• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention provides a metal nanocatalyst, a method of making the same, and a method of controlling the growth types of carbon nanotubes using the same. The metal nanocatalyst can be prepared by heating an aqueous derivative of which contains Co, Fe, Ni or a combination thereof in the presence of a precursor of the supporting substance.
    公开号:BE1019067A3
    申请号:E2009/0762
    申请日:2009-12-09
    公开日:2012-02-07
    发明作者:Yeol Kim Byeong；Yong Bae Seung；Sil Lee Young
    申请人:Cheil Ind Inc；
    IPC主号:
    专利说明:

    Metal nanocatalyst, method for producing it and method for controlling the growth types of carbon nanotubes by using it
    Reference to related applications
    This application is based on the priority of the Korean Patent Application No. 2-008-125453 filed December 10, 2008 with the Korean Intellectual Property Office, the disclosure of which is hereby incorporated by reference in its entirety.
    FIELD OF THE INVENTION
    The present invention relates to a metal nanocatalyst, a method for manufacturing it, and a method for controlling the growth types of carbon nanotubes through their use.
    BACKGROUND OF THE INVENTION
    Recently there has been a lot of research and development into carbon nanotubes (hereafter CNT). Engineered plastic composites containing carbon nanotubes can have electrical conductivity and can therefore be used as a material with a high added value for shielding electromagnetic waves, thereby preventing static electricity and the like. The electrical. conductivity produced by adding carbon nanotubes to a plastic composite can be influenced by the conditions of preparation, the resin used and the characteristics of the carbon nanotubes themselves such as purity, diameter and growth type. Better electrical characteristics can be achieved by using carbon nanotubes with a shorter diameter that are less likely to agglomerate and / or become entangled such as carbon nanotubes with a longer diameter.
    In general, graphite can be rolled into a cylinder to form the surfaces of a carbon nanotube. The carbon nanotubes are classified as single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes following the number of rolled-up surfaces of the cylinder, and have different properties based on the number of such walls. For example, single-walled or double-walled carbon nanotubes can have excellent electrical characteristics and are accordingly widely used in instruments such as electronic emitting parts, elements of an electronic part, sensors and the like. Multi-walled carbon nanotubes can have lower electrical conductivity but can be used in complex high-strength materials due to their excellent physical properties. The development of a manufacturing process that produces high purity carbon nanotubes at a lower cost is important for the successful use of these carbon nanotubes in various industrial areas.
    Carbon nanotubes are mainly synthesized by the electrical discharge method, laser evaporation, high pressure vapor deposition, normal pressure thermo-chemical vapor deposition and the like. Electric discharge methods and laser evaporation can easily be applied due to their simple principles, but are not suitable for mass production and the product produced with it can contain many impurities. The thermo-chemical vapor deposition is currently the most widely used method to mass-produce carbon nanotubes of high purity at lower costs.
    When carbon nanotubes are manufactured using the thermo-chemical vapor deposition, the catalyst used is also important and it is generally a transition metal such as cobalt, iron, nickel and. such aided by a supported substance. Methods for synthesizing a catalyst for manufacturing. of carbon nanotubes includes coprecipitation methods, impregnation methods, combustion methods, and various other methods. The final catalyst can be synthesized by heat treatment at a high temperature of about 500 ° to about 1200 ° C.
    The electrical conductivity shown by CNTs in a high polymer composite is mainly influenced by an even distribution of CNTs in a high polymer matrix, as well as by the electrical property of the CNTs. The CNT distribution rate can be influenced by the growth type of the CNTs. In general, a bundle (fiber) type is more easily divided into a high polymer matrix and, as a result, may exhibit a higher electrical conductivity than a cotton wool (lump) type. However, the technology that regulates the CNT growth type has not been systematically studied and has not yet been theoretically substantiated.
    Summary of the invention
    The present inventors have developed a method for regulating or controlling the carbon nanotube growth type by altering the composition of a metal catalyst for carbon nanotube synthesis, a metal nanocatalyst with a novel composition, and a method for manufacturing the metal nanocatalyst which can save time and costs compared to other manufacturing methods.
