CN102674316A - Method for preparing composition of carbon nano tube and graphene by using sheet material - Google Patents
Method for preparing composition of carbon nano tube and graphene by using sheet material Download PDFInfo
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- CN102674316A CN102674316A CN2012101416496A CN201210141649A CN102674316A CN 102674316 A CN102674316 A CN 102674316A CN 2012101416496 A CN2012101416496 A CN 2012101416496A CN 201210141649 A CN201210141649 A CN 201210141649A CN 102674316 A CN102674316 A CN 102674316A
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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 for preparing carbon nanotube and graphene complex, particularly a kind of method for 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, also are to study two kinds of carbon nanomaterials the most widely.Wherein carbon nanotube can be regarded the one dimension tubular structure that one or more layers graphene film curls and forms as.Carbon atom is sp in ideal carbon nanotube and the graphene-structured
2Hydridization bonding mode, their structural performance have determined the excellent properties of 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, delivery of drug, inductor blocks.In addition, specific surface area that carbon nanotube and Graphene are huge and stability of structure make it have widely in electrochemical field and use.Yet research shows, in the application of reality, no matter is carbon nanotube or Graphene, owing to its stronger each other Van der Waals force makes its easy gathering, thereby seriously hinders the expression of its performance.
The flaky material of unidimensional carbon nanotube and two dimension makes up the three-dimensional group assembling structure that forms through the mode of self-assembly; Wherein carbon nanotube is anchored on the surface of flaky material, makes one of the carbon nanotube dispersive method effectively that is configured to of this three-dimensional structure.For example Zhang etc. use the Fe load clay as catalyzer, directly at the surface growth carbon nanotube of clay, thereby promoted the dispersion of carbon nanotube; Improve it and be applied to performance (the Zhang WD in the matrix material; Et al.Adv.Mater.2006,18,73-77.).It is the complex catalyst precursor thing 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; Single double-walled carbon nano-tube directly grows out on the surface by the calcinate layered di-hydroxyl composite metal oxidate (LDOs) of LDHs in this structure; And be fixed on the LDO sheet, thereby realize good dispersion (Zhao MQ, the et al.Adv.Funct.Mater.2010 of single double-walled carbon nano-tube; 20,677 – 685.).Yet in above-mentioned work, the carbon nanotube dispersiveness tends to introduce a certain amount of inorganic, metal oxide again when improving, and this can greatly limit the expression of its chemical property.
Carbon nanotube is grown directly upon the structure of lip-deep carbon nanotube of Graphene and Graphene hybrid structure, is not only promoting the carbon nanotube dispersive to avoid the introducing of inorganic, metal oxide simultaneously, but also can promote the dispersion of Graphene.In addition, the three-dimensional hybrid structure of carbon nanotube and Graphene can also construct three-dimensional effectively conductive network, thereby the performance that greatly promotes this material in electrochemical field, to use is expressed.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.2011,1,486 – 490.).Yet 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 the Graphene to a certain extent.Fan Zhuanjun etc. are through metal active constituents such as load C o on Graphene; And be carbon source with CO etc., the method for direct growth carbon nanotube is prepared carbon nanotube and graphene complex (Fan ZJ, et al.Adv.Mater.2010 on the surface of Graphene; 22,3723-3728.).Yet, owing to strong interaction between metal nanoparticle and the Graphene at high temperature, make that the quality of this method carbon nanotubes grown is often relatively poor, express thereby influence its performance.
Along with the Graphene Development of Preparation Technology, research shows that the metal of part or the surface of nonmetal oxide all can deposit Graphene, and these metals or nonmetal oxide often are used as the carrier of carbon nano-tube.So Given this aspect is considered; The present invention has developed a kind of method for preparing carbon nanotube and Graphene that the sheet layer material of metal active constituent is arranged based on load, and product is through obtaining carbon nanotube and the graphene complex that carbon nanotube is grown directly upon the Graphene surface after the purifying.The easy engineering of this method is amplified, and realizes producing in batches, 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 for preparing carbon nanotube and graphene complex based on sheet layer material; Enriched the structure kind of carbon nanomaterial; And the easy engineering of this method is amplified, and realizes producing in batches, advances the applied research of carbon nanotube and graphene complex.
