CN101124153A - Porous filamentous nanocarbon and method of forming the same - Google Patents

Porous filamentous nanocarbon and method of forming the same Download PDF

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Publication number
CN101124153A
CN101124153A CNA2005800457209A CN200580045720A CN101124153A CN 101124153 A CN101124153 A CN 101124153A CN A2005800457209 A CNA2005800457209 A CN A2005800457209A CN 200580045720 A CN200580045720 A CN 200580045720A CN 101124153 A CN101124153 A CN 101124153A
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carbon
fiber
mesopore
nano
hexaplanar
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CN101124153B (en
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尹圣昊
持田勲
林成烨
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Mochida Isao
Sunshine Communication Co.,Ltd.
Werner Technology Co.,Ltd.
Yin Shenghao
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Nexen Nano Tech Co Ltd
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D01D5/247—Discontinuous hollow structure or microporous structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28023—Fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
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    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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Abstract

There is provided a porous filamentous nanocarbon and a method for forming the same. A mesopore formed on an outer periphery of the porous filamentous nanocarbon is a tunnel-like pore which is formed along the arrangement direction of the carbon hexagonal plane from the outer periphery toward a fiber axis. The porous filamentous nanocarbon is fabricated by se not lectively removing the carbon hexagonal plane constituting the filamentous nanocarbon through gasification in virtue of a catalyst, after highly dispersing Fe, Ni, Co, Pt, etc, of which size is 2-30 nm, on the surface of the filamentous nanocarbon. That is, the tunnel-like mesopore is formed radially by nano-drilling process. The size of the porous filamentous nanocarbon can be controlled according to the size of the nano-drilling catalyst and nano-drilling conditions.

Description

Porous filamentous nanocarbon and manufacture method thereof
Technical field
The present invention relates on periphery, be formed with the porous filamentous nanocarbon (filamentous nanocarbon) of mesopore (mesopore), more specifically relate to wherein said mesopore along the orientation of carbon hexaplanar from outside the circumferential porous filamentous nanocarbon that radially forms of fiber axis.
Background technology
Recently, along with actively studying, make their method and known by common people to having porous porous material.Particularly, about the method for making active carbon and activated carbon fiber and the method for utilizing metallic catalyst manufacturing Nano carbon fibers peacekeeping CNT, many patents and paper are widely known by the people.At this, CNT is that diameter is 80nm or littler hollow carbon nanotube.According to general activation method, form the porous carbon materials that is commonly called activated carbon by on the surface of material with carbon element, forming a large amount of micropores.
The two kinds of methods of active carbon and activated carbon fiber of making are known by common people.A kind of method is to make carbon-based material carry out the heat treatment of the scheduled time in environment such as steam, air, carbon dioxide under 300 ℃～1100 ℃ temperature, makes active carbon and activated carbon fiber thus.Another kind method is at alkali metal containing salt for example in potassium hydroxide, the NaOH etc., under 300 ℃～1100 ℃ temperature, carbon-based material is carried out the heat treatment of the scheduled time, implement independent rinsing and dry run subsequently, thereby make active carbon and activated carbon fiber.
The international monopoly of submitting in 1986 at the Hyperion Catalytic International Inc. by the U.S. discloses in WO8603455 number, disclosed a kind of technology that is used to have the CNT of hollow tubular structure, the fibre diameter of this nanotube is 3.5nm～70nm, and wherein the carbon hexaplanar is along the fiber axis concentric arrangement.The carbon hexaplanar that CNT mainly is divided into wherein forms the SWCN (SWNT) of a slice single wall and the multi-walled carbon nano-tubes (MWNT) of a plurality of walls of formation.As everyone knows, the fibre diameter of SWNT is 0.4nm～3.5nm, and the fibre diameter of MWNT is 2.5nm～50nm.
