CN103145117A - Method for preparing graphene - Google Patents
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- CN103145117A CN103145117A CN2013100640516A CN201310064051A CN103145117A CN 103145117 A CN103145117 A CN 103145117A CN 2013100640516 A CN2013100640516 A CN 2013100640516A CN 201310064051 A CN201310064051 A CN 201310064051A CN 103145117 A CN103145117 A CN 103145117A
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Abstract
The invention discloses a method for preparing graphene, which is implemented in a way that: in a chemical vapor deposition process, a catalyst is utilized to activate the properties of carbon dioxide, and hydrogenation reaction is carried out to grow graphene on a copper substrate. The flow rate of the carbon dioxide is controlled to change the concentration of the carbon source, thereby achieving the effect of shape evolution. Compared with the traditional method, the method disclosed by the invention greatly enhances the controllable degree of the shape in the graphene preparation process, and prepares the hexagonal-to-round graphene in a controllable way.
Description
Technical field
The present invention relates to a kind of method for preparing Graphene.
Background technology
Grapheme material is the two dimensional crystal of first stable existence, architecture basics as zero dimension soccerballene, one dimension carbon nanotube and three-dimensional graphite, have unique machinery, electricity, optics and thermal property, be with a wide range of applications in fields such as nanoelectronics, matrix material, transparent conductive film and energy storage.Since the Coase Dalmatia Nuo Woxiefu of University of Manchester in 2004 and An Deliegaimu group found Graphene, many physics, chemical process were used to prepare high-quality grapheme material.These methods comprise mechanically peel method, silicon carbide epitaxial growth method, graphite oxide reduction method, ultrasonic auxiliary separating arching pushing, solvent-thermal method, chemical Vapor deposition process and organic synthesis method (K.S.Novoselov, A.K.Geim, Science2004,306,666.; C.Berger, Z.Song, X.Li, Science2006,312,1191.; V.C.Tung, M.J.Allen, Nat.Nanotechnol.2009,4,25.; Y.Hernandez, V.Nicolosi, Nat.Nanotechnol.2008,3,563.; K.S.Kim, Y.Zhao, Nature2009,457,706.; X.Li, W.Cai, Science2009,324,1312; M.Choucair, P.Thordarson, Nature Nanotech.2009,4,30.J.Cai, P.Ruffieux, Nature2010,466,470.).Mechanically peel method and epitaxial growth method mainly are used to the high-quality Graphene sample of preparation in the laboratory, yet output is very low.The graphite oxide reduction method can a large amount of Graphene sample of chemical preparation, satisfies to a certain extent the industrial application requirement, yet due to the introducing of oxygenant, has destroyed the conjugated structure of Graphene.Although chemical reduction and high-temperature heat treatment can be recovered the conjugated structure of Graphene to a certain extent, yet the intrinsic electric property of Graphene reduces greatly.The advantages such as chemical Vapor deposition process is high due to the Graphene quality of its preparation, controllable operating is strong, extensive are considered to the graphene preparation method of tool potentiality always.It is found that recently by chemical Vapor deposition process and can control growth to Graphene, comprising: pattern, size, homogeneity, the number of plies and stack manner etc., this has greatly opened up the application prospect of Graphene.
Involved carbon source generally comprises such as methane, acetylene, ethanol, polymethacrylate and mothball etc. of gas, liquid, solid attitude hydrocarbon polymer in the process of process for preparing graphenes by chemical vapour deposition at present, utilizes pyrolytic decomposition to realize the chemical vapor deposition growth of Graphene.Some potential safety hazards such as that yet these carbon sources in use exist is flammable, toxicity do not meet the requirement of Green Chemistry and large-scale industrial production.Therefore how to seek efficient, environmentally friendly carbon source and realize that the Graphene preparation is in the Graphene field and even the study hotspot of whole Green Chemistry.In addition, carbonic acid gas (CO
2) be main greenhouse gases, be the final product of hydrocarbon combustion, character is very stable, and is not easily-activated.But the renewable energy source application examples of carbonic acid gas such as catalyst reduction prepare the focus that the technology such as Sweet natural gas is also research always.If we can in conjunction with these two aspects, utilize reduction CO
2Activating technology and then preparation Graphene, this maybe will open up tree-covered walkways for realizing the preparation of Graphene heavy industrialization.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing Graphene.
