CN101301618A - Intermediates for manufacturing carbon nanocoils and manufacturing method of carbon nanocoils - Google Patents

Abstract

A catalyst for making carbon nanometer loop is a catalyst that makes the carbon nanometer loop with diameter 1000nm below through a chemical gas phase growth method, characterized in that the catalyst at least contains more than one transitional metal elements such as Al, Cr and Sn.

Description

The manufacture method of carbon nanocoil catalyst for producing and carbon nanocoil

The application is an application number: 200480014742.4, the applying date: the dividing an application of the patent application of on May 28th, 2004, denomination of invention " manufacture method and the carbon nanocoil of carbon nanocoil catalyst for producing, its manufacture method, carbon nanocoil ".

Technical field

The present invention relates to the manufacture method of a kind of carbon nanocoil catalyst for producing and carbon nanocoil.

Background technology

Manufacturing is curled into the carbon nanocoil (carbonnanocoil) of the following coiled type of overall diameter 1000nm.Carbon nanocoil has the characteristic identical with CNT, and electromagnetic induction is remarkable, and is very useful as magnetic head material, absorption of electromagnetic wave material that hard disk is used.Also have, even because have the spring that the length of extending 2 times also can be restored, so attracted attention as the spring (spring) of micromachine or transmission mechanism (actuator) material and as reinforced resin material.

Carbon nanocoil, in 1994 by (Amelinckx such as Amelinckx, X.B.Zhang, D.Bernaerts, X.F.Zhang, V.Ivanov and J.B.Nagy, SCIENCE, 256 (1994) 635), use chemical vapor deposition method (Chemical Vapor Deposition is hereinafter referred to as the CVD method) synthetic first.Relatively from before the noncrystalline structure of carbon micron coil of manufacturing, distinguished that carbon nanocoil is the graphite structure.

Their manufacture method, be to form micro powder as the single metallic catalyst of Co, Fe, Ni, will be heated to 600～700 ℃ near this catalyst, make organic gas circulation as acetylene or benzene, and contact the method that these organic molecules are decomposed with these catalyst.But the shape of the carbon nanocoil that is generated is various, and its yield rate is also low, says that its accidental generation is not excessive.Finally, can not utilize, thereby seek a kind of more effective manufacture method industrial.

1999 (W.Li, S.Xie, W.Liu, R.Zhao, Y.Zhang, W.Zhou andG.Wang, J.Material Sci., 34 (1999) 2745) such as Li, in the generation of new carbon nanocoil, achieve success.Their manufacture method, the catalyst that the periphery of graphite flake is covered by iron particle places central authorities, to be heated to 700 ℃ near this catalyst by nickel filament, the mist that makes the acetylene of by volume 10% and 90% nitrogen catalyst therewith contacts and the method for reacting.But this manufacture method coil yield rate is also little, and is very insufficient as the bulk method of industry.

Make and produce the key that the yield rate of carbon nanocoil increases by the CVD method and be to develop appropriate catalyst.From then on viewpoint is set out, and successfully develop the FeInSn series catalysts for one one of present inventors, and obtained the yield rate more than 90%, its achievement, it is open to open 2001-192204 (patent documentation 1) as the spy.This catalyst, evaporation forms iron thin film on the ito substrate of the mixed film that has formed In oxide and Sn oxide.ITO is the abbreviation of Indium-Tin-Oxide.

Also have, an one of present inventors forms the FeInSn series catalysts by method for distinguishing, and success made carbon nanocoil in a large number, and its achievement is opened 2001-310130 (patent documentation 2) as the spy and disclosed.This catalyst constitutes, In organic compound and Sn organic compound be mixed to form organic solution in the organic solvent, this organic solution is coated on substrate forms organic film, this organic film is burnt till form the InSn oxidation film, on this InSn oxidation film, form iron thin film.The InSn oxidation film is equivalent to above-mentioned ITO film (mixed film).

On the other hand, also carried out compound catalyst is taken on the research of specific carrier (carrier) with the high efficiency of raising catalyst.Research is in this respect carried out in the field of CNT, and opening 2002-255519 (patent documentation 3) and spy by the spy, to open 2003-313017 number (patent documentation 4) disclosed.

These patent documentations 3 and patent documentation 4 are relevant to the manufacture method of single-layer carbon nano-tube.Two public technology homogeneous phases are adsorbed in zeolite about making the CNT catalyst for producing, generate the technology of CNT.The CNT that is generated reports that wired footpath is more even.That is, catalyst is adsorbed in the micro hole of zeolite, and the more uniform CNT that has micro-aperture with manufacturing is the technology of purpose.

[patent documentation 1] spy opens the 2001-192204 communique

[patent documentation 2] spy opens the 2001-310130 communique

[patent documentation 3] spy opens the 2002-255519 communique

[patent documentation 4] spy opens the 2003-313017 communique

Using by patent documentation 1 and patent documentation 2 disclosed FeInSn series catalysts, in the research by CVD manufactured carbon nanocoil, present inventors have noticed the situation that profound meaning is arranged very much.In fact the front end of captured carbon nanocoil in electron micrograph is attached with emboliform material.Present inventors claim that this particle-like substance is a catalyst core.

Present inventors think that the catalyst core of the front end that is attached to carbon nanocoil is genuine catalyst material.That is, infer the carbon compound gas that exists around catalyst core is decomposed for this reason, make the carbon nanocoil growth while introduce carbon atom.Because carbon nanocoil self is minimum carbonizable substance, be nano level ultra micro small-particle so be attached to the catalyst shape material of its front end.

With a carbon nanocoil is test portion, and it is extremely difficult work that a minimum catalyst core that is attached to its front end is directly analyzed.Come off easily because catalyst core is minimum, so determine that by the method for physics or chemistry its structure is extremely difficult.Also have, the high de-agglomeration that obtains this catalyst core can the through mode electron microscope also be the work of difficulty mutually.

But,, determine that so its structure is just of crucial importance if this catalyst core is genuine catalyst.That is, determine that this catalyst core is independent fine of FeInSn series catalysts, or other other materials, present inventors are become extremely important problem.This is because by determining the structure of this catalyst core, might provide a kind of effective catalyst that is used to make carbon nanocoil.

Also have, disclosed known technology in the patent documentation 3 is to make Fe particulate and Ni particulate as catalyst particles be adsorbed in zeolite.Because it is very big that Fe particulate and Ni particulate are compared with the compound molecule of dissolving, so the micropore diameter of zeolite hour can exist catalyst particles can not be adsorbed in shortcoming in the fine pore.Also have, even catalyst particles is adsorbed in the pore, because fine pore self distributes within the specific limits, so the difference in the line footpath of with good grounds its distribution of meeting.In addition, the particle diameter of monodispersed metal microparticle is approximately 10nm with present technical merit.Below 10nm, then mutually combining with metal microparticle becomes the dumpling shape, because the particle diameter of 2 particles of dumplingization reaches more than several 10nm, so be attached to the surface of this zeolite, has the shortcoming of line footpath CNT growth greatly.

Patent documentation 4 discloses and makes the sorption of ferric nitrate molecule in the technology of zeolite in the aqueous solution.That is, the sorption of ferric nitrate molecule is in the pore of zeolite as can be known, and the catalyst filling rate of comparing to pore with above-mentioned catalyst particles uprises.But, be metallic element or its material containing metal of a kind with sorption in the catalyst of zeolite, rather than the metallic element of most kinds or its material containing metal.The catalyst of CNT is because be single Fe particulate or Ni particulate, so the pore of injecting zeolite equably.But, resemble the FeInSn series catalysts, because the carbon nanocoil catalyst for producing is made of the metal of multiple class, so be necessary in same pore, to fill simultaneously the metal of multiple class.In same pore, inject the metal of multiple class simultaneously, it also is very difficult only thinking deeply.Therefore, whether can be the field an of the unknown fully in zeolite with the sorption of a plurality of carbon nanocoil catalyst for producing, do not carry out experiment yet.

Therefore, the objective of the invention is to, the structure of the catalyst core of the front end by determining to be attached to carbon nanocoil indirectly, and determine a kind of genuine carbon nanocoil catalyst for producing, establish the manufacture method of this catalyst, and short time high density and high efficiency manufacturing carbon nanocoil.Also have, the objective of the invention is to develop FeInSn catalyst new carbon nanocoil catalyst for producing in addition.Also have, the object of the present invention is to provide a kind of new carbon nanocoil catalyst for producing that makes these new catalyst materials take on the porous carrier.In addition, purpose also is to establish uses these new carbon nanocoil catalyst for producing to make the method for carbon nanocoil, and the carbon nanocoil of uniform low price is provided to market.

Summary of the invention

The present invention studies for solving above-mentioned problem, draws following understanding, and is over into the present invention.Of the present invention first form is, by chemical vapor deposition manufactured overall diameter is the catalyst of the carbon nanocoil below the 1000nm, and this catalyst is the carbon nanocoil catalyst for producing that the metal carbides by the transition metal that contains more than one at least constitute.Transition metal is the meaning of the transition elements shown in the periodic table, and specifically, Sc～Cu of period 4, Y～Ag of period 5, La～Au of period 6 are known as the catalyst for producing of carbon nanocoil.Present inventors resemble the FeInSn catalyst, by making the coexistence of this transition metal and other element carbon nanocoil are generated, and become carbon compound by this catalyst, and carbon nanocoil is grown up effectively.Above-mentioned catalyst core is metal carbides of the present invention.

Second form of the present invention is to be the catalyst of the carbon nanocoil below the 1000nm by chemical vapor deposition manufactured overall diameter, and this catalyst is the carbon nanocoil catalyst for producing of the carbide catalyst of the transition metal that contains more than one at least, In, C.Transition metal as mentioned above, this transition metal and In and C become effective carbon nanocoil catalyst for producing in conjunction with formed carbide catalyst.

The 3rd form of the present invention, above-mentioned transition metal are the above elements A of choosing any one kind of them from Fe, Co, Ni, and the composition formula of above-mentioned carbide catalyst is at least by A _xIn _yC _zThe carbon nanocoil catalyst for producing of expression.Fe, Co, In are known as the catalyst of CNT, but pass through with A _xIn _yC _zExisting becomes the carbon nanocoil catalyst, still finds first for present inventors.The effect of In also do not understand now, but may be thought of as Fe, Co, Ni grows up CNT, and C is the raw material that is used to form carbon nanocoil, and In curls this CNT.But the principle of its microcosmic is not also understood.Proposed in this carbide catalyst the ratio of components of A and In and C and represented, these ratio of components x, y, z can be designed to the carbide catalyst of desired value by x, y, z.

The 4th form of the present invention, above-mentioned elements A are Fe, and the composition formula of above-mentioned carbide catalyst is at least by Fe ₃InC _0.5The carbon nanocoil catalyst for producing of expression.Present inventors making the contact of carbon compound gas form the substrate of FeIn catalyst film and making in the carbon nanocoil, confirm and at first make FeIn catalyst film corpusculed, and this particulate becomes catalyst core, the situation that carbon nanocoil is grown up.When catalyst particles that is formed at this substrate was carried out the powder X-ray ray analysis, confirming was the carbide catalyst that contains Fe, In, C.From then on diffraction lattice can be distinguished, the composition formula of this carbide catalyst is Fe ₃InC _0.5Therefore, have the carbide catalyst of this composition formula, can make carbon nanocoil efficiently by use.This carbide catalyst is the determined carbon nanocoil catalyst for producing of being found first by present inventors of composition formula, is the genuine catalyst that carbon nanocoil is grown up.

The 5th form of the present invention is the carbon nanocoil catalyst for producing that adds more than one other elements in the carbide catalyst of second form.So-called other element can be the transition metal that constitutes catalyst, the element beyond In, the C, is to promote the element of growth of carbon nanocoil for effectively.For example, transition elements, the typical element beyond the above-mentioned transition metal all can.For example, when above-mentioned transition metal was Fe, other element for example can be Co or Ni etc.More particularly,, for example can in following element, select the Si of carbon family, Ge, Sn, or P, As, Sb, the Bi of the B of boron family, Al, Ga, Tl or nitrogen family, other metallic element, nonmetalloid etc. as other elements.

The element of other that the 6th form of the present invention is the 5th form is the carbon nanocoil catalyst for producing of Sn.At this moment, as carbon nanocoil catalyst for producing of the present invention, for FeInSn is a carbide catalyst.When using existing FeInSn to be carbide catalyst manufacturing carbon nanocoil, because need for a long time, so there is the ineffective shortcoming of reaction unit to making carbon nanocoil grow to certain-length.But the FeInSn that uses form of the present invention is a carbide catalyst, and the catalyst efficiency height can make carbon nanocoil grow up in the break time, therefore has the advantage that can improve the reaction unit operating efficiency.Also have,, then, can control the carbon nanocoil footpath, can make the coil of arbitrary diameter by the particulate footpath of control carbide catalyst if be that particulate constitutes with this carbide catalyst.

The 7th form of the present invention is that the composition formula of carbide catalyst is at least by Fe in above-mentioned the 6th form _xIn _yC _zSn _wRepresented carbon nanocoil catalyst for producing.Proposed in this carbide catalyst the ratio of components of Fe and In and C and Sn and represented that by x, y, z, w these ratio of components x, y, z, w can be designed to the carbide catalyst of desired value.

The 8th form of the present invention, the composition formula that is carbide catalyst is at least by Fe ₃In _1-vC _0.5Sn _wThe carbon nanocoil manufacturing carbide catalyst that the composition formula of (1＞v 〉=0, w 〉=0) is represented.This form catalyst is with Fe ₃InC _0.5Be the carbide catalyst at center, only remove In ratio of components v (1＞v 〉=0) in forming by center from then on, only add Sn ratio of components w (〉=0) and generate.Ratio of components v, w are 0 o'clock, become Fe ₃InC _0.5Composition, remove v amount and add the w amount and in the scope more than 0, be set to desired value.By suitably adjusting ratio of components v, w, can provide the carbide catalyst that to make carbon nanocoil effectively.The interpolation ratio of components w of Sn can freely set in the scope of w＞0, all can up to a large amount of interpolations from the trace interpolation of Sn.Have according to the addition of Sn and can adjust the advantage of formation efficiency.

The 9th form of the present invention, be to be illustrated in the catalyst of the 3rd form, above-mentioned elements A is chosen as Fe, the angle of diffraction 2 θ when this catalyst mensuration is carried out powder x-ray diffraction, near about 40 °, have first intensity peak, near about 46.3 °, have the carbon nanocoil catalyst for producing of the diffracted intensity distribution of second intensity peak.Near above-mentioned about 40 °, definite saying has first intensity peak near 39.6 °, having the carbide catalyst of second intensity peak near 46.3 °, found first by present inventors, is the carbon nanocoil catalyst for producing so proposed with this carbide catalyst.