By utilizing metallic catalyst thermal decomposition carbon monoxide and being known as the method that the appropriate hydrocarbon gas of carbon source is made carbon nano-fiber.For example, U.S. patent No.4,565,683 have disclosed a kind of method that is used to make carbon fiber, wherein make 1 or longer fiber by utilizing to wait at 540～800 ℃ of following thermal decomposition carbon monoxide and hydrocarbon such as the catalyst of iron oxide, iron, nickel etc.In addition, people such as Baker and Rodriguez has disclosed by utilizing and has made the carbon nano-fiber that surface area is 50 /g～800 /g such as the catalyst of iron, nickel, cobalt etc. at 500～700 ℃ of following thermal decomposition hydrocarbon.In addition, people such as Boehm and people such as Murayama and Rodriguez have disclosed a kind of by utilizing the method (Bohem that makes carbon nano-fiber such as the transition metal or their the alloy catalyst thermal decomposition hydrocarbon of iron, cobalt, nickel, Carbon, 11,583 (1973); H.Murayama, T.Maeda, Nature, 245,791; Rodriguez, N.M., 1993, J.Master.Res.8 (3233)).
In various carbon nano-fibers, a kind of carbon nano-fiber has the laminated structure that the carbon hexaplanar is arranged perpendicular to fiber axis, another kind of carbon nano-fiber has herringbone (Herringbone) structure (Rodriguez of carbon hexaplanar with respect to 20～80 ° of fiber axis inclinations, N.M., 1993, J.Master.Res.8 (3233)).They are not hollow, and this is different from nanotube significantly.Fig. 1 a, 1b and 1c are respectively transmission electron microscope (TEM) figure that CNT, flake nano carbon fiber and herringbone filamentous nanocarbon are shown.Because active carbon, CNT and carbon nano-fiber all have high surface area, so they can be applicable to adsorbent or catalyst carrier.Be of a size of 2nm or littler micropore because they have, so they can adsorb the halogenated hydrocarbons of for example environmentally harmful gas of small-size molecules, contaminant water etc. effectively.Therefore, they can be used for eliminating by plant gas produced pollution thing, purifying drinking water etc.But, be difficult to they are applied to for example catalyst carrier of oil of the adsorbent of polymer or transition polymers material.In order to make active carbon, carbon nano-fiber etc. can be applicable to these situations, need have the size adsorbent of mesopore very uniformly with the low cost manufacturing, wherein said mesopore is of a size of 2nm～100nm.
The technology of several formation mesopores is known by common people.
According to a kind of technology wherein, polymerization wherein contains the material of the removable portion of some size, so that described part is attached in the solid product.Remove described part, stay porosu solid thing with hole.For example, if the polymer that burning mixes with organic material and inorganic material, then organic material is burnt, and makes to produce pore in inorganic material, and the size of pore is corresponding to the size of organic material.The porosu solid thing that is produced can have the very narrow pore size distribution in the mesopore scope, and still, it is very expensive and time-consuming to prepare such material.
Recently, the achievement in research of utilizing silica and silica alumina to synthesize the material with mesopore is disclosed, referring to as in U.S. Patent No. 5,108,725 and U.S. Patent No. 5,378,440 in disclosed MCM-41 and M41-S.But because it is an insulator and very unstable in aqueous slkali, so it is not suitable for fuel cell, battery, electrolytic cell, capacitor etc.
Another kind of technology relates to the optionally synthetic material with carbon element that wherein has mesopore.Particularly, will be injected into the template for example in zeolite, aluminium oxide, the silica etc. that wherein has mesopore as the polymer of carbon source.Perhaps, will be on template from the RESEARCH OF PYROCARBON chemical deposition of appropriate hydrocarbon gas.Afterwards, utilize hydrofluoric acid etc. to remove template.But the shortcoming of this method is that from manufacturing cycle and output, its manufacturing cost is too high and productivity ratio is low excessively.
Simultaneously, owing to most of solids with mesopore by the said method manufacturing are grain shape, although therefore have high specific area, filtration has difficulties.
Summary of the invention
Technical problem
The invention provides a kind of porous filamentous nanocarbon and manufacture method thereof, described porous filamentous nanocarbon comprises the carbon nano-fiber with porosity height and the uniform mesopore of each hole dimension, and wherein said mesopore is of a size of 20nm～30nm.