The method for preparing Graphene provided by the invention comprises the steps:
Quartz boat and the substrate that 1) will be loaded with methanation catalyst are placed successively along the direction of gas communication, both be positioned at same plane, again described silica tube is put into electric furnace, make the center of the described electric furnace of described substrate alignment, pass into the hydrogen post-heating, when making the temperature at described electric furnace center be 800-1050 ℃, keep stabilizing annealing 10-60 minute;
2) the described step 1 of maintenance), the electric furnace central zone is temperature-resistant, after the described quartz boat that is loaded with methanation catalyst is heated to temperature and is 50～300 ℃, be filled with carbon source in the described silica tube and hydrogen carries out chemical vapour deposition, at described Grown Graphene, deposit the gas mixture that passes into argon gas and hydrogen after complete cooling after, obtain described Graphene on described substrate.
The step 1 of aforesaid method) in, described methanation catalyst is specially Ni/Al
2O
3The type methanation catalyst can be bought by open commercial sources and obtain, and as can be available from this Science and Technology Ltd. in the Kate of Beijing, product specification be N1118; The consumption of catalyzer is relevant with the final carbon source amount that transforms, and the consumption of methanation catalyst is more, and the active carbon source that catalysis obtains is also just more;
described methanation catalyst and described step 2) amount ratio of carbon source is 20g: 1-30sccm, specifically can be 20g: 1sccm, 20g: 3sccm, 20g: 5sccm, 20g: 10sccm, 20g: 15sccm, 20g: 20sccm, 20g: 30sccm, 20g: 1-20sccm, 20g: 1-15, 20g: 1-10, 20g: 1-5, 20g: 1-3, 20g: 3-30sccm, 20g: 3-20sccm, 20g: 3-15sccm, 20g: 3-10sccm, 20g: 3-5sccm, 20g: 5-30sccm, 20g: 5-20sccm, 20g: 5-15sccm, 20g: 5-10sccm, 20g: 10-30sccm, 20g: 10-20sccm, 20g: 20-30sccm, 20g: 15-30sccm, 20g: 15-20sccm or 20g: 10-15sccm,
Described substrate is Copper Foil;
The thickness of described Copper Foil is the 10-100 micron, is specially 25 microns.
At a distance of 1-80cm, be specially 20cm between the central point of described quartz boat and substrate;
Described passing in the hydrogen step, the flow of hydrogen is 50-250scm, is specially 150scm; Time is 5-50 minute, is specially 20 minutes;
The temperature of described electric furnace central zone is 1000 ℃;
In described annealing steps, the time is 30 minutes.
Described step 2) in, described carbon source is selected from least a in carbonic acid gas and carbon monoxide;
The throughput ratio of described carbon source and hydrogen is 1: 200-30: 200, be specially 1: 200,3: 200; 5: 200,10: 200,15: 200,20: 200,30: 200,1-20: 200,1-15: 200,1-10: 200,1-5: 200,1-3: 200,3-30: 200,3-20: 200,3-15: 200,3-10: 200,3-5: 200,5-30: 200,5-20: 200,5-15: 200,5-10: 200,10-30: 200,10-20: 200,20-30: 200,15-30: 200,15-20: 200 or 10-15: 200;
The flow of described carbon source is 1-30sccm, specifically can be 1,3,5,10,15,20,30,1-20,1-15,1-10,1-5,1-3,3-30,3-20,3-15,3-10,3-5,5-30,5-20,5-15,5-10,10-30,10-20,20-30,15-30,15-20 or 10-15sccm;
The flow of described hydrogen is 200sccm;
In described deposition step, the time is 10-60 minute, is specially 30 minutes; Pressure is 0-1.01 * 10
5Pa, but be not 0, described pressure is specially 1.01 * 10
5Pa.