The tenth form of the present invention, be to be the catalyst of the carbon nanocoil below the 1000nm by chemical vapor deposition manufactured overall diameter, this catalyst is the carbon nanocoil catalyst for producing of the carbide catalyst of the transition metal that contains more than one at least, Sn, C.It is the carbide catalyst that the In of the catalyst of the second above-mentioned form is replaced as Sn.(transition metal, Sn, C) carbide catalyst, with (transition metal, In, C) carbide catalyst be the carbon nanocoil catalyst for producing of finding first by present inventors jointly.Transition metal as mentioned above, this transition metal and Sn and C in conjunction with and the carbide catalyst of row becomes effective carbon nanocoil catalyst for producing.The concrete selection of transition metal is suitably freely carried out according to making efficient and synthesis condition.

The 11 form of the present invention, in the catalyst of the tenth form, above-mentioned transition metal is for choosing any one kind of them above elements A from Fe, Co, Ni, and the composition formula of above-mentioned carbide catalyst is at least by A _xSn _yC _zRepresented carbon nanocoil catalyst for producing.Fe, Co, Ni as CNT ground catalyst with widely known, but by there being A _xSn _yC _zAs the catalyst of carbon nanocoil, still find first by present inventors.The effect of Sn also do not understand now, but may be thought of as Fe, Co, Ni grows up CNT, and C is the raw material that is used to form carbon nanocoil, and Sn curls this CNT.But the principle of its microcosmic is not also understood.Proposed in this carbide catalyst the ratio of components of A and Sn and C and represented, these ratio of components x, y, z can be designed to the carbide catalyst of desired value by x, y, z.

The present invention's the 12 form is in the 11 form, and above-mentioned elements A is Fe, and the composition formula of above-mentioned carbide catalyst is at least by Fe ₃The carbon nanocoil catalyst for producing that SnC is represented.Present inventors making the contact of carbon compound gas form the substrate of FeSn catalyst film and making in the carbon nanocoil, confirm and at first make FeSn catalyst film corpusculed, and this particulate becomes catalyst core, the situation that carbon nanocoil is grown up.When catalyst particles that is formed at this substrate was carried out the powder X-ray ray analysis, confirming was the carbide catalyst that contains Fe, Sn, C.From then on diffraction lattice can be distinguished, the composition formula of this carbide catalyst is Fe ₃SnC.Therefore, have the carbide catalyst of this composition formula, can make carbon nanocoil efficiently by use.This carbide catalyst is the determined carbon nanocoil catalyst for producing of being found first by present inventors of composition formula, is the catalyst that carbon nanocoil is grown up.

The 13 form of the present invention is in the tenth form ground catalyst, adds more than one other element ground carbon nanocoil catalyst for producing in above-mentioned carbide catalyst.So-called other element can be the transition metal that constitutes catalyst, the element beyond Sn, the C, is to promote the element of growth of carbon nanocoil for effectively.For example, transition elements, the typical element beyond the above-mentioned transition metal all can.For example, when above-mentioned transition metal was Fe, other element for example can be Co or Ni etc.More particularly, as other elements, for example can in following element, select, freely add the Si of carbon family, Ge, Sn, or P, As, Sb, the Bi of the B of boron family, Al, Ga, Tl or nitrogen family in right amount according to purpose, other metallic element, nonmetalloid etc.

The 14 form of the present invention, be to be illustrated in the 11 form ground catalyst, above-mentioned elements A is Fe, by the angle of diffraction 2 θ instrumentations, has the carbon nanocoil catalyst for producing of the diffracted intensity distribution of first intensity peak near about 40 ° when described catalyst is carried out powder x-ray diffraction.Having the carbide catalyst of first intensity peak near 40 °, found by present inventors, is the carbon nanocoil catalyst for producing so proposed with this carbide catalyst.

The 15 form of the present invention is the carbon nanocoil catalyst for producing of the element of the transition metal, Al and the Sn that contain more than one at least.This catalyst is the new metallic catalyst that present inventors find, rather than carbide catalyst.Transition metal can utilize suitable transition metal according to purpose as mentioned above.If use this catalyst, be applicable to by CVD method etc. syntheticly, can make carbon nanocoil effectively, help the industrialized mass production of carbon nanocoil.

The 16 form of the present invention is the carbon nanocoil catalyst for producing that above-mentioned transition metal, Al and Sn exist as oxide.If the catalyst of the 15 form is burnt till in the oxygen atmosphere and generates, just can obtain oxide catalyst.Iron, aluminium or tin use with the form of iron oxide, aluminium oxide or tin oxide, constitute the carbon nanocoil catalyst for producing, so even these use the oxidation that does not also have more than this in air, can provide stable catalyst.

The 17 form of the present invention is in the catalyst of the 15 form or the 16 form, and above-mentioned transition metal is Fe, is forming (Fe _x-Al _y-Sn _z) ratio of components (mol ratio) in, under the pro rate of (x, y, z) during x=3, the carbon nanocoil catalyst for producing of y≤1, z≤3.If form with this and to try out, can make carbon nanocoil with high formation efficiency.Catalyst (the Fe of this form _x-Al _y-Sn _z), for example the ratio of components by x=3, y=1, z=0.1 constitutes.

The 18 form of the present invention is the carbon nanocoil catalyst for producing of the element of the transition metal, Cr and the Sn that contain more than one at least.This catalyst is another new metallic catalyst that present inventors find, rather than carbide catalyst.Transition metal can utilize various transition metals according to purpose as mentioned above.If use this catalyst, be applicable to by CVD method etc. syntheticly, can make carbon nanocoil effectively, help the industrialized mass production of carbon nanocoil.

The 19 form of the present invention is in the catalyst of the 18 form, the carbon nanocoil catalyst for producing that above-mentioned transition metal, Cr and Sn exist as oxide.If the catalyst of the 18 form is burnt till in the oxygen atmosphere and generates, just can obtain oxide catalyst.Transition metal, chromium or tin use with the form of transiting metal oxidation iron, aluminium oxide or tin oxide, constitute the carbon nanocoil catalyst for producing, even, can provide stable catalyst so these use the oxidation that does not also have more than this in air.

The 20 form of the present invention is in the catalyst of the 18 form or the 19 form, and above-mentioned transition metal is Fe, is forming (Fe _x-Cr _y-Sn _z) ratio of components (mol ratio) in, under the pro rate of (x, y, z) during x=3, the carbon nanocoil catalyst for producing of y≤1, z≤3.If use this catalyst, can make carbon nanocoil with high formation efficiency.Catalyst (the Fe of this form _x-Cr _y-Sn _z), for example the ratio of components by x=3, y=0.3, z=0.1 constitutes.

The 21 form of the present invention contains the composition (Fe that the element of Fe, In and Sn constitutes at least _x-In _y-Sn _z) and in the ratio of components (mol ratio) of each element, under the pro rate of (x, y, z) during x=3, the carbon nanocoil catalyst for producing of y≤9, z≤3.Present inventors, though the FeInSn catalyst is disclosed, in this form, by limit respectively constitute element composition in particular range, can successfully carry out the manufacturing of carbon nanocoil more efficiently.Catalyst (the Fe of this form _x-In _y-Sn _z), for example the ratio of components by x=3, y=0.3, z=0.1 constitutes.

The 22 form of the present invention is in the catalyst of the 21 form, the carbon nanocoil catalyst for producing that Fe, In and Sn exist with oxide.Iron, indium or tin use with the form of iron oxide, indium oxide or tin oxide, constitute the carbon nanocoil catalyst for producing, so even these use the oxidation that does not also have more than this in air, can provide stable catalyst.

The 23 form of the present invention is in arbitrary form of first form to the, 22 forms, the carbon nanocoil catalyst for producing that above-mentioned catalyst obtains as particulate.Present inventors find that catalyst core is present in the front end of the carbon nanocoil of growth, while this catalyst core decomposition carbon compound is obtained carbon atom carbon nanocoil are grown up.Based on this understanding, if carbide catalyst can be provided as particulate, these particulates self have the function of catalyst core, thereby can make carbon nanocoil effectively.By adjusting atomic particle diameter, having coil footpath and the coil overall diameter that can control carbon nanocoil equably is the advantage of desired value.

The 24 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of second form or the tenth form, on substrate, form the film that contains (transition metal, In) or (transition metal, Sn) at least, under heated condition, the film surface of aforesaid substrate is carried out carbonization, form the manufacture method of carbon nanocoil catalyst for producing of the carbide catalyst of the element that contains (transition metal, In, C) or (transition metal, Sn, C) at least by carbon compound gas.Only the film catalyst that is formed at substrate is carried out the carbide catalyst that carbonization can be produced at least the element that contains (transition metal, In, C) or (transition metal, Sn, C) in batches.Transition metal has varied as mentioned above, can the qurer batch process contain the carbide catalyst of transition metal arbitrarily.

The 25 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of second form or the tenth form, form the particulate that contains (transition metal, In) or (transition metal, Sn) at least, under heated condition, make this particulate carburet thing gas reaction, form the manufacture method of carbon nanocoil catalyst for producing of the carbide catalyst of the element contain (transition metal, In, C) or (transition metal, Sn, C) at least.Apply flexibly the whole bag of tricks, can produce at least the carbide catalyst of the element that contains (transition metal, In, C) or (transition metal, Sn, C) in batches, can make contributions the reduction of catalyst price.In above-mentioned atomic formation method, can utilize the chemical vapor deposition method (CVD etc.) of the vapour deposition method (PVD) of physics of evaporation sputtering ion plating plasma molecular beam etc. or gas-phase decomposition method spray heating decomposition etc.

The 26 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of second form or the tenth form, be formed on and add liquation or the dispersion liquid that contains (transistion metal compound and In compound) or (transistion metal compound and Sn compound) at least in the solvent, from then on liquation or dispersion liquid separating solids composition, above-mentioned solid constituent is contacted with carbon compound gas carry out carbonization, form and contain (transition metal at least, In, C) or (transition metal, Sn, the manufacture method of the atomic carbon nanocoil catalyst for producing of the carbide catalyst of element C).As transistion metal compound and In compound and Sn compound, transition metal oxide and In oxide and Sn oxide are for example arranged, with these even hybrid separation solid constituents in solvent.If these solid constituents are carried out carbonization treatment by carbon compound gas, then can synthetic in a large number simply (transition metal, In, C) carbide catalyst particulate or (transition metal, Sn, C) carbide catalyst particulate.As material that can carbonization, can utilize all cpds beyond the oxide.

The 27 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of second form or the tenth form, be formed on and add liquation or the dispersion liquid that contains (transistion metal compound and In compound) or (transistion metal compound and Sn compound) at least in the solvent, from then on liquation or dispersion liquid separating solids composition, the solid constituent that is separated is burnt till, at least generate (transition metal, In) or (transition metal, Sn) particulate, this particulate is contacted with carbon compound gas carry out carbonization, form and contain (transition metal at least, In, C) or (transition metal, Sn, the manufacture method of the atomic carbon nanocoil catalyst for producing of the carbide catalyst of element C).As transistion metal compound and In compound and Sn compound, transition metal organometallic compound, In organic compound, Sn organic compound are for example arranged, with these even hybrid separation solid constituents in solvent, this solid constituent is burnt till, burn till organic matter, can make the particulate of (transition metal, In) or (transition metal, Sn) simply.If carry out burning till under the oxygen atmosphere, generate oxide microparticle or hydroxide particulate etc., if carry out burning till under other the atmosphere, generate this particulate in addition with ining addition.Can utilize and be converted into the atomic particulate arbitrarily of aim carbon compound.If this particulate is carried out carbonization treatment by hydrocarbon gas, can the synthetic in a large number simply carbide catalyst particulate that contains the element of (transition metal, In, C) or (transition metal, Sn, C).

The 28 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of second form or the tenth form, in the reactive tank under the heated condition, at least make (transistion metal compound gas and In chemical compound gas) or (transistion metal compound gas and Sn chemical compound gas) carburet thing gas haptoreaction, form the manufacture method of the atomic carbon nanocoil catalyst for producing of carbide catalyst of the element that contains (transition metal, In, C) or (transition metal, Sn, C) at least.In this form, utilize the gas of catalyst raw material composition to react the particulate of the carbide catalyst of productive target in a large number by aerochemistry, the reduction of catalyst price is made contributions.

The 29 form of the present invention is in the 24 form～the 28 form arbitrary, and above-mentioned transition metal is for choosing any one kind of them above elements A from Fe, Co, Ni, and the composition formula of above-mentioned carbide catalyst is at least by A _xIn _yC _zOr A _xSn _yC _zThe manufacture method of represented carbon nanocoil catalyst for producing.Fe, Co, Ni are widely known as the catalyst of CNT, but by and InC or SnC combination, as the catalyst of carbon nanocoil, found by present inventors.In this carbide catalyst, ratio of components is represented that by x, y, z these ratio of components x, y, z can provide the carbide catalyst that is designed to desired value.

The 30 form of the present invention is in the 29 form, and above-mentioned elements A is Fe, and the composition formula of above-mentioned carbide catalyst is at least by Fe ₃InC _0.5Or Fe ₃The manufacture method of the carbon nanocoil catalyst for producing that SnC is represented.In this form, among FeCoNi, selected Fe especially.Under the situation of Fe, has the advantage that carbon compound is generated.By Fe ₃InC _0.5Or Fe ₃The formed carbon compound of SnC as the carbon nanocoil catalyst for producing, is the material that the present inventors world at first finds.

The 31 form of the present invention is in the 24 form～the 30 form arbitrary, adds the manufacture method of carbon nanocoil catalyst for producing of more than one other elements in above-mentioned carbide catalyst.So-called other element can be (transition metal, In, C) or (transition metal, Sn, the C) element in addition that constitutes catalyst, is to promote the element of growth of carbon nanocoil for effectively.For example, transition elements or the typical element beyond the above-mentioned transition metal all can.For example, when above-mentioned transition metal was Fe, other element for example can be Co or Ni etc.More particularly, as other elements, for example can in following element, select, freely add the Si of carbon family, Ge, Sn, or P, As, Sb, the Bi of the B of boron family, Al, Ga, Tl or nitrogen family in right amount according to purpose, other metallic element, nonmetalloid etc.

The 32 form of the present invention is to make the carbide catalyst of carbon nanocoil manufacturing usefulness and/or the carbon nanocoil catalyst for producing that oxide catalyst is taken on porous row carrier.The employed catalyst of this form is carbide catalyst and/or oxide catalyst, can make carbon nanocoil efficiently.Also have, because make these catalyst take on the porous carrier, so the carbon nanocoil catalyst for producing can be filled in the uniform pore with porous row carrier.The full-size that the pore of porous row carrier is arranged is example with the y-type zeolite, approximately is 0.5～2nm, and the lowest calibre of pore is 0.74nm in zeolite.So, in having the long-pending pore of uniform section, be adsorbed with the carbon nanocoil catalyst for producing, then can reach homogenising to the catalyst amount of taking on (loading) of pore.That is, can reach by the homogenization of the catalyst area due to the pore basal area of porous carrier with by the homogenization of the catalyst component due to the volume with this pore.Therefore, grow up because be equivalent to the carbon nanocoil in the line footpath of fine pore, so can access the homogenization in line footpath.According to present inventors' research, the dependency relation in the overall diameter of carbon nanocoil and the line of carbon nanocoil footpath is high, and the homogenization by the line footpath can realize the homogenization of coil overall diameter.Moreover, by making the catalyst area and the homogenization of catalyst component of the line key element directly that limits carbon nanocoil, can make the line footpath homogenization of carbon nanocoil, its result has successfully realized the batch process catalyst of the carbon nanocoil of coil overall diameter homogenization.Also have, in porous row carrier, have and much have pore, can form and the proportional carbon nanocoil of its pore number.Therefore, has the advantage that to produce carbon nanocoil efficiently in batches.In addition, the shape of porous carrier exists bulk, sheet, tabular, granular, finely particulate, ultramicron shape etc. multiple.