The present invention also provides a kind of porous filamentous nanocarbon and manufacture method thereof, described porous filamentous nanocarbon as isolating polymer for example protein etc. adsorbent, chromatographic material, be used for the electrode material of fuel cell and electrochemical reaction etc. etc.
The present invention also provides a kind of porous filamentous nanocarbon and manufacture method thereof, described porous filamentous nanocarbon is the fibrous solids with mesopore of several nanometers by forming diameter, rather than form granular solids with mesopore, eliminate the inconvenience of its processing.
Technical scheme
Embodiment of the present invention provide the porous filamentous nanocarbon with mesopore, the tunnel-like hole that wherein said mesopore radially forms for the central shaft from the outer circumferential carbon nano-fiber of carbon nano-fiber.
In some embodiments, carbon nano-fiber is the nano-sized carbon with laminated structure, and wherein the carbon hexaplanar is with respect to the central shaft vertical stacking.Perhaps, the hexaplanar of fiber is the nanofiber with herringbone structure, and described herringbone structure forms the V-arrangement at 20～80 ° of angles of relative inclined.At this, the direction that described mesopore is arranged along the carbon hexaplanar forms.
In another embodiment, the diameter of carbon nano-fiber is 2～100nm, for example preferred 10～200nm, and draw ratio is 4 or bigger, for example preferred 10 or bigger.Mesopore is of a size of 2～100nm, for example preferred 2～30nm, and porosity is at least 20% or bigger, for example preferred 50% or bigger.
In another embodiment of the present invention, the method that forms porous filamentous nanocarbon is provided, described method comprises by making material with metallic catalyst attached on the periphery of carbon nano-fiber and utilize metallic catalyst to remove the carbon hexaplanar by gasification, and from carbon nano-fiber outer circumferentially wherein axle radially form the tunnel-like mesopore.
In another embodiment, when the predetermined portions of the carbon nano-fiber of adhesion metal catalyst on it optionally reacts with metallic catalyst, form mesopore thus.Therefore, the predetermined portions of carbon hexaplanar is removed, and forms mesopore along the orientation of carbon hexaplanar.Because selective reaction therefore can be according to size and the porosity of controlling the tunnel-like mesopore attached to the size or the nanometer borehole conditions of the metallic catalyst on the carbon nano-fiber.
Therefore, be the nano-scale mesopore of 2nm～30nm owing on the periphery of carbon nano-fiber, form diameter, so this porous filamentous nanocarbon electrode of can be applicable to separation/absorption protein, oil etc. and being used for fuel cell.
Beneficial effect
According to the present invention, can obtain to have the porous filamentous nanocarbon of mesopore, the porosity of described porous filamentous nanocarbon is high and size each hole is even, and wherein said mesopore is of a size of 20nm～30nm.This porous filamentous nanocarbon can be widely used in adsorbent, chromatographic material, catalyst carrier etc.Simultaneously, when nano-sized carbon of the present invention need to be applied in the electrochemical applications of electric conductivity, can utilize fiber shape further to strengthen electric conductivity between the particle.In addition, the invention provides favourable advantage, promptly eliminate it and handle the inconvenience of for example filtering, this is to have the fiber shape that diameter is several nanometers because have the solids of mesopore, rather than grain shape.
Description of drawings
Fig. 1 a is transmission electron microscope (TEM) figure that the carbon nano-fiber with tubular structure is shown;
Fig. 1 b is the TEM figure that the carbon nano-fiber with laminated structure is shown;
Fig. 1 c is the TEM figure that the carbon nano-fiber with herringbone structure is shown;
Fig. 2 illustrates schematic diagram and the TEM figure that has the carbon nano-fiber of tubular structure according to of the present invention;
Fig. 3 illustrates schematic diagram and the TEM figure that has the carbon nano-fiber of laminated structure according to of the present invention;
Fig. 4 illustrates schematic diagram and the TEM figure that has the carbon nano-fiber of herringbone structure according to of the present invention;
Fig. 5 illustrates schematic diagram and the TEM figure that forms the carbon nano-fiber of mesopore according to the present invention by nanometer boring;
Fig. 6～9th illustrates the TEM figure that forms the carbon nano-fiber of mesopore according to the present invention by the nanometer boring procedure;
Figure 10 illustrates according to the present invention and the comparison diagram of the electro-chemical activity of the carbon nano-fiber of prior art.
