CN103787318B - Restoration method for reduced graphene oxide - Google Patents
Restoration method for reduced graphene oxide Download PDFInfo
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- CN103787318B CN103787318B CN201410023730.3A CN201410023730A CN103787318B CN 103787318 B CN103787318 B CN 103787318B CN 201410023730 A CN201410023730 A CN 201410023730A CN 103787318 B CN103787318 B CN 103787318B
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Abstract
A method for repairing reduced graphene oxide comprises the steps of dispersing the reduced graphene oxide in a solvent to obtain a graphene dispersion solution, adding a first Lewis acid and a compound containing methyl or methylene to obtain a first mixture, reacting the first mixture for 0.5 to 2 hours in a microwave environment of 300 to 900 watts, and performing reflux reaction for 3 to 5 hours to obtain a first crude product; adding the first crude product into a second Lewis acid, adding an aromatic hydrocarbon repairing agent to obtain a second mixture, reacting the second mixture to obtain a melt solid, and separating and purifying the melt solid to obtain a second crude product; mixing the second crude product, the metal powder catalyst and a third Lewis acid to obtain a third mixture, reacting the third mixture for 1 to 2 hours at the temperature of between 450 and 500 ℃ in the atmosphere of protective gas containing a carbon source, and annealing for 5 to 8 hours at the temperature of between 200 and 350 ℃ in a vacuum environment. The method can better repair the reduced graphene oxide.
Description
Technical field
The present invention relates to carbon material technical field, particularly relate to a kind of restorative procedure of redox graphene.
Background technology
Since AndreGeim and KonstantinNovoselof of Univ Manchester UK in 2004 successfully peels off pyrolytic graphite first and since observing Graphene, just never disappeared in educational circles for the research temperature of new carbon.The successful separation of Graphene means that theory is abolished for the prophesy of two dimensional crystal thermodynamic instability, also just brings the possibility of much frontier research.
Perfect Graphene has desirable two-dirnentional structure, it is made up of hexagonal lattice, each carbon atom is combined with other three carbon atoms on direction, lattice plane by σ key, does not become the electronics of σ key then as π-electron, constitutes the π track system perpendicular to lattice plane.π-electron can movement arbitrarily in the plane, this gives the electroconductibility that Graphene is fabulous, can bear the current density of six orders of magnitude higher than copper.Equally, Graphene also has record-breaking thermal conductivity, and the thermal conductivity of pure Graphene is up to 2000 ~ 4000Wm
-1.K
-1, and there is fabulous intensity and high surface-area.Moreover, the energy band structure of its uniqueness also given by the special construction of Graphene, makes it have the specific conductivity that perfect tunneling effect and half integral quantum hall effect and it never disappear.The performance of these uniquenesses makes it in material and electronic circuit etc., have great application prospect.Also therefore, great demand is had to a large amount of synthesis of Graphene.
Traditional Graphene synthetic method can be divided into two kinds, is physical method and chemical process respectively.The proterties of the Graphene that physical method and chemical process obtain is also different.Have the different schemes such as mechanical stripping method, arc discharge method, ultrasonic dispersion in Physical, the graphene sheet layer obtained is more complete, but it is too low all to there is productive rate, unstable product quality, needs the problem of special equipment and high cost.And chemical process can be divided into organic synthesis method, oxidation reduction process, solvent-thermal method and chemical Vapor deposition process from bottom to top several.Wherein, organic synthesis method is strict to equipment and ingredient requirement, is difficult to volume production; Solvent-thermal method cannot stabilized product quality, and average quality is poor; The high cost of chemical Vapor deposition process, and cannot large-scale production.The equipment of the oxidation reduction process in the middle of this is simple, the Graphene steady quality obtained, and is therefore most possibly as the scheme of Graphene suitability for industrialized production.But there are two main problems in the Graphene after oxidization-reduction, the first is after the redox processes of fierceness, six-membered carbon ring structure in graphene sheet layer has destroyed part, namely defines so-called defect, thus affects and disturb the performance of grapheme material body; It two is that obtained grapheme material can not reduce thoroughly, therefore result in the residual oxygen on graphene layer, also has a great impact the performance of grapheme material.Therefore, the grapheme material obtained generally is referred to as " redox graphene ", and in comparison, the defect through the grapheme material of chemical Vapor deposition process acquisition wants less, also can not residual oxygen.Therefore, in certain range of application, this grapheme material more meets our needs, more can be referred to as " Graphene ".
For redox graphene, the defect on its surface can be divided into following several main condition: 1, Stone-Wales(SW) topological defect, namely on graphene layer, two six-ring carbon atoms there occurs rearrangement, destroy two hexa-atomic annulars, have become the structure of a five-ring and a seven-membered ring., in the six-membered carbon ring namely on graphene layer, there is one or more carbon atom disappearance, thus made to define room in Graphene in 2, vacancy defect.This includes single vacancy and divacancy defect.3, adsorbing contaminant atom or heteroatoms substitute, and namely carbon atom have adsorbed impurity atoms to Graphene thus the defect formed, or impurity atoms directly enters alternative carbon atom in graphene-structured.Due to above-mentioned several defect, the characteristic of the Graphene finally prepared through chemical method is caused to have certain difference compared with Graphene prepared by Physical.This difference includes in the ratio of carbon oxygen element in the size of specific surface area, one-piece construction and energy band structure with or without energy gap etc.
Because the characteristic difference between the Graphene that redox graphene and chemical vapor deposition obtain is larger, and this characteristic mainly comes from the impact that the defect on Graphene is brought, therefore, to some catalytic steps for surface reconstruction of the faultiness design on Graphene, thus the defect on Graphene can be made to eliminate through reconstruct, residual oxygen on Graphene can be removed simultaneously, thus redox graphene prepared by chemical method, change and be close to high-quality Graphene, reach the object that low cost prepares high-quality graphene material, imperative research.
But the research being reconstructed Graphene defect and repairing is that domestic report is less on the one hand, there is large quantifier elimination blank; On the other hand, report main in the world at present concentrates on and carries out in the repairing of chemical vapor deposition method with carbon source molecule Graphene, and it is extremely rare to carry out the report of Graphene repairing with traditional methodology of organic synthesis.