The 33 form of the present invention is in the 32 form, the carbon nanocoil catalyst for producing that the either carbon compound catalyst of first form～the 14 form is taken on.The carbide catalyst of first form～the 14 form is the catalyst that present inventors find, has the advantage that can make carbon nanocoil efficiently.

The 34 form of the present invention is to make each described catalyst of the 15 form～the 22 form take on the carbon nanocoil catalyst for producing of porous row carrier.The catalyst of the 15 form～the 22 form is the catalyst that present inventors find, rather than carbide catalyst, but identical with carbide catalyst have the advantage that can make carbon nanocoil efficiently.

The 35 form of the present invention is the carbon nanocoil catalyst for producing that the transition metal InSn series catalysts, transition metal AlSn series catalysts, transition metal CrSn series catalysts, transition metal In series catalysts or the transition metal Sn series catalysts that make carbon nanocoil manufacturing usefulness taken on the porous carrier.The pore that makes these catalyst take on the porous carrier then can be produced the carbon nanocoil in homogeneous diameter homogeneous coil footpath in batches.These catalyst are 2 yuan of prime systems, 3 yuan of prime systems, can take on the kind of multielement according to catalyst according to the present invention simultaneously in pore, and the formation efficiency of carbon nanocoil is also various.Therefore, by suitably adjusting the combination of catalyst, can freely adjust the formation efficiency of carbon nanocoil.

The 36 form of the present invention is in the catalyst of the 35 form, and above-mentioned transition metal is the carbon nanocoil catalyst for producing of above element of choosing any one kind of them among Fe, Co, the Ni.Even in transition metal, Fe, Co, the Ni that can make carbon nanocoil effectively also are used.Its result by the catalyst of this form, can produce carbon nanocoil in a large number, can help the reduction of price.

The 37 form of the present invention, be in the 32 form～the 36 form, above-mentioned porous carrier be from zeolite, aluminium phosphate, silicoaluminophosphate, porous body, porous ceramics, molecular sieve (molecular sieve), burning system porous body, silicon porous body or carbon be carbon nanocoil catalyst for producing optional in the porous body.Zeolite is to have SiO ₄And AlO ₄The general name of porous body of the structure that mutually combines of the total oxygen of tetrahedron.Natural goods, synthetic be logical calculates the lattice structure that has more than 100 kinds, determines the character that they are different by the ratio of Si atom and Al atom (Si/Al than).Also have, so because an one of Si atom has negative electrical charge by the Al atomic substitutions, so the carbon nanocoil catalyst for producing is taken on by ion-exchange.ALPO (aluminate or phosphate) has AlO ₄And PO ₄The structure that mutually combines of the total oxygen of tetrahedron.The pore structure of ALPO and zeolite facies are same, so but because neutrality does not have the ion-exchange energy.Replace an one of P atom of ALPO by the Si atom, become and zeolite facies with have exchange of particles can SAPO (silicoaluminophosphate).Therefore, SAPO can easily take on the carbon nanocoil catalyst for producing by ion-exchange.Because resin sorbent, porous ceramics, burning system porous body and silicon porous body are also constructed with having pore with zeolite facies, so can take on the carbon nanocoil catalyst for producing.The fine pore of zeolite, ALPO, SAPO is 0.5～2nm, in the silicon porous body, has the big pore of 1.5～10nm.In addition, also can utilize the carbon of the carbon nanostructure etc. of active carbon, CNT etc. is porous body.Therefore, the catalyst of taking on by the pore of these porous row carriers is made carbon nanocoil, have can produce in batches to have to exist with ... these fine pore, and the advantage of the carbon nanocoil of coil overall diameter homogeneous.

The 38 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of the 32 form～the 37 form, the particulate of the catalyst of above-mentioned carbon nanocoil manufacturing usefulness is disperseed in solvent, dipping porous carrier in this solvent, load is held the manufacture method of catalyst of the carbon nanocoil manufacturing usefulness of above-mentioned catalyst particles in the surface of porous carrier and/or pore.Catalyst particles is disperseed in solvent, and then the sub-homogeneous of catalyst particles disperses in this solvent.Then flood the porous carrier in this solvent, then homogeneous is adsorbed with the carbon nanocoil catalyst for producing in the identical pore of porous carrier.In order to adsorb efficiently, the porous carrier is flooded in solvent after, stir solvent, carry out ultrasonic wave and handle, by homogenizer and atomizer processing etc., can also append arbitrarily and handle.

The 39 form of the present invention, it is the manufacture method of the carbon nanocoil catalyst for producing of the 32 form～the 37 form, make in the space, filling or circulation of above-mentioned carbon nanocoil manufacturing usefulness, configuration porous carrier in this space, the manufacture method that load is held the carbon nanocoil catalyst for producing of above-mentioned catalyst particles in the surface of porous carrier and/or pore.Because make catalyst particles in the space, fill or circulate, so, just can be easily in the surface of porous carrier and/or pore, adsorb above-mentioned catalyst particles by configuration porous carrier in this space only.The porous carrier can also rest in the process chamber, also can atomize, stir, and can use the known method that adsorption efficiency is risen from gas phase.Also have, the condition of the physics in the process chamber can be adjusted arbitrarily.For example, place the porous carrier under the high pressure, place under the vacuum, also have heating, cooling all can.Method makes carbon nanocoil catalyst for producing particulate be adsorbed in the porous carrier thus, can make carbon nanocoil in high performance cheap ground.

The 40 form of the present invention is in the 38 form or the 39 form, burns till the manufacture method of the carbon nanocoil catalyst for producing that makes the porous carrier that catalyst particles takes on.By burning till, catalyst particles is bonded in the pore of porous carrier, can improve and take on intensity.

The 41 form of the present invention, be that either carbon nanocoil catalyst for producing in first～22 form and the 32～37 form is placed inside reactor, make more than the temperature that the carbon compound gas that uses as raw material decomposes by catalyst action being heated near this catalyst, make above-mentioned carbon compound gas communication, contact with above-mentioned catalyst, grow into the manufacture method that overall diameter is the carbon nanocoil of the carbon nanocoil below the 1000nm on the surface of above-mentioned catalyst near above-mentioned catalyst while above-mentioned carbon compound gas decomposes.The carbide catalyst of the application of the invention, metallic catalyst, its oxide catalyst or porous carrier catalyst, can make the carbon compound gas of hydrocarbon etc. effectively generate carbon nanocoil efficiently, can make the industrial batch processization of existing carbon nanocoil while decomposing at this catalyst surface.

The 42 form of the present invention, be to make the catalyst precarsor material carburet thing gas contact under heated condition that contains transition metal, In at least, form the carbide catalyst that contains transition metal, In, C at least, decomposing carbon compound gas by above-mentioned carbide catalyst under the heated condition continuously, making the manufacture method of the carbon nanocoil of carbon nanocoil growth.Make the catalyst precarsor material that contains transition metal, In be varied to carbide catalyst, two sections method for continuous production of a large amount of production carbon nanocoils can be provided in addition.Outside transition metal, In,, can further improve the manufacturing efficient of carbon nanocoil if use other the catalyst of effective element added more than one to play precursor substance.

The 43 form of the present invention, be to make the catalyst precarsor material carburet thing gas contact under heated condition that contains transition metal, Sn at least, form the carbide catalyst that contains transition metal, Sn, C at least, decomposing carbon compound gas by above-mentioned carbide catalyst under the heated condition continuously, making the manufacture method of the carbon nanocoil of carbon nanocoil growth.Make the catalyst precarsor material that contains transition metal, Sn be varied to carbide catalyst, two sections method for continuous production of a large amount of production carbon nanocoils can be provided in addition.Outside transition metal, Sn,, can further improve the manufacturing efficient of carbon nanocoil if use other the catalyst of effective element added more than one to play precursor substance.

The 44 form of the present invention, be to make the catalyst precarsor material carburet thing gas contact under heated condition that contains transition metal, In, Sn at least, form the carbide catalyst that contains transition metal, In, Sn, C at least, decomposing carbon compound gas by above-mentioned carbide catalyst under the heated condition continuously, making the manufacture method of the carbon nanocoil of carbon nanocoil growth.Provide to make the catalyst precarsor material that contains transition metal, In, Sn be varied to carbide catalyst, can produce two sections method for continuous production of carbon nanocoil in addition in a large number.Outside transition metal, In, Sn,, can further improve the manufacturing efficient of carbon nanocoil if use other the catalyst of effective element added more than one to play precursor substance.

The 45 form of the present invention, be in the 41 form～the 44 form, on substrate, form the film or the particulate film of above-mentioned carbon nanocoil catalyst for producing, make the manufacture method of the carbon nanocoil that carbon nanocoil grows up by this catalyst decomposes carbon compound gas on substrate.Use catalyst film, then can on catalyst film, generate carbon nanocoil to high-density.Also having, use the particulate film of catalyst, is that catalyst core can be produced carbon nanocoil in a large number on substrate with catalyst particles then.If reduce the particle diameter of catalyst particles, then can the little carbon nanocoil of manufacturing dimension, if the opposite particle diameter that increases catalyst particles, then could the big carbon nanocoil of manufacturing dimension.So, has the advantage that freely to produce carbon nanocoil in a large number by the particle diameter of control catalyst particles.

The 46 form of the present invention, be in the 41 form～the 44 form, the particulate of above-mentioned carbon nanocoil catalyst for producing is swum in reactive tank, decompose the carbon nanocoils circle manufacturing method that carbon compound gas makes carbon nanocoil grow up with floating state by this catalyst particles.By the conversion zone of limiting catalyst particulate circulation, the one-tenth that can control carbon nanocoil long-time fairly simplely, can easily control the size of carbon nanocoil.

The 47 form of the present invention, be in the 41 form～the 44 form, the particulate of above-mentioned carbon nanocoil catalyst for producing is piled up in reactive tank, decompose carbon compound gas, the carbon nanocoils circle manufacturing method that carbon nanocoil is grown up while catalyst particles that stirs this accumulation under stirring.For example, the powder of catalyst particles is piled up in converter, while make the carbon compound gas communication make the converter rotation, then catalyst fines is in stirring, can be that catalyst core is produced carbon nanocoil in a large number with catalyst particles.As stirring means, can adopt spinning solution, method for oscillating, other known method.

The 48 state of the present invention is by the carbon nanocoil in each the described nanocoil manufacture method manufacturing of the 41 form～the 44 form.Therefore, because synthesize nano carbon coil in a large number, so carbon nanocoil at a low price can be provided.Also have, make, can provide the line footpath carbon nanocoil identical with the coil overall diameter by the catalyst that the porous carrier is taken on.Therefore, if use this line footpath carbon nanocoil identical with the coil overall diameter, then can make high-quality nano-substance, for example nanometer spring, nano-machine, electromagnetic wave absorb, electronic emitter (emitter), nanoelectronic equipment, hydrogen occlusion body etc. can be tackled the requirement in each field.

Description of drawings

Fig. 1 is the approximate three-dimensional map of carbon nanocoil 1.

Fig. 2 is the approximate three-dimensional map of carbon nanocoil 1 manufacturing installation.

Fig. 3 represents to be made by catalyst film 14 ideograph of carbon nanocoil developmental process.

Fig. 4 is a process chart of making carbide catalyst first method.

Fig. 5 is a process chart of making carbide catalyst second method.

Fig. 6 is to use the process chart of the present invention ground third party's method of catalyst particles 18 of liquation manufactured carbon compound.

Fig. 7 is to use the process chart of first autofrettage of carbide catalyst particulate 18 ground carbon nanocoils 1.

Fig. 8 is from the enclose the land process chart of second autofrettage of the carbon nanocoils of FeInSn series catalysts film 14s.

Fig. 9 is the diagrammatic illustration figure that carbide catalyst particulate 18 is swum make third party's method (autofrettage flows) of carbon nanocoil 1.

Figure 10 is the diagrammatic illustration figure that makes the cubic method (autofrettage flows) of carbon nanocoil 1 from oxide microparticle 26 formation catalyst particles 18 that are atomized.

Figure 11 is the scanning electron microscope picture with the FeInSn sull of 50,000 times of shootings.

Figure 12 is the powder x-ray diffraction intensity map of catalyst particles after 10 seconds.

Figure 13 is the time course figure of first peak value that 2 θ are approximately 40 ° diffracted intensity.

Figure 14 is the scanning electron microscope picture of 650 ℃ the carbide catalyst particulate carbon nanocoil of growing up.

Figure 15 is the scanning electron microscope picture of 700 ℃ the carbide catalyst particulate carbon nanocoil of growing up.

Figure 16 is the full electron microscopic mirror image of the mounted scout Mi County that generated by the Fe-Sn-C catalyst and the X-ray diffraction crystal lattice pattern of catalyst.

The electron microscopic mirror image that Figure 17 mounted scout Mi County that to be other conditions generated by the Fe-Sn-C catalyst is complete and the X-ray diffraction crystal lattice pattern of catalyst.

Figure 18 is the summary construction diagram of the major part of the employed manufacturing installation 1 of embodiments of the present invention.

Figure 19 is by the ratio of components Fe that establishes catalyst: In: Sn, Fe: Al: Sn and Fe: Cr: Sn is the electron microscopic mirror image of the one-tenth biology that forms of 3: 0.3: 0.1 o'clock manufacturing installation 1.

Figure 20 is relative Fe, the electron microscopic mirror image of the product of the manufacturing installation the when catalyst that In and Al mix with 1/3 ratio is formed.

Figure 21 carries out the electron microscopic mirror image of product that CNC generates the manufacturing installation 1 of experiment with various ratio of components in the mixed catalyst Fe-Sn-O of only iron and tin.

Figure 22 is Fe _x-In _y-Sn _zThe CNC of the various compositions of-O catalyst generates the electron microscopic mirror image of the product of experiment.

Figure 23 is at Fe _x-In _y-Sn _zIn-O the catalyst, the electron microscopic mirror image of the product of the ratio of components different with Fig. 5.

Figure 24 is Fe _x-Al _y-Sn _zThe CNC of the various compositions of-O catalyst generates the electron microscopic mirror image of the product of experiment.

Figure 25 is Fe _x-Cr _y-Sn _zThe CNC of the various compositions of-O catalyst generates the electron microscopic mirror image of the product of experiment.

Figure 26 is the Fe of the ratio of components different with Figure 25 _x-Cr _y-Sn _zThe CNC of the various compositions of-O catalyst generates the electron microscopic mirror image of the product of experiment.

Figure 27 is the crystal structure figure of y-type zeolite.

