CN101348901B - Preparation and apparatus of high quality and high yield carbon nano-tube array - Google Patents
Preparation and apparatus of high quality and high yield carbon nano-tube array Download PDFInfo
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- CN101348901B CN101348901B CN2008100542989A CN200810054298A CN101348901B CN 101348901 B CN101348901 B CN 101348901B CN 2008100542989 A CN2008100542989 A CN 2008100542989A CN 200810054298 A CN200810054298 A CN 200810054298A CN 101348901 B CN101348901 B CN 101348901B
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Abstract
The invention relates to a method and a device for preparing high-quality high-yield carbon nanotube arrays (CNTAs). The method adopts an aerosol-CVD method, uses cyclohexane as a carbon source, and comprises the following steps that: (1) ferrocene as a catalyst matrix and the cyclohexane carbon source are respectively purified; (2) a reaction solution containing the catalyst matrix with the masspercentage between 2 and 6 percent is prepared and then transferred into a spraying bottle; (3) a reaction system is sealed up, and argon is used to pump and displace the air in the reaction system by means of a vacuum pump; and (4) a quartz reaction tube is heated to between 700 and 900 DEG C, and a flowmeter is regulated to ensure that the flow rate of the argon is between 3 and 9 liters per minute, so as to directly jet the reaction solution into the quartz reaction tube, and a CNTAs crude product can be obtained after the jet continues for 4 to 15 minutes. As the invention (1) uses the cyclohexane as the carbon source, prepared CNTAs are high in purity, fast in average growth rate and good in the orientation of CNTs; the yield of the product reaches about 20 percent for the first time; the CNTAs are fast in growth rate, and the average growth rate can reach more than 25 microns per minute.
Description
Technical field
The invention belongs to field of nanometer technology, particularly relating to the hexanaphthene is carbon source, the method and the device of the carbon nano pipe array of preparation high quality, high yield.
Background technology
Carbon nano pipe array (carbon nanotube arrays-CNTAs or aligned carbon nanotubes-ACNTs, patent of the present invention is got the former abbreviated form) is carbon nanotube (a kind of important existence form of carbon nanotubes-CNTs).In CNTAs, CNTs with arrange in order, highly parallel, highdensity form exists.CNTAs has not only kept performances such as the mechanics, electricity, calorifics of the excellence of CNTs, but also had the constructional feature of height-oriented property, high-density and the collimation of CNTs, so has good application prospects in fields such as mould material, nano capacitor and the ultracapacitor of field emission display, nano composite material, special purpose, nano electron device, nanometer film transmitter, special coating, sun power utilization, hydrogen storage materials.
From (Li W Z such as Li, Xie S S, Qian L X, et al..Large-Scale Synthesis of Aligned CarbonNanotubes.Science, 1996,274 (5293): 1701-1703) reported first utilize duct restriction CNTs epitaxial method to prepare since the CNTAs, the researchdevelopment of relevant CNTAs preparation is very fast, reported multiple CNTAs preparation method in the document, as template, the chemical vapor deposition (CVD) method, plasma enhanced CVD (PECVD) method, electron cyclotron resonace CVD (ECR-CVD) method, the catalytic cracking solution, catalyst film method etc.; Above-listed method all can be summed up as chemical method.
Adopt physical method, the CNTs for preparing with catalystic pyrolysis or arc discharge method is a raw material, also can prepare CNTAs; As adding under the action of a magnetic field, utilize the magneticanisotropy of CNTs to prepare CNTAs; The suspension of preparation CNTs utilizes the self-assembly performance of CNTs to prepare CNTAs; Adopt the method for cutting CNTs-polymer composites to prepare CNTAs etc.
Result for retrieval to domestic and international patent documentation shows, U.S.'s patent of invention of relevant CNTAs preparation has hundreds of, and the world inventions patent has tens, and it is 20 multinomial that Chinese invention patent has.No matter but the paper of having delivered, or in the patent of invention, all clearly do not provide the yield of CNTAs both at home and abroad.
In the various preparation CNTAs methods of bibliographical information, quite a few method can make the CNTAs of high quality (purity height, favorable orientation, degree of collimation height), but because yield is very low, preparation cost is very high, makes the applied research of CNTAs and exploitation be subjected to very big restriction.
