CN102674316B - Method for preparing composition of carbon nano tube and graphene by using sheet material - Google Patents
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Abstract
The invention relates to a method for preparing composition of a carbon nano tube and graphene by using a sheet material; the composition comprises the carbon nano tube and the graphene material, wherein the carbon nano tube directly grows on the surface of graphene. According to the preparation method, the sheet material loaded with a catalyst active component is used as a catalyst, the carbon nano tube and the graphene are deposited on the sheet material by chemical vapor deposition, and the composition of carbon nano tube and graphene can be obtained after purification. The method enriches the variety of nano carbon materials; and the method can be easily applied to industrial production to realize batch production, thus promoting the application study of the composition of carbon nano tube and graphene.
Description
Technical field
The present invention relates to a kind of method of preparing carbon nanotube and graphene complex, particularly a kind of method of preparing carbon nanotube and graphene complex based on sheet layer material.Belong to novel material and preparing technical field thereof.
Background technology
Carbon nanotube and Graphene are the most common at present, are also to study two kinds of carbon nanomaterials the most widely.Wherein carbon nanotube can be regarded the curling one dimension tubular structure forming of one or more layers graphene film as.In desirable carbon nanotube and graphene-structured, carbon atom is sp
2hydridization bonding mode, their structural performance has determined the excellent properties of the aspects such as its electromagnetism, mechanics, calorifics, thereby they are with a wide range of applications in fields such as electron device, matrix material, thermally conductive material, drug conveying, inductor blocks.In addition the specific surface area that, carbon nanotube and Graphene are huge and the stability of structure make it in electrochemical field, have a wide range of applications.No matter but study, show, in actual application, be carbon nanotube or Graphene, because it easily assembles it compared with strong Van der Waals force each other, thereby seriously hinders the expression of its performance.
The carbon nanotube of one dimension and two-dimentional flaky material build the three-dimensional group assembling structure forming by the mode of self-assembly, wherein carbon nanotube is anchored on the surface of flaky material, makes one of the carbon nanotube dispersed method effectively that is configured to of this three-dimensional structure.Such as Zhang etc. are used the clay of Fe load as catalyzer, directly at the surface growth carbon nanotube of clay, thereby have promoted the dispersion of carbon nanotube, improve it and be applied to performance (the Zhang WD in matrix material, et al.Adv.Mater.2006,18,73-77.).It is catalyst precursors that the Wei Fei of Tsing-Hua University etc. adopt laminated dihydroxy composite metal hydroxide (LDHs), prepare the tridimensional network that single double-walled carbon nano-tube and inorganic, metal oxide sheet assemble, in this structure, single double-walled carbon nano-tube directly grows out on the surface by the calcinate layered di-hydroxyl composite metal oxidate (LDOs) of LDHs, and be fixed on LDO sheet, thereby realize good dispersion (the Zhao MQ of single double-walled carbon nano-tube, et al.Adv.Funct.Mater.2010,20,677 – 685.).But in above-mentioned work, carbon nanotube dispersed tends to again introduce a certain amount of inorganic, metal oxide when improving, this can greatly limit the expression of its chemical property.
Carbon nanotube is grown directly upon to the structure of the lip-deep carbon nanotube of Graphene and Graphene hybrid structure, not only when promoting carbon nanotube dispersed, has avoided the introducing of inorganic, metal oxide, but also can promote the dispersion of Graphene.In addition, the hybrid structure of carbon nanotube and Graphene three-dimensional can also construct three-dimensional conductive network effectively, thereby greatly promotes the performance that this material is applied in electrochemical field to express.Cheng Huiming etc. successfully prepare carbon nano pipe array and graphene complex structure, and have studied its chemical property as lithium ion battery negative material (Li SS, et al.Adv.Energy Mater.2011, Isosorbide-5-Nitrae 86 – 490.).But in this material, the growth of carbon nanotube is based on the thick Al of Graphene electroplating surface last layer 5nm
2o
3with the thick Fe of 1nm, this has hindered contacting and electric transmission between carbon nanotube and Graphene to a certain extent.Fan Zhuanjun etc. are by metal active constituents such as load C o on Graphene, and take CO etc. as carbon source, on the surface of Graphene, the method for direct growth carbon nanotube is prepared carbon nanotube and graphene complex (Fan ZJ, et al.Adv.Mater.2010,22,3723-3728.).But, due at high temperature strong interaction between metal nanoparticle and Graphene, make the quality of carbon nanotube of the method growth often poor, thereby affect its performance, express.