Figure 28 takes on body (zeolite) and the scanning electron microscope picture of the carbon nanocoil that forms with 650 ℃ of catalyst that burn till.

Figure 29 is the pore distribution map of employed zeolite.

Figure 30 takes on body (zeolite) and the scanning electron microscope picture of the carbon nanocoil that forms with 700 ℃ of catalyst that burn till.

Figure 31 is the enlarged drawing of Fig. 4.

The specific embodiment

The detailed description of embodiments of the present invention is to be made of following four parts.Below, in this order embodiments of the present invention are described with reference to accompanying drawing.

[1] to the explanation of the carbide catalyst of (transition metal, In, C)

[2] to the explanation of the carbide catalyst of (transition metal, Sn, C)

[3] to the explanation of metallic catalyst

[4] to the explanation of the porous carrier catalyst of taking on catalyst

[1] to the explanation of the carbide catalyst of (transition metal, In, C)

In first segment, as the typical example of transition metal, to propose Fe, an example of (transition metal, In, C) carbide catalyst describes (Fe, In, C) carbide catalyst.As substituting of Fe, use transition metals such as Co or Ni also can access same effect.

Present inventors found that for a large amount of researchs with keen determination of producing carbon nanocoil and carrying out Fe, the In, the Sn series catalysts that use as starting catalyst carry out carbonization by the carbon compound gas as unstrpped gas in reactive tank.Analyze this carbon compound as can be known, be to major general Fe, In, C as the carbon compound that constitutes element, find the situation that this carbide catalyst is grown up carbon nanocoil, thereby finished the present invention.

This discovery procedure is as described below.By the CVD method carbon nanocoil is grown up, then can see that from its electron microscopic mirror image the front end at the pipe of carbon nanocoil is attached with catalyst core.Present inventors think that this catalyst core is the direct catalyst material that carbon nanocoil is grown up.

Present inventors etc. think that this catalyst core is decomposed carbon compound gas and generated carbon atom, with the process of this carbon atom in the accumulation of pipe front end, thus the crooked on one side growth carbon nanocoil that extends on one side of pipe.

Fig. 1 is the approximate three-dimensional map of carbon nanocoil 1.This carbon nanocoil 1 has overall diameter D, loop length L and the coil pitch P of coil by managing 3 crooked formation.So-called pipe is the meaning of carbon fiber (carbon fiber).Importantly, pipe front end 3a is attached with this situation of catalyst core 5.

Diameter with this catalyst core 5 is g.Think: these catalyst core 5 nucleation pile up thereby carbon compound gas decomposes carbon atom, thereby cross section diameter are pipe 3 elongations of d.It is CNT that pipe 3 is observed.

The shape of catalyst core 5 has ball-type, angle type, bolt type etc. various, but the diameter of its representative part is d.The pipe diameter d and catalyst core diameter g and do not require equal, but think that both sizes have dependency relation.

Observation according to present inventors learns that the little diameter d of then managing of catalyst core diameter g diminishes, and catalyst core diameter g greatly then manages diameter d and becomes big.From then on situation as can be known, g is more little for the catalyst core diameter, just should be able to form pipe diameter d little carbon nanocoil 1.

In pursuing this point, there are present inventors to find to manage between diameter d and the coil overall diameter D certain incidence relation is arranged.Promptly have the little then coil of catalyst core diameter g overall diameter D and diminish, catalyst core diameter g is big, and then coil overall diameter D becomes big tendency.

From then on the discovery of the dependency relation of the two can draw as drawing a conclusion.Have that to access catalyst core diameter g more little, pipe diameter d and coil overall diameter D diminish, and opposite catalyst core diameter g is big more, and pipe diameter d and coil overall diameter D become the tendency of big carbon nanocoil 1.In other words,, then can make more small-sized carbon nanocoil,, then can make the carbon nanocoil 1 of single-size if also have the catalyst core 5 of using diameter g homogeneous if use the little catalyst core 5 of diameter g.

Then, present inventors have discussed catalyst core 5 that the pipe front end 3a of carbon nanocoil 1 adheres to from where.Present inventors infer, form in the substrate method of catalyst film at substrate, and be as described below.At first, the process by to the circulation of the catalyst film on substrate carbon compound gas makes the catalyst film particlized be varied to catalyst particles.This catalyst particles thereunder piles up carbon atom while decomposing carbon compound, and carbon nanocoil 1 is grown up upward.Its result thinks that catalyst particles is brought to the front end 3a that is attached to pipe.In order to confirm this situation, carried out the growth experiment of carbon nanocoil 1.

The approximate three-dimensional map of Fig. 2 carbon nanocoil 1 manufacturing installation.In this carbon nanocoil manufacturing installation, be provided with heater 6 in the periphery of reactive tank 4, in reactive tank 4, formed the reative cell 8 of isothermal area.

In the position of wanting of reative cell 8, be provided with the substrate 12 that forms catalyst film 14.This catalyst film 14 is the previous catalyst for producing of carbon nanometer, is present inventors' a FeInSn series catalysts film that has been found that.The ratio of Fe and In and Sn can carry out freely adjusting, and the relative In of Fe is that the relative In of 10～99.99mol%, Sn is the scope of 0～30mol% but for example preferably be adjusted into.

Think reative cell supply carrier gas and carbon compound gas (unstrpped gas) along the direction of arrow a.Carbon compound gas is the carbon-source gas that carbon nanocoil is grown up, and is not limited only to hydrocarbon, and the organic gas that contains the organic gas, sulfur-bearing organic gas, phosphorous organic gas etc. of nitrogen is widely used.Wherein, do not generate hydrocarbon the best of unnecessary material.

As hydrocarbon, can utilize the alkanisation compound of methane, ethane etc., the chain ene compound of ethene, butadiene etc., the chain alkine compounds of acetylene etc., the aryl hydrocarbon of benzene, toluene, polyphenyl alkene etc., the naphthenic compound of the aromatic series hydrocarbon of naphthalene, phenanthrene etc., cyclopropane, cyclohexane etc. etc.Mixing hydrocarbon gas that in addition also can be two or more, particularly preferred being suitable for hanged down molecule hydrocarbon, for example acetylene, propine, ethene, benzene, toluene etc.

As carrier gas, can utilize He, Ne, Ar, N ₂, H ₂Deng gas, use He gas in the present embodiment.Carrier gas is the gas of conveyance carbon compound gas, and for the consumption of carbon compound gas by reaction, what carrier gas was used is not react the gas that does not carry out consuming fully.

In the reative cell 8, be heated to set point of temperature.Heating-up temperature can be adjusted into more than the minimum temperature of carbon compound gas by catalyst decomposes.And according to catalyst type and carbon compound gaseous species, heating-up temperature can be regulated change, but preferably sets for example more than 600 ℃.

Carbon compound gas and carrier gas feed to arrow a direction as mist, are provided with the surperficial contacted substrate 12 that makes this carbon compound gas and catalyst.Carbon compound gas is to be decomposed in the contact process of catalyst film 14, decomposes the carbon atom that is generated and piles up at catalyst surface, forms carbon nanocoil 1.

On the surface of catalyst film 14, generate countless carbon nanocoils 1.As mentioned above, catalyst film 14 is FeInSn series catalysts films, uses this catalyst, then from the carbon amount of carbon compound gas and the growing amount of carbon nanocoil, can judge that yield rate is approximately 90%.

Fig. 3 represents to be made by catalyst film 14 ideograph of carbon nanocoil developmental process.In the present embodiment, the carbon compound gas that uses is the C of 60sccm ₂H ₂Gas.Carrier gas is the He gas of 200sccm, and in order to decompose acetylene, setting heating-up temperature is 700 ℃.

Catalyst film 14 is that the mixed oxide catalyst film by Fe oxide and In oxide and Sn oxide forms.The composition formula of oxide catalyst constitutes the cooperation ratio of oxide and difference has for example been used by Fe according to each ₅InSn _0.1O _v, Fe ₃InSn _0.1O _v, FeInSn _0.1O _vCatalyst film etc. represented mixed oxide.In this embodiment, use be composition formula Fe ₃InSn _0.1O _vThe mixed oxide catalyst film.The thickness t of catalyst is set at 200nm.

In (3A), along the C of arrow b direction circulation ₂H ₂Gas contacts with catalyst film 14 on one side and carries out reaction decomposes on one side.By scan-type microscope (below, be called SEM) this course of reaction is observed, find that catalyst film 14 is by granulation before carbon nanocoil 1 is grown up.

Represented that in (3B) catalyst film 14 is by the state of particlized.Catalyst film 14 is varied to the catalyst particle film 16 that is made of catalyst particles 18.Make C ₂H ₂Gas circulates continuously, and then catalyst film 14 is divided into the interval successively, and each interval changes shape becomes catalyst particles 18.Diameter (particle diameter) s that also confirms catalyst particles 18 is in time through diminishing successively from big to small.

In (3C), make C ₂H ₂Gas to these catalyst particles 16 circulations, is then observed carbon nanocoil 1 and is grown up continuously.The front end of being observed carbon nanocoil 1 by SEM is attached with catalyst core 5.Also confirm in the stage of catalyst particles 18 minimizations, carbon nanocoil 1 begins to grow up.

Because catalyst particles 18 begins to grow up at the minimization stage carbon nanocoil 1 that SEM can not see, so inerrably judging catalyst particles 18 of this minimization, present inventors become catalyst core 5, carbon nanocoil 1 is grown up.Therefore, catalyst core 5 is designated as catalyst core 5 (18) in (3C).

Present inventors in order to resolve the structure of matter of catalyst particles 18 shown in (3B), have carried out x-ray bombardment to the catalyst face, have been measured the intensity of diffracted ray by diffractometer and have carried out the parsing of powder X-ray ray.Its X ray intensity distributions confirms, and when measuring the angle of diffraction with 2 θ, has first intensity peak near 2 θ are approximately 39.6 °, has second intensity peak near about 46.3 °.This intensity distributions and known substances intensity data compare, and the structure of catalyst particles 18 is estimated as Fe substantially ₃InC _0.5Therefore, the composition formula of this catalyst is judged as Fe ₃InC _0.5

Fe ₃InC _0.5Be the carbon compound of FeIn, the catalyst film and the C that form by the FeInSn series catalysts ₂H ₂Gas carries out chemical reaction and is carbonized and becomes practical work.Also as can be known Sn as Fe ₃InC _0.5In foreign atom and exist.

So, carbide catalyst of the present invention is the carbide catalyst that is made of Fe, In, C at least, is at least by Fe in the composition formula _xIn _yC _zThe carbide catalyst of expression.Particularly, in the form that is limited, in the composition formula at least by Fe ₃InC _0.5The carbide catalyst of expression.

Consider that in addition carbide catalyst of the present invention is the carbide catalyst that is made of Fe, In, C, Sn at least as the Sn that adds element, composition formula is at least by Fe _xIn _yC _zSn _wRepresented carbide catalyst.Particularly, in the form that is limited, in the composition formula at least by Fe ₃InC _0.5Sn _wThe carbide catalyst of (w＞0) expression.Because the adding rate of Sn can be adjusted, so have the condition of w＞0.

In addition, illustrate in greater detail, the composition formula of the catalyst film 14 before being carbonized is Fe ₃InSn _0.1C _x, the containing ratio of Sn is 1/30 of Fe, is 1/10 of In simultaneously.Therefore thinking, also is the degree of only having added impurity level from initial from measuring Sn, becomes carbon compound and has Fe with impurity ₃InC _0.5In.From then on viewpoint is set out, this carbon compound, and souvenir is Fe when containing Sn ₃InC _0.5Sn _w(w＞0).Ratio of components w gets final product greatly than 0, adds according to the ratio of hope.

From the above fact as can be known, the genuine catalyst that carbon nanocoil 1 is grown up is the carbon compound that the FeInSn series catalysts is generated by the carbonization of carbon compound gas, i.e. Fe ₃InC _0.5Or Fe ₃InC _0.5Sn _w(w＞0).Therefore, these carbon compounds are referred to as carbide catalyst in the present invention, distinguish mutually with the FeInSn series catalysts.

The formation element of this carbide catalyst mostly is boron group element (3 family) and the carbon group element (4 family) as In, C, Sn, and the Sn under the carbon group element makes an addition in the catalyst with element as the growth of carbon nanocoil.Confirm in addition, Sn is added, and then carbon nanocoil is grown up to high-density, we can say that also Sn grows up to promote to use element.

From then on viewpoint is set out, and grows up to promote with element can utilize the carbon group element of Si, Fe etc., the boron group element of B, Al, Ga, Tl etc., the nitrogen group element of N, P, As, Sb, Bi etc. except that Sn.Also have, also boron group element and nitrogen group element can be made up, also can utilize the combination of the oxygen group elements (S, Se, Te, Po) of the alkali earths element (Be, Mg, Ca, Sr, Ba) of 2 families and 6 families.In addition, much less can also utilize having of other to grow up and promote active metallic element, nonmetalloid etc.

Fig. 4 is a process chart of making carbide catalyst first method.In (4A), formed the catalyst film 14 that constitutes by the FeInSn series catalysts on the surface of substrate 12.This FeInSn series catalysts gets final product if contain the film of the three elements of Fe, In, Sn at least.For example, during oxide, being made of the mixed oxide of Fe oxide, In oxide, Sn oxide, is that composition formula is Fe ₅InSn _0.1O _x, FeInSn _0.1O _xDeng oxide.Certainly, the alloy of compound in addition, FeInSn all can.

The thickness t of this catalyst film 14 is suitably in the scope of 10nm～number μ m, but does not limit this numerical value.The little diameter s that can reduce catalyst particles 18 described later of thickness t.Along arrow b direction circulation carbon compound gas, the surface of catalyst film 14 contacts therewith, begins to be carbonized by this carbon compound gas catalysis agent film 14.

In (4B), catalyst film 14 is carbonized, and generates the sub-film 16 of catalyst particles that catalyst particles 18 by carbon compound constitutes.The diameter s of catalyst particles 18 is along with carbonisation ground diminishes.Therefore, if in the suitable moment, the circulation of blocking-up carbon compound gas, then the diameter s of catalyst particles 18 just determines the size in the moment for this reason.

The reason that the diameter s of catalyst particles 18 changes is by following consideration.When catalyst film 14 was oxide catalyst, catalyst film 14 expanded in the process that absorbs the C atom, shrinks in the process of emitting the O atom, carries out particlized.Then catalyst particles 18 expands in the process that absorbs the C atom, shrinks in the process of emitting the O atom, because a large amount of O atoms is emitted particle diameter s and diminished successively.If stop heating constantly arbitrarily, providing of carbon compound gas is provided, the expansion of catalyst particles 18 is shunk and is stopped, and diameter s is also determined.

Fig. 5 is a process chart of making carbide catalyst second method.In (5A), formed the catalyst film 14 that constitutes by the FeInSn series catalysts on the surface of substrate 12.This catalyst film 14 forms the two-layer catalyst film of Fe film 14b on InSn series catalysts film 14a.In InSn series catalysts film 14a, be for example the mixed oxide film of In oxide and Sn oxide, i.e. ito thin film.To the surface of this catalyst film 14, press arrow b direction circulation carbon compound gas.