With benzene is carbon source, though adopt aerosol-CVD method can make CNTAs, quality is not fine (Mayne M, Grobert N, Terrones M, et al..Chem.Phys.Lett., 2001,338 (2-3): 101-107); Through improvement to this method, the quality of CNTAs product significantly improves, but still very low (the Scharff P of yield, Cui S.Frontiers ofMultifunctional Integrated Nanosystems.Edited By Buzaneva E and Scharff P, KluwerAcademic Publ ishers, NATO Sci.Ser.II.Math., Phys.﹠amp; Chem., Vol.152,2004, pp.153-166); And the benzene environmental pollution is serious, is unwell to suitability for industrialized production.
Adopting a step pyrolysis installation, is carbon source with the hexanaphthene, though can make CNTAs, yield is still very low, and second-rate (Mahanandia P, Nanda K K.Nanotechnology, 2008,19 (15): 155602 (7pp)).
Summary of the invention
The invention provides a kind of is carbon source with the hexanaphthene, under high temperature, normal pressure, argon atmospher condition, adopts known aerosol-CVD method, the CNTAs of preparation high quality, high yield.The present invention has important and practical meanings for the applied research and the exploitation that promote CNTAs.
The carbon nano pipe array preparation method of high quality of the present invention, high yield adopts aerosol-CVD method, it is characterized in that with the hexanaphthene being carbon source.
The carbon nano pipe array preparation method of high quality of the present invention, high yield is characterized in that described method steps is as follows:
(1) at first respectively catalyst Precursors ferrocene and hexanaphthene carbon source are carried out purifying;
(2) preparation contains the reaction soln of the catalyst Precursors of mass percent 2-6% concentration, is transferred in the spray bottle then;
(3) sealed reaction system by vacuum pump, is taken out the air of washing, replacing in it with argon gas;
(4) heating crystal reaction tube to 700-900 degree centigrade, regulating under meter to argon flow amount is 3-9 liter per minutes, makes reaction soln inject directly into crystal reaction tube, sustained firing 4-15 minutes can obtain the carbon nano pipe array crude product.
Described high quality carbon nano-pipe array is listed in to be positioned on interior quartz plate of crystal reaction tube and the monocrystalline silicon piece and also can generates.
Before using, described liquid cyclohexane needs to soak processed through rectifying or 5A molecular sieve.
Described catalyst Precursors ferrocene need be handled through distillation or conventional drying before use.
Described high yield is that carbon nano pipe array crude product yield is in 1-20% mass percent; The average growth velocity of carbon nano pipe array reaches 10-50 microns per minutes.
Described vertical reservoir is directly to be communicated with horizontal spray bottle, and the imbibition kapillary is directly to insert in the solution of vertical reservoir, and the imbibition kapillary is connected with glass stick with gas ejector pipe.
The carbon nano pipe array preparation method's of high quality of the present invention, high yield device, it is characterized in that described vertical reservoir is directly to be communicated with horizontal spray bottle, be that the imbibition kapillary is directly to insert in the solution of vertical reservoir, the imbibition kapillary is connected with glass stick with gas ejector pipe, sees Fig. 1; This kind structure design makes the manufacture difficulty of spray bottle reduce significantly, thereby its cost of manufacture is significantly reduced.
Vertical reservoir of reporting in the document directly is not communicated with horizontal spray bottle, is communicated with by a Glass tubing; The imbibition kapillary passes the horizontal spray bottle and the vertical bottle wall of reservoir, i.e. imbibition outer wall capillaceous and horizontal spray bottle and vertically the bottle wall of reservoir be sintering together, insert then in the solution of vertical reservoir, see Fig. 2; Such structure makes that the manufacture difficulty of spray bottle is very big, thereby its cost of manufacture is higher.