    An aspect of the present invention provides a metal nanocatalyst with a new composition.
    Another aspect of the present invention provides a metal nanocatalyst that can regulate carbon nanotube growth type.
    Another aspect of the present invention provides a metal nanocatalyst that can regulate the carbon nanotube diameter.
    Another aspect of the present invention provides a method for manufacturing a metal nanocatalyst, which method can be stable.
    Another aspect of the present invention provides a carbon nanotube of the bundle growth type or wadding growth type.
    Another aspect of the present invention provides a method for manufacturing carbon nanotubes that can be used to mass-produce carbon nanotubes and that can save time and costs.
    Another aspect of the present invention provides a new method that can regulate the growth type of carbon nanotubes.
    Other aspects, features and advantages of the present invention will become apparent from the following disclosure and appended claims.
    An aspect of the present invention provides a metal nanocatalyst with a new composition.
    The metal nanocatalyst can have a composition as follows: (Ni, Co, Fe) x (Mo, Va) y (Al 2 O 3, MgO, SiO 2) z where x, y and z are molecular ratios and 1 <x <10, 0 < y <5, and 2 <z <15).
    Another aspect of the present invention provides a method for manufacturing a metal nanocatalyst. The method of manufacturing comprises synthesizing an aqueous derivative of the metal catalyst containing Co, Fe, Ni, or a combination thereof, absorbed on the surface of a supporting substance containing Al 2 O 3, MgO, SiO 2 or a combination thereof.
    In exemplary embodiments, the aqueous derivative of the metal catalyst may be a metal hydrate. The metal hydrate may contain iron (III) nitrate hydrate, nickel nitrate hydrate, cobalt nitrate hydrate or a combination thereof.
    In exemplary embodiments, the efficiency of the catalyst can be increased by promoting the adsorption stability of the metal particle on a surface of the supporting substance by molybdenum (Mo), vanadium. (V), or a combination thereof.
    In exemplary embodiments, the supporting substance may be formed from a precursor containing aluminum nitrate hydrate, magnesium nitrate hydrate, silica citrate hydrate or a combination thereof.
    In one exemplary embodiment, the manufacturing method may include a combustion carried out at a temperature of about 300 to about 900 ° C, for example about 500 to about 600 ° C.
    In exemplary embodiments, the aqueous derivative of the metal catalyst and the precursor of the supported substance can be used in an aqueous phase.
    Another aspect of the present invention provides a method for regulating or controlling the growth type of carbon nanotubes by using the metal nanocatalyst. In the process, the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance (z) can be regulated to be x: z = about 1 to about 10: about 2 to about 15 in a process for synthesizing carbon nanotubes comprising the steps of: manufacturing a metal nanocatalyst by using an aqueous derivative of the metal catalyst comprising Co, Fe, Ni or a combination thereof in the presence of a precursor of the supporting substance; and manufacturing the carbon nanotubes by supplying carbon gas in the presence of the synthesized metal nanocatalyst. In another exemplary embodiment, the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance (z) may be x: z = about 1 to about 10: about 7.5 to about 15.
    In one exemplary embodiment, the surface stability of the metal particle of the aqueous derivative of the metal catalyst and of the precursor of the supporting substance can be increased by using molybdenum (Mo), vanadium (V), or a combination thereof.
    Another aspect of the present invention provides a carbon nanotube synthesized with the manufacturing process. The carbon nanotube can contain a bundle of growth type or a cotton wool growth type.
    Brief description of the drawings
    Figs. 1-6 are scanning electron microscopic (SEM) images of carbon nanotubes (CNTs) made in accordance with respective Examples 1-6.
    DETAILED DESCRIPTION OF THE INVENTION
    The present invention will now be described more fully hereinafter in the following detailed description of the invention describing some, but not all, embodiments of the invention. Indeed, this invention can be implemented in many different forms and should not be construed as being limited to the embodiments shown herein; rather, these embodiments are provided so that this disclosure will meet applicable legal requirements.