In (5B), generate the catalytic materials particle membrane 16 that constitutes by carbide catalyst particulate 18.Although be the catalyst film of two-layer, also same with (4b), carry out the carbonisation of carbon compound gas.Its result, catalyst film 14 is carbonized and is varied to carbide catalyst particulate 18.The diameter s of catalyst particles 18 diminishes with carbonisation, if stop the circulation of carbon compound gas in the suitable moment, the diameter s of catalyst particles 18 is just by this size decision constantly.

So because think reason that the diameter s of catalyst particles 18 changes and Fig. 4 is identical is omitted.Therefore, if stop heating constantly arbitrarily, stop to provide of carbon compound gas, the expansion of catalyst particles 18 is shunk and is stopped, and diameter s is also determined.

The other preparation method of the FeInSn series catalysts film 14 of Fig. 4 and Fig. 5 has vapor phase method, liquid phase method, solid phase method.In vapor phase method, can utilize physical vapor deposition (PVD method, Physical Vapor Deposition) and chemical vapor coating method (CVD method, Chemical VaporDeposition).The CVD method also is known as the chemical vapor deposition method.

As the PVD method, vacuum evaporation, electron beam evaporation plating, laser ablation (laser ablation), molecular beam epitaxy (MBE, molecular beam epitaxy), reactive evaporation, ion plating, ion beam, glow-discharge sputtering, ion beam sputtering, reactive sputtering etc. are arranged.In the MBE method, also can utilize the MOMBE that uses organic metal raw material (MO, Metal Organic) and chemical lines extension (CBE, chemical beam epitaxy), gas source extension (GSE, gas source epotaxy).

As the CVD method, hot CVD, organic metal CVD (MOCVD) RF plasma CVD, ECR plasma CVD, optical cvd, laser CVD, mercury sensitizing method etc. are arranged.

In liquid phase method, liquid phase epitaxy, plating, electroless plating, coating process are arranged.Also have in solid phase method, solid phase epitaxial, crystallisation, diagram extension, laser beam method, sol-gel process etc. are again arranged.

Fig. 6 is to use the process chart of the present invention ground third party's method of catalyst particles 18 of liquation manufactured carbon compound.This solwution method is characterized in that can making in a large number by the substrate method powder of catalyst particles 18.

In (6A), store solvent 22 in the container 20, in this solvent 22, add Fe compound and In compound and Sn compound.Mix agitating solution, then this compound mixed colloidalization equably in 3 forms countless colloidal ions 24 in solution.

In the process of colloidization, above-mentioned three kinds compound forms intermediate by physical reactions or chemical reaction, and this intermediate forms colloidal particle 24.By adjusting the interpolation concentration of compound, can freely control the particle diameter of colloidal particle 24.Superfluous colloidal particle 24 also can be deposited to the bottom of container 20 sometimes.

In (6B), colloidal particle 24 separates from solvent 22, is put in the heating container as solid constituent 27.This solid constituent 27 is burnt till in the oxygen atmosphere by heater 28, then generate the oxide microparticle 26 of FeInSn.By the particle diameter of colloidal particle 24 is controlled, can control the diameter of oxide microparticle 26.The particle diameter control of colloidal particle 24 for example can realize by regulating concentration and temperature.

In (6C), generate carbide catalyst particulate 18 from oxide microparticle 26.Firing furnace 29 is heated to suitable firing temperature by heater 36, drops into oxide microparticle 26 from blast tube 30 along arrow c direction.Import along arrow e from the mist of supply pipe 32 carbon compound gas and carrier gas.

In firing furnace 29, oxide microparticle 26 is carbonized the carbonization of compound gas.Firing temperature is preferably 300～1200 ℃, carbonization time be adjusted into from the several seconds by several 10 minutes.Carbonization time also can be adjusted according to the carbon compound gas concentration.Carrier gas and carbon compound gas are selected from the above-mentioned gas kind.

The carbide catalyst particulate 18 that generates by burning till falls, and piles up in the bottom of firing furnace 29.Reacted gas is discharged from discharge pipe 34 along arrow f direction.So, shown in (6D), manufacture Fe ₃InC _0.5Or Fe ₃InC _0.5Sn _xThe carbide catalyst particulate 18 of (x＞0) etc.

The diameter s of this carbide catalyst particulate 18 exists with ... the particle diameter of colloidal particle 24, is adjusted at the scope of 1nm～100 μ m.S is more little for diameter, and the pipe diameter d of carbon nanocoil 1 also diminishes, and can make small-sized carbon nanocoil 1.

As employed Fe compound, In compound, Sn compound in the method, use be known inorganic compound organic compound.Iron chloride, ferric sulfate, ferric nitrate, ferric bromide, carbonyl iron, inidum chloride, indium sulfate, indium nitrate, carbonic acid indium, Indium Tris acetylacetonate, stannic chloride, artificial gold, nitric acid tin, carbonic acid tin etc. are for example arranged.Also can use this known all cpds in addition.Particularly, use organic compound, be removed fully by burning, can make pure FeInSn carbide catalyst by burning till organic matter.

Can form the mixed solution of Fe compound and In compound, or the mixed solution of Fe compound and In compound and Sn compound, the growth that also can add other promotes to use the compound of element.The concentration of the total metal ion in the solution is not particularly limited, if the concentration that reaction is carried out smoothly gets final product.Usually can be made as 0.01～50 quality %, be preferably 0.1～20 quality %.

As described below from the concrete operation that solution is formed into till burning till.For example, be modulated into the alkaline mixed aqueous solution of molysite, indium salt, pink salt after, the separating solids material carries out drying to this solid matter, pulverizes according to necessity, and is final by burning till the carbon compound particulate 18 that manufactures carbonization.Also have, the organic compound of iron, indium, tin is disperseed in solvent,, form the predecessor of FeInSn based compound by the chemical reaction of water decomposition reaction etc.To this predecessor separate, dry, pulverize according to necessity, finally burn till carbonization and manufacture the carbon compound particulate.

Can all utilize known separation method from the separation of the solid constituent of solution.Drying is usually in room temperature～300 ℃, and the scope that is preferably 50～200 ℃ is carried out, and pulverizing can be adopted known inorganic substances breaking method.

By the oxide microparticle 26 of solwution method gained, common 10～99.99 (mol%) of the ratio of components of iron/indium (mol%) are preferably 20～99 (mol%).The ratio of components of tin/indium is 0～30 (mol%), is preferably 0.1～10 (mol%).The diameter s of the final carbide catalyst particulate 18 that generates is 1nm～100 μ m, exists with ... the solution parameter in colloidal particle footpath etc.

As other manufacture method of carbide catalyst, can utilize sputtering method.At least the target that contains Fe, In carries out sputter by ion flies out the target particulate.This target particulate carburet thing gas haptoreaction and being carbonized under heated condition manufactures the carbide catalyst of the element that contains Fe, In, C at least.By the Sn as other elements is added in the target, can manufacture the carbide catalyst of the element that contains Fe, In, C, Sn at least.

As the manufacture method of other other of carbide catalyst, can utilize gas-phase reaction method.In the reactive tank under the heated condition, make Fe chemical compound gas and In chemical compound gas carburet thing gas haptoreaction carry out carbonization at least again, manufacture the particulate of the carbide catalyst of the element that contains Fe, In, C at least.In gas-phase reaction method, can utilize known gas-phase reaction technology.If the Sn chemical compound gas as other elemental gas is added, then can make the carbide catalyst of the element that contains Fe, In, C, Sn at least.

Then, the manufacture method to the carbon nanocoil of use carbide catalyst of the present invention describes.First basic principle of the manufacture method of this carbon nanocoil, make the carbide catalyst carburet thing gas contact of the element that contains Fe, In, C, Sn at least, carbide catalyst decomposes above-mentioned carbon compound gas thus under heated condition, and carbon nanocoil is grown up.Thereby only have by carbon compound gas is contacted under heated condition with carbide catalyst, can produce the advantage of carbon nanocoil in a large number.If with the particulate of carbide catalyst, can carry out the size Control of carbon nanocoil.

Second basic principle is 2 stage manufacture methods.In first operation, make the catalyst precarsor material carburet thing gas contact under heated condition that contains Fe, In at least, form the carbide catalyst that contains Fe, In, C at least.Then this first operation in second operation, makes carbon compound gas decompose under heated condition by carbide catalyst carbon nanocoil is grown up.First operation and second operation are carried out continuously, and the catalyst precarsor material is varied to carbide catalyst, and then the growth of carbon nanocoil begins.The material that sets out is the catalyst precarsor material, and this point is different with described first basic principle.Below, concrete carbon nanocoils circle manufacturing method is described.

In first basic principle, use other the carbide catalyst of element S n added as beyond Fe, In, the C, then carbon nanocoil can be grown up expeditiously.Also have, in second basic principle, also added other element S n, carbon nanocoil is grown up as the catalyst precarsor material.

Fig. 7 is to use the process chart of first autofrettage of carbide catalyst particulate 18 ground carbon nanocoils 1.In (7A), coating carbide catalyst particulate 18 forms the sub-film 16 of catalyst particles on substrate 12.This substrate 12 being heated to proper temperature on one side makes carbon compound gas and carrier gas circulate to arrow b direction jointly on one side.

In (7B), carbide catalyst particulate 18 becomes catalyst core 5, and countless carbon nanocoils 1 are grown up on substrate 12.After carbon nanocoil 1 is grown up, carbon nanocoil 1 is scraped from substrate 12 by scraper plate, reclaim carbon nanocoil 1.

Fig. 8 is from the enclose the land process chart of second autofrettage of the carbon nanocoils of FeInSn series catalysts film 14s.In (8A), on substrate, form FeInSn series catalysts film 14.When this substrate 12 is heated to proper temperature, carbon compound and carrier gas are together circulated towards arrow b direction.

In (8B), make 14 carbonizations of FeInSn series catalysts film by carbon compound gas, form catalyst particles 18 of carbon compound, catalyst particles 18 forms on substrate 12.From FeInSn series catalysts film 14 carbonisations, from taking place the several seconds to several 10 minutes to catalyst particles 18.This carbonization time exists with ... flow and the concentration and the heating-up temperature of carbon compound gas.

In (8C), the formation of the sub-film 16 of catalyst particles is continuous, makes carbon compound gas press the circulation of arrow b direction, and then by the sub-film 18 of catalyst particles, countless carbon nanocoils 1 is grown up on substrate 12.Illustrated is the catalyst core 5 that catalyst particles 18 becomes carbon nanocoil 1.

Fig. 9 is the diagrammatic illustration figure that carbide catalyst particulate 18 is swum make third party's method (autofrettage flows) of carbon nanocoil 1.This carbon nanocoil manufacturing installation 2 is provided with heater 6 in the periphery of reactive tank 4, and reative cell 8 is marked.At the left end of reactive tank 4, be provided with spray nozzle 40.

Carbon compound gas and carrier gas circulate to arrow a direction together.In this carbon compound gas, spray the powder that constitutes by carbide catalyst particulate 18 to arrow h direction from spray nozzle 40.Catalyst particles 18 that spreads in the space becomes catalyst core 5, and carbon nanocoil 1 is grown up.Along with flowing of carrier gas, catalyst particles 18 flows, and in this flow process, carbon nanocoil 1 is grown up, and reclaims carbon nanocoil 1 by not shown retracting device.

Figure 10 is the diagrammatic illustration figure that makes the cubic method (autofrettage flows) of carbon nanocoil 1 from oxide microparticle 26 formation catalyst particles 18 that are atomized.Because this carbon nanocoil manufacturing installation 2 is identical with Fig. 9, so only difference is described.Reative cell 8 is formed field Y and is constituted by child field X and the carbon nanocoil of forming of catalyst particles, is used to heat the heater 6 in two fields, compares with Fig. 9 and disposes longlyer.

Carbon compound gas and carrier gas circulate to arrow a direction together.In this carbon compound gas, from spray nozzle 40 ejection oxide microparticles 26.This oxide microparticle 26 is carbonized the carbonization of compound gas at the sub-formation of catalyst particles field X, forms carbon compound particulate 18.

This carbide catalyst particulate 18 forms field Y at carbon nanocoil and moves with floating state.In the Y of this field, carbide catalyst particulate 18 becomes catalyst core 5, and carbon compound coil 1 is grown up.Along with flowing of carrier gas, catalyst particles 18 flows, and in this flow process, carbon nanocoil 1 is grown up, and reclaims carbon nanocoil 1 by not shown retracting device

Outside aforesaid substrate method and flow method, also utilized paddling process as the manufacture method of carbon nanocoil.In the method, the particulate of carbide catalyst is piled up in reactive tank, decompose carbon compound gas while stir catalyst particles of this accumulation, carbon nanocoil is grown up under stirring.

More specifically describe in addition, promptly for example making the carbide catalyst particulate get powder piles up in converter, while making the carbon compound gas communication rotate converter, then catalyst fines becomes stirring, can make catalyst particles produce carbon nanocoil in a large number as catalyst core.As stirring means, can adopt spinning solution, method for oscillating, other known method.

[embodiment 1: from the manufacturing of the carbon nanocoil of FeInSn sull]

Forming thickness on (001) of Si substrate face is the FeInSn sull of 200nm.By carbon nanocoil manufacturing installation shown in Figure 2, be that starting catalyst is made carbon nanocoil at about 700 ℃ with this sull.C with 60sccm ₂H ₂Gas uses as the carbon compound gas of unstrpped gas, and the He gas of 200sccm uses as carrier gas.

Make gas communication, after 1 second, after 5 seconds, after 10 seconds, after 1 minute, take out substrate after 5 minutes and after 30 minutes, by the state of scanning electron-microscopic observation substrate surface.From the state of each substrate surface, confirm the length that becomes of the variation of FeInSn sull and carbon nanocoil.

Figure 11 is the SEM picture with the FeInSn sull of 50,000 times of shootings.FeInSn sull particlized after one second as can be known, particlized is finished substantially after 5 seconds and after 10 seconds.This particle is the carbide catalyst particulate that the FeInSn sull is carbonized formation.Shape of particle is mixed the different shape there is spherical, diamond shaped etc.

Catalyst particles after one second, with 5 seconds after and 10 seconds after catalyst particles to compare size big, its reason has been carried out following consideration.Grow up by 1 second CVD, from C ₂H ₂The C that decomposes is absorbed in the catalyst, by the atomic volumetric expansion of this absorbing catalyst.Think, emit O and shrink the smaller volume of catalyst particles thereafter.This process is carried out repeatedly, and the size of catalyst particles is shunk till carbonization finishes simultaneously, and downsizing stops to certain size.

After about 1 minute, be catalyst core with above-mentioned carbide catalyst particulate, carbon nanocoil begins to grow up.And observe, the carbon nanocoil that size is little after a minute is grown up, and the carbon nanocoil that then size was big in 5 minutes is grown up.In addition, through 30 minutes, confirm the long long carbon nanocoil of coil and grow up.