Technical scheme of the present invention is following:
The invention provides and a kind ofly prepare the method for carbon nanotube and graphene complex, it is characterized in that this method carries out as follows based on sheet layer material:
1) sheet layer material that load is had the catalyst activity component is as catalyzer, and said activity of such catalysts component is Fe, Co, Ni, Cu, Mo or W, and its content accounts for 0.1%～50% of catalyst quality;
2) this catalyzer is placed reactor drum; Pass through chemical vapor deposition processes; Deposition of carbon nanotubes and Graphene on the surface of catalyzer; Product with gained places the product purification device to purify then, obtains carbon nanotube and graphene complex, and carbon nanotube is grown directly upon on the surface of Graphene in carbon nanotube and the graphene complex.
Described sheet layer material is laminated dihydroxy composite metal hydroxide, Natural manganese dioxide, aluminium sesquioxide, silicon-dioxide, kaolin, polynite, vermiculite, mica or pseudo-boehmite; In the 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 ℃; Described chemical vapor deposition processes uses one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the YLENE below seven carbon to be carbon source; Use argon gas, nitrogen, helium, hydrogen or their mixture as carrier gas, the dividing potential drop of control carbon source is less than 80% of total pressure; Described reactor types is fixed bed, moving-bed, fluidized-bed or their combination.
Compare prior art, the present invention has following advantage 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 novel carbon nanomaterial that gathers the unity structure.The various catalyzer, the carbon source that adopt in this method are cheap and easy to get, are convenient to engineering amplification and batch process, for the practical applications of carbon nanotube and graphene complex is laid a good foundation.
Description of drawings
Fig. 1 is a catalyzer with FeMgAl LDH, the low power stereoscan photograph of carbon nanotubes grown and graphene complex.
Fig. 2 is a catalyzer with FeMgAl LDH, the high power stereoscan photograph of carbon nanotubes grown and graphene complex.
Fig. 3 is a catalyzer with FeMgAl LDH, the transmission electron microscope photo of carbon nanotubes grown and graphene complex.
Fig. 4 is a catalyzer with FeMgAl LDH, the high-resolution-ration transmission electric-lens photo of carbon nanotubes grown and graphene complex.
Fig. 5 is a catalyzer with FeMoMgAl LDH, the low power stereoscan photograph of carbon nanotubes grown and graphene complex.
It is catalyzer that Fig. 6 has the Natural manganese dioxide of Co component with load, the low power stereoscan photograph of carbon nanotubes grown and graphene complex.
It is catalyzer that Fig. 7 has the Natural manganese dioxide of Co component with load, the transmission electron microscope photo of carbon nanotubes grown and graphene complex.
It is catalyzer that Fig. 8 load has the vermiculite of Fe component, the low power stereoscan photograph of carbon nanotubes grown and graphene complex.
Embodiment
The invention provides and a kind ofly prepare the method for carbon nanotube and graphene complex, it is characterized in that this method carries out as follows based on sheet layer material:
1) sheet layer material that load is had the catalyst activity component is as catalyzer, and said activity of such catalysts component is Fe, Co, Ni, Cu, Mo or W, and its content accounts for 0.1%～50% of catalyst quality;
2) this catalyzer is placed reactor drum; Pass through chemical vapor deposition processes; Deposition of carbon nanotubes and Graphene on the surface of catalyzer; Product with gained places the product purification device to purify then, obtains carbon nanotube and graphene complex, and carbon nanotube is grown directly upon on the surface of Graphene in carbon nanotube and the graphene complex.
Described sheet layer material is laminated dihydroxy composite metal hydroxide, Natural manganese dioxide, aluminium sesquioxide, silicon-dioxide, kaolin, polynite, vermiculite, mica or pseudo-boehmite; In the 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 ℃; Described chemical vapor deposition processes uses one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the YLENE below seven carbon to be carbon source; Use argon gas, nitrogen, helium, hydrogen or their mixture as carrier gas, the dividing potential drop of control carbon source is less than 80% of total pressure; Described reactor types is fixed bed, moving-bed, fluidized-bed or their combination.
Through several concrete embodiment the present invention is further described below.
Embodiment 1: with FeMgAl LDH is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content be 10% FeMgAl LDHs as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 950 ℃ by room temperature; Afterwards with maintain at 950 ℃, feed 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.Close carbon source methane and H behind the 20min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6hr with the NaOH aqueous solution of 3mol/L down at 180 ℃ earlier remove the aluminum oxide in the product in the purification of products device; Again its HCl aqueous solution with 1mol/L is handled 6hr down at 80 ℃ and remove the Natural manganese dioxide in the 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 that carbon nanotube is grown directly upon on the Graphene surface in this carbon nanotube and the graphene complex.The transmission electron microscope photo that Fig. 3 shows further specifies effective connection the between the carbon nanotube and Graphene in resulting carbon nanotube and the graphene complex.The high-resolution-ration transmission electric-lens photo of Fig. 4 explains in resulting carbon nanotube and the graphene complex that the carbon nanotube of gained is a SWCN, and the number of plies of the Graphene of gained is 1 ~ 3 layer, can see graphite linings structure clearly.