The specific embodiment
Fig. 1 illustrates respectively to have for example high resolution transmission electron microscope of the conventional carbon nano-fiber of tubular structure, laminated structure and herringbone structure (TEM) figure of three kinds of exemplary configuration, and the typical 2D model corresponding to each structure is shown.
Fig. 2～4 explanations form the carbon nano-fiber with described three kinds of structures by meticulous nanometer rods of piling up as construction unit.That is, form according to tunnel-like mesopore of the present invention based on the carbon nano-fiber new construction that constitutes by the carbon nano rod that piles up.
Nanometer rods as the elementary cell that constitutes carbon nano-fiber has certain structure, fullerene pipes overlapping and one end sealing in this structure along identical axle, wherein the fullerene tube bundle is configured as cylindrically, makes the carbon hexaplanar overlapped (referring to Fig. 3 a).Usually, nanometer rods is configured as the hexagonal prism with 4～6 coaxial numbers, and the diameter of each is about 2.5nm, and each is of a size of 20nm～80nm.Detailed description (S.-H.Yoon, S.Lim, S.-h.Hong, I.Mochida, B.An, K.Yokogawa.2004, Carbon, 42 (15), the 3087-3095 of nanometer rods are more fully disclosed in people's such as S.-H.Yoon paper; B.An, K.Yokogawa, S.Lim, S.-H.Yoon, I.Mochida.In:Carbon 2004 International Conference, BrownUniversity:RI (USA), 2004).
In the present invention, utilize the nanometer boring procedure on the periphery of carbon nano-fiber, to form the mesopore of nano-scale.If on the periphery of nanocatalyst attached to carbon nano-fiber, in hydrogen or oxygen environment, the carbon nano-fiber that adheres to nanocatalyst on it is implemented heat treatment then, hydrogenation or oxidation gasification reaction take place, form from outer surface like this and be penetrated into inner tunnel, its size is corresponding to the size of nanocatalyst.The boring pattern that is formed by the inventive method compared with prior art is not at random, but evenly forms along the orientation of carbon hexaplanar.Therefore, nanocatalyst removes carbon nano-fiber in the nanometer rods stacked structure adheres to the part of nanocatalyst from it under hydrogenation or oxidation environment, thus by boring forms nano tunnel to carbon nano-fiber.With reference to figure 5, its predetermined portions that nanometer rods is shown is removed and forms thus the tunnel.
This reaction is by being caused because of the metal gasification with respect to carbon such as hydrogen, oxygen.Mesopore forms tunnel-shaped reason and is: because it is more active to form the surface ratio basal surface of carbon hexaplanar sidewall, therefore the decomposition on the carbon plane that caused because of gasification takes place along the orientation of nanometer rods unit, and wherein said nanometer rods unit forms the hexagonal prism of carbon hexaplanar.Therefore, the main shaft of nanometer boring reaction from the outer thoughtful fibrillar center of carbon nano-fiber along nanometer rods carries out.Can preferably gasify and remove by the nanometer rods that in hydrogen or oxygen environment, makes an end that is attached with catalyst.At this moment, because therefore one or more nanometer rods can, form the nano tunnel of width greater than 2～30nm of nanometer rods diameter by catalyst and reacting gas reaction.Therefore, the tunnel-like mesopore from outside circumferentially the center of fiber along the arrangement diameter of axle of nanometer rods to formation.
Be used for nanometer boring for example the metallic catalyst of gasification can adopt the element of V, VI, VII and the family of the periodic table of elements.Preferred catalyst is iron (Fe), cobalt (Co), nickel (Ni), molybdenum (Mo), vanadium (V), chromium (Cr), platinum (Pt), palladium (Pd), ruthenium (Ru), copper (Cu), silver (Ag), zinc (Zn), tin (Sn) and their alloy.The preferred alloy catalyst adopts Ni-Cu, Fe-Ni,, Fe-Pt, Fe-Mo, Ni-Mo, Co-Mo, Pt-Ru etc.Preferred catalyst is of a size of 2nm～50nm.Too hour, produce micropore.On the contrary, when too big, may remove a large amount of carbon nano-fibers.