Figure 12 is the powder x-ray diffraction intensity map of catalyst particles after 10 seconds.Whether catalyst particles is that carbon compound passes through powder X-ray ray parsing decision.The intensity distributions of upper is the track profile (line profile) of the diffracted intensity of actual measurement.Represent the angle of diffraction with 2 θ, then near 39.6 °, have first intensity peak, near 46.3 °, have second intensity peak.Near 39.6 °, be called near about 40 °.Also have, strength ratio is first intensity peak: second intensity peak=7.0: 2.7.

Under above-mentioned track profile, drawing the intensity map of known substance.7 kinds known substance is Fe ₃C, C (graphite), Fe ₂O ₃, In ₂O ₃, Fe ₇C ₃, FeC and Fe ₃InC _0.5Can learn that the most consistent with track profile is the Fe of hypomere ₃InC _0.5That is the Fe that has only of first peak value of track profile and second peak value, can be described ₃InC _0.5Also has Fe ₃InC _0.5Strength ratio, first intensity peak: second intensity peak=7.0: 2.7.Consider the error of strength detection, it is that composition formula is Fe that catalyst particles is judged as ₃InC _0.5Material.

[embodiment 2: by the C of 1sccm ₂H ₂The atomic formation of carbide catalyst that produces]

In embodiment 1, because with the supply raw materials C of gas of 60sccm ₂H ₂Gas, the atomic growth rate of carbide catalyst is too fast.Therefore, discussed with 1sccm C is provided ₂H ₂Gas is by Fe ₃InC _0.5How first intensity peak of the diffracted intensity that produces is passed through in time and is increased.

C ₂H ₂Gas setting is 1sccm, and He is set at 50sscm, and heating-up temperature is 700 ℃.Form with the substrate of the identical FeInSn sull of Figure 12 and be located at reative cell.This substrate is continued to carry out x-ray bombardment, measure in time diffracted intensity through near resulting 2 θ of first peak value=39.6 ° (about 40 °).

Figure 13 is that 2 θ are the time course figure of first peak value of the diffracted intensity of 39.6 ° (being approximately 40 °).The movement of this first peak value demonstrates Fe ₃InC _0.5The process of growing up.Also it by the effluxion of first peak value, can observe the growth rate of catalyst particles.

As can be seen from Figure 13, from making C ₂H ₂Behind the gas to 125 second, first peak value is projection sharply, reaches maximum after 135 seconds substantially.In this stage, stop to supply with C ₂H ₂Gas stops the increase of first peak value.Between about 10 seconds, form as can be known by Fe ₃InC _0.5The carbide catalyst particulate that constitutes.

[embodiment 3:Fe ₃InC _0.5The particle diameter control of catalyst particles]

For Fe ₃InC _0.5Particle diameter (diameter s) control of catalyst particles, can be varied to elongate member.In this embodiment 2, can be with the growth temperature, promptly the heating-up temperature of substrate (temperature of reative cell) is varied to 650 ℃ and 700 ℃, forms the carbide catalyst particulate, uses this carbide catalyst particulate that carbon nanocoil is grown up.

C ₂H ₂Gas setting is 1sccm, and He is set at 50sscm, and heating-up temperature is 650 ℃ and 700 ℃.Forming with Figure 12 identically, is that the substrate of starting catalyst is located at reative cell with the FeInSn sull.On this substrate, make Fe ₃InC _0.5Catalyst particles grow up, utilize this substrate that carbon nanocoil is grown up.

Figure 14 is the scanning electron microscope picture of 650 ℃ the carbide catalyst particulate carbon nanocoil of growing up.Also have, Figure 15 is the scanning electron microscope picture of 700 ℃ the carbide catalyst particulate carbon nanocoil of growing up.

From Figure 14 and Figure 15 more as can be known, at the atomic diameter s of the carbide catalyst of 650 ℃ of formation, compare little with 700 ℃.That is, confirm in that the more atomic diameter of the formed carbide catalyst of low temperature is little.Therefore, by the temperature of reacting condition chamber, can freely change control carbide catalyst particulate.

Also have, atomic diameter s is little for carbide catalyst, should be able to the little carbon nanocoil of manufacturing dimension.Figure 14 and Figure 15 being compared, can learn 650 ℃ catalyst, can be that the little carbon nanocoil of size is grown up.Confirm that thus atomic diameter s is little for carbide catalyst, can the little carbon nanocoil of manufacturing dimension.

[2] explanation of the carbide catalyst of (transition metal, Sn, C)

In this second joint, enumerate as the typical example of transition metal with Fe, describe as an example of the carbide catalyst of (transition metal, Sn, C) with (Fe, Sn, C).As substituting of Fe, use the transition metal of Co or Ni etc. also can obtain identical result.

[the atomic CNC of the carbide catalyst of embodiment 4:Fe-Sn-C grows up]

At first, make (Fe, Sn, C) catalyst.The details of carbide catalyst, only describes different piece so avoid repetition herein because be illustrated in first segment.At first, mix the iron chloride of concentration of 0.1mol/l and the aqueous solution of stannic chloride with 3: 0.1 ratio.In the mixed aqueous solution, splash into the aqueous ammonium of the concentration of 0.3mol/l in right amount once more, modulate the mixed sediment of the hydroxide of iron and tin by neutralization reaction.By this mixed sediment is carried out burning till in 2 hours synthetic (Fe, Sn, C) oxide catalyst at 400 ℃.

Use this fine catalyst, carry out CVD with 700 ℃ of growth temperature, helium 250sccm, acetylene 10sscm, the long-time 30 minutes condition of one-tenth.Its result, carbon nanocoil is grown up on catalyst.Figure (16A) is the electron microscopic mirror image of the dialogue machine of carbon nanocoil growth.Therefore as can be known, from the oxide catalyst of (Fe, Sn, O), carbon nanocoil is grown up.

In the stage of growth, whether be varied to other catalyst in order to confirm (Fe, Sn, O) oxide catalyst, Yi Bian carry out CVD, Yi Bian measured the X-ray diffraction lattice of (Fe, Sn, O) catalyst.The CVD condition of this moment is the growth temperature: 700 ℃, helium 50sccm, acetylene 1sscm.

Figure (16B) is that acetylene gas is introduced the X-ray diffraction brilliant map grid of reacting furnace through (Fe, Sn, the O) catalyst after 3 minutes.Remove cementite Fe ₃C, iron oxide FeO also can see near the Fe that has first peak value (peak-peak) 2 θ=40 ° ₃The peak value of SnC.This peak value is the peak value of can't see in the process that carbon nanocoil is grown up by iron catalyst.Therefore think that (Fe, Sn, C) oxide catalyst is in developmental process, changing becomes Fe ₃The oxide catalyst of SnC.

In addition, in the metal chloride aqueous solution 200ml of the concentration of iron chloride 0.03mol/l, stannic chloride 0.01mol/l, make magnesium oxide powder 4g reaction, make the complex hydroxide precipitation of Fe and Sn.This sediment is overanxious, clean, dry, obtain complex hydroxide or the oxide powder of Fe and Sn and Mg.Use rotation CVD reacting furnace to make this fine catalyst 2g carbonization,

The condition of carbonization is 675 ℃ of growth temperature, helium 400sccm, acetylene 60sscm, stove rotation number 1rpm, carbonization time 10 minutes.After this, the hydrochloric acid with concentration 17.5% removes metals such as detin, clean overanxious formation carbide catalyst.Figure (17A) is the X ray color crystal lattice pattern that generates.Confirming in 2 θ=about 40 ° position and first peak value occurs, is Fe ₃SnC.

Also have, this fine catalyst 0.1g is disperseed in the acetone of 5ml after, on the Si substrate, launch, use small-sized stove, carry out 700 ℃, 10 minutes the CVD of acetylene 60sscm, helium 200sccm.Observe product with SEM, its result is expression in figure (17B).Carbon nanocoil is being grown up as can be known.So, confirmed that from Figure 16 and Figure 17 the carbide catalyst of (Fe, Sn, C) is effective carbon nanocoil catalyst for producing.

[3] explanation of metallic catalyst

In this 3rd joint, (transition metal, Al, Sn) catalyst, (transition metal, Cr, Sn) catalyst and (Fe, In, Sn) catalyst are described.These catalyst are metallic catalysts, rather than carbide catalyst.Transition metal can be selected suitable transition metal according to purpose as mentioned above.Following, be an example of the representative of transition metal with Fe, be elaborated.

Present inventors have carried out studying with keen determination to a large amount of synthetic of carbon nanocoil, have discussed based on the mixed catalyst of meaning through the iron indium tin system of exploitation, can create the catalyst material that makes new advances by add what element in the base material of iron tin is formed.Also carried out the discussion of the ratio of components of 3 kinds of metallic elements in the above-mentioned catalyst best in the growth of carbon nanocoil.

In embodiment, based on experimental result, the concrete example to the carbon nanocoil catalyst for producing of the 3 compositions system of three kinds of elements of interpolation indium In, aluminium Al, chromium Cr in iron tin system forms carries out following explanation.

[embodiment 5: by the manufacturing of the CNC of Fe-In-Sn, Fe-Al-Sn and Fe-Cr-Sn]

(making with extra care of mixed catalyst)

By being that the mixed catalyst and the siderochrome tin of mixed catalyst, iron aluminium tin system is that the mixed catalyst precipitation is made with extra care with iron indium tin.For example, iron indium tin is the situation of mixed catalyst, will change iron FeCl ₃, inidum chloride InCl ₃And stannic chloride SnCl ₃In water, dissolve identical (for example, aqueous solution 0.1mol/l) of the concentration of making Fe ion, In ion, Sn ion.Then, mix these aqueous solution, make the mixed aqueous solution of 3 metal ion species with suitable ratio.In this mixed aqueous solution, add alkaline solution (for example, ammonium carbonate (NH ₄) ₂CO ₃The aqueous solution) neutralization, the metal ingredient in the reduction of dissolved liquid is separated out it.By this reduction, separating metal hydroxide, that is, and Fe (OH) ₃, In (OH) ₃And Sn (OH) ₃, be deposited in the bottom of solution container as sediment.This sediment is the mixture of above-mentioned metal hydroxides aggegation, reclaims sediment by the overanxious processing of solution.Burn till at 400 ℃ by the sediment that will reclaim, can access oxide catalyst Fe-In-Sn-O.Equally, the situation of the mixed catalyst of iron aluminium tin system is made the aluminum nitrate Al (NO of 0.1mol/l ₃) ₃, iron chloride FeCl ₃, stannic chloride SnCl ₃The aqueous solution, mix these aqueous solution with suitable ratio, make mixed aqueous solution, use ammonium carbonate solution to make the catalyst component precipitation, to its recovery, burn till, obtain Fe-Al-Sn-O.Also having, is under the situation of mixed catalyst at siderochrome tin, makes the aluminum nitrate Cr (NO of 0.1mol/l ₃) ₃, iron chloride FeCl ₃, stannic chloride SnCl ₃The aqueous solution, mix these aqueous solution with suitable ratio, make mixed aqueous solution, use ammonium carbonate solution to make the catalyst component precipitation, to its recovery, burn till, obtain Fe-Cr-Sn-O.In addition, by changing each nitrate compound and the muriatic mixing ratio (mol ratio) of raw material, the refining slightly different mixture catalyzer of multiple ratio of components provides to following carbon nanocoil generation experiment use.

(by the generation of the carbon nanocoil of CVD method)

To using three kinds of above-mentioned mixed catalysts, the generation experiment of the carbon nanocoil of Fe-In-Sn-O, Fe-Al-Sn-O, Fe-Cr-Sn-O (below, carbon nanocoil is called CNC) describes.

In the manufacturing of CNC, use the CVD method of carbon-containing compound gas.In the present invention, as carbon compound, can utilize various alkanes, alkene, alkyne, aromatic series hydrocarbon etc. from methane, ethane, wherein acetylene, propine, benzene etc. are effective, and particularly acetylene is efficient.Also have, heating-up temperature is effective more than the temperature of carbon compound by catalyst action two boundary.The heat decomposition temperature of acetylene is approximately 400 degree, but be to use the synthesis temperature of the CNC of acetylene be about 600～about 800 ℃ suitable.But synthesis temperature is not limited thereto temperature, if more than the catalyst decomposes temperature of carbon compound, can freely set according to synthetic effect.

Figure 18 is the summary construction diagram of the major part of the employed manufacturing installation of embodiments of the present invention.This manufacturing installation 101 is the flow reactors (flow reactor) that place under the atmospheric pressure, and reative cell is surrounded by the quartz ampoule 103 of diameter 30mm, length 700mm.In the periphery of the central portion of quartz ampoule 103 are tubular heaters 104 by long 450mm, in the central authorities of reative cell 102, are set at the isothermal field 105 of the about 250mm of length.In this isothermal field 105, be provided with the substrate (quartz or silicon) 107 that has carried the catalyst of making by the precipitation method 106.

In the manufacturing installation of the carbon nanocoil (CNC) of above-mentioned formation, at first, the flow with 200sccm in quartz ampoule 103 is filled helium, and the programming rate of the catalyst on the substrate 107 106 with 20 ℃ of per minutes is heated to till 700 ℃.This helium is in order to prevent in reative cell that metal is oxidized and import.After arriving 700 ℃, provide acetylene gas with the flow of 60sccm, the full flow of the mist of helium and acetylene is adjusted to 260sccm.Reaction time is set at about 30 minutes, stops acetylene thereafter and only makes helium flow moving, makes in this helium atmosphere the cool to room temperature lentamente of the catalyst 106 on the substrate 107.A large amount of carbon nanocoils 108 (being also referred to as CNC) generate on the catalyst 106.

Reacted catalyst is analyzed by sweep electron microscope (SEM S-4500 Hitachi) and the attached energy-dispersive X-ray analysis (EDX) device (EDX) of SEM.SEM picture shown below in the present embodiment all is the multiplying power more than 10000 times.Figure 19 is by the ratio of components Fe that establishes catalyst: In: Sn, Fe: Al: Sn and Fe: Cr: Sn is the SEM picture of the one-tenth biology that forms of 3: 0.3: 0.1 o'clock manufacturing installation 1.(19a) and (20b) Fe-In-Sn-O catalyst, (19b) and (20a) existence of the CNC when Fe-Al-Sn-O catalyst, (19c) expression use Fe-Cr-Sn-O catalyst are used in expression are used in expression.(19d), use the situation of the Fe-Sn-O catalyst that has only iron and tin that does not contain In, Al, Cr for relatively.From these SEM pictures, judge from the accumulating amount of carbon atom and the growing amount of coil, infer that the generation aluminium of coil is 95%, use manufacturing installation 101 to demonstrate high efficiency by the method for making of these catalyst.