Along with the development of Graphene technology of preparing, research shows, the metal of part or the surface of nonmetal oxide all can deposit Graphene, and these metals or nonmetal oxide are often used as the carrier of carbon nano-tube.So Given this aspect is considered, the present invention has developed a kind of method of preparing carbon nanotube and Graphene of the sheet layer material that has metal active constituent based on load, and product is grown directly upon carbon nanotube and the graphene complex on Graphene surface through obtaining carbon nanotube after purifying.The easy engineering of the method is amplified, and realizes batch production, can greatly advance the applied research of carbon nanotube and graphene complex.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing carbon nanotube and graphene complex based on sheet layer material, enriched the structure species of carbon nanomaterial, and the easy engineering of the method is amplified, and realizes batch production, advances the applied research of carbon nanotube and graphene complex.
Technical scheme of the present invention is as follows:
The invention provides a kind of method of preparing carbon nanotube and graphene complex based on sheet layer material, it is characterized in that the method carries out as follows:
1) load is had to the sheet layer material of catalyst activity component as catalyzer, the active ingredient of described catalyzer is Fe, Co, Ni, Cu, Mo or W, and its content accounts for 0.1%～50% of catalyst quality;
2) this catalyzer is placed in to reactor, pass through chemical vapor deposition processes, deposition of carbon nanotubes and Graphene on the surface of catalyzer, then the product of gained being placed in to product purification device purifies, obtain carbon nanotube and graphene complex, in carbon nanotube and graphene complex, carbon nanotube is grown directly upon on the surface of Graphene.
Described sheet layer material is laminated dihydroxy composite metal hydroxide, magnesium oxide, aluminium sesquioxide, silicon-dioxide, kaolin, polynite, vermiculite, mica or pseudo-boehmite; In described chemical vapor deposition processes, being deposited as of carbon nanotube and Graphene carried out simultaneously or successively carried out, and wherein the temperature of reaction of deposition of carbon nanotubes is 500～1000 ℃, and the temperature of reaction of deposition Graphene is 600～1200 ℃; It is carbon source that described chemical vapor deposition processes is used one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the dimethylbenzene below seven carbon; Use argon gas, nitrogen, helium, hydrogen or their mixture as carrier gas, the dividing potential drop of controlling carbon source is less than 80% of total pressure; Described reactor types is fixed bed, moving-bed, fluidized-bed or their combination.
Compared to existing technology, tool of the present invention has the following advantages and beneficial effect: the present invention can obtain carbon nanotube and graphene complex in enormous quantities; In this mixture, carbon nanotube is grown directly upon the surface of Graphene, is a kind of carbon nanomaterial of novel agglomerate structure.The various catalyzer, the carbon source that in the method, adopt are cheap and easy to get, are convenient to engineering and amplify and produce in batches, for the engineering application of carbon nanotube and graphene complex is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is take FeMgAl LDH as catalyzer, the low power stereoscan photograph of the carbon nanotube of growth and graphene complex.
Fig. 2 is take FeMgAl LDH as catalyzer, the high power stereoscan photograph of the carbon nanotube of growth and graphene complex.
Fig. 3 is take FeMgAl LDH as catalyzer, the carbon nanotube of growth and the transmission electron microscope photo of graphene complex.
Fig. 4 is take FeMgAl LDH as catalyzer, the high-resolution-ration transmission electric-lens photo of the carbon nanotube of growth and graphene complex.
Fig. 5 is take FeMoMgAl LDH as catalyzer, the low power stereoscan photograph of the carbon nanotube of growth and graphene complex.
Fig. 6 has the magnesium oxide of Co component take load be catalyzer, the low power stereoscan photograph of the carbon nanotube of growth and graphene complex.
Fig. 7 has the magnesium oxide of Co component take load be catalyzer, the carbon nanotube of growth and the transmission electron microscope photo of graphene complex.
It is catalyzer that Fig. 8 load has the stratiform vermiculite of Fe component, the low power stereoscan photograph of the carbon nanotube of growth and graphene complex.