Summary of the invention
Based on this, be necessary the restorative procedure that a kind of redox graphene is provided, to repair the defect on redox graphene and to carry out deoxidation to redox graphene.
A restorative procedure for redox graphene, comprises the steps:
Redox graphene is scattered in solvent, obtain graphene dispersing solution, in described graphene dispersing solution, add first via Lewis acid and obtain the first mixture containing the compound of methyl or methylene radical, described first mixture is reacted 0.5 hour ~ 2 hours under the microwave environment of 300 watts ~ 900 watts, then back flow reaction 3 hours ~ 5 hours, separation and purification is also dry, obtains the first crude product;
Described first crude product is added in the second Lewis acid, and add aromatic hydrocarbons healant, mix and obtain the second mixture, described second mixture is carried out being obtained by reacting melts solid, after described melts solid is carried out separation and purification, obtain the second crude product; And
Described second crude product, metal powdered catalysts and the 3rd Lewis acid are mixed; mix and obtain the 3rd mixture; in the shielding gas atmosphere of carbonaceous sources; described 3rd mixture is reacted 1 hour ~ 2 hours at 450 DEG C ~ 500 DEG C; then under vacuum conditions; anneal 5 hours ~ 8 hours at 200 DEG C ~ 350 DEG C, after being cooled to room temperature, separation and purification obtains the redox graphene after repairing.
Wherein in an embodiment, described solvent is selected from methylene dichloride, 1, at least one in 2 ethylene dichloride, tetracol phenixin, trichloromethane, hexanaphthene, normal hexane, benzene and oil of mirbane.
Wherein in an embodiment, in described graphene dispersing solution, the concentration of described redox graphene is 0.1mg/mL ~ 1mg/mL.
Wherein in an embodiment, described first via Lewis acid and the second Lewis acid are all selected from least one in iron(ic) chloride, aluminum chloride, zinc chloride, boron trifluoride, magnesium chloride, cupric chloride and lithium chloride, and described 3rd Lewis acid is selected from least one in iron protochloride, iron(ic) chloride, lithium chloride, chromium chloride, cobalt chloride, zinc chloride and cupric chloride.
Wherein in an embodiment, the mass ratio of described first via Lewis acid and described redox graphene is 1:3 ~ 10.
Wherein in an embodiment, the described compound containing methyl or methylene radical is trioxymethylene, methyl alcohol, methyl chloride or methyl iodide.
Wherein in an embodiment, described is 1:5 ~ 20 containing methyl or the compound of methylene radical and the mass ratio of redox graphene.
Wherein in an embodiment, described described first mixture is reacted under the microwave environment of 300 watts ~ 900 watts the step of 0.5 hour ~ 2 hours before, also comprise the step adding strong acid in described first mixture, the mass ratio of described strong acid and described redox graphene is 1:0.1 ~ 1.
Wherein in an embodiment, described strong acid is selected from least one in sulfuric acid, methylsulfonic acid, Phenylsulfonic acid, Nitromethane 99Min., nitric acid, hydrochloric acid, trichoroacetic acid(TCA) and perchloric acid.
Wherein in an embodiment, described first crude product and described second lewis acidic mass ratio are 1:20 ~ 100.
Wherein in an embodiment, described aromatic hydrocarbons healant be selected from naphthalene, anthracene, phenanthrene, cool, pyrene and at least one.
Wherein in an embodiment, the mass ratio of described first crude product and described aromatic hydrocarbons healant is 1:5 ~ 10.
Wherein in an embodiment, the described step carrying out described second mixture to be obtained by reacting melts solid is specially:
Described second mixture is reacted 3 hours ~ 5 hours at 200 DEG C ~ 350 DEG C; Or
Described second mixture is reacted 0.1 hour ~ 0.5 hour under the microwave environment of 300 watts ~ 800 watts.
Wherein in an embodiment, the quality of described metal powdered catalysts is 5% ~ 10% of the quality of described second crude product.
Wherein in an embodiment, described metal powdered catalysts is selected from least one in copper powder, zinc powder, silver powder, palladium powder and platinum powder end.
Wherein in an embodiment, described 3rd lewis acidic quality is 0.1% ~ 5% of the quality of described second crude product.
Wherein in an embodiment, the shielding gas atmosphere of described carbonaceous sources is the gas mixture atmosphere of organic phase gas and rare gas element, and described organic phase gas is at least one in methane, ethene and gaseous state ethanol.
Wherein in an embodiment, the volume ratio of described organic phase gas and described rare gas element is 1 ~ 3:7 ~ 9.
In the restorative procedure of above-mentioned redox graphene, under the first lewis acidic catalysis, there is Friedel-Crafts and to react and Scholl reacts in redox graphene and the compound containing methyl or methylene radical, thus has carried out effectively tentatively repairing to the vacancy defect of redox graphene and divacancy defect; Under the second lewis acidic catalysis, aromatic hydrocarbons healant is by Friedel-Crafts reactive grafting and add in the large size defect of redox graphene, further moderate reparation is effectively carried out to the vacancy defect of redox Graphene, and reduction deoxidation is carried out to redox Graphene; , effectively Graphene there is remaining Stone-Wales(SW in the anneal of redox graphene under metal powdered catalysts) topological defect repairs, and effectively activated remaining single vacancy and divacancy defect., supplement through the carbon source under metal catalyst catalysis meanwhile, by the in addition degree of depth reparation of highly active single vacancy and divacancy defect, thus obtain the grapheme material of high-quality.
Accompanying drawing explanation
Fig. 1 is the schema of the restorative procedure of the redox graphene of an embodiment.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the restorative procedure of the redox graphene of an embodiment, comprises the steps:
Step S110: redox graphene is scattered in solvent, obtain graphene dispersing solution, in graphene dispersing solution, add first via Lewis acid and obtain the first mixture containing the compound of methyl or methylene radical, first mixture is reacted 0.5 hour ~ 2 hours under the microwave environment of 300 watts ~ 900 watts, then back flow reaction 3 hours ~ 5 hours, separation and purification is also dry, obtains the first crude product.