As described below in the generation result set of various catalyst CNC by using Figure 19 and Figure 20.When replacing In use Cr, with the situation comparison of In, can not see coil substantially, coil footpath and caliber also become big.This is considered to Cr and mixes in cementite, and the stable effect of the cementite of making is arranged.It is inferred as and CVD after the SEM picture relatively, by mixed C r in the Fe-Sn-O catalyst, separate out effectively in order not make graphite (carbon fiber material), compare the product that can not form tubulose and coiled type with other catalyst.On the other hand, compare when replacing In and using Al and when using the Fe-Sn-O catalyst, the quantity of the product of web-like increases.Compare with the product by the Fe-In-Sn-O catalyst, in the Fe-Al-Sn-O catalyst, can not see the narrow coil of joint square (pitch) of the bigger coil in coil footpath that can be seen by the Fe-In-Sn-O catalyst, directly little dual spiral helicine product is more.This is inclined to as can be seen from Figure 20, and (Fe: In or Al: Sn=3: 1: 0.1) was more remarkable when the ratio of the relative Fe of In and Al was big.

Can not see the reason of the coil that coil footpath big joint square when using the Fe-Al-Sn-O catalyst is narrow, deduction is because coil generates the size of the catalyst particle of " kind ", compares during with use In to diminish.Therefore think that In has makes catalyst particle become big tendency, it is suppressed when using Al.(the parsing experiment that the best of In, Al, Cr is formed)

Generate experimental result from Figure 19 and CNC shown in Figure 20, clear and definite Al and Cr are the effective catalyst elements that is equivalent to In, according to the various ratio of components of forming for the optimum catalyst of seeking out these elements, carried out using the CNC of manufacturing installation 101 to generate experiment.

Carried out being used to investigate the only experiment of effective ratio of components of the mixed catalyst Fe-Sn-O of iron and tin.At Fe _x-Sn _yIn the constitutive molar ratio of-O, divide into x=3, in all compositions of conversion y value, investigated CNC and generated state in the pro rate of (x, y).Figure 21 is one one the SEM picture that this CNC generates result of the test.(21a) be Fe: Sn=3: 0.05, (21c) is for Fe: Sn=3: 0.1, (21e) is Fe: Sn=3: the situation of 1 ratio of components, (21b), (21d), (21f) be respectively 30,000 times the expansion picture of (21a), (21c), (21e).Also have, at Fe _x-In _y-Sn _zIn the constitutive molar ratio of-O, carried out fixedly Fe: In=3: 1 carries out the experiment of various variations with the ratio of components of Sn.Figure 22 is the SEM picture that CNC generates result of the test.(22a)～(22h) be to have fixed Fe: In=3: 1 ratio of components of establishing Sn is 0,0.03,0.1,0.15,0.3,0.5,1,3 situation.Draw following result according to this experiment, at Fe _x-Sn _yIn the constitutive molar ratio of-O, when the pro rate of (x, y) is divided into x=3, be necessary to make y≤3, what formation efficiency was best in addition is 0＜y≤0.15.

According to the result of the relativeness in the ratio of components of the iron of the catalyst of above-mentioned only iron and tin and tin, carried out seeking the experiment that the best of In, Al, Cr is formed.Specifically, utilize above-mentioned Fe _x-Sn _yThe result of the test of the best ratio of components of-O, with Fe: In=3: 0.1 serves as to form fixed information.At first, carried out for Fe _x-In _y-Sn _zThe iron tin that the catalyst of-O is formed, the CNC that is used to investigate the relativeness of indium generates experiment.That is fixing Fe: In=3: 0.1 carries out the experiment of various variations with the composition of In.Figure 23 is one one the SEM picture that these CNC generates experimental result.(23a)～(23g) be to have fixed Fe: In=3: 0.1 ratio of components of establishing In is 0,0.05,0.1,0.3,1,3,9 situation.According to this experiment, when In divided into x=3, z=0.1 for the pro rate of (x, y, z), y=9 became the limit of formation efficiency, the most effective 0.3＜y≤1 that consists of.Can obtain from these SEM pictures that coil footpath is big, the narrow product of coil joint square.

Then carried out for Fe _x-Al _y-Sn _zThe iron tin that the catalyst of-O is formed, the CNC that is used to investigate the relativeness of aluminium generates experiment.Figure 24 is one one the SEM picture that this CNC generates result of the test.(24a), (24c), (24e) are fixing Fe: Sn=3: 0.1 ratio of components of establishing Al is 0.3,1,9 situation.(24b), (24d), (24e) are respectively 50,000 times the expansion pictures of (24a), (24c), (24e).According to this experiment, when the pro rate of (x, y, z) is divided into x=3, z=0.1, surpass then formation efficiency reduction of y=1, then can not see the coiled type product during y=9.From these SEM pictures as can be known, Al is at Fe _x-Al _y-Sn _zAmong-the O, when containing Al, the spiral that generates thin web-like installs coil.

Also have, carried out for Fe _x-Cr _y-Sn _zThe iron tin that the catalyst of-O is formed, the CNC that is used to investigate the relativeness of chromium generates experiment.Figure 25 and Figure 26 are one one the SEM pictures that this CNC generates result of the test.(25a) be fixing Fe: Sn=3: 0.1 ratio of components of establishing Cr is 0.3,1 situation.It (25b) is the enlarged drawing of (25a).Figure 26 is 30000 times a SEM picture.According to this experiment, Cr is at Fe _x-Cr _y-Sn _zAmong-the O, when the pro rate of (x, y, z) is divided into x=3, z=0.1, among the y=1, can see growth at a part of coil of catalyst.From these SEM pictures as can be known, when containing Cr, the coil of establishing the then thick web-like of y=0.3 forms, and establishes y=1 and then saves the narrow coil formation of square.

[4] take on the explanation of the porous carrier catalyst of catalyst

At last, use above-mentioned carbide catalyst, metallic catalyst, oxide catalyst, the method for more effectively making carbon nanocoil is described.That is, these catalyst are taken on for having the porous carrier of countless pores, taken on this that porous of catalyst carrier is arranged is the carbon nanocoil catalyst for producing.

Present inventors, in order to make carbon nanocoil efficiently, draw the conclusion of the important role of two or more metallic elements, not only in order to generate carbon nanocoil efficiently, and for the overall diameter homogeneous of the big or small same carbon nanocoil that makes its line footpath, and the manufacture method of thinkable carbon nanocoil.That is, proposed to make metallic compound take on the catalyst base of porous carrier, made the method for carbon nanocoil.

[embodiment 6: the CNC that is taken on catalyst by zeolite grows up]

In the used porous monomer of the present invention, can utilize various porous materials.For example, zeolite, ALPO (phosphate of aluminium), SAPO (silicoaluminophosphate), resin sorbent, porous ceramics, molecular sieve (molecular sieve), burning system porous body, silicon porous body or carbon are porous body etc.Also can use this known porous material in addition etc.Particularly, even burning till the zeolite that also has stable structure, high temperature is suitable for the present invention most.In an embodiment of the present invention, use is y-type zeolite.

Figure 27 is the crystal structure figure of y-type zeolite.So-called zeolite is the general name of the nitrate of crystalline porous matter aluminium, by having tetrahedron structure (SiO ₄) ^4-And (AlO ₄) ^5-The base unit ternary ground be combined into that constitutes.Ratio of components is SiO ₂: 99.6wt%, Al ₂O ₃: 0.4wt%, Na ₂O＜0.01wt%, common zeolite has a large amount of pores, and its fine pore has the roughly value of homogeneous, so can be used in the molecular screening of selecting molecular size.

As the used catalyst of the present invention, can use the multielement series catalysts of FeInSn series catalysts, FeAlSn series catalysts, FeCrSn series catalysts, FeSn series catalysts, CoSn series catalysts or NiSn series catalysts etc.As the Fe series catalysts, be the metallic compound that contains Fe, be ferriferous oxide, ferric organic compounds etc.For example, as ferric organic compounds, ferric carbonate, carbonyl (carbonyl) iron, carbonyl iron inductor, nitrous acid iron, nitrous acid inductor etc. are arranged.

As the In series catalysts, be the metallic compound that contains indium, i.e. indium oxide, indium organic compound etc.For example, as the indium organic compound, trimethyl (trimethyl) indium, triphenyl (triphenyl) indium, octyl group acid indium, carbonic acid indium etc. are arranged, as the Sn series catalysts, tin-oxide, tin organic compound, for example triethyl group (triethyl) tin, tin trimethyl, tetraphenyl (tetrapheny) tin, octyl group acid tin, carbonic acid tin etc. are arranged.As Co and Ni series catalysts, be the metallic compound that contains Co and Ni, metallo-organic compound.For example, cobalt compound, carbonyl cobalt, nickel compound, carbonyl nickel with and complex.In these metallo-organic compounds, particularly the soluble metal organic compound is useful in organic solvent.In metallic elements such as Al and Cr, also can utilize metallic compound same as described above.Metallo-organic compound.

In the porous carrier of zeolite etc., make in the method that the metallic compound that contains above-mentioned multiple metallic element takes on, liquid phase method and vapor phase method etc. are arranged.The situation of liquid phase method is dissolved multiple metallic compound in solvent, porous carrier dipping adheres to solvent in this solvent.Make its method of adhering to, there is no particular limitation, can use the several different methods by the simple natural sorption etc. of dipping.For example, in the porous carrier of ion exchangeable, the inorganic salts of above-mentioned metallic element and organic salt carry out ion-exchange, can sorption in the porous carrier.Also have, in the porous carrier of nonionic exchangeability, can pass through the nature sorption.In order to carry out sorption efficiently, can carry out agitating solution, ultrasonic wave is handled, and is handled by homogenizer and atomizer.The porous carrier of sorption solvent is burnt till after the air dry, forms the catalyst that is made of multiple metallic element and takes on body.Firing temperature is 400～700 ℃, firing time be about 1 hour for suitable.Burn till in the oxidation atmosphere, then organic compound combustion disappears, and metallic compound is varied to metal oxide.In the burning till in non-oxide atmosphere, organic matter is removed in pore to metal variation etc., and multiple metal object etc. generates in pore.

As the used organic solvent of the present invention, acetone, toluene, ethanol etc. are arranged.It is useful particularly making the organic solvent of the organic compound dissolving of the metallic element that contains Fe, In, Sn, Co, Ni, Al, Cr etc.

By the situation of vapor phase method, the metal compound gas that will contain above-mentioned multiple metallic element imports in the process chamber porous carrier of the zeolite of sorption in placing process chamber etc.Porous carrier to the above-mentioned metal compound gas of sorption carries out burning till after the air dry, forms the catalyst that is made of multiple metallic element and takes on body.As metal compound gas, the mist that has the inorganic matter that contains above-mentioned metallic element and organic matter to constitute.For example, can utilize the gas of the inorganic salts, organic salt etc. of above-mentioned metallic element.Make this mist sorption by vapor phase method, the physical condition of suitably adjusting in the process chamber can easily make its sorption.Particularly, pressurization, heating etc. are effective.

Then, the catalyst that uses load to hold the zeolite etc. of catalyst being taken on the method that body generates carbon nanocoil describes.At first, the above-mentioned catalyst of configuration is taken on body in reactor, Yi Bian make the inert carrier gas circulation of nitrogen, helium, argon etc., Yi Bian reactor is heated to set point of temperature.After arriving set point of temperature, make the gas communication that contains carbon jointly with above-mentioned carrier gas.The flow that contains the gas of carbon is preferably catalyst 1g, 100～1000cm ³, but can carry out suitable adjustment.Currency of gas of containing carbon is according to employed gas and difference, but for example about 5～100 minutes, this reaction time also can freely be adjusted.As the gas that contains carbon that is imported, can utilize methane, ethane, various alkane, alkene, alkyne, aromatic series hydrocarbon etc., particularly acetylene, propine, benzene etc. are effective, and wherein acetylene be the high effect that reclaims.

Make the above-mentioned heating-up temperature that contains the gas thermal decomposition of carbon, be set at more than the temperature that carbon compound gas decomposes by the effect of catalyst.Use the synthesis temperature of the carbon nanocoil of acetylene, be chosen as for example 600～800 ℃, but be not limited thereto temperature range, if more than the catalyst decomposes temperature of the gas that contains carbon, can freely set according to combined coefficient.

After reaction finishes, in reactor, make above-mentioned carrier gas circulation be cooled to room temperature.Take out the porous carrier from reactor, isolate carbon nanocoil from the porous carrier.Separation method has multiple, for example has catalyst base is flooded in fluoridizing hydracid, hydrochloric acid, nitric acid, sodium hydrate aqueous solution etc., and dissolving porous carrier takes out methods such as carbon nanocoil.So, in the porous carrier, make it take on multiple metallic catalyst and metal oxide catalyst, generate carbon nanocoil, then can obtain the identical carbon nanocoil in homogeneous coil footpath, line footpath high-recovery, and produce in batches easy.

[embodiment 6-1: 650 ℃ of firing temperatures]

Zeolite has used the zeolite of the HSZ-390HUA of eastern ソ one system, mol ratio (SiO ₂/ Al ₂O ₃) be more than 200, specific area (BET) is 660m ²/ g, averaged particles footpath (D50) is 6.5 μ m, pore is distributed in 0.2nm and 10nm has peak value.This zeolite of weighing 0.5g disperses to put into porcelain dish, 100 ℃ of air dries of carrying out 30 minutes.Be modulated into Fe (No ₃) 9H ₂O is 151.94g, In (NO ₃) 3H ₂O is 42.11g, SnC ₂O ₄The solution that in ion exchange water 600ml, dissolves for 1.30g.In this solution 40ml, drop into above-mentioned zeolite 0.5g, stirred 30 minutes with ultrasonic wave.Its placement was made the zeolite precipitation in 24 hours.Remove the liquid of top clarification, the zeolite of precipitation and solution take out air dry in porcelain dish by dropper.With the zeolite of air dry once again 100 ℃ of dryings of in air, carrying out 30 minutes, thereafter in helium with 650 ℃, carry out 1 hour burn till.Burn till by this, the FeInSn oxide catalyst is taken in the surface of zeolite and pore.

This zeolite that burns till is pulverized in mortar, the 0.02g crushed material is put in the 3g ethanol, carry out 15 minutes dispersion by ultrasonic wave.It placing in the quartz ampoule that silicon substrate drips, is made helium 200sccm circulation, made near the temperature the silicon substrate rise to 700 ℃ in 100 ℃/5 minutes with programming rate.After arriving 700 ℃ (retention times: 10 minutes), acetylene was circulated 10 minutes with the flow of 60sccm., stop acetylene only making helium flow logical, make its cool to room temperature thereafter.

Figure 28 takes on body (zeolite) and the scanning electron microscope picture (100,000 times of multiplying powers) of the carbon nanocoil that forms with 650 ℃ of catalyst that burn till.The line footpath of the fibre object that is generated is judged to be 20～25nm from photo.The line of a plurality of carbon nanocoils that confirms growth is directly for comparable size, and the coil footpath is homogeneous roughly also.

Figure 29 is the pore distribution map of employed zeolite.The longitudinal axis represent not have surface area (sq/g) transverse axis of 1g represent radius (

).From then on figure considers, thinks that then catalyst is concentrated and taken near fine pore is radius 10nm the pore, and carbon nanocoil is shaped.In the pore of the pore radius 0.2nm of the peak value that is equivalent to a little side, do not confirm taking on of catalyst.