The reacting gas that is preferred for activating adopts hydrogen or oxygen.In addition, carbon dioxide (CO 2) gas, sulfur dioxide (SO 2) gas, nitric oxide (NO) gas, nitrogen dioxide (NO 2) gas and water can be used as reacting gas.If reaction condition is not suitably controlled in activation process, then the graphite linings of nanometer rods may be melted or be inserted in the intermediate, so the adjustment process temperature is extremely important.For example, when hydrogenation, preferably under 400～1200 ℃, more preferably implement activation process down for 500～900 ℃.In addition, when oxidation, preferably under 100～500 ℃, more preferably implement activation process down for 200～400 ℃.
Invention embodiment
Now will be at length with reference to the preferred embodiments of the invention, embodiment illustrates in the accompanying drawings.But the embodiment shown in the present invention is not limited to hereinafter, the embodiment of this paper aim to provide comprehensively to be understood the simple of scope of the present invention and essence.
To briefly explain the method for the manufacturing carbon nano-fiber that uses in the present invention at first, below.
The first, will set forth the method for making carbon nano-fiber with tubular structure.Preparation is as the Fe/Ni alloy of metallic catalyst at first, according to the methods below.At room temperature nickel oxide and nitrided iron are dissolved in the distilled water.Then, add carbonic hydroammonium and stirring.The precipitation of utilizing the washing of distilled water and ethanol from this solution, to produce, dry under vacuum state then.In the dry air environment in the precipitation of 400 ℃ of following calcination dryings, with preparation Fe-Ni oxide.The Fe-Ni oxide under 400 ℃ at H 2Reduce in/He the environment.Afterwards, again at O 2At room temperature carry out post processing in the/He environment, obtain the Fe-Ni alloy catalyst thus.The catalyst that utilizes this method preparation is put into the quartz ampoule of reacting furnace.Afterwards, at H 2Implement heat treatment 2 hours down at 625 ℃ in the/He environment.Afterwards, at input CO/H 2Mist the time, implement down heat treatments 2 hours at 625 ℃, obtain carbon fiber thus.
The carbon fiber of making has certain structure, and the carbon hexaplanar is parallel to fiber axis and wherein has cavity (Fig. 2) in described structure.The external diameter of described fiber is 5～35nm, and draw ratio is 30 or bigger.Fig. 2 a is TEM figure, and Fig. 2 b is the schematic diagram of explanation nanometer rods stacked structure.Fig. 2 C and 2D are PSTM (STM) figure of fiber surface.Can observe from figure, nanometer rods is connected to each other and piles up.
The second, will set forth the method for making carbon nano-fiber with laminated structure.Utilizing after said method makes iron catalyst by nitrided iron, the Fe catalyst is being put into the quartz ampoule of reacting furnace.Afterwards, at input CO/H 2Mist the time, implement down heat treatments 2 hours at 600 ℃.Prepared carbon fiber has laminated structure, and the carbon hexaplanar piles up (Fig. 3) perpendicular to fiber axis in described laminated structure.The external diameter of described fiber is 90nm～300nm, and draw ratio is 30 or bigger.Fig. 3 a and 3b are TEM figure, and Fig. 3 c is the STM figure on the surface of nano-sized carbon.Fig. 3 d is the schematic diagram of explanation nanometer rods stacked structure.Can observe from figure, nanometer rods is piled up perpendicular to fiber axis.