Embodiment
The invention provides a kind of method of preparing carbon nanotube and graphene complex based on sheet layer material, it is characterized in that the method carries out as follows:
1) load is had to the sheet layer material of catalyst activity component as catalyzer, the active ingredient of described catalyzer is Fe, Co, Ni, Cu, Mo or W, and its content accounts for 0.1%～50% of catalyst quality;
2) this catalyzer is placed in to reactor, pass through chemical vapor deposition processes, deposition of carbon nanotubes and Graphene on the surface of catalyzer, then the product of gained being placed in to product purification device purifies, obtain carbon nanotube and graphene complex, in carbon nanotube and graphene complex, carbon nanotube is grown directly upon on the surface of Graphene.
Described sheet layer material is laminated dihydroxy composite metal hydroxide, magnesium oxide, aluminium sesquioxide, silicon-dioxide, kaolin, polynite, vermiculite, mica or pseudo-boehmite; In described chemical vapor deposition processes, being deposited as of carbon nanotube and Graphene carried out simultaneously or successively carried out, and wherein the temperature of reaction of deposition of carbon nanotubes is 500～1000 ℃, and the temperature of reaction of deposition Graphene is 600～1200 ℃; It is carbon source that described chemical vapor deposition processes is used one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the dimethylbenzene below seven carbon; Use argon gas, nitrogen, helium, hydrogen or their mixture as carrier gas, the dividing potential drop of controlling carbon source is less than 80% of total pressure; Described reactor types is fixed bed, moving-bed, fluidized-bed or their combination.
Below by several specific embodiments, the present invention is further illustrated.
Embodiment 1: prepare carbon nanotube and graphene complex by fixed bed take FeMgAl LDH as catalyzer.
The FeMgAl LDHs that is 10% using Fe content, as catalyzer, gets 50mg uniform spreading in porcelain boat, is then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 950 ℃ by room temperature; Temperature of reaction is maintained to 950 ℃ afterwards, pass into the gas mixture of carbon source methane, hydrogen and argon gas, wherein the dividing potential drop of carbon source methane is 80%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 20min, close carbon source methane and H
2, take out solid product be cooled to room temperature under argon gas atmosphere after.By solid product in purification of products device first the NaOH aqueous solution with 3mol/L at 180 ℃, process 6hr and remove the aluminum oxide in product, used again the HCl aqueous solution of 1mol/L at 80 ℃, to process 6hr and removed the magnesium oxide in product, can obtain carbon nanotube and graphene complex, its macro morphology is referring to Fig. 1, carbon nanotube and graphene complex that the product that can see gained is.The further high power stereoscan photograph of Fig. 2 can see, in this carbon nanotube and graphene complex, carbon nanotube is grown directly upon on Graphene surface.The transmission electron microscope photo that Fig. 3 shows further illustrates effective connection the between carbon nanotube and Graphene in obtained carbon nanotube and graphene complex.In carbon nanotube and graphene complex that the high-resolution-ration transmission electric-lens photo of Fig. 4 obtains, the carbon nanotube of gained is Single Walled Carbon Nanotube, and the number of plies of the Graphene of gained is 1 ~ 3 layer, can see graphite linings structure clearly.
Embodiment 2: prepare carbon nanotube and graphene complex by fixed bed take FeMgAl LDH as catalyzer.
The FeMgAl LDHs that is 50% using Fe content, as catalyzer, gets 50mg uniform spreading in porcelain boat, is then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1200 ℃ by room temperature; Temperature of reaction is maintained to 1200 ℃ afterwards, pass into the gas mixture of carbon source methane and argon gas, wherein the dividing potential drop of carbon source methane is 80%, carries out chemical vapor deposition processes deposition Graphene.After 10min, close carbon source methane, under argon gas atmosphere, by reactor cooling to 750 ℃, pass into afterwards the gas mixture of carbon source ethene, hydrogen and argon gas again, wherein the dividing potential drop of carbon source ethene is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes.After 30min, close carbon source ethene and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the NaOH aqueous solution with 3mol/L at 180 ℃, process 6hr and remove the aluminum oxide in product, used again the HCl aqueous solution of 1mol/L at 80 ℃, to process 6hr and removed the magnesium oxide in product, can obtain carbon nano pipe array and be grown in the lip-deep carbon nanotube of Graphene and graphene complex.
Embodiment 3: prepare carbon nanotube and graphene complex by fixed bed take FeMoMgAl LDH as catalyzer.