Present method has following advantage:
(1) with the hexanaphthene is carbon source, the purity height of the CNTAs of preparation, average fast growth, the favorable orientation of CNTs;
(2) with the hexanaphthene be carbon source, the CNTAs crude product yield of preparation has reached about 19.8% (mass percent, down together) first;
(3) fast growth of CNTAs, the average speed of growth can reach per minute more than 25 microns;
(4) be placed on the quartz plate in the crystal reaction tube and also can grow high-quality CNTAs, its average speed of growth can reach per minute more than 22.5 microns;
(5) be placed on the monocrystalline silicon piece in the crystal reaction tube and also can grow high-quality CNTAs, its average speed of growth can
To reach per minute more than 13 microns;
(6) the spray bottle structure design is simple, makes easily;
(7) the CNTAs preparation cost reduces significantly;
(8) environmental pollution degree goes to zero.
Description of drawings
Fig. 1 spray bottle structural representation of the present invention;
(A) gas ejector pipe; (B) imbibition kapillary (internal diameter 0.5-1 millimeter); (C) gas blow pipe; (D) produce aerosol;
(E) hexanaphthene/ferrocene solution; (F) connect glass stick; (G) glass threeway; (H) glass ground joint;
The known spray bottle structural representation of Fig. 2;
Scanning electron microscope (SEM) photo of the CNTAs product among Fig. 3 embodiment 1;
(a) low power SEM photo; (b) be the SEM photo of the amplification of rectangle frame inner compartment in (a); (c) be the SEM photo of the amplification of rectangle frame inner compartment in (b);
High-resolution-ration transmission electric-lens (HRTEM) photo of the CNTAs product among Fig. 4 embodiment 1
(a) low power HRTEM photo; (b) high power HRTEM photo;
The stereoscan photograph of the CNTAs product on the quartz plate among Fig. 5 embodiment 2;
(a) the low power SEM photo of the CNTAs product on the quartz plate that is streaked by sharp blade; (b) be the SEM photo of the amplification of rectangle frame inner compartment in (a); (c) be the SEM photo of the amplification of rectangle frame inner compartment in (b);
The stereoscan photograph of the CNTAs product on the monocrystalline silicon piece among Fig. 6 embodiment 3;
(a) the low power SEM photo of the CNTAs product on the monocrystalline silicon piece that is streaked by sharp blade; (b) the SEM photo of the vertical section of the CNTAs product on the monocrystalline silicon piece; (c) be the SEM photo of the amplification of rectangle frame inner compartment in (b);
The stereoscan photograph of the CNTAs product among Fig. 7 embodiment 4;
(a) the SEM photo of the vertical section of CNTAs product; (b) be the SEM photo of the amplification of rectangle frame inner compartment in (a);
The stereoscan photograph of the vertical section of the CNTAs product among Fig. 8 embodiment 9;
The stereoscan photograph of the CNTAs product among Fig. 9 embodiment 12;
(a) the SEM photo of the vertical section of CNTAs product; (b) the high power SEM photo of the vertical section of CNTAs product;
The stereoscan photograph of the vertical section of the CNTAs product among Figure 10 embodiment 13;
The stereoscan photograph of the vertical section of the CNTAs product among Figure 11 embodiment 14;
The stereoscan photograph of the CNTAs product in Figure 12 Comparative Examples 1;
(a) low power SEM photo; (b) the SEM photo of the vertical section of CNTAs product;
The stereoscan photograph of the CNTAs product in Figure 13 Comparative Examples 2;
(a) the SEM photo of the CNTAs product on the quartz plate that is streaked by sharp blade; (b) the SEM photo of the vertical section of the CNTAs product on the quartz plate;
The stereoscan photograph of the product in Figure 14 Comparative Examples 3.
Embodiment
Adopt device as shown in Figure 1, be equipped with the spray bottle of carbon nano pipe array as aerosol-CVD legal system, (A) gas ejector pipe wherein, (B) imbibition kapillary (internal diameter 0.5-1 millimeter), (C) gas blow pipe (D) produces aerosol, (E) hexanaphthene/ferrocene solution, (F) connect glass stick, (G) glass threeway, (H) glass ground joint.