Embodiment 2: with FeMgAl LDH is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content be 50% FeMgAl LDHs as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1200 ℃ by room temperature; Afterwards with maintain at 1200 ℃, feed 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 and deposits Graphene.Close carbon source methane behind the 10min, under argon gas atmosphere, with reactor cooling to 750 ℃, feed the gas mixture of carbon source ethene, hydrogen and argon gas afterwards again, wherein the dividing potential drop of carbon source ethene is 10%, carries out the chemical vapor deposition processes deposition of carbon nanotubes.Close carbon source ethene and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the NaOH aqueous solution of 3mol/L down at 180 ℃ earlier remove the aluminum oxide in the product in the purification of products device; Again its HCl aqueous solution with 1mol/L is handled 6hr down at 80 ℃ and remove the Natural manganese dioxide in the product, can obtain carbon nano pipe array and be grown in lip-deep carbon nanotube of Graphene and graphene complex.
Embodiment 3: with FeMoMgAl LDH is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 20%, Mo content be 0.2% FeMoMgAl LDHs as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use nitrogen to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 750 ℃ by room temperature, feeds the gas mixture of carbon source propylene, hydrogen and nitrogen afterwards again, wherein the dividing potential drop of carbon source propylene is 10%, carries out the chemical vapor deposition processes deposition of carbon nanotubes.Close carbon source propylene and H behind the 30min
2, afterwards temperature of reactor is risen to 1000 ℃, feed the gas mixture of carbon source methane and argon gas again, wherein the dividing potential drop of carbon source methane is 50%, carries out chemical vapor deposition processes deposition Graphene.Close carbon source methane behind the 20min, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the NaOH aqueous solution of 3mol/L down at 180 ℃ earlier remove the aluminum oxide in the product in the purification of products device; Again its HCl aqueous solution with 1mol/L is handled 6hr down at 80 ℃ and remove the Natural manganese dioxide in the product; Can obtain carbon nano pipe array and be grown in lip-deep carbon nanotube of Graphene and graphene complex, its macro morphology is as shown in Figure 5.
Embodiment 4: with Co and Mo and MgO is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Co content is 1%, Mo content be 0.1% flaky Co/Mo/MgO as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use helium to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1000 ℃ by room temperature; Afterwards with maintain at 1000 ℃, feed 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 while deposition of carbon nanotubes and Graphene.Close carbon source CO behind the 20min, take out solid product after under helium atmosphere, being cooled to room temperature.Solid product is handled 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ remove the Natural manganese dioxide in the product in the purification of products device; 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 that carbon nanotube is grown directly upon on the Graphene surface in this carbon nanotube and the graphene complex.
Embodiment 5: with the Ni/ vermiculite is that catalyzer prepares carbon nanotube and graphene complex through fluidized-bed.
With Ni content be 0.1% Ni/ vermiculite as catalyzer, get 1g and put into the fluidized-bed reactor that diameter is 20mm.Use argon gas to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 650 ℃ by room temperature, afterwards with maintain at 650 ℃, feed the gas mixture of carbon source ethene, hydrogen and argon gas, wherein the dividing potential drop of carbon source ethene is 20%, carries out the chemical vapor deposition processes deposition of carbon nanotubes.Close carbon source ethene behind the 30min, under argon gas atmosphere, temperature of reactor is risen to 1000 ℃, feed the gas mixture of carbon source methane and argon gas afterwards, wherein the dividing potential drop of carbon source methane is 60%, carries out chemical vapor deposition processes deposition Graphene.Close carbon source methane behind the 15min, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product HF aqueous solution with 0.5mol/L in the purification of products device is handled 6hr down at 80 ℃; Handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ 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 lamella overlap carbon nanotube and graphene complex.
Embodiment 6: with the Cu/ vermiculite is that catalyzer prepares carbon nanotube and graphene complex through moving-bed.