The 3rd, will set forth the method for making carbon nano-fiber with herringbone structure.Utilizing after said method makes the Ni-Cu alloy catalyst by nickel oxide and copper nitride, the Ni-Cu alloy catalyst is being put into the quartz ampoule of reacting furnace.Afterwards, at H 2Implement heat treatment 2 hours down at 580 ℃ in the/He environment, import the mist of ethene/hydrogen simultaneously, thereby obtain carbon fiber.Prepared carbon fiber has herringbone structure, and the carbon hexaplanar forms the V-type (Fig. 4) that becomes 20～80 ° of angles with respect to fiber axis in described herringbone structure.The external diameter of described fiber is 80nm～350nm, and draw ratio is 30 or bigger.Fig. 4 a and 4b are TEM figure, and Fig. 4 c is the STM figure of fiber surface.Fig. 4 d is the schematic diagram of explanation nanometer rods stacked structure.Can observe from figure, nanometer rods tilts with predetermined angle with respect to fiber axis and piles up.
Then, will set forth the method for utilizing nanometer boring procedure of the present invention to make porous filamentous nanocarbon below.
＜embodiment 1 〉
By with herringbone filamentous nanocarbon dipping be dispersed in the nickel oxide solution and will be attached on the periphery of herringbone filamentous nanocarbon as the hole nickel particle of catalyst of nanometer.At 150 ℃ of following vacuum drying carbon nano-fibers, to prepare the nanofiber that is attached with Raney nickel on it.Described carbon nano-fiber is put into the quartz ampoule of reacting furnace.Afterwards, at H 2Implement heat treatment 2 hours down at 800 ℃ in the mixed-gas environment of/He.
Shown in TEM figure among Fig. 6, prepared porous filamentous nanocarbon becomes the nanofiber of the very porous that wherein is formed with nano tunnel.Nano tunnel forms along the orientation of carbon hexaplanar, and the structure of carbon nano-fiber is without any change.The diameter of nano tunnel is 5～30nm.Utilize N 2The volume that Brunauer-Emitter-Teller (BET) method records specific area and mesopore is respectively 352 /g and 0.42 /g.
＜embodiment 2 〉
By with herringbone filamentous nanocarbon dipping be dispersed in the nickel oxide solution and will be attached on the periphery of herringbone filamentous nanocarbon as the hole nickel particle of catalyst of nanometer.At 150 ℃ of following vacuum drying carbon nano-fibers, to prepare the nanofiber that is attached with Raney nickel on it.The carbon nano-fiber that is attached with Raney nickel on it is put into the quartz ampoule of reacting furnace.Afterwards, at O 2Implement heat treatment 3 hours down at 350 ℃ in the environment.
Shown in TEM figure among Fig. 7, prepared porous filamentous nanocarbon becomes the nanofiber of the very porous that wherein is formed with nano tunnel.Nano tunnel forms along the orientation of carbon hexaplanar, and the structure of carbon nano-fiber is without any change.The diameter of nano tunnel is 2～10nm.At this, though the average-size of mesopore less than first embodiment, is compared with first embodiment, mesopore is evenly distributed.Utilize N 2The volume that the BET method records specific area and mesopore is respectively 298 /g and 0.39 /g.
＜embodiment 3 〉
By with herringbone filamentous nanocarbon dipping be dispersed in the nitrided iron solution and will be attached on the periphery of herringbone filamentous nanocarbon as the hole iron particle of catalyst of nanometer.At 150 ℃ of following vacuum drying carbon nano-fibers, to prepare the nanofiber that is attached with iron catalyst on it.The carbon nano-fiber that is attached with iron catalyst on it is put into the quartz ampoule of reacting furnace.Afterwards, at He/H 2Mixed-gas environment in implement down heat treatments 3 hours at 850 ℃.
Shown in TEM figure among Fig. 8, prepared porous filamentous nanocarbon becomes the nanofiber of the very porous that wherein is formed with nano tunnel.Nano tunnel forms along the orientation of carbon hexaplanar.But, because catalyst is different from first and second embodiments, thereby local in gasification graphitization takes place, so the carbon structure around the mesopore changes slightly, have good graphited porous material around causing being created in mesopore.Utilize N 2The volume that the BET method records specific area and mesopore is respectively 254 /g and 0.33 /g.