Redox graphene (RGO) refers to that adopting oxidation reduction process to prepare exists surface imperfection and oxygen containing Graphene.
Solvent is selected from methylene dichloride, 1, at least one in 2 ethylene dichloride, tetracol phenixin, trichloromethane, hexanaphthene, normal hexane, benzene and oil of mirbane.Preferably, solvent is selected from least one in methylene dichloride, trichloromethane, oil of mirbane and normal hexane.
Preferably, before redox graphene being scattered in solvent, also comprising and carry out washing and dry step to redox graphene.Redox graphene is used absolute ethanol washing and water washing successively, and carries out drying, to remove the inorganic salt and organic impurities that may exist, obtain the redox graphene that purity is higher.
Preferably, will wash and dried redox graphene in ultrasonic lower dispersion in a solvent, to make redox graphene dispersed.
Preferably, in graphene dispersing solution, the concentration of redox graphene is 0.1mg/mL ~ 1mg/mL, to ensure certain treatment capacity and certain speed of reaction.
First via Lewis acid is selected from iron(ic) chloride (FeCl
3), aluminum chloride (AlCl
3), zinc chloride (ZnCl
2), boron trifluoride (BF
3), magnesium chloride (MgCl
26H
2o), cupric chloride (CuCl
22H
2o) and lithium chloride (LiCl) at least one.Preferably, first via Lewis acid is selected from iron(ic) chloride (FeCl
3), aluminum chloride (AlCl
3) and the middle at least one of lithium chloride (LiCl).
First via Lewis acid is as catalyzer.Preferably, the mass ratio of first via Lewis acid and redox graphene is 1:3 ~ 10.
Containing the compound of methyl or methylene radical as another reactant, there is Friedel-Crafts with redox graphene and react and react with Scholl.Preferably, be 1:5 ~ 20 containing methyl or the compound of methylene radical and the mass ratio of redox graphene, react to make Friedel-Crafts carrying out fast of reacting with Scholl.
Compound containing methyl or methylene radical is preferably trioxymethylene, methyl alcohol, methyl chloride or methyl iodide.The methyl of this several compound containing methyl or methylene radical or methylene radical are comparatively active, make this compound containing methyl or methylene radical can under relatively mild condition, Friedel-Crafts occurs with redox graphene preferably and to react and Scholl reacts.
Preferably, before the first mixture being reacted under the microwave environment of 300 watts ~ 900 watts the step of 0.5 hour ~ 2 hours, the step adding strong acid in the first mixture is also comprised.
Strong acid, for promoting the compound depolymerization containing methyl or methylene radical, is also electrophilic reagent, as the promotor of first via Lewis acid to redox graphene coordination simultaneously.Strong acid is selected from least one in sulfuric acid, methylsulfonic acid, Phenylsulfonic acid, Nitromethane 99Min., nitric acid, hydrochloric acid, trichoroacetic acid(TCA) and perchloric acid.The mass concentration of above-mentioned strong acid is 39% ~ 98%.Preferably, strong acid is selected from least one in sulfuric acid, methylsulfonic acid and Nitromethane 99Min..
Preferably, the mass ratio of strong acid and redox graphene is 1:0.1 ~ 1.
Add strong acid in the first mixture after, ultrasonic disperse is carried out 0.5 hour ~ 4 hours under 120W ~ 300W, make each component disperses even, finely dispersed first mixture is reacted 0.5 hour ~ 2 hours under the microwave environment of 300 watts ~ 900 watts, then back flow reaction 3 hours ~ 5 hours, separation and purification is also dry, obtains the first crude product.
Separation and purification dry step are specially: the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then by washing with alcohol precipitation 1 ~ 2 time, dry, obtain the first crude product.
First crude product is the redox graphene through tentatively repairing.
In step S110, under the first lewis acidic catalysis, there is Friedel-Crafts and to react and Scholl reacts in redox graphene and the compound containing methyl or methylene radical, thus has carried out effectively tentatively repairing to the vacancy defect of redox graphene and divacancy defect.
Step S120: the first crude product is added in the second Lewis acid, and add aromatic hydrocarbons healant, mix and obtain the second mixture, the second mixture is carried out being obtained by reacting melts solid, after melts solid is carried out separation and purification, obtain the second crude product.
Second Lewis acid is selected from iron(ic) chloride (FeCl
3), aluminum chloride (AlCl
3), zinc chloride (ZnCl
2), boron trifluoride (BF
3), magnesium chloride (MgCl
26H
2o), cupric chloride (CuCl
22H
2o) and lithium chloride (LiCl) at least one.Preferably, the second Lewis acid is selected from iron(ic) chloride (FeCl
3), aluminum chloride (AlCl
3) and the middle at least one of lithium chloride (LiCl).
Preferably, the first crude product and the second lewis acidic mass ratio are 1:20 ~ 100.
Above-mentioned second Lewis acid is solid Lewis acid.This solid Lewis acid is melted, the first crude product is added in the solid Lewis acid of thawing, and adds aromatic hydrocarbons healant, mix and obtain the second mixture.
Aromatic hydrocarbons healant be selected from naphthalene, anthracene, phenanthrene, cool, pyrene and at least one.Preferably, aromatic hydrocarbons healant be selected from naphthalene, phenanthrene and at least one.
Preferably, the mass ratio of the first crude product and aromatic hydrocarbons healant is 1:5 ~ 10.
This second mixture is carried out being obtained by reacting melts solid.
Preferably, in a particular embodiment, the step that this second mixture carries out being obtained by reacting melts solid is specially: the second mixture is reacted 3 hours ~ 5 hours at 200 DEG C ~ 300 DEG C, obtains melts solid.
Preferably, in the embodiment that another is concrete, the step that this second mixture carries out reacting is specially: the second mixture is reacted 0.1 hour ~ 0.5 hour under the microwave environment of 300 watts ~ 800 watts, obtains melts solid.