In described cooling step, the throughput ratio of argon gas and hydrogen is 100-200: 50; Wherein, the flow of described argon gas is specially 100-200sccm, is more specifically 150sccm; The flow of hydrogen is specially 50sccm;
Described method also comprises the steps: in described step 1) before, described substrate is handled as follows: described substrate is used by hydrochloric acid and water successively with volume ratio 1: 1-1: 50 (being specially 1: 20) mix and each ultrasonic cleaning of hydrochloric acid soln, acetone and ethanol 3 minutes, nitrogen dries up.
Described step 2) in the chemical vapour deposition step, the throughput ratio of described carbon source and hydrogen is 1-5: 200 o'clock, the pattern of gained Graphene was sexangle; The flow of described carbon source is specially 1 or 3 or 5 or 1-3 or 3-5sccm, and the flow of described hydrogen is 200sccm;
The throughput ratio of described carbon source and hydrogen is 20-30: 200 o'clock, the pattern of gained Graphene was circular; Wherein, the flow of described carbon source is specially 20 or 30sccm, and the flow of described hydrogen is 200sccm;
The throughput ratio of described carbon source and hydrogen is 5-20: 200 o'clock, the pattern of gained Graphene was by the arbitrary shape of sexangle to circular transition; Wherein, the flow of described carbon source is specially 10sccm, and the flow of hydrogen is specially 200sccm.
In addition, the Graphene for preparing according to the method described above also belongs to protection scope of the present invention.Wherein, the pattern of described Graphene is sexangle or circle or is by the arbitrary shape of sexangle to circular transition.
The method for preparing Graphene provided by the invention is in the process of chemical vapour deposition, utilizes the character of catalyst activation carbonic acid gas, and then by hydrogenation reaction growing graphene in the copper substrate.Thereby change by the flow of controlling carbonic acid gas the effect that carbon source concentration reaches Morphology.The method has feature and advantage:
1. the present invention discloses the method for preparing Graphene in chemical vapor deposition processes by the technique of carbonic acid gas being carried out the catalyst activation hydrogenation reaction for the first time.
2. the present invention discloses the technique of coming the graphene nano material of controlled preparation Morphology by the method that changes carbonic acid gas and hydrogen flowing quantity proportioning for the first time.
3. method disclosed by the invention, compare with traditional method, greatly increased the controllable degree of its pattern in preparation Graphene process, controllably prepared by sexangle to be converted to circular Graphene.
Description of drawings
Fig. 1 is low power and the powerful microscope photo of the sexangle Graphene of embodiment 1 preparation;
Fig. 2 is transmission electron microscope picture and the border high-resolution-ration transmission electric-lens figure of the sexangle Graphene of embodiment 1 preparation;
Fig. 3 is low power and the high power stereoscan photograph of the circular Graphene of embodiment 2 preparations;
Fig. 4 is transmission electron microscope picture and the border high-resolution-ration transmission electric-lens figure of the circular Graphene of embodiment 2 preparations;
Fig. 5 is that the Graphene pattern of embodiment 3 preparations is roughly developed the atomic force microscope figure of circular pattern by hexagonal;
Fig. 6 is the graphite Raman spectrogram with Typical Representative that the present invention prepares.
Fig. 7 is 7 kinds of scanning electron microscope (SEM) photographs corresponding to different Graphenes of 7 value gained of carbon dioxide flow.
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 starting material all can get from open commercial sources if no special instructions.
1) clean the Copper Foil growth substrate:
Be hydrochloric acid soln, acetone, each ultrasonic cleaning of ethanol 3 minutes of 1: 20 with volume ratio successively with Copper Foil, nitrogen dries up;
2) will be loaded with 20 gram Ni/Al
2O
3The quartz boat of type methanation catalyst and through step 1) clean substrate (Copper Foils of 25 micron thickness) places successively along the direction of gas communication, both is positioned at same plane, and between the central point of quartz boat and substrate at a distance of 20cm.Again silica tube is put into electric furnace, the core temperature district of Copper Foil substrate alignment Electric stove passed into 150sccm hydrogen after 20 minutes, began heating, when the temperature of electric furnace central zone reaches 1000 ℃, kept stabilizing annealing 30 minutes;
3) growing graphene:
Keep step 2) in temperature in the tube furnace silica tube be 1000 ℃, utilize the heating zone to Ni/Al
2O
3The type methanation catalyst heats, and temperature is controlled at 100～200 ℃, and the temperature of keeping in the tube furnace silica tube is 1000 ℃, and passing into flow is the carbonic acid gas of 5sccm and the hydrogen of 200sccm, 1.01 * 10
5Under pascal's pressure, growth is after 30 minutes, then close the carbonic acid gas as carbon source, be reduced under the hydrogen of 50sccm and 150sccm argon gas mixed airflow furnace cooling to room temperature at flow, obtain sexangle Graphene provided by the invention, as shown in Figure 1, and the preparation sample characterizes through transmission electron microscope, as shown in Figure 2.