Through sublimation purification, liquid carbon source (solvent) hexanaphthene is through the rectifying purifying with the catalyst Precursors ferrocene; Preparation catalyst Precursors concentration is the reaction soln of 5% (mass percent, together following), is transferred to then in the above-mentioned spray bottle, and its (H) glass ground joint is connected with the glass ground joint of the crystal reaction tube that inserts the electrical heater inner chamber; Sealed reaction system then by vacuum pump, is taken out the air of washing, replacing in it with argon gas; Heating crystal reaction tube to 850 degree centigrade is regulated under meter to argon flow amount and is about 7 liter per minutes, makes reaction soln inject directly into crystal reaction tube, sustained firing (reaction) 8 minutes; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 7%.By low power SEM photo Fig. 3 a as seen, the CNTAs product is almost not have particle, laminar and fragmental thing with comparison rule, regular block.In order better to observe CNTAs degree of purity of production, orientation, degree of collimation and to measure its length, choose rectangle frame inner compartment among Fig. 3 a (cross section of the vertical section of CNTAs-CNTAs direction of growth) and further amplify, obtain Fig. 3 b.One dimension Nano structure by can see ordered arrangement among Fig. 3 b more clearlyly does not almost have other impurity; The area arrangement that has is a bit chaotic, is (to scrape the destruction of causing when getting product from the quartz reaction inside pipe wall) owing to be subjected to due to the outside destroy.Carry out SEM when characterizing, choosing that any product amplifies observation among Fig. 3 a, can determine that it is the CNTAs product.By the length that records CNTAs among Fig. 3 b is 200 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has reached 25 microns per minutes.Choose among Fig. 3 b the rectangle frame inner compartment and further amplify, obtain Fig. 3 c; One dimension Nano structure by being clear that ordered arrangement among Fig. 3 c does not almost have other impurity, and some bright spots in zone, middle and upper part should be the end points of CNTs.Fig. 4 a is the low power high-resolution-ration transmission electric-lens photo of the CNTAs product in the present embodiment 1, and the CNTs among the visible CNTAs is more straight, is not sinuate, does not also have the phenomenon of winding mutually, and impurity seldom; Fig. 4 b is the high power high-resolution-ration transmission electric-lens photo of the CNTAs product in the present embodiment 1, as seen the CNTs among the CNTAs is multi-walled carbon nano-tubes (multi-walled carbonnanotubes-MWCNTs), its external diameter is distributed in 11-89 nanometers, internal diameter is distributed in 4-14 nanometers, does not almost have impurity.The characterization result of comprehensive scanning Electronic Speculum and high-resolution-ration transmission electric-lens (Fig. 3 and Fig. 4) can confirm that CNTAs product purity height, favorable orientation, the degree of collimation in the present embodiment 1 is better.
Embodiment 2
Experiment condition is with embodiment 1, but what obtain is CNTAs product on the quartz plate that is placed in the crystal reaction tube.Use the CNTAs product of sharp blade on quartz plate to mark a cruciform, choose the position of digging then, and can observe the vertical section of CNTAs product, see Fig. 5 a.Choose among Fig. 5 a the rectangle frame inner compartment and further amplify, obtain Fig. 5 b; CNTs by can see ordered arrangement among Fig. 5 b more clearlyly does not almost have other impurity; By the length that can record CNTAs among Fig. 5 b is 180 microns, and according to (reaction) time of injection, the average speed of growth that can calculate the CNTAs on the quartz plate has reached 22.5 microns per minutes.Choose among Fig. 5 b the rectangle frame inner compartment and further amplify, obtain Fig. 5 c; CNTs by being clear that ordered arrangement among Fig. 5 c does not almost have other impurity; The CNTs of some fall into disarray of surface should be because sharp blade streaks due to the CNTAs product on the quartz plate.Comprehensive scanning Electronic Speculum characterization result (Fig. 5) can confirm that CNTAs product purity height, favorable orientation, the degree of collimation on the quartz plate in the present embodiment 2 is better.