The step of separation and purification is specially: by the melts solid dispersal that obtains in water, adding dilute sulphuric acid regulates pH to 5, suction filtration elimination solvent again, with ethanol purge 2 ~ 3 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product, i.e. the redox graphene of moderate reparation.
In step S120, the redox graphene of preliminary reparation is through the second lewis acidic process of melting, large-sized aromatic hydrocarbons renovation agent is by Friedel – Crafts reactive grafting and add in the large size defect of the preliminary redox graphene repaired, thus has carried out effectively repairing to the excessive vacancy defect on the preliminary redox graphene repaired further.
And, the redox graphene of preliminary reparation is through the second Lewis acid process of melting, the part Stone-Wales(SW existed) topological defect there occurs rearrangement under the effect of metal powdered catalysts, thus make the structure of five-ring-seven-membered ring go back to the structure of six-ring-six-ring in graphite linings, and make the Stone-Wales(SW in the preliminary redox graphene repaired) topological defect minimizing.
Further, the redox graphene of preliminary reparation is through the second Lewis acid process of melting, the part oxygen-containing functional group existed is captured by the second Lewis acid, make unreduced oxidation site on redox graphene effectively be reduced deoxidation, make the carbon-to-oxygen ratio of the preliminary redox graphene repaired effectively increase.
Step S130: the second crude product, metal powdered catalysts and the 3rd Lewis acid are mixed; mix and obtain the 3rd mixture; in the shielding gas atmosphere of carbonaceous sources; 3rd mixture is reacted 1 hour ~ 2 hours at 450 DEG C ~ 500 DEG C; then under vacuum conditions; anneal 5 hours ~ 8 hours at 200 DEG C ~ 350 DEG C, after being cooled to room temperature, separation and purification obtains the redox graphene after repairing.
3rd Lewis acid is selected from iron protochloride (FeCl
2), iron(ic) chloride (FeCl
3), lithium chloride (LiCl), chromium chloride (CrCl
3), cobalt chloride (CoCl
2), zinc chloride (ZnCl
2) and cupric chloride (CuCl
22H
2o) at least one in.Preferably, the 3rd Lewis acid is selected from iron protochloride (FeCl
2), chromium chloride (CrCl
3) and iron(ic) chloride (FeCl
3) at least one.
Preferably, the 3rd lewis acidic quality is 0.1% ~ 5% of the quality of the second crude product.
Metal powdered catalysts is selected from least one in copper powder, zinc powder, silver powder, palladium powder and platinum powder end.
Preferably, metal powdered catalysts is selected from size and is at least one in the copper powder of 200 molybdenums, zinc powder, silver powder, palladium powder and platinum powder end.More preferably, metal powdered catalysts is selected from size and is at least one in 200 object nickel by powder, palladium powder and platinum powder end.
Preferably, the quality of metal powdered catalysts is 5% ~ 10% of the quality of the second crude product.
The shielding gas atmosphere of carbonaceous sources is the gas mixture atmosphere of organic phase gas and rare gas element.Wherein, organic phase gas is at least one in methane, ethene and gaseous state ethanol.Rare gas element is argon gas or helium etc.
Organic phase gas supplements as carbon source, highly active single vacancy and divacancy defect is repaired.Passing into of rare gas element prevents oxygen from adsorbing again, prevents Graphene to be oxidized.
In the shielding gas atmosphere of carbonaceous sources; 3rd mixture is reacted 1 hour ~ 2 hours at 450 DEG C ~ 500 DEG C; then under vacuum conditions; anneal 5 hours ~ 8 hours at 200 DEG C ~ 350 DEG C; after being cooled to room temperature, the step that separation and purification obtains the redox graphene after repairing is specially:
3rd mixture is positioned in retort furnace; pass into the shielding gas of carbonaceous sources; be heated to 450 DEG C ~ 500 DEG C, maintain 450 DEG C ~ 500 DEG C, react 1 hour ~ 2 hours; be transferred in vacuum drying oven; under vacuum conditions, keep 200 DEG C ~ 350 DEG C, anneal 5 hours ~ 8 hours; after being cooled to room temperature, separation and purification obtains the redox graphene after repairing.
The method of separation and purification is specially: be poured into water by the mixture being cooled to room temperature, carries out suction filtration in 120W ultrasonication after 2 hours, and filter residue mass concentration is the hydrochloric acid drip washing 3 ~ 5 times of 10%, then suction filtration, get filter residue, dry, obtain the redox graphene after repairing.
In step S130, the anneal of redox graphene under metal powdered catalysts catalysis that moderate is repaired, effectively there is remaining Stone-Wales(SW by the redox graphene of moderate reparation) topological defect repairs, simultaneously, Graphene, in the further reformation of transiting metal surface, has activated remaining single vacancy and divacancy defect effectively.
Further, the redox graphene that moderate is repaired is supplementary through transition metal-catalyzed lower carbon source, highly active single vacancy and divacancy defect is repaired, thus obtains the grapheme material of high-quality.
In the restorative procedure of above-mentioned redox graphene, under the first lewis acidic catalysis, there is Friedel-Crafts and to react and Scholl reacts in redox graphene and the compound containing methyl or methylene radical, thus has carried out effectively tentatively repairing to the vacancy defect of redox graphene and divacancy defect; Under the second lewis acidic catalysis, aromatic hydrocarbons healant, by Friedel-Crafts reactive grafting and add in the large size defect of redox graphene, carries out moderate reparation effectively to the vacancy defect of redox Graphene further, and reduces deoxidation; , effectively Graphene there is remaining Stone-Wales(SW in the anneal of redox graphene under metal catalyst) topological defect repairs, and effectively activated remaining single vacancy and divacancy defect., supplement through the carbon source under metal powdered catalysts catalysis meanwhile, by the in addition degree of depth reparation of highly active single vacancy and divacancy defect, thus obtain the grapheme material of high-quality.
Set forth further below by way of specific embodiment.