By Fe content be 20%, Mo content be 0.2% FeMoMgAl LDHs as catalyzer, get 50mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use nitrogen is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 750 ℃ by room temperature, passes into afterwards the gas mixture of carbon source propylene, hydrogen and nitrogen again, wherein the dividing potential drop of carbon source propylene is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes.After 30min, close carbon source propylene and H
2, temperature of reactor is risen to 1000 ℃ afterwards, then pass into the gas mixture of carbon source methane and argon gas, wherein the dividing potential drop of carbon source methane is 50%, carries out chemical vapor deposition processes deposition Graphene.After 20min, close carbon source methane, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the NaOH aqueous solution with 3mol/L at 180 ℃, process 6hr and remove the aluminum oxide in product, used again the HCl aqueous solution of 1mol/L at 80 ℃, to process 6hr and removed the magnesium oxide in product, can obtain carbon nano pipe array and be grown in the lip-deep carbon nanotube of Graphene and graphene complex, its macro morphology as shown in Figure 5.
Embodiment 4: prepare carbon nanotube and graphene complex by fixed bed take Co and Mo and MgO as catalyzer.
By Co content be 1%, Mo content be the Co/Mo/MgO of 0.1% sheet as catalyzer, get 50mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use helium is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1000 ℃ by room temperature; Temperature of reaction is maintained to 1000 ℃ afterwards, pass into the gas mixture of carbon source CO and helium, wherein the dividing potential drop of carbon source CO is 50%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 20min, close carbon source CO, take out solid product be cooled to room temperature under helium atmosphere after.Solid product is processed to 6hr with the HCl aqueous solution of 1mol/L in purification of products device at 80 ℃ and remove the magnesium oxide in product, can obtain carbon nanotube and graphene complex, its macro morphology is referring to Fig. 6, carbon nanotube and graphene complex that the product that can see gained is.The further transmission electron microscope photo of Fig. 7 can see, in this carbon nanotube and graphene complex, carbon nanotube is grown directly upon on Graphene surface.
Embodiment 5: prepare carbon nanotube and graphene complex by fluidized-bed take Ni/ vermiculite as catalyzer.
The Ni/ vermiculite that is 0.1% using Ni content, as catalyzer, is got 1g and is put into the fluidized-bed reactor that diameter is 20mm.Use argon gas is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 650 ℃ by room temperature, temperature of reaction is maintained to 650 ℃ afterwards, pass into the gas mixture of carbon source ethene, hydrogen and argon gas, wherein the dividing potential drop of carbon source ethene is 20%, carries out chemical vapor deposition processes deposition of carbon nanotubes.After 30min, close carbon source ethene, under argon gas atmosphere, temperature of reactor is risen to 1000 ℃, pass into afterwards the gas mixture of carbon source methane and argon gas, wherein the dividing potential drop of carbon source methane is 60%, carries out chemical vapor deposition processes deposition Graphene.After 15min, close carbon source methane, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.Solid product HF aqueous solution with 0.5mol/L in purification of products device is processed to 6hr at 80 ℃, with the HCl aqueous solution of 1mol/L, at 80 ℃, process 6hr again, can obtain carbon nanotube and graphene complex, its macro morphology is referring to Fig. 8, the product that can see gained be carbon nano pipe array and graphene sheet layer overlapping carbon nanotube and graphene complex.
Embodiment 6: prepare carbon nanotube and graphene complex by moving-bed take Cu/ vermiculite as catalyzer.
The Cu/ vermiculite that is 10% using Cu content, as catalyzer, is got 1g and is put into the moving-burden bed reactor that diameter is 100mm.Use argon gas is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1000 ℃ by room temperature, temperature of reaction is maintained to 1000 ℃ afterwards, pass into the gas mixture of carbon source methane and argon gas, wherein the dividing potential drop of carbon source methane is 20%, carries out chemical vapor deposition processes deposition Graphene.After 15min, close carbon source methane, under argon gas atmosphere, temperature of reactor is down to 500 ℃, pass into afterwards the gas mixture of carbon source acetylene, hydrogen and argon gas, wherein the dividing potential drop of carbon source acetylene is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes.After 30min, close carbon source acetylene, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the HF aqueous solution with 0.5mol/L at 80 ℃, process 6hr, with the HCl aqueous solution of 1mol/L, at 80 ℃, process 6hr again, can obtain carbon nano pipe array and graphene sheet layer overlapping carbon nanotube and graphene complex.
Embodiment 7: with Fe/W/Al
2o
3for catalyzer is prepared carbon nanotube and graphene complex by fixed bed.