With Cu content be 10% Cu/ vermiculite as catalyzer, get 1g and put into the moving-burden bed reactor that diameter is 100mm.Use argon gas to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 1000 ℃ by room temperature, afterwards with maintain at 1000 ℃, feed 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 and deposits Graphene.Close carbon source methane behind the 15min, under argon gas atmosphere, temperature of reactor is reduced to 500 ℃, feed the gas mixture of carbon source acetylene, hydrogen and argon gas afterwards, wherein the dividing potential drop of carbon source acetylene is 10%, carries out the chemical vapor deposition processes deposition of carbon nanotubes.Close carbon source acetylene behind the 30min, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the HF aqueous solution of 0.5mol/L down at 80 ℃ earlier in the purification of products device; Handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ again, can obtain carbon nano pipe array and Graphene lamella overlapping carbon nanotube and graphene complex.
Embodiment 7: with Fe/W/Al
2O
3For catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 5%, and W content is the Fe/W/Al of 0.5% sheet
2O
3As catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 1000 ℃ by room temperature; Afterwards with maintain at 1000 ℃; Feed 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.Close carbon source methyl alcohol and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product NaOH aqueous solution with 3mol/L in the purification of products device is handled 6hr down at 180 ℃, can obtain carbon nanotube and graphene complex.
Embodiment 8: with Fe/Mo/SiO
2For catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 5%, and Mo content is 0.5% flaky Fe/Mo/SiO
2As catalyzer, get 100mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 900 ℃ by room temperature; Afterwards with maintain at 900 ℃; Feed the gas mixture of carbon source ethanol, hydrogen and argon gas, wherein carbon source alcoholic acid dividing potential drop is 10%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.Close carbon source ethanol and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product HF aqueous solution with 0.5mol/L in the purification of products device is handled 6hr down at 80 ℃, can obtain carbon nanotube and graphene complex.
Embodiment 9: with Fe/Mo/ kaolin is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 10%, Mo content be 1% Fe/Mo/ kaolin as catalyzer, get 100mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 800 ℃ by room temperature; Afterwards with maintain at 800 ℃; Feed 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.Close carbon source benzene and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the HF aqueous solution of 0.5mol/L down at 80 ℃ earlier in the purification of products device, handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ again, can obtain carbon nanotube and graphene complex.
Embodiment 10: with the Fe/Mo/ polynite is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 7%, Mo content be 0.7% Fe/Mo/ polynite as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 850 ℃ by room temperature; Afterwards with maintain at 850 ℃; Feed 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.Close carbon source hexanaphthene and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the HF aqueous solution of 0.5mol/L down at 80 ℃ earlier in the purification of products device, handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ again, can obtain carbon nanotube and graphene complex.
Embodiment 11: with the Fe/Mo/ mica is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 1%, Mo content be 0.1% Fe/Mo/ mica as catalyzer, get 100mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 850 ℃ by room temperature; Afterwards with maintain at 850 ℃; Feed 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.Close carbon source normal hexane and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the HF aqueous solution of 0.5mol/L down at 80 ℃ earlier in the purification of products device, handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ again, can obtain carbon nanotube and graphene complex.
Embodiment 12: with the Fe/Mo/ pseudo-boehmite is that catalyzer prepares carbon nanotube and graphene complex through fixed bed.
With Fe content is 10%, Mo content be 1% Fe/Mo/ pseudo-boehmite as catalyzer, get 100mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 700 ℃ by room temperature; Afterwards with maintain at 700 ℃; Feed 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.Close carbon source toluene and H behind the 30min
2, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the NaOH aqueous solution of 3mol/L down at 180 ℃ earlier in the purification of products device, handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ again, can obtain carbon nanotube and graphene complex.
Embodiment 13: the combined reactor that is catalyzer through fixed bed and fluidized-bed with the Fe/Mo/ vermiculite prepares carbon nanotube and graphene complex.
With Fe content is 1%, Mo content be 0.1% Fe/Mo/ vermiculite as catalyzer, get 1g and put into the fluidized-bed reactor that diameter is 20mm, use argon gas to be carrier gas, its flow is 1000sccm.Under this atmosphere, temperature of reactor is raised to 650 ℃ by room temperature, afterwards with maintain at 650 ℃, feed the gas mixture of carbon source ethene, hydrogen and argon gas, wherein the dividing potential drop of carbon source ethene is 20%, carries out the chemical vapor deposition processes deposition of carbon nanotubes; Using atmosphere speed that the solid product of gained is blown into temperature afterwards is in 950 ℃ the fixed-bed reactor, feeds 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 and deposits Graphene.Close carbon source methane behind the 10min, under argon gas atmosphere with taking out solid product after reactor cooling to the room temperature.Solid product is handled 6hr with the HF aqueous solution of 0.5mol/L down at 80 ℃ earlier in the purification of products device, handle 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ again, can obtain carbon nanotube and graphene complex.