Embodiment 1
1, redox graphene is used absolute ethanol washing and water washing successively, then dry; Be scattered in methylene dichloride by washing and dried redox graphene, obtain graphene dispersing solution, wherein, the concentration of redox Graphene is 1mg/mL; Iron(ic) chloride, aluminum chloride and trioxymethylene is added in graphene dispersing solution, stir and obtain the first mixture, wherein, iron(ic) chloride and redox graphene and mass ratio be 1:3, aluminum chloride and redox graphene and mass ratio be 1:3, the mass ratio of trioxymethylene and redox graphene is 1:5; In the first mixture, add the sulfuric acid that mass concentration is 98%, the mass ratio of sulfuric acid and redox graphene is 1:0.1; The mixture of the first mixture and sulfuric acid after 0.5 hour in 120W ultrasonic disperse, is reacted 2 hours, then carries out back flow reaction 3 hours in the microwave environment of 300W; React complete, the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then precipitates 1 time by washing with alcohol, dry, obtains the first crude product;
2, be that the iron(ic) chloride of 1:1 and aluminum chloride melt by mass ratio, then in the iron(ic) chloride the second crude product being added thawing and aluminum chloride, and add naphthalene, mix and obtain the second mixture, wherein, the mass ratio of the first crude product and iron(ic) chloride is 1:10, and the mass ratio of the first crude product and aluminum chloride is 1:10, and the mass ratio of the first crude product and naphthalene is 1:5; Second mixture is reacted 5 hours in 200 DEG C of stopped pipes, obtains melts solid; By the melts solid dispersal that obtains in water, add dilute sulphuric acid and regulate pH to 5, then suction filtration elimination solvent, with ethanol purge 2 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product;
3, the second crude product, 200 object palladium powder and iron(ic) chloride are mixed, mix and obtain the 3rd mixture, wherein, the quality of palladium powder is 5% of the quality of the second crude product, and the quality of iron(ic) chloride is 5% of the quality of the second crude product; Second mixture is put into retort furnace, passes into the mixed gas of argon gas and methane, be heated to 450 DEG C, maintain reaction 2h, then transfer in vacuum drying oven, under vacuum environment, keep baking oven at 200 DEG C of annealing 8h, progressively cool to room temperature again, wherein, the volume ratio of methane and argon gas is 1:9; Be poured into water by the mixture being cooled to room temperature, after 120W ultrasonication 2h, carry out suction filtration, filter residue mass concentration is the hydrochloric acid drip washing 3 times of 10%, removes suction filtration after catalyzer completely, gets filter residue, dry, obtains the redox graphene after repairing.
After measured, the carbon-to-oxygen ratio 8:1 of the redox graphene (RGO) do not repaired, and the redox graphene after repairing can bring up to 23:1 effectively.Can determine that the oxygen level in the redox graphene after the reparation obtained reduces greatly thus.
The electric conductivity of the redox graphene after above-mentioned reparation also brings up to 500 ~ 650S/cm from 30 ~ 90S/cm of the redox graphene do not repaired at first, illustrate that the resistivity of the redox graphene after repairing reduces effectively, defect on redox graphene is repaired, make the quality of the redox graphene after repairing higher, after reparation, obtain the grapheme material of high-quality.
Embodiment 2
1, redox graphene is used absolute ethanol washing and water washing successively, then dry; Washing and dried redox graphene are scattered in 1, in 2 ethylene dichloride, obtain graphene dispersing solution, wherein, the concentration of redox Graphene is 0.1mg/mL; Aluminum chloride, zinc chloride and trioxymethylene is added in graphene dispersing solution, stir and obtain the first mixture, wherein, the mass ratio of aluminum chloride and redox graphene is 1:5, the mass ratio of zinc chloride and redox graphene is 1:5, and the mass ratio of trioxymethylene and redox graphene is 1:20; In the first mixture, add the methylsulfonic acid that mass concentration is 95%, the mass ratio of methylsulfonic acid and redox graphene is 1:1; The mixture of the first mixture and methylsulfonic acid after 1 hour in 220W ultrasonic disperse, is reacted 0.5 hour, then carries out back flow reaction 5 hours in the microwave environment of 900W; React complete, the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then precipitates 2 times by washing with alcohol, dry, obtains the first crude product;
2, melted by magnesium chloride, then added in the magnesium chloride of thawing by the second crude product, and add phenanthrene, mix and obtain the second mixture, wherein, the mass ratio of the first crude product and magnesium chloride is 1:100, and the first crude product is 1:10 with luxuriant and rich with fragrance mass ratio; Second mixture is reacted 3 hours in 350 DEG C of stopped pipes, obtains melts solid; By the melts solid dispersal that obtains in water, add dilute sulphuric acid and regulate pH to 5, then suction filtration elimination solvent, with ethanol purge 3 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product;
3, the second crude product, 200 object nickel by powder, iron protochloride and chromium chloride are mixed, mix and obtain the 3rd mixture, wherein, the quality of nickel by powder is 10% of the quality of the second crude product, the quality of iron protochloride is 1% of the quality of the second crude product, and the quality of chromium chloride is 1% of the quality of the second crude product; Second mixture is put into retort furnace, passes into the mixed gas of argon gas and ethene, be heated to 500 DEG C, maintain reaction 1h, then transfer in vacuum drying oven, under vacuum environment, keep baking oven at 350 DEG C of annealing 5h, progressively cool to room temperature again, wherein, the volume ratio of ethene and argon gas is 3:7; Be poured into water by the mixture being cooled to room temperature, after 120W ultrasonication 2h, carry out suction filtration, filter residue mass concentration is the hydrochloric acid drip washing 5 times of 10%, removes suction filtration after catalyzer completely, gets filter residue, dry, obtains the redox graphene after repairing.
After measured, the carbon-to-oxygen ratio 7:1 of the redox graphene (RGO) do not repaired, and the redox graphene after repairing can bring up to 24:1 effectively.Can determine that the oxygen level in the redox graphene after the reparation obtained reduces greatly thus.
The electric conductivity of the redox graphene after above-mentioned reparation also brings up to 550 ~ 650S/cm from 30 ~ 90S/cm of the redox graphene do not repaired at first, illustrate that the resistivity of the redox graphene after repairing reduces effectively, defect on redox graphene is repaired, make the quality of the redox graphene after repairing higher, after reparation, obtain the grapheme material of high-quality.