By Fe content, be that 5%, W content is the Fe/W/Al of 0.5% sheet
2o
3as catalyzer, get 50mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 1000 ℃ by room temperature, temperature of reaction is maintained to 1000 ℃ afterwards, pass into the gas mixture of carbon source methyl alcohol, hydrogen and argon gas, wherein the dividing potential drop of carbon source methyl alcohol is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 30min, close carbon source methyl alcohol and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.Solid product NaOH aqueous solution with 3mol/L in purification of products device is processed to 6hr at 180 ℃, can obtain carbon nanotube and graphene complex.
Embodiment 8: with Fe/Mo/SiO
2for catalyzer is prepared carbon nanotube and graphene complex by fixed bed.
By Fe content, be that 5%, Mo content is the Fe/Mo/SiO of 0.5% sheet
2as catalyzer, get 100mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 900 ℃ by room temperature, temperature of reaction is maintained to 900 ℃ afterwards, pass into the gas mixture of carbon source ethanol, hydrogen and argon gas, wherein the dividing potential drop of carbon source ethanol is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 30min, close carbon source ethanol and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.Solid product HF aqueous solution with 0.5mol/L in purification of products device is processed to 6hr at 80 ℃, can obtain carbon nanotube and graphene complex.
Embodiment 9: prepare carbon nanotube and graphene complex by fixed bed take Fe/Mo/ kaolin as catalyzer.
By Fe content be 10%, Mo content be 1% Fe/Mo/ kaolin as catalyzer, get 100mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 800 ℃ by room temperature, temperature of reaction is maintained to 800 ℃ afterwards, pass into the gas mixture of carbon source benzene, hydrogen and argon gas, wherein the dividing potential drop of carbon source benzene is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 30min, close carbon source benzene and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the HF aqueous solution with 0.5mol/L at 80 ℃, process 6hr, then at 80 ℃, process 6hr with the HCl aqueous solution of 1mol/L, can obtain carbon nanotube and graphene complex.
Embodiment 10: prepare carbon nanotube and graphene complex by fixed bed take Fe/Mo/ polynite as catalyzer.
By Fe content be 7%, Mo content be 0.7% Fe/Mo/ polynite as catalyzer, get 50mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 850 ℃ by room temperature, temperature of reaction is maintained to 850 ℃ afterwards, pass into the gas mixture of carbon source hexanaphthene, hydrogen and argon gas, wherein the dividing potential drop of carbon source hexanaphthene is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 30min, close carbon source hexanaphthene and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the HF aqueous solution with 0.5mol/L at 80 ℃, process 6hr, then at 80 ℃, process 6hr with the HCl aqueous solution of 1mol/L, can obtain carbon nanotube and graphene complex.
Embodiment 11: prepare carbon nanotube and graphene complex by fixed bed take Fe/Mo/ mica as catalyzer.
By Fe content be 1%, Mo content be 0.1% Fe/Mo/ mica as catalyzer, get 100mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 850 ℃ by room temperature, temperature of reaction is maintained to 850 ℃ afterwards, pass into the gas mixture of carbon source normal hexane, hydrogen and argon gas, wherein the dividing potential drop of carbon source normal hexane is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 30min, close carbon source normal hexane and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the HF aqueous solution with 0.5mol/L at 80 ℃, process 6hr, then at 80 ℃, process 6hr with the HCl aqueous solution of 1mol/L, can obtain carbon nanotube and graphene complex.
Embodiment 12: prepare carbon nanotube and graphene complex by fixed bed take Fe/Mo/ pseudo-boehmite as catalyzer.
By Fe content be 10%, Mo content be 1% Fe/Mo/ pseudo-boehmite as catalyzer, get 100mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 700 ℃ by room temperature, temperature of reaction is maintained to 700 ℃ afterwards, pass into the gas mixture of carbon source toluene, hydrogen and argon gas, wherein the dividing potential drop of carbon source toluene is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 30min, close carbon source toluene and H
2, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the NaOH aqueous solution with 3mol/L at 180 ℃, process 6hr, then at 80 ℃, process 6hr with the HCl aqueous solution of 1mol/L, can obtain carbon nanotube and graphene complex.
Embodiment 13: prepare carbon nanotube and graphene complex by the combined reactor of fixed bed and fluidized-bed take Fe/Mo/ vermiculite as catalyzer.
