graphene/cadmium sulfide quantum dot composite material applied to photoelectric conversion |
| CN101863463A (en) * | 2010-05-18 | 2010-10-20 | 北京化工大学 | Method for preparing water dispersible carbon nano tube |
Non-Patent Citations (2)
| Title |
|---|
| 《中国博士学位论文全文数据库 工程科技I辑》 20101015 郭鹏 石墨烯的制备，组装及应用研究 第32页2.3.1.1部分 1-10 , 第10期 * |
| 《材料开发与应用》 20110430 肖淑华,沈明,朱沛英,张东 水合肼还原氧化石墨烯的研究 全文 1-10 第26卷, 第2期 * |
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