[embodiment 6-2: 700 ℃ of firing temperatures]

By the composing method identical catalyst is taken in zeolite with embodiment 1.Also have, carry out drying, make dry zeolite temperature with 700 ℃ in helium carry out 1 hour burning till by the method identical with embodiment 1.Take on body with this catalyst, generate carbon nanocoil by the method identical with embodiment 1.

Figure 30 takes on body (zeolite) and the scanning electron microscope picture (100,000 times of multiplying powers) of the carbon nanocoil that forms with 700 ℃ of catalyst that burn till.Compare as can be known with embodiment 1, the quantity of the carbon nanocoil that embodiment 2 grows up is more relatively.The line of carbon nanocoil directly is 20～25nm as can be known, and is identical with embodiment 1.

Figure 31 is the enlarged drawing of Figure 30.As can be seen from Figure 31, the coil of carbon nanocoil footpath (coil overall diameter) is 50～70nm.In these carbon nanocoil to line footpath and coil directly the size of (coil overall diameter) confirm, obtained the result identical with embodiment 2.That is, the line of formed carbon nanocoil directly is 20～25nm, and coil footpath (coil overall diameter) is 50～70nm.Therefore, proved by the present invention the line footpath of carbon nanocoil is formed equably, and its result, the coil footpath (coil overall diameter) of carbon nanocoil is roughly formed equably.

The present invention and not only be confined to above-mentioned embodiment and embodiment is included in the interior various variation of the scope of thinking of the technology this labyrinth in that do not surmount in its technical scope, design alteration etc.

(industrial utilizability)

According to first form of the present invention, draw following understanding, and be over into the present invention, as FeInSn Catalyst generates carbon nanocoil by making the coexistence of this transition metal and other element, and Become carbon compound by this catalyst, and carbon nanocoil is grown up effectively. Above-mentioned catalyst core Metal carbides of the present invention.

According to second form of the present invention, transition metal and In and C urge in conjunction with formed carbide Change agent and become effective carbon nanocoil catalyst for producing.

According to the 3rd form of the present invention, the group of A and In and C in carbide catalyst has been proposed Become than being represented by x, y, z, these ratio of components x, y, z can be designed to the carbide of desired value Catalyst.

According to the 4th form of the present invention, by using Fe₃InC _0.5Carbide catalyst can be efficient Carbon nanocoil is made on ground. This carbide catalyst is by forming that present inventors find first The determined carbon nanocoil catalyst for producing of formula is the genuine catalysis that carbon nanocoil is grown up Agent.

According to the 5th form of the present invention, by in carbide catalyst, adding more than one other The carbon nanocoil catalyst for producing of element can be made carbon nanocoil (CNC) effectively.

According to the 6th form of the present invention, using FeInSn is carbide catalyst, catalyst The efficient height can make carbon nanocoil grow up at short notice, therefore has and can improve reaction unit The advantage of operating efficiency. Also have, if consist of take this carbide catalyst as particulate, then pass through The carbon nanocoil footpath can be controlled in the particulate footpath of control carbide catalyst, can make arbitrarily straight The coil in footpath.

According to the 7th form of the present invention, Fe and In and C and Sn in carbide catalyst have been proposed Ratio of components represented that by x, y, z, w these ratio of components x, y, z, w can be designed to desired value Carbide catalyst.

According to the 8th form of the present invention, by Fe₃In _1-vC _0.5Sn _wThe group of (1＞v 〉=0, w 〉=0) The represented carbon nanocoil manufacturing of an accepted way of doing sth is used in the carbide catalyst, by suitably adjusting ratio of components V, w can provide the carbide catalyst that can effectively make carbon nanocoil.

According to the 9th form of the present invention, proposed as the carbon nanocoil catalyst for producing 39.6 have first intensity peak near °, near 46.3 °, have the carbide of second intensity peak Catalyst.

According to the tenth form of the present invention, transition metal and Sn and C in conjunction with and the carbonization of row The thing catalyst becomes effective carbon nanocoil catalyst for producing. The concrete selection of transition metal, Suitably freely carry out according to making efficient and synthesis condition.

According to the 11 form of the present invention, the composition of transition metal A and Sn and C has been proposed Than being represented that by x, y, z the carbide that these ratio of components x, y, z can be designed to desired value is urged Change agent.

According to the 12 form of the present invention, by using Fe₃The SnC carbide catalyst can be high Carbon nanocoil is made on effect ground. This carbide catalyst is the group of being found first by present inventors The determined carbon nanocoil catalyst for producing of an accepted way of doing sth is the catalyst that carbon nanocoil is grown up.

According to the 13 form of the present invention, proposed in above-mentioned carbide catalyst to add a kind of with The carbon nanocoil catalyst for producing of upper other elements can be made carbon nanocoil efficiently.

According to the 14 form of the present invention, the carbide catalyst that above-mentioned elements A is Fe has been proposed, Near the carbon nanocoil manufacturing that has the Diffraction intensity distribution of first intensity peak about 40 ° is used Catalyst.

According to the 15 form of the present invention, if use the transition metal unit of containing at least more than one The catalyst of the element of plain, Al and Sn, be applicable to by CVD method etc. synthetic, can be effectively Make carbon nanocoil, help the industrialized mass production of carbon nanocoil.

According to the 16 form of the present invention, transition metal, Al and Sn have been proposed as oxygen The carbon nanocoil catalyst for producing that compound exists does not have more than this even use in air yet Oxidation, stable catalyst can be provided.

According to the 17 form of the present invention, proposed forming (Fe_x-Al _y-Sn _z) ratio of components In (mol ratio), during x=3, the carbon of y≤1, z≤3 is received under the pro rate of (x, y, z) Rice noodles circle catalyst for producing.

According to the 18 form of the present invention, contain the transition gold that contains at least more than one if use The catalyst that belongs to the element of element, Cr and Sn is applicable to by CVD method etc. syntheticly, can have Carbon nanocoil is made on effect ground, helps the industrialized mass production of carbon nanocoil.

According to the 19 form of the present invention, transition metal, chromium or tin with transiting metal oxidation iron, The form of aluminium oxide or tin oxide is used, and consists of the carbon nanocoil catalyst for producing, so namely Make these in air, use the oxidation that does not also have more than this, stable catalyst can be provided.

According to the 20 form of the present invention, proposed at (Fe_x-Cr _y-Sn _z) ratio of components (rub You than) in, under the pro rate of (x, y, z) during x=3, the carbon nanocoils of y≤1, z≤3 The circle catalyst for producing.

According to the 21 form of the present invention, proposed at (Fe_x-In _y-Sn _z) in, (x, Y, z) pro rate under during x=3, the carbon nanocoil catalyst for producing of y≤9, z≤3.

According to the 22 form of the present invention, iron, indium or tin are with iron oxide, indium oxide or tin oxide Form and use, consist of the carbon nanocoil catalyst for producing, so even these make in air Oxidation with also not having more than this can provide stable catalyst.

According to the 23 form of the present invention, by adjusting atomic particle diameter, having can be even Coil footpath and the coil overall diameter of ground control carbon nanocoil are the advantage of desired value.

According to the 24 form of the present invention, from containing transition metal, In) or (transition gold Belong to element, Sn) film, can produce in batches and contain (transition metal, In, C) or (mistake Cross metallic element, Sn, C) the carbide catalyst of element. Transition metal has as mentioned above Varied, can the qurer batch production contain the arbitrarily carbides catalytic of transition metal Agent.

According to the 25 form of the present invention, from containing (transition metal, In) or (transition Metallic element, Sn) particulate, can make and contain (transition metal, In, C) or (mistake Cross metallic element, Sn, C) the carbide catalyst of element.

According to the 26 form of the present invention, from (transistion metal compound and In compound) or Liquation or the dispersion liquid of (transistion metal compound and Sn compound) can be made (transition metal Element, In, C) or the carbide catalyst particulate of (transition metal, Sn, C). As Material that can carbonization can utilize the various compounds beyond the oxide.

According to the 27 form of the present invention, by solwution method, generate (transition metal, In) Or the particulate of (transition metal, Sn), this particulate of carbonization, make (transition metal, In, C) or the particulate of the carbide catalyst of (transition metal, Sn, C). Having can The advantage of a large amount of synthesizing carbide catalyst particles.

According to the 28 form of the present invention, utilize the gas of catalyst raw material composition by aerifying Learn the in a large number particulate of the carbide catalyst of productive target of reaction, to the reduction of catalyst price Make contributions.

According to the 29 form of the present invention, contain transition metal A, can make by A_xIn _yC _zOr A_xSn _yC _zRepresented carbon nanocoil catalyst for producing. These ratio of components have been proposed X, y, z can provide the carbide catalyst that is designed to desired value.

According to the 30 form of the present invention, provide the composition formula of carbide catalyst at least by Fe₃InC _0.5Or Fe₃The carbon nanocoil catalyst for producing that SnC is represented. By Fe₃InC _0.5Or Fe₃The formed carbon compound of SnC as the carbon nanocoil catalyst for producing, is present inventors The material that the world at first finds.

According to the 31 form of the present invention, in above-mentioned carbide catalyst, add more than one The manufacture method of the carbon nanocoil catalyst for producing of other elements. Add suitable element, can Adjust the rerum natura of catalyst.

According to the 32 form of the present invention, provide the carbides catalytic that makes carbon nanocoil manufacturing usefulness Agent and/or oxide catalyst are taken on the carbon nanocoil catalyst for producing of porous row carrier. Can be real The homogenization in the wire diameter of existing carbon nanocoil and coil footpath. The shape of porous carrier, the existence bulk, Sheet, tabular, granular, finely particulate, ultramicron shape etc. are multiple.

According to the 33 form of the present invention, can realize the various catalysis that present inventors are found The catalyst of porous carrier is taken in agent, has the advantage that can make efficiently carbon nanocoil.

According to the 34 form of the present invention, can realize the metal catalytic that present inventors are found The catalyst of porous carrier is taken in agent, has the advantage that can make efficiently carbon nanocoil.

According to the 35 form of the present invention, provide the catalyst that makes 2 yuan of prime systems, 3 yuan of prime systems The carbon nanocoil catalyst for producing of taking in the porous carrier can freely be adjusted the carbon nanometer The formation efficiency of coil.

According to the 36 form of the present invention, transition metal is to choose one wantonly among Fe, Co, the Ni The carbon nanocoil catalyst for producing of the element more than kind can be produced carbon nanocoil, energy in a large number Enough help the reduction of price.

According to the 37 form of the present invention, be phosphorus from zeolite, aluminium as above-mentioned porous carrier Hydrochlorate, silicoaluminophosphate, middle porous body, porous ceramics, molecular sieve, burning system porous Body, silicon porous body or carbon are optional in the porous body.

According to the 38 form of the present invention, be provided at dipping porous carrier in this solvent, many The interior homogeneous absorption of the pore that the permeability carrier is identical has the catalyst of carbon nanocoil catalyst for producing.

According to the 39 form of the present invention, be provided at and make catalyst particles in porous in the space The carbon nanocoil catalyst for producing of taking in the carrier. Method makes the carbon nanocoil manufacturing with urging thus Change the agent particulate and be adsorbed in the porous carrier, can make carbon nanocoil in high performance cheap ground.

According to the 40 form of the present invention, the porous carrier that catalyst particles is taken on is advanced The carbon nanocoil catalyst for producing of durability OK, is provided.

According to the 41 form of the present invention, use various catalyst of the present invention, make above-mentioned carbonization The compound gas communication, therewith catalyst contact, thus can make carbon nanocoil. At the catalyst table Face is the Formed nanocoil efficiently, can make the industrial batch production of existing carbon nanocoil.

According to the 42 form of the present invention, provide to make non-carbide catalyst in course of reaction Carbonization, carbide catalyst decomposes carbon compound gas thus under the laser heating state, can provide A large amount of two sections method for continuous production producing carbon nanocoil.

According to the 43 form of the present invention, provide to make the catalysis that contains transition metal, Sn The agent precursor substance is varied to carbide catalyst, can provide two of a large amount of production carbon nanocoils in addition The section method for continuous production.

According to the 44 form of the present invention, provide to make and contain urging of transition metal, In, Sn Change the agent precursor substance and be varied to carbide catalyst, can produce in a large number in addition carbon nanocoil two sections Method for continuous production.

According to the 45 form of the present invention, can be on catalyst film Formed nanometer to high-density Coil. Have by the particle diameter of control catalyst particles and can freely produce in a large number carbon nanocoil Advantage.

According to the 46 form of the present invention, provide by this catalyst particles decomposition carbonization and closed The carbon nanocoils circle manufacturing method that thing gas makes carbon nanocoil grow up with floating state. Relatively letter The one-tenth of singly controlling carbon nanocoil is long-time, can easily control the size of carbon nanocoil.

According to the 47 form of the present invention, for example, make the powder of catalyst particles in converter Pile up, while make the carbon compound gas communication make the converter rotation, then catalyst fines is in stirring State can be produced in a large number take catalyst particles as catalyst core carbon nanocoil.

According to the 48 form of the present invention, provide by above-mentioned nanocoil manufacture method institute The carbon nanocoil of the low price of making. Also have, can provide the wire diameter carbon identical with the coil overall diameter to receive The rice noodles circle. If use this wire diameter carbon nanocoil identical with the coil overall diameter, then can make height The nano-substance of quality, for example nanometer spring, nano-machine, electromagnetic wave absorb, electronic emitter (emitter), nanoelectronic equipment, hydrogen occlusion body etc., can tackle the requirement in each field.

Claims (7)

1. carbon nanocoil catalyst for producing, be to be the catalyst of the carbon nanocoil below the 1000nm by chemical vapor deposition manufactured overall diameter, it is characterized in that this catalyst contains more than one transition metal, Al or Cr, the element of Sn at least.

2. according to the described carbon nanocoil catalyst for producing of claim 1, it is characterized in that described transition metal, Al or Cr, Sn exist as oxide.

3. according to the described carbon nanocoil catalyst for producing of claim 1, it is characterized in that described transition metal is Fe, forming (Fe _x-Al _y-Sn _z) the mole ratio of components in, under the pro rate of (x, y, z) during x=3, y≤1, z≤3.

4. according to the described carbon nanocoil catalyst for producing of claim 1, it is characterized in that above-mentioned transition metal is Fe, forming (Fe _x-Cr _y-Sn _z) the mole ratio of components in, under the pro rate of (x, y, z) during x=3, y≤1, z≤3.

5. according to the described carbon nanocoil catalyst for producing of claim 1, it is characterized in that described catalyst obtains as particulate.

6. according to the described carbon nanocoil catalyst for producing of claim 1, it is characterized in that described carbide catalyst is held by porous carrier load.

7. the manufacture method of a carbon nanocoil, it is characterized in that, the described carbon nanocoil catalyst for producing of claim 57 is placed inside reactor, to be heated near this catalyst more than the temperature that the carbon compound gas that uses as raw material decomposes by catalyst action, make above-mentioned carbon compound gas communication in the mode that contacts with above-mentioned catalyst, when near above-mentioned catalyst, above-mentioned carbon compound gas being decomposed, the carbon nanocoil below the overall diameter 1000nm is grown up at above-mentioned catalyst surface.

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