    The metal nanocatalyst of the present invention has a novel composition as follows: (Ni, Co, Fe) x (Mo, Va) y (Al 2 O 3, MgO, SiO 2) z where x, y and z are molecular ratios and KxdO, 0 < y <5, and 2 <z <15. In one exemplary embodiment, 1 <x <7, 0 <y <1.5, and 2 <z <7.5. In another exemplary embodiment, 1 <x <7, 0 <y <1, 5, and 7.5 <z <15. In another exemplary embodiment, 1 <x <3, 0 <y <1.5, and 2 <z <15.
    As used herein, the formula of the composition (Ni, Co, Fe) x (Mo, Va) y (Al 2 O 3, MgO, SiO 2) 2 will be understood to include (Ni or Co or Fe or a combination thereof) χ (Mo or Va or a combination thereof) y (Al 2 O 3 or MgO or ~ SiO 2 or a combination thereof) z.
    The metal nanocatalyst can be useful for carbon nanotube synthesis.
    When the metal nanocatalyst is used for carbon nanotube synthesis, if the value of z is increased compared to the value of x, a bundle type of carbon nanotube can be easily synthesized, and if the value of z is lowered, a watt type of carbon nanotube can be easily synthesized .
    In one exemplary embodiment, the metal nanocatalyst of the present invention has the structure wherein the metal particles containing Co, Fe, Ni, or a combination thereof, are evenly distributed over. and absorbed on the surface of Al 2 O 3, MgO, SiO 2, or a combination thereof, and as another example on the surface of Al 2 O 3.
    The metal nanocatalyst of the preparation can be synthesized by absorbing an aqueous derivative of the metal catalyst containing Co, Fe, Ni, or a combination thereof, on the surface of a supporting substance containing ΆΙ2Ο3, MgO, SiC> 2 or a combination and by thermal treatment. In one exemplary embodiment, the metal nanocatalyst can be synthesized by the steps of: producing, respectively, an aqueous solution of a derivative of the metal catalyst and an aqueous solution of a precursor of the supporting substance, by respectively an aqueous derivative of the metal catalyst containing Co , Fe, Ni, or a combination thereof and a precursor of the supporting substance in a separate aqueous solution; preparing a mixed aqueous solution by mixing the individual aqueous solutions; and strongly heat the mixed aqueous solution.
    In exemplary embodiments, the aqueous derivative of the metal catalyst may contain a metal hydrate. Examples of the metal hydrate may include, without limitation, iron (III) nitrate hydrate, nickel nitrate hydrate, cobalt nitrate hydrate, and the like combinations thereof. The aqueous derivative of the metal catalyst may further contain, in addition to the metal nitrate hydrate, any derivative that can be dissolved in water or an alcohol-based solvent such as methanol, ethanol, isopropanol, and the like.
    In exemplary embodiments, the metal nanocatalyst can be synthesized in the presence of an activator such as, but not limited to, molybdenum (Mo), vanadium (V) or a combination thereof. The molybdenum (Mo) or vanadium (V) can be molybdenum hydrate or vanadium hydrate, respectively. The activator can be used in the form of an aqueous solution. The activator can also act as a stabilizer that can help stabilize the metal catalyst derivative on the surface of the supporting substance. The use of molybdenum (Mo) or vanadium (V) can prevent caking of the nanosized metal catalyst during the heating of the metal particle at high temperatures. In addition, the CNT diameter can be reduced, a high yield can be achieved and the growth type of CNT can be a cotton wool type if molybdenum (Mo) or vanadium (V) is used with the catalyst in carbon nanotube synthesis.
    Exemplary supporting substances may include, without limitation, magnesium oxide, aluminum oxide, zeolite, and the like, and combinations thereof.
    In one exemplary embodiment, an activator such as citric acid may be added to facilitate the synthetic reaction of the metal nanocatalyst. The citric acid can be added in a molar ratio of about 2 to about 15. Other examples of the activator include, but are not limited to, tartaric acid, polyethylene glycol, and the like as well as citric acid, and combinations thereof.