Embodiment 3
1, redox graphene is used absolute ethanol washing and water washing successively, then dry; Washing and dried redox graphene being scattered in volume ratio is that in the oil of mirbane of 1:1 and the mixed solvent of trichloromethane, obtain graphene dispersing solution, wherein, the concentration of redox Graphene is 0.5mg/mL; In graphene dispersing solution, add cupric chloride and methyl alcohol, stir and obtain the first mixture, wherein, the mass ratio of cupric chloride and redox graphene is 1:3, and the mass ratio of methyl alcohol and redox graphene is 1:10; In the first mixture, add the Phenylsulfonic acid that mass concentration is 68%, the mass ratio of Phenylsulfonic acid and redox graphene is 1:0.5; The mixture of the first mixture and Phenylsulfonic acid after 1 hour in 300W ultrasonic disperse, is reacted 1 hour, then carries out back flow reaction 4 hours in the microwave environment of 600W; React complete, the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then precipitates 2 times by washing with alcohol, dry, obtains the first crude product;
2, be that the iron(ic) chloride of 1:1 and lithium chloride melt by mass ratio, then in the iron(ic) chloride the second crude product being added thawing and lithium chloride, and add mass ratio be 1:1 phenanthrene and, mix and obtain the second mixture, wherein, the mass ratio of the first crude product and iron(ic) chloride is 1:25, and the mass ratio of the first crude product and lithium chloride is 1:25, first crude product is 1:4 with luxuriant and rich with fragrance mass ratio, the first crude product and mass ratio be 1:4; Second mixture is reacted 4 hours in 300 DEG C of stopped pipes, obtains melts solid; By the melts solid dispersal that obtains in water, add dilute sulphuric acid and regulate pH to 5, then suction filtration elimination solvent, with ethanol purge 3 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product;
3, the second crude product, 200 object nickel by powder, 200 object platinum powder ends and chromium chloride are mixed, mix and obtain the 3rd mixture, wherein, the quality of nickel by powder is 4% of the quality of the second crude product, the quality at platinum powder end is 4% of the quality of the second crude product, and the quality of chromium chloride is 1% of the quality of the second crude product; Second mixture is put into retort furnace, passes into the mixed gas of argon gas and gaseous state ethanol, be heated to 500 DEG C, maintain reaction 1h, then transfer in vacuum drying oven, under vacuum environment, keep baking oven at 250 DEG C of annealing 6h, progressively cool to room temperature again, wherein, the volume ratio of gaseous state ethanol and argon gas is 2:8; Be poured into water by the mixture being cooled to room temperature, after 120W ultrasonication 2h, carry out suction filtration, filter residue mass concentration is the hydrochloric acid drip washing 5 times of 10%, removes suction filtration after catalyzer completely, gets filter residue, dry, obtains the redox graphene after repairing.
After measured, the carbon-to-oxygen ratio 8:1 of the redox graphene (RGO) do not repaired, and the redox graphene after repairing can bring up to 19:1 effectively.Can determine that the oxygen level in the redox graphene after the reparation obtained reduces greatly thus.
The electric conductivity of the redox graphene after above-mentioned reparation also brings up to 450 ~ 600S/cm from 30 ~ 60S/cm of the redox graphene do not repaired at first, illustrate that the resistivity of the redox graphene after repairing reduces effectively, defect on redox graphene is repaired, make the quality of the redox graphene after repairing higher, after reparation, obtain the grapheme material of high-quality.
Embodiment 4
1, redox graphene is used absolute ethanol washing and water washing successively, then dry; Be scattered in oil of mirbane by washing and dried redox graphene, obtain graphene dispersing solution, wherein, the concentration of redox Graphene is 0.7mg/mL; In graphene dispersing solution, add cupric chloride and methyl chloride, stir and obtain the first mixture, wherein, the mass ratio of cupric chloride and redox graphene is 1:6, and the mass ratio of methyl chloride and redox graphene is 1:15; In the first mixture, add the hydrochloric acid that mass concentration is 39%, the mass ratio of hydrochloric acid and redox graphene is 1:0.2; The mixture of the first mixture and hydrochloric acid after 4 hours in 150W ultrasonic disperse, is reacted 1.5 hours, then carries out back flow reaction 4 hours in the microwave environment of 700W; React complete, the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then precipitates 2 times by washing with alcohol, dry, obtains the first crude product;
2, lithium chloride is melted, then the second crude product is added in the lithium chloride of thawing, and add the naphthalene and phenanthrene that mass ratio is 1:1, mix and obtain the second mixture, wherein, the mass ratio of the first crude product and lithium chloride is 1:40, and the mass ratio of the first crude product and naphthalene is 1:3.5, and the first crude product is 1:3.5 with luxuriant and rich with fragrance mass ratio; Second mixture is reacted 0.5 hour under 300W microwave environment, obtains melts solid; By the melts solid dispersal that obtains in water, add dilute sulphuric acid and regulate pH to 5, then suction filtration elimination solvent, with ethanol purge 2 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product;
3, the second crude product, 200 object palladium powder and cupric chloride are mixed, mix and obtain the 3rd mixture, wherein, the quality of palladium powder is 6% of the quality of the second crude product, and the quality of cupric chloride is 0.5% of the quality of the second crude product; Second mixture is put into retort furnace, pass into the mixed gas of argon gas, methane and ethene, be heated to 480 DEG C, maintain reaction 1.5h, transfer to again in vacuum drying oven, keep baking oven at 280 DEG C of annealing 6.5h under vacuum environment, more progressively cool to room temperature, wherein, the volume ratio of methane, ethene and argon gas is 1.5:1.5:7; Be poured into water by the mixture being cooled to room temperature, after 120W ultrasonication 2h, carry out suction filtration, filter residue mass concentration is the hydrochloric acid drip washing 5 times of 10%, removes suction filtration after catalyzer completely, gets filter residue, dry, obtains the redox graphene after repairing.
