CN102502597B - Graphene and preparation method thereof - Google Patents
Graphene and preparation method thereof Download PDFInfo
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- CN102502597B CN102502597B CN2011103216659A CN201110321665A CN102502597B CN 102502597 B CN102502597 B CN 102502597B CN 2011103216659 A CN2011103216659 A CN 2011103216659A CN 201110321665 A CN201110321665 A CN 201110321665A CN 102502597 B CN102502597 B CN 102502597B
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Abstract
The invention discloses graphene and a preparation method of the graphene. The method comprises the following steps of: dispersing graphite oxide into an organic solvent to obtain suspension solution of the graphite oxide; uniformly mixing a Grignard reagent with the suspension solution of the graphite oxide and carrying out reflowing reaction; and after the reaction is finished, obtaining the graphene. According to the invention, the quality of the graphene can be adjusted and controlled by adjustment of the use amount of the Grignard reagent, the reaction time and the reaction temperature. The graphene and the preparation method of the graphene, provided by the invention, have the advantages of abundant raw material sources, low price, easiness of operation, simple process and good repeatability, and is suitable for large-scale production.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of Graphene and preparation method thereof.
Background technology
Graphene is that the professors such as British scientist Geim in 2004 have found by carbon atom with sp
2The New Two Dimensional atomic crystal that the monoatomic layer that hydridization connects consists of, its basic structural unit is that (Science 2004,306,666-669) for benzene six-ring the most stable in organic materials.The Graphene special construction has contained abundant and novel physical phenomenon, makes it show many excellent properties.For example, the intensity of Graphene is the highest in test material, reaches 130GPa, is more than 100 times of steel, and its carrier mobility reaches 15000cm
2V
-1s
-1, be present known twice with indium antimonide material of high mobility, surpass more than 10 times of commercial silicon chip mobility, under given conditions (as cryogenic quenching etc.), its mobility even can reach 250000cm
2V
-1S
-1Its thermal conductivity can reach 5000Wm
-1K
-1, be adamantine 3 times; Also have the special propertys such as room temperature quantum hall effect and room-temperature ferromagnetic.Therefore, a small amount of graphene nano is filled in polymeric matrix, can improves the performance of polymeric matrix, as electroconductibility, barrier property, mechanical property and heat conductivility etc.
The preparation method of Graphene mainly contains two large classes at present: (Macromolecules 2010,43,6515-6530) for inverted type (Bottom-Up graphene) and sequential method (Top-Down graphene).In inverted type, mainly comprise chemical Vapor deposition process (chemical vapor deposition, CVD) and epitaxial growth method (epitaxial growth on SiC).Although this method can be prepared large size, the less graphene sheet layer of defective, its productive rate is lower, is applicable to the application of basic research and electronics aspect, is not suitable for the polymer composites field that needs a large amount of Graphenes.
In sequential method, mainly comprise micromechanics stripping method and reduction method (chemical reduction and hot reducing method).The productive rate of micromechanics stripping method is lower, is not suitable for Graphene and prepares on a large scale.Because graphite oxide source is abundant, can realize large-scale preparation and use, so in reduction method take graphite oxide as raw material, thereby it is more to add reductive agent to reduce the report of preparation Graphene to it.Report mainly contains the method for graphene oxide reduction at present: chemical process and hot reducing method.No matter adopt which kind of method of reducing, its objective is that gained redox graphene and original Graphene are similar, and can satisfy the application of different field.Hot reducing method is namely by rapid heating graphene oxide to 1100 ℃ in rare gas element, effective redox graphene, and still this method needs hot conditions, to having relatively high expectations of equipment and environment.Chemical reduction method is to add strong reductant such as trap, and dimethyl trap etc. carries out reduction reaction to graphene oxide, thereby recovers the graphene mesh structural integrity, gives this redox graphene electroconductibility.Although the cost of trap is lower, trap severe toxicity, easy-clear not can cause personal injury, environmental pollution and structure deteriorate.
Summary of the invention
The purpose of this invention is to provide a kind of Graphene and preparation method thereof.