    The aqueous derivative of the metal catalyst and the precursor of the supporting substance can be made by strong heating. The strong heating can be carried out under conditions to remove the solvent (to achieve drying of the solution) and to simultaneously promote calcination of the metal particles and to synthesize a large amount of catalyst in a short time. The method can also evenly distribute and bond the metal particles to the surface of a supporting substance. In exemplary embodiments, the mixed metal nanocatalyst solution containing the aqueous derivative of the metal catalyst and the precursor of the supporting substance is heated in air at a temperature of about 300 to 900 ° C, for example at about 450 to 600 ° C C for about 15 minutes to about 3 hours, for example about 30 minutes to about 1 hour,
    The final metal nanocatalyst can be made by trituration after calcination as a result of the heat treatment. The manufactured metal nanocatalyst can be in powder form.
    Another aspect of the present invention provides a carbon nanotube synthesized by using the metal nanocatalyst. In one exemplary embodiment, the carbon nanotube can be synthesized by supplying carbon gas and reacting in the presence of the metal nanocatalyst. For example, the carbon gas can be supplied at a temperature of about 600 to about 950 ° C.
    In exemplary embodiments, the carbon nanotube can be synthesized by normal pressure thermal chemical vapor deposition. For example, the metal nanocatalyst synthesized in powder form can be placed on a ceramic dish and the carbon nanotube can be synthesized by supplying carbon gas at a temperature of about 600 to about 950 ° C for about 30 minutes to about 1 hour through a fixed bed reactor to use. In other exemplary embodiments, about 0.01 to about 10 g of metal nanocatalyst synthesized in powder form can be uniformly applied to a ceramic dish, and the ceramic dish can be placed in the fixed bed reactor. Thereafter, the reactor can be closed to be isolated from contact with the outside world and heated to a reaction temperature of about 600 to about 950 ° C with the increase of about 30 ° C / minute. During heating, an inert gas such as nitrogen, argon, and the like, can be injected in an amount of from about 100 to about 1000 sccm (standard cubic centimeters per minute), for example about 200 to about 500 sccm to remove the oxygen contained in the reactor remains. When the temperature reaches the reaction temperature, the inert gas injection is stopped - and the synthesis is started by injecting the carbon gas in an amount of about 20 to about 500 sccm, for example about 50 to about 200 sccm. The carbon nanotube can be synthesized by supplying the carbon gas for about 30 minutes to about 2 hours, for example about 30 minutes to about 1 hour of synthesis time.
    The carbon gas can be hydrocarbon gas such as methane, ethylene, acetylene, LPG, and the like, and combinations thereof.
    The present invention can continuously produce carbon nanotubes in mass, which can regulate their growth type by changing the composition of the metal catalyst in the nano-size metal catalyst present on a supporting substance. In other words, the growth type of the carbon nanotubes can be regulated by changing the composition of the elements present in the catalyst.
    The present invention provides a method for regulating the growth type of the carbon nanotubes by using the metal nanocatalyst. The method of regulation is characterized in that the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance, (z) is regulated to be x: z = about 1 to about 10: about 2 to about 15 in a process of synthesizing carbon nanotubes that includes the steps of: manufacturing a metal nanocatalyst by using a derivative of the metal catalyst containing Co, Fe, Ni, or a combination thereof, in the presence of a precursor of the supporting substance; and manufacturing the carbon nanotubes by supplying carbon gas in the presence of the synthesized metal nanocatalyst.
    In one exemplary embodiment, the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance (z) is x: z = about 1 to about 10: about 2 to about 7.5. In another exemplary embodiment, the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance (z) is x: z = about 1 to about 10: about 7.5 to about 15. The molar ratio (x) can be in the range of about 1 to about 7, about 1 to about 5, or about 1 to about 3.
    In exemplary embodiments, non-limiting examples of the supporting substance may include magnesium oxide, aluminum oxide, zeolite, and the like, and combinations thereof, e.g., aluminum oxide.
    In one exemplary embodiment, the aqueous derivative of the metal catalyst and the precursor of the supporting substance can be heated in the presence of the molybdenum (Mo) activator, vanadium (V) activator, or a combination thereof.