＜embodiment 4 〉
By with the flake nano impregnated carbon fiber be dispersed in the nickel oxide solution and will be attached on the periphery of sheet shape carbon nano-fiber as the hole nickel particle of catalyst of nanometer.At 150 ℃ of following vacuum drying carbon nano-fibers, to prepare the nanofiber that is attached with Raney nickel on it.The carbon nano-fiber that is attached with Raney nickel on it is put into the quartz ampoule of reacting furnace.Afterwards, at H 2Implement heat treatment 3 hours down at 800 ℃ in the mixed-gas environment of/He.
Shown in TEM figure among Fig. 9, prepared porous filamentous nanocarbon becomes the nanofiber of the very porous that wherein is formed with nano tunnel.Nano tunnel forms along the orientation of carbon hexaplanar, and the structure of carbon nano-fiber is without any change.The diameter of nano tunnel is 6～32nm.Utilize N 2The volume that the BET method records specific area and mesopore is respectively 154 /g and 0.24 /g.
＜comparative example 1 〉
In first comparative example, herringbone filamentous nanocarbon is used conventional alkali activation method.Mixture (nano-sized carbon: KOH=1: 4 w/w) be placed on the dish with herringbone filamentous nanocarbon and KOH.Afterwards, at H 2Implement heat treatment 2 hours down at 850 ℃ in the mixed-gas environment of/He.
Can find out that from TEM figure the predetermined portions of carbon hexaplanar is removed at interval with rule, thereby form stairstepping.According to BET result, find to have formed the mesopore that specific area and size are respectively 154 /g and 1.0nm.Therefore, find that conventional alkali activation method is not suitable for the mesopore that selectivity forms porous filamentous nanocarbon of the present invention.
＜comparative example 2 〉
Carbon nano-fiber dipping by will having kop structure (butte structure) and be dispersed in the nickel oxide solution and will be attached on the periphery of herringbone filamentous nanocarbon as the hole nickel particle of catalyst of nanometer.At 150 ℃ of following vacuum drying carbon nano-fibers, to prepare the nanofiber that is attached with Raney nickel on it.The carbon nano-fiber that is attached with Raney nickel on it is put into the quartz ampoule of reacting furnace.Afterwards, at H 2Implement heat treatment 3 hours down at 800 ℃ in the mixed-gas environment of/He.
Different with described embodiment, the weight change of carbon nano-fiber before and after reaction of finding second comparative example is less than 5%.Can observe mesopore in TEM figure does not well evenly form.Utilize N 2The BET method records specific area and pore volume is respectively 122 /g and 0.21 /g.Hence one can see that, and nanometer boring method of the present invention is that CNT is invalid for the tubular nanometer carbon fiber.Because second comparative example, consider that the nanometer boring method does not have the tubular structure that exposes invalid to nanometer rods end wherein, therefore implement the preparation of the tunnel-like mesopore of nanometer boring, make catalyst selectivity ground on the end that exposes attached to nanometer rods that the nanometer rods around it is gasified according to the present invention.
＜comparative example 3 〉
By with carbon black dipping be dispersed in the nickel oxide solution and will be attached on the carbon black as the hole nickel particle of catalyst of nanometer.At 150 ℃ of following vacuum drying carbon blacks, to prepare the carbon black that is attached with Raney nickel on it.The carbon black that is attached with Raney nickel on it is put into the quartz ampoule of reacting furnace.Afterwards, at H 2Implement heat treatment 3 hours down at 800 ℃ in the mixed-gas environment of/He.
Weight change is very little before and after the reaction, and therefore nanometer boring method according to the present invention as can be known is invalid to carbon black.
To set forth the example of the porous filamentous nanocarbon application of making below by nanometer boring method of the present invention.
The first, porous filamentous nanocarbon can be applicable to adsorbent and chromatogram.Owing to have the maximum path that about 200nm grows according to the mesopore of porous filamentous nanocarbon of the present invention, so molecule was diffused into the other end about 2 seconds consuming time from an end of mesopore.Like this, diffusion time is very short, makes nano-sized carbon of the present invention be applied to adsorbent and chromatogram is very effective.Particularly, under the situation of chromatogram, it is suitable for separating bio and learns upward important molecule for example enzyme, steroids, alkaloid, hormone, protein etc. very much.