After measured, the carbon-to-oxygen ratio 6:1 of the redox graphene (RGO) do not repaired, and the redox graphene after repairing can bring up to 20:1 effectively.Can determine that the oxygen level in the redox graphene after the reparation obtained reduces greatly thus.
The electric conductivity of the redox graphene after above-mentioned reparation also brings up to 430 ~ 550S/cm from 30 ~ 40S/cm of the redox graphene do not repaired at first, illustrate that the resistivity of the redox graphene after repairing reduces effectively, defect on redox graphene is repaired, make the quality of the redox graphene after repairing higher, after reparation, obtain the grapheme material of high-quality.
Embodiment 5
1, redox graphene is used absolute ethanol washing and water washing successively, then dry; Be scattered in oil of mirbane by washing and dried redox graphene, obtain graphene dispersing solution, wherein, the concentration of redox Graphene is 0.6mg/mL; In graphene dispersing solution, add boron trifluoride and methyl iodide, stir and obtain the first mixture, wherein, the mass ratio of boron trifluoride and redox graphene is 1:4, and the mass ratio of methyl iodide and redox graphene is 1:8; In the first mixture, add the Nitromethane 99Min. that mass concentration is 40%, the mass ratio of Nitromethane 99Min. and redox graphene is 1:0.3; The mixture of the first mixture and Nitromethane 99Min. after 3 hours in 250W ultrasonic disperse, is reacted 1.8 hours, then carries out back flow reaction 4.5 hours in the microwave environment of 800W; React complete, the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then precipitates 2 times by washing with alcohol, dry, obtains the first crude product;
2, melted by aluminum chloride, then added in the aluminum chloride of thawing by the second crude product, and add cool, mix and obtain the second mixture, wherein, the mass ratio of the first crude product and aluminum chloride is 1:60, and the first crude product and cool mass ratio are 1:6; Second mixture is reacted 0.1 hour under 800W microwave environment, obtains melts solid; By the melts solid dispersal that obtains in water, add dilute sulphuric acid and regulate pH to 5, then suction filtration elimination solvent, with ethanol purge 2 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product;
3, the second crude product, 200 object platinum powder ends and cobalt chloride are mixed, mix and obtain the 3rd mixture, wherein, the quality at platinum powder end is 8% of the quality of the second crude product, and the quality of cobalt chloride is 2% of the quality of the second crude product; Second mixture is put into retort furnace, passes into the mixed gas of argon gas and methane, be heated to 460 DEG C, maintain reaction 1.8h, then transfer in vacuum drying oven, under vacuum environment, keep baking oven at 300 DEG C of annealing 7h, progressively cool to room temperature again, wherein, the volume ratio of methane and argon gas is 2:8; Be poured into water by the mixture being cooled to room temperature, after 120W ultrasonication 2h, carry out suction filtration, filter residue mass concentration is the hydrochloric acid drip washing 5 times of 10%, removes suction filtration after catalyzer completely, gets filter residue, dry, obtains the redox graphene after repairing.
After measured, the carbon-to-oxygen ratio 6:1 of the redox graphene (RGO) do not repaired, and the redox graphene after repairing can bring up to 21:1 effectively.Can determine that the oxygen level in the redox graphene after the reparation obtained reduces greatly thus.
The electric conductivity of the redox graphene after above-mentioned reparation also brings up to 460 ~ 600S/cm from 30 ~ 40S/cm of the redox graphene do not repaired at first, illustrate that the resistivity of the redox graphene after repairing reduces effectively, defect on redox graphene is repaired, make the quality of the redox graphene after repairing higher, after reparation, obtain the grapheme material of high-quality.
Embodiment 6
1, redox graphene is used absolute ethanol washing and water washing successively, then dry; Be scattered in normal hexane by washing and dried redox graphene, obtain graphene dispersing solution, wherein, the concentration of redox Graphene is 0.3mg/mL; In graphene dispersing solution, add aluminum chloride and methyl iodide, stir and obtain the first mixture, wherein, the mass ratio of aluminum chloride and redox graphene is 1:5, and the mass ratio of methyl iodide and redox graphene is 1:12; Add in the first mixture mass concentration be 98% sulfuric acid and mass concentration be the methylsulfonic acid of 95%, the mass ratio of sulfuric acid and redox graphene is 1:0.3, and the mass ratio of methylsulfonic acid and redox graphene is 1:0.3; The mixture of the first mixture, sulfuric acid and methylsulfonic acid after 2.5 hours in 180W ultrasonic disperse, is reacted 2 hours, then carries out back flow reaction 4 hours in the microwave environment of 500W; React complete, the solvent in suction filtration removing reaction solution is precipitated, and washes precipitation with water 1 time, then precipitates 2 times by washing with alcohol, dry, obtains the first crude product;
2, melted by boron trifluoride, then added in the boron trifluoride of thawing by the second crude product, and add pyrene, mix and obtain the second mixture, wherein, the mass ratio of the first crude product and boron trifluoride is 1:70, and the mass ratio of the first crude product and pyrene is 1:9; Second mixture is reacted 0.3 hour under 500W microwave environment, obtains melts solid; By the melts solid dispersal that obtains in water, add dilute sulphuric acid and regulate pH to 5, then suction filtration elimination solvent, with ethanol purge 2 times, by cyclohexane 1 time, then clean 1 time with dilute hydrochloric acid, finally wash, obtain the second crude product;
3, the second crude product, 200 object palladium powder and zinc chloride are mixed, mix and obtain the 3rd mixture, wherein, the quality of palladium powder is 7% of the quality of the second crude product, and the quality of zinc chloride is 0.1% of the quality of the second crude product; Second mixture is put into retort furnace, pass into the mixed gas of argon gas, methane and ethene, be heated to 470 DEG C, maintain reaction 1.5h, transfer to again in vacuum drying oven, keep baking oven at 320 DEG C of annealing 5.5h under vacuum environment, more progressively cool to room temperature, wherein, the volume ratio of methane, ethene and argon gas is 1:1:8; Be poured into water by the mixture being cooled to room temperature, after 120W ultrasonication 2h, carry out suction filtration, filter residue mass concentration is the hydrochloric acid drip washing 5 times of 10%, removes suction filtration after catalyzer completely, gets filter residue, dry, obtains the redox graphene after repairing.