The method for preparing Graphene provided by the invention, comprise the steps: graphite oxide is scattered in the suspension that obtains graphite oxide in organic solvent, with back flow reaction after the suspension mixing of grignard reagent and described graphite oxide, react and obtain described Graphene after complete.
In aforesaid method, the general structure of described grignard reagent is R-MgX, and wherein, R is that the total number of carbon atoms is any one in the alkyl of 1-10, and preferable methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, X are fluorine, chlorine, bromine or iodine.
The particle diameter of described graphite oxide is 1～200um, preferred 40～100um; In described graphite oxide, the mol ratio of carbon, oxygen element and protium is 6: 2～4: 1～3, and is preferred 6: 2.33～3.7: 1.2～2.83, specifically can be 6: 2.33-2.8: 1.2-2.3 or 6: 2.8-3.7: 2.3-2.83.In the suspension of described graphite oxide, the concentration of graphite oxide is 0.1～20mg/mL, preferred 1～10mg/mL specifically can be 4-10mg/mL, 4-6mg/mL, 5-6mg/mL, 5-10mg/mL, 6-10mg/mL, 1-4mg/mL, 1-5mg/mL, 1-6mg/mL or 4-5mg/mL.
Described Grignard reagent is 0.1: 1～20: 1 with the mole dosage ratio that feeds intake of described graphite oxide, preferred 1: 1～10: 1, specifically can be 1-5: 1,1-6: 1,5-10: 1 or 6-10: 1, wherein, the molar weight of described graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
In described back flow reaction step, temperature is 40～150 ℃, preferred 40-120 ℃, specifically can be 40-120 ℃, 40-90 ℃ or 90-120 ℃; Time is 0.5～96 hour, preferred 4～48 hours, specifically can be 8-48 hour, 8-20 hour, 8-10 hour, 10-48 hour, 10-20 hour or 20-48 hour.Described back flow reaction is carried out in inert atmosphere; Described inert atmosphere is nitrogen or argon gas;
It is that alkane, the total number of carbon atoms of 5～10 are that aromatic hydrocarbon, the total number of carbon atoms of 6～9 are that naphthenic hydrocarbon, the total number of carbon atoms of 6～9 are at least a in 2～12 ether and tetrahydrofuran (THF) that described organic solvent is selected from the total number of carbon atoms, at least a in preferred tetrahydrofuran (THF), hexane, heptane, decane, ether, positive propyl ether, butyl ether, isopropyl ether, amyl ether, isoamyl ether, toluene, dimethylbenzene and hexanaphthene.
The described method for preparing Graphene also comprises the steps: after described back flow reaction step, with reaction product with described organic solvent washing after vacuum-drying again.In described washing step, number of times is 3-5 time; In described vacuum drying step, temperature is 40～100 ℃, preferred 50～70 ℃, specifically can be 50-60 ℃ or 60-70 ℃, vacuum tightness is 0.1～0.01MPa, preferred 0.05～0.01MPa, more preferably 0.01MPa, time is 1-72 hour, preferred 10～24 hours, specifically can be 10-20 hour, 10-15 hour, 15-24 hour, 15-20 hour or 20-24 hour.
The Graphene for preparing according to the method described above also belongs to protection scope of the present invention.The electric conductivity of this Graphene is 6.10 * 10
2S/m to 6.80 * 10
3S/m specifically can be 6.10 * 10
2S/m to 9.83 * 10
2S/m, 6.10 * 10
2S/m to 6.05 * 10
3S/m, 6.10 * 10
2S/m to 6.80 * 10
3S/m, 9.83 * 10
2S/m to 6.05 * 10
3S/m, 9.83 * 10
2S/m to 6.80 * 10
3S/m, 6.05 * 10
3S/m to 6.80 * 10
3S/m or 2.55 * 10
3S/m to 6.80 * 10
3S/m.
The method for preparing Graphene provided by the invention is to utilize Grignard reagent reduction-oxidation graphite-made standby and get.The method has the following advantages:
1. Graphene provided by the invention, visual inspection is black powder, high resolution transmission electron microscopy is observed and is made sheet structure, some fold of the part of sheet structure.