By Fe content be 1%, Mo content be 0.1% Fe/Mo/ vermiculite as catalyzer, get 1g and put into the fluidized-bed reactor that diameter is 20mm, using argon gas is carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 650 ℃ by room temperature, temperature of reaction is maintained to 650 ℃ afterwards, pass into the gas mixture of carbon source ethene, hydrogen and argon gas, wherein the dividing potential drop of carbon source ethene is 20%, carries out chemical vapor deposition processes deposition of carbon nanotubes; Using afterwards atmosphere speed that the solid product of gained is blown into temperature is in the fixed-bed reactor of 950 ℃, passes into the gas mixture of carbon source methane and argon gas, and wherein the dividing potential drop of carbon source methane is 50%, carries out chemical vapor deposition processes deposition Graphene.After 10min, close carbon source methane, under argon gas atmosphere, reactor cooling is taken out to solid product to room temperature.By solid product in purification of products device first the HF aqueous solution with 0.5mol/L at 80 ℃, process 6hr, then at 80 ℃, process 6hr with the HCl aqueous solution of 1mol/L, can obtain carbon nanotube and graphene complex.
Embodiment 14: prepare carbon nanotube and graphene complex by fixed bed take Fe/Mo/MgO as catalyzer.
By Fe content be 1%, Mo content be the Fe/Mo/MgO of 0.1% sheet as catalyzer, get 50mg uniform spreading in porcelain boat, be then placed in tubular fixed-bed reactor.Use helium is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 600 ℃ by room temperature; Temperature of reaction is maintained to 600 ℃ afterwards, pass into the gas mixture of carbon source dimethylbenzene, hydrogen and helium, wherein the dividing potential drop of carbon source dimethylbenzene is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 20min, close carbon source dimethylbenzene and H
2, take out solid product be cooled to room temperature under helium atmosphere after.Solid product is processed to 6hr with the HCl aqueous solution of 1mol/L in purification of products device at 80 ℃ and remove the magnesium oxide in product, can obtain carbon nanotube and graphene complex.
Embodiment 15: prepare carbon nanotube and graphene complex by fixed bed take Co/MgO as catalyzer.
The Co/MgO of the sheet that is 5% using Co content, as catalyzer, gets 50mg uniform spreading in porcelain boat, is then placed in tubular fixed-bed reactor.Use argon gas is carrier gas, and its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 950 ℃ by room temperature; Temperature of reaction is maintained to 950 ℃ afterwards, pass into the gas mixture of carbon source methane, ethene, hydrogen and argon gas, wherein the dividing potential drop of carbon source methane is 5%, and the dividing potential drop of ethene is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.After 20min, close carbon source methane, ethene and H
2, take out solid product be cooled to room temperature under argon gas atmosphere after.Solid product is processed to 6hr with the HCl aqueous solution of 1mol/L in purification of products device at 80 ℃ and remove the magnesium oxide in product, can obtain carbon nanotube and graphene complex.
Claims (3)
1. based on sheet layer material, prepare a method for carbon nanotube and graphene complex, it is characterized in that the method carries out as follows:
1) load is had to the sheet layer material of catalyst activity component as catalyzer, the active ingredient of described catalyzer is Fe, Co, Ni, Cu, Mo or W, and its content accounts for 0.1%～50% of catalyst quality; Described sheet layer material is laminated dihydroxy composite metal hydroxide, magnesium oxide, aluminium sesquioxide, silicon-dioxide, kaolin, polynite, vermiculite, mica or pseudo-boehmite.
2) this catalyzer is placed in to reactor, by chemical vapor deposition processes, deposition of carbon nanotubes and Graphene on the surface of catalyzer; Being deposited as of carbon nanotube and Graphene carried out simultaneously or successively carried out, and wherein the temperature of reaction of deposition of carbon nanotubes is 500～1000 ℃, and the temperature of reaction of deposition Graphene is 600～1200 ℃; Then the product of gained is placed in to product purification device and purifies, obtain carbon nanotube and graphene complex, in carbon nanotube and graphene complex, carbon nanotube is grown directly upon on the surface of Graphene.
2. according to a kind of method of preparing carbon nanotube and graphene complex based on sheet layer material claimed in claim 1, it is characterized in that: step 2) described in chemical vapor deposition processes to use one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the dimethylbenzene below seven carbon be carbon source; Use argon gas, nitrogen, helium, hydrogen or their mixture as carrier gas, the dividing potential drop of controlling carbon source is less than 80% of total pressure.
3. according to a kind of method of preparing carbon nanotube and graphene complex based on sheet layer material described in claim 1 or 2, it is characterized in that: step 2) described in chemical vapor deposition processes adopt reactor types be fixed bed, moving-bed, fluidized-bed or their combination.
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