The second, porous filamentous nanocarbon can be applicable to catalyst carrier.Because aforesaid short the evolving path, so it can importantly be applied to the conversion of polymeric material, for example the refining of synthetic, the oil of steroids and enzyme etc.
The 3rd, porous filamentous nanocarbon can be applicable to the electrode of electrochemical reaction.Be impregnated in the catalyst metals solution carbon nano-fiber according to the present invention and the coated catalysts metal, on the surface of porous filamentous nanocarbon, form electrode thus.Because so the material of preparation is alkaline-resisting or sour, therefore nano-sized carbon of the present invention can be applicable to require the electrochemical reaction of severe rugged environment.For example, the Pt-Ru catalyst of coating can be used as the catalyst of oxidation methyl alcohol in the methanol fuel cell.Figure 10 is the methanol oxidation cyclic voltammogram that explanation utilizes Pt-Ru catalyst electrode and Ag/AgCl electrode, and it shows that the activity that records in the present invention is about twice of prior art.
Industrial applicibility
Porous filamentous nanocarbon of the present invention can be widely used in adsorbent, chromatographic material, catalysis Agent carrier etc. That is, this porous filamentous nanocarbon can be applied to the separation of protein, oil etc. / absorption and the electrode that is used for fuel cell.

Claims (14)

1. porous filamentous nanocarbon with mesopore, the tunnel-like hole that wherein said mesopore radially forms for the central shaft from the outer circumferential described carbon nano-fiber of described carbon nano-fiber.
2. porous filamentous nanocarbon as claimed in claim 1, wherein said carbon nano-fiber is the nano-sized carbon with laminated structure, the carbon hexaplanar is with respect to described central shaft vertical stacking in described laminated structure, and described mesopore forms along the orientation of described carbon hexaplanar.
3. porous filamentous nanocarbon as claimed in claim 1, wherein said fibrous hexaplanar is the nanofiber with herringbone structure, described herringbone structure forms with respect to the V-arrangement of described central shaft with 20～80 ° angle inclination, and described mesopore forms along the orientation of described carbon hexaplanar.
4. as each described porous filamentous nanocarbon in the claim 1～3, wherein said carbon nano-fiber has the diameter and 4 or bigger draw ratio of 2～100nm.
5. as each described porous filamentous nanocarbon in the claim 1～3, wherein said mesopore has the size and at least 20% or bigger porosity of 2～100nm.
6. method of making porous filamentous nanocarbon, described method comprises: by making material attached on the periphery of carbon nano-fiber and utilize described metallic catalyst to remove the carbon hexaplanar by gasification with metallic catalyst, thereby from described carbon nano-fiber outer circumferentially wherein axle radially form the tunnel-like mesopore.
7. method as claimed in claim 6, wherein said metallic catalyst comprise and are selected from least a in V, VI, VII and the family.
8. method as claimed in claim 7, wherein said metallic catalyst are at least a in chosen from Fe (Fe), nickel (Ni), copper (Cu), platinum (Pt), manganese (Mn), vanadium (V) and their alloy.
9. method as claimed in claim 6 wherein utilizes described metallic catalyst to remove the predetermined portions of the carbon nano-fiber that is attached with described metallic catalyst on it by the selectivity gasification reaction, forms described mesopore thus.
10. method as claimed in claim 9 wherein when removing the predetermined portions of the carbon hexaplanar that is attached with described metallic catalyst on it by the selectivity gasification reaction, forms described mesopore along the orientation of described carbon hexaplanar.
11. method as claimed in claim 6 wherein utilizes described metallic catalyst to make the reactant of described carbon hexaplanar gasification comprise hydrogen.
12. method as claimed in claim 11, wherein said gasification temperature are 500 ℃～900 ℃.
13. method as claimed in claim 6 wherein utilizes described metallic catalyst to make the reactant of described carbon hexaplanar gasification comprise oxygen.
14. method as claimed in claim 13, wherein activation temperature is 200 ℃～400 ℃.
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