2. the present invention can realize the quality (comprising spacing between number, lamella and the lamella of functional group on graphene sheet layer and the size of lamella etc.) of Graphene, namely by regulating Grignard reagent and the mole dosage of graphite oxide, kind, reaction times and the temperature of reaction etc. of organic solvent.
3. Graphene provided by the invention has higher electroconductibility, and the carrier that can be used as olefin polymerization catalysis realizes that in-situ polymerization prepares polyolefine/graphene composite material.
4. the Graphene of the Grignard reagent reduction method preparation adopted of the present invention, compared with the prior art, its maximum characteristics are that raw material sources are abundant, and cheap, environmental pollution and structure deteriorate are lower, and the experiment favorable reproducibility is suitable for large-scale production.
Description of drawings
The Graphene field emission scanning electron microscope photo (embodiment 1) of Fig. 1 chemical preparation.
The Graphene of Fig. 2 chemical preparation
13C solid state nmr spectrogram (embodiment 1)
The Graphene high resolution transmission electron microscopy photo (embodiment 2) of Fig. 3 chemical preparation.
The Graphene C1s photoelectron spectrum figure (embodiment 2) of Fig. 4 chemical preparation
The typical laser Raman spectroscopy figure of the Graphene of Fig. 5 chemical preparation (embodiment 3).
The X-ray diffraction curve of the Graphene of Fig. 6 chemical preparation (embodiment 4).
The Graphene of Fig. 7 chemical preparation
13C solid state nmr spectrogram (embodiment 5).
The thermal weight loss decomposition curve of the Graphene of Fig. 8 chemical preparation (embodiment 5).
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described raw material all can get from open commercial sources if no special instructions.In following embodiment, the electric conductivity of Graphene all adopts the four electrode method test of standard.
Embodiment 1
In argon atmosphere, the 1g graphite oxide is scattered in the 100mL tetrahydrofuran (THF), the particle diameter of graphite oxide is 40～100um, wherein the mol ratio of C in graphite oxide: O: H is 6: 2.8: 2.3, obtains the suspension liquid of graphite oxide; Add the tetrahydrofuran solution (10mL) that contains 0.0235mol grignard reagent chlorination normal-butyl magnesium in this suspension liquid, reflux in the time of 90 ℃, the reaction times is 48 hours.After reaction finishes, filter, with 3～5 products of tetrahydrofuran (THF) washing, 70 ℃ of dryings of 0.01MPa vacuum 10 hours obtain Graphene.
In aforesaid method, the concentration of graphite oxide in tetrahydrofuran solvent is 10mg/mL, and the mol ratio of grignard reagent chlorination normal-butyl magnesium and graphite oxide is 1: 1, and the molar weight of graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
The field emission scanning electron microscope photo of gained Graphene as shown in Figure 1, Graphene structure in the form of sheets still as shown in Figure 1.The gained Graphene
13C solid state nmr spectrogram as shown in Figure 2, as shown in Figure 2, chemical shift be 60 and the peak at 70ppm place weaken, illustrate that C-OH and the C-O on graphene sheet layer disappears substantially.
The electric conductivity that four electrode method by standard records the gained Graphene is 6.10 * 10
2S/m.
In nitrogen atmosphere, the 1g graphite oxide is scattered in the 200mL ether, the particle diameter of graphite oxide is 40～100um, wherein the mol ratio of C in graphite oxide: O: H is 6: 2.33: 1.2, obtains the suspension liquid of graphite oxide; Add the diethyl ether solution (20mL) that contains 0.105mol grignard reagent chlorination normal-butyl magnesium in this suspension liquid, reflux in the time of 40 ℃, the reaction times is 20 hours.After reaction finishes, filter, with 3～5 products of ether washing, 60 ℃ of dryings of 0.01MPa vacuum 15 hours obtain Graphene.
In aforesaid method, the concentration of graphite oxide in ether solvent is 5mg/mL, and the mol ratio of grignard reagent chlorination normal-butyl magnesium and graphite oxide is 5: 1, and the molar weight of graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
The high-resolution-ration transmission electric-lens photo of gained Graphene as shown in Figure 3, Graphene structure in the form of sheets still as shown in Figure 3.The C 1s photoelectron spectrum figure of gained Graphene as shown in Figure 4, as shown in Figure 4, in conjunction with substantially disappearing for the peak that 286.6eV (C-O) locates.