Experiment condition is with embodiment 1, but what obtain is CNTAs product on the monocrystalline silicon piece that is placed in the crystal reaction tube.Use the CNTAs product of sharp blade on monocrystalline silicon piece to mark a cruciform, its low power SEM photo is seen Fig. 6 a.Choose the vertical section of the CNTAs product of digging then and take pictures, see Fig. 6 b; CNTs by can see ordered arrangement among Fig. 6 b more clearlyly does not almost have other impurity; By the length that can record CNTAs among Fig. 6 b is 104 microns, and according to (reaction) time of injection, the average speed of growth that can calculate the CNTAs on the monocrystalline silicon piece has reached 13 microns per minutes.Choose among Fig. 6 b the rectangle frame inner compartment and further amplify, obtain Fig. 6 c; CNTs by being clear that ordered arrangement among Fig. 6 c does not almost have other impurity; The CNTs of some fall into disarray of surface should be because sharp blade streaks due to the CNTAs product on the monocrystalline silicon piece.Comprehensive scanning Electronic Speculum characterization result (Fig. 6) can confirm that CNTAs product purity height, favorable orientation, the degree of collimation on the monocrystalline silicon piece in the present embodiment 3 is better.
Regulate under meter to argon flow amount and be about 9 liter per minutes, make reaction soln inject directly into crystal reaction tube, other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 4.8%.The SEM photo of the vertical section of CNTAs product is seen Fig. 7 a, can see the CNTs of ordered arrangement more clearlyly, does not almost have other impurity; By the length that can record CNTAs among Fig. 7 a is 193 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has reached 24.1 microns per minutes.Choose among Fig. 7 a the rectangle frame inner compartment and further amplify, obtain Fig. 7 b; CNTs by being clear that ordered arrangement among Fig. 7 b does not almost have other impurity.Comprehensive scanning Electronic Speculum characterization result (Fig. 7) can confirm that CNTAs product purity height, favorable orientation, the degree of collimation in the present embodiment 4 is better.
Embodiment 5
The reaction soln sustained firing is gone into the time lengthening to 15 minute of crystal reaction tube, and other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 12.8%.
Regulate under meter to argon flow amount and be about 3 liter per minutes, make reaction soln inject directly into crystal reaction tube, other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 19.8%.
Embodiment 7
Preparation catalyst Precursors concentration is 2% reaction soln, and other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 1.0%.
Embodiment 8
Preparation catalyst Precursors concentration is 6% reaction soln, makes reaction soln inject directly into crystal reaction tube, but can only sustained firing 4 minutes, and other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 8%.
Embodiment 9
Heating crystal reaction tube to 750 degree centigrade sprays 7.5 minutes (reaction) time; Other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product on the quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 1.4%.The SEM photo of the vertical section of CNTAs product is seen Fig. 8, can see the CNTs of ordered arrangement more clearlyly, but purity slightly reduces, and does not promptly resemble the vertical section of the CNTAs product among the embodiment 1 to embodiment 4 clean, neat.By the length that can record CNTAs among Fig. 8 is 104 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has reached 13.9 microns per minutes.
Heating crystal reaction tube to 700 degree centigrade; Other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates product yield and is about 0%, does not promptly have the deposit carbon product substantially.
Embodiment 11
Heating crystal reaction tube to 900 degree centigrade; Other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 2.6%.
Embodiment 12
The catalyst Precursors ferrocene sprays 7 minutes (reaction) time 110 degrees centigrade of dryings 2 hours; Other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 2.4%.The CNTAs product the SEM photo of vertical section see Fig. 9 a, the order that visible CNTs arranges obviously reduces, and the CNTAs both sides are relatively more chaotic; By the mean length that can record CNTAs among Fig. 9 a is 96 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has reached 13.7 microns per minutes.Fig. 9 b is the high power SEM photo of the vertical section of CNTAs product, can be clear that the CNTs that arrangement is more orderly, is mingled with some granule foreigns therebetween.Comprehensive scanning Electronic Speculum characterization result (Fig. 9) can confirm that CNTAs degree of purity of production, the orientation in the present embodiment 8 decreases.
Liquid carbon source (solvent) hexanaphthene soaked 2 days through the 5A molecular sieve, and other experiment condition is with embodiment 8; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 2.8%.The CNTAs product the SEM photo of vertical section see Figure 10, can see the CNTs of ordered arrangement more clearlyly.By the length that can record CNTAs among Figure 10 is 111 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has reached 15.9 microns per minutes.