According to the identical method of embodiment 1, only with step 3) in pass into carbon dioxide flow and be increased to 20sccm.Thereby change the concentration of carbon atom by the flow that increases carbonic acid gas, and then affect the pattern of gained Graphene, circular Graphene low power and the high power scanning electron microscope (SEM) photograph of Fig. 3 for obtaining.And the circular Graphene of gained prepares sample and characterizes through transmission electron microscope, as shown in Figure 4.
According to the identical method of embodiment 1, only with step 3) in pass into carbon dioxide flow respectively value 5,10,20sccm.Get the differentiation of Graphene pattern by observation post, find that the pattern of gained Graphene changes to circular pattern by hexagonal, as shown in Figure 5 in atomic force microscope, and its circular Graphene has been done the Raman sign, as shown in Figure 6.
Embodiment 4, carbon dioxide activation hydrogenation reaction growth hexagonal are transitioned into the Graphene of circular pattern gradually
According to the identical method of embodiment 1, only with step 3) in pass into carbon dioxide flow respectively value 1,3,5,10,15,20,30sccm, observation post gets the trickle differentiation of Graphene pattern, the pattern of finding the gained Graphene is transitioned into circular pattern gradually by hexagonal, is illustrated in figure 7 as 7 kinds of scanning electron microscope (SEM) photographs corresponding to different Graphenes of 7 value gained of carbon dioxide flow.
Claims (10)
1. a method for preparing Graphene, comprise the steps:
Quartz boat and the substrate that 1) will be loaded with methanation catalyst are placed successively along the direction of gas communication, both be positioned at same plane, again described silica tube is put into electric furnace, make the center of the described electric furnace of described substrate alignment, pass into the hydrogen post-heating, when making the temperature at described electric furnace center be 800-1050 ℃, keep stabilizing annealing 10-60 minute;
2) the described step 1 of maintenance), the electric furnace central zone is temperature-resistant, after the described quartz boat that is loaded with methanation catalyst is heated to temperature and is 50～300 ℃, be filled with carbon source in the described silica tube and hydrogen carries out chemical vapour deposition, at described Grown Graphene, deposit the complete gas mixture that passes into argon gas and hydrogen cooling after, obtain described Graphene on described substrate.
2. method according to claim 1, it is characterized in that: described methanation catalyst is Ni/A1
2O
3The type methanation catalyst; Or,
Described substrate is Copper Foil; Or,
The thickness of described Copper Foil is the 10-50 micron, is specially 25 microns.
3. method according to claim 1 and 2, is characterized in that: described step 1), at a distance of 1-80cm, be specially 20cm between the central point of quartz boat and substrate.
4. according to claim 1-3 arbitrary described methods, it is characterized in that: described step 1) pass in the hydrogen step, the flow of hydrogen is 50-250scm, is specially 150scm; Or,
Time is 5-50 minute, is specially 20 minutes.
5. according to claim 1-4 arbitrary described methods, it is characterized in that: described step 1) temperature of electric furnace central zone is 1000 ℃; Or,
In described annealing steps, the time is 30 minutes.
6. according to claim 1-5 arbitrary described methods is characterized in that: described step 2), described carbon source is selected from least a in carbonic acid gas and carbon monoxide; Or,
The throughput ratio of carbon source and hydrogen is 1: 200-30: 200; Or,
The flow of described carbon source is 1-30sccm; Or,
The flow of described hydrogen is 200scm.