The electric conductivity that four electrode method by standard records the gained Graphene is 9.83 * 10
2S/m.
Embodiment 3
In nitrogen atmosphere, the 1g graphite oxide is scattered in 1000mL toluene, the particle diameter of graphite oxide is 40～100um, wherein the mol ratio of C in graphite oxide: O: H is 6: 3.7: 1.2, obtains the suspension liquid of graphite oxide; Add the amyl ether solution (40mL) that contains 0.279mol grignard reagent bromination isopropyl-magnesium in this suspension liquid, reflux in the time of 120 ℃, the reaction times is 10 hours.After reaction finishes, filter, with amyl ether and 3～5 products of toluene wash, 60 ℃ of dryings of 0.01MPa vacuum 24 hours obtain Graphene.
In aforesaid method, the concentration of graphite oxide in toluene solvant is 1mg/mL, and the mol ratio of grignard reagent bromination isopropyl-magnesium and graphite oxide is 10: 1, and the molar weight of graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
The laser Raman spectroscopy of gained Graphene as shown in Figure 5.
The electric conductivity that four electrode method by standard records the gained Graphene is 6.80 * 10
3S/m.
Embodiment 4
In argon atmosphere, the 1.2g graphite oxide is scattered in the 200mL butyl ether, the particle diameter of graphite oxide is 40～100um, wherein the mol ratio of C in graphite oxide: O: H is 6: 3.7: 2.83, obtains the suspension liquid of graphite oxide; Add the butyl ether solution (10mL) that contains 0.200mol grignard reagent ethyl-magnesium-bromide in this suspension liquid, reflux in the time of 120 ℃, the reaction times is 8 hours.After reaction finishes, filter, with 3～5 products of butyl ether washing, 50 ℃ of dryings of 0.01MPa vacuum 20 hours obtain Graphene.
In aforesaid method, the concentration of graphite oxide in toluene solvant is 6mg/mL, and the mol ratio of grignard reagent ethyl-magnesium-bromide and graphite oxide is 6: 1, and the molar weight of graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
The X-ray diffraction curve of gained Graphene as shown in Figure 6.As shown in Figure 6, the sheet interlayer spacing of Graphene is state of disarray.
The electric conductivity that four electrode method by standard records the gained Graphene is 6.05 * 10
3S/m.
Embodiment 5
In argon atmosphere, the 0.8g graphite oxide is scattered in the 200mL heptane, the particle diameter of graphite oxide is 40～100um, wherein the mol ratio of C in graphite oxide: O: H is 6: 3.0: 2.83, obtains the suspension liquid of graphite oxide; Add in this suspension liquid and contain the 0.118mol grignard reagent and fluoridize the tetrahydrofuran solution of propyl group magnesium (5mL), reflux in the time of 120 ℃, the reaction times is 8 hours.After reaction finishes, filter, with tetrahydrofuran (THF) and 3～5 products of heptane wash, 50 ℃ of dryings of 0.01MPa vacuum 20 hours obtain Graphene.
In aforesaid method, the concentration of graphite oxide in toluene solvant is 4mg/mL, and the mol ratio of grignard reagent ethyl-magnesium-bromide and graphite oxide is 6: 1, and the molar weight of graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
The gained Graphene
13C solid state nmr spectrogram as shown in Figure 7, as shown in Figure 7, chemical shift be 60 and the peak at 70ppm place disappear, C-OH and C-O disappearance on graphene sheet layer be describeds.The thermal weight loss decomposition curve of gained Graphene as shown in Figure 8, as seen from Figure 8, the thermostability of gained Graphene obviously improves.
The electric conductivity that four electrode method by standard records the gained Graphene is 2.55 * 10
3S/m.
Claims (15)
1. a method for preparing Graphene, comprise the steps: graphite oxide is scattered in the suspension that obtains graphite oxide in organic solvent, with back flow reaction after the suspension mixing of Grignard reagent and described graphite oxide, reacts and obtain described Graphene after complete;
The general structure of described Grignard reagent is R-MgX, and wherein, R is methyl, ethyl, propyl group, sec.-propyl, butyl or isobutyl-, and X is fluorine, chlorine, bromine or iodine.