Embodiment 14
Preparation catalyst Precursors concentration is 3% reaction soln, and other experiment condition is with embodiment 9; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield and is about 1.8%.The SEM photo of the vertical section of CNTAs product is seen Figure 11, can see the CNTs of ordered arrangement more clearlyly, but the surface in CNTAs left side is not very level and smooth, neat.By the length that can record CNTAs among Figure 11 is 125 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has reached 17.9 microns per minutes.
Comparative Examples 1
Carbon source (solvent) is a benzene, and other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, calculates CNTAs crude product yield less than 0.5%.The low power SEM photo of CNTAs product is seen Figure 12 a, as seen based on relatively more neat, certain thickness flap is arranged, but its edge is not very neat, also has some dispersed particles shape by-product impurities.The high power SEM photo of the vertical section of CNTAs product is seen Figure 12 b, can be clear that the CNTs of ordered arrangement, therebetween impurity seldom, but the surface in CNTAs left side it is apparent that by one deck have certain thickness particulate state by-product impurities to constitute.By the length that can record CNTAs among Figure 12 b is 22 microns, according to spraying (reaction) time, and the average speed of growth that can the calculate CNTAs 2.8 microns per minutes of only having an appointment.Comprehensive scanning Electronic Speculum characterization result (Figure 12) can confirm that the CNTAs degree of purity of production in this Comparative Examples 1 is better than higher, favorable orientation, degree of collimation, but the average speed of growth is very slow.
Comparative Examples 2
Spray 13.5 minutes (reaction) time; Other experiment condition is with Comparative Examples 1; But what obtain is the CNTAs product that is placed on the interior quartz plate of crystal reaction tube.By the side-view of the vertical section of the visible CNTAs product of Figure 13 a, but its surface coverage has one deck by-product impurities.Can see the CNTs that arrangement is more orderly by the white edge inner compartment among Figure 13 b, impurity is less therebetween more clearlyly, but the upper end of CNTAs can see that certain thickness, flaky by-product impurities is arranged; The length that can be recorded CNTAs by Figure 13 b is 34 microns, and according to (reaction) time of injection, the average speed of growth that can calculate CNTAs has only 2.5 microns per minutes.
Comparative Examples 3
Liquid carbon source (solvent) is a dehydrated alcohol, soaks 2 days through the 5A molecular sieve; Preparation catalyst Precursors concentration is 3% reaction soln, sprays 5 minutes (reaction) time; Other experiment condition is with embodiment 1; Reaction finishes postcooling to room temperature, collects the product of quartz reaction inside pipe wall, and calculated product carbon product yield is less than 0.1%; Based on particulate material, also have 1-dimention nano product some irregularities, that orientation is very poor in the product, do not have CNTAs, see Figure 14.
The high quality that the present invention proposes, the carbon nano pipe array preparation method and the device of high yield, be described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to device as herein described with technological method is changed or suitably change and combination, realize the technology of the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (4)
1. the carbon nano pipe array preparation method of a high quality, high yield adopts aerosol-CVD method, it is characterized in that with the hexanaphthene being carbon source; Method steps is as follows:
(1) at first respectively catalyst Precursors ferrocene and hexanaphthene are carried out purifying;
(2) preparation contains the reaction soln of the catalyst Precursors of mass percent 2-6% concentration, is transferred in the spray bottle then;
(3) sealed reaction system by vacuum pump, is taken out the air of washing, replacing in it with argon gas;
(4) the heating crystal reaction tube is to 750-900 degree centigrade, and regulating under meter to argon flow amount is 3-9 liter per minute, makes reaction soln inject directly into crystal reaction tube, sustained firing 4-15 minute, can obtain the carbon nano pipe array crude product.
2. the carbon nano pipe array preparation method of high quality as claimed in claim 1, high yield is characterized in that described carbon nano-pipe array is listed on the quartz plate that is positioned in the crystal reaction tube or the monocrystalline silicon piece to generate.
3. the carbon nano pipe array preparation method of high quality as claimed in claim 1, high yield is characterized in that needing before described hexanaphthene uses to soak processed through rectifying or 5A molecular sieve.
4. the carbon nano pipe array preparation method of high quality as claimed in claim 1, high yield is characterized in that described catalyst Precursors ferrocene before use need be through distillation or conventional drying processing.
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