    Another aspect of the present invention provides a carbon nanotube synthesized by the method of the invention. The growth type of the carbon nanotube can be the bundle type or cotton wool type.
    The invention can be better understood with reference to the following examples which are intended to illustrate the present invention, and do not limit the scope of the present invention as defined in the appended claims.
    Examples
    Example 1
    An aqueous solution of a derivative of a metal catalyst is prepared by dissolving a 2.0 molar ratio of iron (III) nitrate hydrate (Fe (NO3) 3 · 9H 2 O) - and a 2.0 molar ratio of cobalt nitrate hydrate (Co (NO 3) ) 2 * 6H 2 O) in 20 ml of water, and an aqueous solution of the precursor of the supporting substance is prepared separately by dissolving a 7.5 molar ratio of aluminum nitrate hydrate (Al (NO 3) 3 · 9H 2 O) and a 7, 5 molar ratio of citric acid (C 6 H 10 O 8). activator in 150 ml of water. Then, a catalytic composite solution is prepared by mixing the aqueous solution of the metal catalyst derivative and the aqueous solution of the precursor of the supporting substance, and a catalyst is synthesized by heating the catalytic composite solution at a temperature of about 550 ° C and atmospheric pressure for about 35 minutes. About 0.03 g of synthesized catalyst is placed on a ceramic dish of a fixed bed reactor, and a carbon nanotube can be synthesized by supplying 100/100 sccm of C 2 H 4 / H 2 at a temperature of about 700 ° C for about 1 hour. The synthesized CNT shows the beam type and the scanning electron microscopic (SEM) image of the CNT is shown in Fig. 1.
    Example 2
    An aqueous solution of a derivative of a metal catalyst is prepared by dissolving a 2.0 molar ratio of iron (III) nitrate hydrate (Fe (NO 3) 3 · 9H 2 O) and a 2.0 molar ratio of cobalt nitrate hydrate (Co (NO 3) ) 2 * 6H 2 O) in 20 ml of water, and a 1.0 molar ratio of molybdenum hydrate ((NH 4) 6 MO 7 O 24 * 4H 2 O) is separately dissolved in 10 ml of water. A 15.0 molar ratio of aluminum nitrate hydrate (A1 (NO3) 3 · 9H2 O) is dissolved in 140 ml of water to make an aqueous solution of the precursor of the supporting substance. A catalyst is prepared in the same manner as in Example 1 except that a catalytic composite solution is prepared by mixing the above solutions well. The synthesized CNT shows both beam and watt type and the scanning electron microscopic (SEM) image of the CNT is shown in Fig. 2.
    Example 3
    An aqueous solution of a derivative of a metal catalyst is prepared by dissolving a 2.0 molar ratio of iron (III) nitrate hydrate (Fe (NO3) 3 * 9H 2 O) and a 2.0 molar ratio of cobalt nitrate hydrate (Co (NO 3) 2 · 6H 2 O) in 20 ml of water, and 1.0 molar ratio of molybdenum hydrate ((NH 4) 6 Mo7024 · 4H 2 O) is separately dissolved in 10 ml of water. A 5.0 molar ratio of aluminum nitrate hydrate (Al (NO 3) 3 · 9H 2 O) is dissolved in 140 ml of water to make an aqueous solution of the precursor of the supporting substance. A catalyst is prepared in the same manner as in Example 1 except that a catalytic composition solution is prepared by mixing the above solutions well. The synthesized CNT shows the watt type and the scanning electron microscopic (SEM) image of the CNT is shown in Fig. 3.
    Example 4
    An aqueous solution of a derivative of the metal catalyst is prepared by dissolving a 2.0 molar ratio of iron (III) nitrate hydrate (Fe (NO3) 3 · 9H2 O) in 10 ml of water, and a 0.1 molar molybdenum hydrate ratio ((NH 4) 6 Mo7024 * 4H 2 O) is separately dissolved in 5 ml of water. An aqueous solution of the precursor of the supporting substance is prepared by dissolving a 2.5 molar ratio of aluminum nitrate hydrate (Al (NO3) 3 · 9H2 O) in 70 ml of water. A catalyst is prepared in the same manner as in Example 1 except that a catalytic composite solution is prepared by mixing the above solutions well. The synthesized CNT shows both bundling watt-type and the scanning electron microscopic (SEM) image of the CNT is shown in FIG. 4.