2. method according to claim 1, it is characterized in that: the particle diameter of described graphite oxide is 1 ~ 200 μ m;
In described graphite oxide, the mol ratio of carbon, oxygen element and protium is 6:2 ~ 4:1 ~ 3.
3. method according to claim 2, it is characterized in that: the particle diameter of described graphite oxide is 40 ~ 100 μ m;
In described graphite oxide, the mol ratio of carbon, oxygen element and protium is 6:2.33 ~ 3.7:1.2 ~ 2.83.
4. method according to claim 1 is characterized in that: described Grignard reagent feeds intake mole dosage than being 0.1:1 ~ 20:1 with described graphite oxide, and wherein, the molar weight of described graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
5. method according to claim 4 is characterized in that: described Grignard reagent feeds intake mole dosage than being 1:1 ~ 10:1 with described graphite oxide, and wherein, the molar weight of described graphite oxide is calculated by the mole dosage that wherein contains Sauerstoffatom.
6. method according to claim 1, it is characterized in that: in described back flow reaction step, temperature is 40 ~ 150 ° of C; Time is 0.5 ~ 96 hour.
7. method according to claim 6, it is characterized in that: in described back flow reaction step, temperature is 40-120 ℃; Time is 4 ~ 48 hours.
8. method according to claim 1, it is characterized in that: in the suspension of described graphite oxide, the concentration of graphite oxide is 0.1 ~ 20mg/mL.
9. method according to claim 8, it is characterized in that: in the suspension of described graphite oxide, the concentration of graphite oxide is 1 ~ 10mg/mL.
10. method according to claim 1, it is characterized in that: described back flow reaction is carried out in inert atmosphere; Described inert atmosphere is nitrogen or argon gas;
It is that alkane, the total number of carbon atoms of 5 ~ 10 are that aromatic hydrocarbon, the total number of carbon atoms of 6 ~ 9 are that naphthenic hydrocarbon, the total number of carbon atoms of 6 ~ 9 are at least a in 2 ~ 12 ether and tetrahydrofuran (THF) that described organic solvent is selected from the total number of carbon atoms.
11. method according to claim 10 is characterized in that: described organic solvent is selected from least a in tetrahydrofuran (THF), hexane, heptane, decane, ether, positive propyl ether, butyl ether, isopropyl ether, amyl ether, isoamyl ether, toluene, dimethylbenzene and hexanaphthene.
12. method according to claim 1 is characterized in that: the described method for preparing Graphene also comprises the steps: after described back flow reaction step, with reaction product with described organic solvent washing after vacuum-drying again; In described washing step, number of times is 3-5 time; In described vacuum drying step, temperature is 40～100 ℃, and vacuum tightness is 0.1 ~ 0.01MPa, and the time is 1-72 hour.
13. method according to claim 12 is characterized in that: in described vacuum drying step, temperature is 50～70 ℃, and vacuum tightness is 0.05 ~ 0.01MPa, and the time is 10 ~ 24 hours.
14. the Graphene that in claim 1-13, arbitrary described method prepares.
15. Graphene according to claim 14 is characterized in that: the electric conductivity of described Graphene is 6.10 * 10
2S/m to 680 * 10
3S/m.
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| JP7042282B2 (en) | 2017-03-16 | 2022-03-25 | ライテン・インコーポレイテッド | Fusion of carbon and elastomer |
| US10920035B2 (en) | 2017-03-16 | 2021-02-16 | Lyten, Inc. | Tuning deformation hysteresis in tires using graphene |
| WO2019126196A1 (en) | 2017-12-22 | 2019-06-27 | Lyten, Inc. | Structured composite materials |
| CN112105922A (en) | 2018-01-04 | 2020-12-18 | 利腾股份有限公司 | Resonant gas sensor |
| CN108398577B (en) * | 2018-01-30 | 2020-12-11 | 中国科学院青海盐湖研究所 | Method for testing reduction degree of graphene oxide |
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