After measured, the carbon-to-oxygen ratio 8:1 of the redox graphene (RGO) do not repaired, and the redox graphene after repairing can bring up to 25:1 effectively.Can determine that the oxygen level in the redox graphene after the reparation obtained reduces greatly thus.
The electric conductivity of the redox graphene after above-mentioned reparation also brings up to 560 ~ 650S/cm from 30 ~ 90S/cm of the redox graphene do not repaired at first, illustrate that the resistivity of the redox graphene after repairing reduces effectively, defect on redox graphene is repaired, make the quality of the redox graphene after repairing higher, after reparation, obtain the grapheme material of high-quality.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (18)
1. a restorative procedure for redox graphene, is characterized in that, comprises the steps:
Redox graphene is scattered in solvent, obtain graphene dispersing solution, in described graphene dispersing solution, add first via Lewis acid and obtain the first mixture containing the compound of methyl or methylene radical, described first mixture is reacted 0.5 hour ~ 2 hours under the microwave environment of 300 watts ~ 900 watts, then back flow reaction 3 hours ~ 5 hours, separation and purification is also dry, obtains the first crude product;
Described first crude product is added in the second Lewis acid, and add aromatic hydrocarbons healant, mix and obtain the second mixture, described second mixture is carried out being obtained by reacting melts solid, after described melts solid is carried out separation and purification, obtain the second crude product; And
Described second crude product, metal powdered catalysts and the 3rd Lewis acid are mixed; mix and obtain the 3rd mixture; in the shielding gas atmosphere of carbonaceous sources; described 3rd mixture is reacted 1 hour ~ 2 hours at 450 DEG C ~ 500 DEG C; then under vacuum conditions; anneal 5 hours ~ 8 hours at 200 DEG C ~ 350 DEG C, after being cooled to room temperature, separation and purification obtains the redox graphene after repairing.
2. the restorative procedure of redox graphene according to claim 1, is characterized in that, described solvent is selected from methylene dichloride, 1, at least one in 2 ethylene dichloride, tetracol phenixin, trichloromethane, hexanaphthene, normal hexane, benzene and oil of mirbane.
3. the restorative procedure of redox graphene according to claim 1 and 2, is characterized in that, in described graphene dispersing solution, the concentration of described redox graphene is 0.1mg/mL ~ 1mg/mL.
4. the restorative procedure of redox graphene according to claim 1, it is characterized in that, described first via Lewis acid and the second Lewis acid are all selected from least one in iron(ic) chloride, aluminum chloride, zinc chloride, boron trifluoride, magnesium chloride, cupric chloride and lithium chloride, and described 3rd Lewis acid is selected from least one in iron protochloride, iron(ic) chloride, lithium chloride, chromium chloride, cobalt chloride, zinc chloride and cupric chloride.
5. the restorative procedure of redox graphene according to claim 1, is characterized in that, the mass ratio of described first via Lewis acid and described redox graphene is 1:3 ~ 10.
6. the restorative procedure of redox graphene according to claim 1, is characterized in that, the described compound containing methyl or methylene radical is trioxymethylene, methyl alcohol, methyl chloride or methyl iodide.
7. the restorative procedure of the redox graphene according to claim 1 or 6, is characterized in that, described is 1:5 ~ 20 containing methyl or the compound of methylene radical and the mass ratio of redox graphene.
8. the restorative procedure of redox graphene according to claim 6, it is characterized in that, described described first mixture is reacted under the microwave environment of 300 watts ~ 900 watts the step of 0.5 hour ~ 2 hours before, also comprise the step adding strong acid in described first mixture, the mass ratio of described strong acid and described redox graphene is 1:0.1 ~ 1.
9. the restorative procedure of redox graphene according to claim 8, is characterized in that, described strong acid is selected from least one in sulfuric acid, methylsulfonic acid, Phenylsulfonic acid, Nitromethane 99Min., nitric acid, hydrochloric acid, trichoroacetic acid(TCA) and perchloric acid.
10. the restorative procedure of redox graphene according to claim 1, is characterized in that, described first crude product and described second lewis acidic mass ratio are 1:20 ~ 100.
The restorative procedure of 11. redox graphenes according to claim 1, is characterized in that, described aromatic hydrocarbons healant is selected from least one in naphthalene, anthracene, phenanthrene, cool and pyrene.
The restorative procedure of 12. redox graphenes according to claim 1, is characterized in that, the mass ratio of described first crude product and described aromatic hydrocarbons healant is 1:5 ~ 10.
The restorative procedure of 13. redox graphenes according to claim 1, is characterized in that, the described step carrying out described second mixture to be obtained by reacting melts solid is specially:
Described second mixture is reacted 3 hours ~ 5 hours at 200 DEG C ~ 350 DEG C; Or
Described second mixture is reacted 0.1 hour ~ 0.5 hour under the microwave environment of 300 watts ~ 800 watts.
The restorative procedure of 14. redox graphenes according to claim 1, is characterized in that, the quality of described metal powdered catalysts is 5% ~ 10% of the quality of described second crude product.
The restorative procedure of 15. redox graphenes according to claim 1 or 14, it is characterized in that, described metal powdered catalysts is selected from least one in copper powder, zinc powder, silver powder, palladium powder and platinum powder end.
The restorative procedure of 16. redox graphenes according to claim 1, is characterized in that, described 3rd lewis acidic quality is 0.1% ~ 5% of the quality of described second crude product.
The restorative procedure of 17. redox graphenes according to claim 1; it is characterized in that; the shielding gas atmosphere of described carbonaceous sources is the gas mixture atmosphere of organic phase gas and rare gas element, and described organic phase gas is at least one in methane, ethene and gaseous state ethanol.
The restorative procedure of 18. redox graphenes according to claim 17, is characterized in that, the volume ratio of described organic phase gas and described rare gas element is 1 ~ 3:7 ~ 9.
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