Embodiment 14: be that catalyzer prepares carbon nanotube and graphene complex through fixed bed with Fe/Mo/MgO.
With Fe content is 1%, Mo content be 0.1% flaky Fe/Mo/MgO as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use helium to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 600 ℃ by room temperature; Afterwards with maintain at 600 ℃, feed the gas mixture of carbon source YLENE, hydrogen and helium, wherein the dividing potential drop of carbon source YLENE is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.Close carbon source YLENE and H behind the 20min
2, take out solid product after under helium atmosphere, being cooled to room temperature.Solid product is handled 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ remove the Natural manganese dioxide in the product in the purification of products device, can obtain carbon nanotube and graphene complex.
Embodiment 15: be that catalyzer prepares carbon nanotube and graphene complex through fixed bed with Co/MgO.
With Co content be 5% flaky Co/MgO as catalyzer, get 50mg and evenly be layered in the porcelain boat, be placed in the tubular fixed-bed reactor then.Use argon gas to be carrier gas, its flow is 600sccm.Under this atmosphere, temperature of reactor is raised to 950 ℃ by room temperature; Afterwards with maintain at 950 ℃, feed the gas mixture of carbon source methane, ethene, hydrogen and argon gas, wherein the dividing potential drop of carbon source methane is 5%, the dividing potential drop of ethene is 5%, carries out chemical vapor deposition processes deposition of carbon nanotubes and Graphene simultaneously.Close carbon source methane, ethene and H behind the 20min
2, take out solid product after under argon gas atmosphere, being cooled to room temperature.Solid product is handled 6hr with the HCl aqueous solution of 1mol/L down at 80 ℃ remove the Natural manganese dioxide in the product in the purification of products device, can obtain carbon nanotube and graphene complex.
Claims (5)
1. one kind prepares the method for carbon nanotube and graphene complex based on sheet layer material, it is characterized in that this method carries out as follows:
1) sheet layer material that load is had the catalyst activity component is as catalyzer, and said activity of such catalysts component is Fe, Co, Ni, Cu, Mo or W, and its content accounts for 0.1%～50% of catalyst quality;
2) this catalyzer is placed reactor drum; Pass through chemical vapor deposition processes; Deposition of carbon nanotubes and Graphene on the surface of catalyzer; Product with gained places the product purification device to purify then, obtains carbon nanotube and graphene complex, and carbon nanotube is grown directly upon on the surface of Graphene in carbon nanotube and the graphene complex.
2. a kind ofly prepare the method for carbon nanotube and graphene complex based on sheet layer material according to claim 1 is described, it is characterized in that: described sheet layer material is laminated dihydroxy composite metal hydroxide, Natural manganese dioxide, aluminium sesquioxide, silicon-dioxide, kaolin, polynite, vermiculite, mica or pseudo-boehmite.
3. according to claim 1 or 2 described a kind of methods that prepare carbon nanotube and graphene complex based on sheet layer material; It is characterized in that: step 2) described in chemical vapor deposition processes in; Being deposited as of carbon nanotube and Graphene carried out simultaneously or successively carried out; Wherein the temperature of reaction of deposition of carbon nanotubes is 500～1000 ℃, and the temperature of reaction of deposition Graphene is 600～1200 ℃.
4. describedly a kind ofly prepare the method for carbon nanotube and graphene complex according to claim 1 or 2, it is characterized in that: step 2 based on sheet layer material) described in chemical vapor deposition processes use one or several the mixture in low-carbon (LC) gas, methyl alcohol, ethanol, benzene, hexanaphthene, normal hexane, toluene and the YLENE below seven carbon to be carbon source; Use argon gas, nitrogen, helium, hydrogen or their mixture as carrier gas, the dividing potential drop of control carbon source is less than 80% of total pressure.
5. describedly a kind ofly prepare the method for carbon nanotube and graphene complex according to claim 1 or 2, it is characterized in that: step 2 based on sheet layer material) described in the reactor types that adopts of chemical vapor deposition processes be fixed bed, moving-bed, fluidized-bed or their combination.
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