7. according to claim 1-6 arbitrary described methods, it is characterized in that: described step 2) in deposition step, the time is 10-60 minute, is specially 30 minutes; Or,
Pressure is 0-1.01 * 10
5Pa, but be not 0, described pressure is specially 1.01 * 10
5Pa.
8. according to claim 1-7 arbitrary described methods, it is characterized in that: described method also comprises the steps: in described step 1) before, described substrate is handled as follows: described substrate is used by hydrochloric acid and water successively with volume ratio 1: 1-1: 50 mix and each ultrasonic cleaning of hydrochloric acid soln, acetone and ethanol 3 minutes, nitrogen dries up.
9. the Graphene for preparing of the arbitrary described method of claim 1-8.
10. Graphene according to claim 9 is characterized in that: the pattern of described Graphene is sexangle or circular or by the arbitrary shape of sexangle to circular transition.
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| CN103935996A (en) * | 2014-05-06 | 2014-07-23 | 重庆大学 | Method for directly synthesizing graphene by using CO2 |
| CN104495815A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Device and method for preparing graphene from carbon dioxide |
| WO2016149934A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院上海微***与信息技术研究所 | Growing method for graphene |
| CN106495136A (en) * | 2016-09-27 | 2017-03-15 | 南昌大学 | A kind of preparation method of circular graphitic alkene |
| CN107311157A (en) * | 2016-07-19 | 2017-11-03 | 中国石油大学(北京) | One kind is with CO2For the method for carbon source low temperature preparation graphene |
| CN107670668A (en) * | 2017-10-23 | 2018-02-09 | 新沂市中诺新材料科技有限公司 | A kind of preparation method of foam type synthesis gas methanation catalyst |
| CN110203912A (en) * | 2019-07-17 | 2019-09-06 | 西北有色金属研究院 | A kind of method that low molten carbon material surface ties up preparation two-dimensional graphene film layer surely |
| CN112919455A (en) * | 2021-02-07 | 2021-06-08 | 正大能源材料(大连)有限公司 | Method for preparing graphene film by carbon dioxide combined with low-pressure chemical vapor deposition |
| TWI762205B (en) * | 2021-02-22 | 2022-04-21 | 中原大學 | Method for preparing graphene film on insulating substrate |
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| CN103529099A (en) * | 2013-09-23 | 2014-01-22 | 西南交通大学 | Method for preparing graphene chemically modified electrode through in-situ growth |
| CN103935996A (en) * | 2014-05-06 | 2014-07-23 | 重庆大学 | Method for directly synthesizing graphene by using CO2 |
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| CN104495815A (en) * | 2014-12-12 | 2015-04-08 | 中国科学院重庆绿色智能技术研究院 | Device and method for preparing graphene from carbon dioxide |
| WO2016149934A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院上海微***与信息技术研究所 | Growing method for graphene |
| CN107311157A (en) * | 2016-07-19 | 2017-11-03 | 中国石油大学(北京) | One kind is with CO2For the method for carbon source low temperature preparation graphene |
| CN106495136A (en) * | 2016-09-27 | 2017-03-15 | 南昌大学 | A kind of preparation method of circular graphitic alkene |
| CN107670668A (en) * | 2017-10-23 | 2018-02-09 | 新沂市中诺新材料科技有限公司 | A kind of preparation method of foam type synthesis gas methanation catalyst |
| CN110203912A (en) * | 2019-07-17 | 2019-09-06 | 西北有色金属研究院 | A kind of method that low molten carbon material surface ties up preparation two-dimensional graphene film layer surely |
| CN112919455A (en) * | 2021-02-07 | 2021-06-08 | 正大能源材料(大连)有限公司 | Method for preparing graphene film by carbon dioxide combined with low-pressure chemical vapor deposition |
| CN112919455B (en) * | 2021-02-07 | 2022-11-01 | 正大能源材料(大连)有限公司 | Method for preparing graphene film by carbon dioxide combined low-pressure chemical vapor deposition |
| TWI762205B (en) * | 2021-02-22 | 2022-04-21 | 中原大學 | Method for preparing graphene film on insulating substrate |
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