    Example 5
    An aqueous solution of a metal catalyst derivative is prepared by dissolving a 2.0 molar ratio or iron (III) nitrate hydrate (Fe (NO3) 3 · 9H 2 O) in 10 ml of water, and a 0.7 molar ratio of molybdenum hydrate (NH 4) 6 · 07024 * 4H 2 O) is separately dissolved in 7 ml of water. An aqueous solution of the precursor of the supporting substance is prepared by dissolving a 2.5 molar ratio of aluminum nitrate hydrate (Al (NO3) 3 · 9H2 O) in 70 ml of water. A catalyst is prepared in the same manner as in Example 1 except that a catalytic composite solution is prepared by mixing the above solutions well. When the morphology of the synthesized CNT is viewed, the clump type is shown and the scanning electron microscopic (SEM) image of the CNT is shown in FIG. 5.
    Example 6
    An aqueous solution of a derivative of the metal catalyst is prepared by dissolving a 2.0 molar ratio of iron (III) nitrate hydrate (Fe (NO3) 3 · 9H 2 O) and a 2.0 molar ratio of cobalt nitrate hydrate (Co ( NO 3) 2 * 6H 2 O) in 20 ml of water, and a 1.0 molar ratio of molybdenum hydrate ((NH 4) 6 · 7024 · 4 · 20) is separately dissolved in 10 ml of water. A 7.5 molar ratio of aluminum nitrate hydrate (A1 (NO3) 3 · 9H2 O) is dissolved in 100 ml of water to make an aqueous solution of the precursor of the supporting substance. A catalyst is prepared in the same manner as in Example 1 except that a catalytic composition solution is prepared by mixing the above solutions well. The synthesized CNT shows beam type and the scanning electron microscopic (SEM) image of the CNT is shown in FIG. 6.
    [Table 1]
    Examples 1 2 3 4 5 6 "(A) iron" ... ........ 2.0 2.0 2.0 "2.0 2.0 2.0
    Composite ------- (molar (B> cobalt) -2- ° 2- ° 2.0 0 0 2.0
    Ratio) (C) molybdenum - 1.0 1.0 0.1 0.7 0.1 (D) alumina 7.5 15.0 5.0 2.5 2.5 7.5 CNT growth type bundle wadding bundle wadding bundle and cotton wool
    As shown in Table 1, the growth type of CNT differs according to the content or amount of each component of the metal catalyst. For example, as the content of alumina increases, the CNT growth type can be a bundle type, not a cotton wool type. However, if the content of the supporting substance is present in excess, the synthetic yields may deteriorate significantly. In addition, as the molybdenum content increases that can help to stabilize the metal catalysts (Fe and Co) on the surface of the supporting substance, the CNT growth type can be a cotton wool type, not a bundle type. Increased CNT diameter can also be prevented by reducing or preventing the aggregation of the nano-size metal catalysts during the heating process at a high temperature by controlling the molybdenum content. Accordingly, the composition of the metal nanocatalyst and the supporting substance can control the diameter, the synthetic yields, and the growth type of CNT.
    Many changes and other embodiments of the invention will be contemplated by the person skilled in the art to which this invention belongs, who has the advantage of the lessons presented in the preceding descriptions. Therefore, it is to be understood that the invention should not be limited to the specific described embodiments and that changes and other embodiments are intended to be included within the scope of the appended claims Although specific terms are used herein, they are used only in a generic and descriptive sense and not for purposes of limitation, the scope of which of the invention is defined in the claims.
    权利要求:
    Claims (19)
    [1]
    A metal nanocatalyst having a composition as follows: (Ni, Co, Fe) x (Mo, Va) y (Al 2 O 3, MgO, SiO 2), wherein x, y and z are molar ratios and 1 <x <10, 0 <y <5, and 2 <z <15.
    [2]
    The metal nanocatalyst according to claim 1, wherein the metal nanocatalyst has a structure that contains Co, Fe, Ni or a combination thereof, absorbed on a surface of Α1203.
    [3]
    The metal nanocatalyst according to claim 1, wherein the metal nanocatalyst synthesizes carbon nanotubes.
    [4]
    A method for manufacturing a metal nanocatalyst, which comprises highly heating an aqueous derivative of the metal catalyst containing Co, Fe, Ni, or a combination thereof, in the presence of a precursor of the supporting substance around a metal nanocatalyst to provide with a composition as follows: (Ni, Co, Fe) x (Mo, Va) y (Al 2 O 3, MgO, SiO 2) z wherein x, y and z are molar ratios and 1 <x <10, 0 <y < 5, and 2 <z <15.
    [5]
    The method for manufacturing a metal nanocatalyst according to claim 4, wherein said aqueous derivative of the metal catalyst is a metal hydrate.
    [6]
    The method for manufacturing a metal nanocatalyst according to claim 5, wherein said metal hydrate is iron (III) nitrate hydrate, nickel nitrate hydrate, cobalt nitrate hydrate, or a combination thereof.
    [7]
    The method for manufacturing a metal nanocatalyst according to claim 4, wherein the metal nanocatalyst is heated in the presence of a molybdenum (Mo) activator, a vanadium (V) activator, or a combination thereof.
    [8]
    8. Method of manufacturing a. a metal nanocatalyst according to claim 4, wherein said precursor of the supporting substance is an aluminum nitrate hydrate, a. magnesium nitrate hydrate, a silica citrate hydrate, or a combination thereof.
    [9]
    The method for manufacturing a metal nanocatalyst according to claim 4, wherein the heating is carried out at a temperature of about 300 to about 900 ° C.
    [10]
    The method for manufacturing a metal nanocatalyst according to claim 4, wherein said derivative of the metal catalyst and the precursor of the supporting substance are in an aqueous phase.
    [11]
    A method for manufacturing a metal nanocatalyst according to claim 4, wherein the metal nanocatalyst has a structure containing Co, Fe, Ni, or a combination thereof, absorbed on the surface of a supporting substance formed from the precursor of the supporting substance .
    [12]
    A carbon nanotube manufactured by using the metal nanocatalyst of claim 1.
    [13]
    A carbon nanotube manufactured by using the metal nanocatalyst of claim 2.
    [14]
    A method for controlling the growth types of carbon nanotubes by using a metal nanocatalyst in a process of synthesizing carbon nanotubes, comprising the steps of: preparing a metal nanocatalyst by using an aqueous derivative of a metal catalyst ( x) containing Co, Fe, Ni, or a combination thereof, in the presence of a precursor of a supporting substance (z), wherein the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance (z) is regulated to be x: z = about 1 to about 10: about 2 to about 15; and producing a carbon nanotube by supplying carbon gas in the presence of the synthesized metal nanocatalyst.
    [15]
    The method of claim 14, wherein the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of the supporting substance (z) 'is regulated to be x: z = about 1 to about 10: about 2 to around 7.5.
    [16]
    The method of claim 14, wherein the molar ratio of the aqueous derivative of the metal catalyst (x) and the precursor of. the supporting substance (z) is regulated to be x: z = about 1 to about 10: about 7.5 to about 15.
    [17]
    The method of claim 14, wherein the aqueous derivative of the metal catalyst and the precursor of the supporting substance are heated in the presence of a molybdenum (Mo) activator, a vanadium (V) activator, or a combination thereof.
    [18]
    The method of claim 14, wherein the metal nanocatalyst has a composition as follows: (Ni, Co, Fe) x (Mo, Va) y (Al 2 O 3, MgO, SiO 2) z wherein x, y and z are molar ratios and 1 <x <10, 0 <y <5, and 2 <z <15.
    [19]
    A carbon nanotube that has a bundle of growth type or a cotton wool growth type, manufactured according to the method of claim 14.
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    KR20080125453|2008-12-10|
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