JP2010000496A - Catalyst for producing carbon nanocoil and method for producing the same - Google Patents
Catalyst for producing carbon nanocoil and method for producing the same Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 121
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 239000002245 particle Substances 0.000 claims abstract description 279
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 128
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000000203 mixture Substances 0.000 claims abstract description 88
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 77
- 150000003606 tin compounds Chemical class 0.000 claims abstract description 73
- 239000011164 primary particle Substances 0.000 claims abstract description 56
- 229910052718 tin Inorganic materials 0.000 claims description 98
- 229910052742 iron Inorganic materials 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 55
- 229910052738 indium Inorganic materials 0.000 claims description 47
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 44
- 239000007864 aqueous solution Substances 0.000 claims description 37
- 150000002472 indium compounds Chemical class 0.000 claims description 30
- -1 iron ions Chemical class 0.000 claims description 21
- 239000013078 crystal Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 229910001432 tin ion Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 229910001449 indium ion Inorganic materials 0.000 claims description 8
- 239000011817 metal compound particle Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- 229910002588 FeOOH Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 238000000151 deposition Methods 0.000 abstract description 3
- 239000012808 vapor phase Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 description 46
- 238000000921 elemental analysis Methods 0.000 description 18
- 239000010419 fine particle Substances 0.000 description 18
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 10
- 238000000634 powder X-ray diffraction Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GFBZUOBHZYBBBR-UHFFFAOYSA-N [Fe].[In].[Sn] Chemical compound [Fe].[In].[Sn] GFBZUOBHZYBBBR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011812 mixed powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002505 iron Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- YMZYMLBYRHOCIN-UHFFFAOYSA-L dichlorotin tetrahydrate Chemical compound O.O.O.O.Cl[Sn]Cl YMZYMLBYRHOCIN-UHFFFAOYSA-L 0.000 description 2
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 2
- DHKWOBKCNIDKCO-UHFFFAOYSA-K iron(3+);trichloride;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Fe+3] DHKWOBKCNIDKCO-UHFFFAOYSA-K 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003153 β-FeOOH Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GBOGAFPRHXVKNT-UHFFFAOYSA-N [Fe].[In] Chemical compound [Fe].[In] GBOGAFPRHXVKNT-UHFFFAOYSA-N 0.000 description 1
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical group [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NIZZTWBXRSFJAW-UHFFFAOYSA-K indium(3+);trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[In+3] NIZZTWBXRSFJAW-UHFFFAOYSA-K 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical group [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910006540 α-FeOOH Inorganic materials 0.000 description 1
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- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Compounds Of Iron (AREA)
Abstract
Description
本発明は、気相法でカーボンナノコイルを作製する場合の好適なカーボンナノコイル製造用触媒に関する。 The present invention relates to a catalyst for producing carbon nanocoils suitable for producing carbon nanocoils by a gas phase method.
鉄、ニッケル、インジウム、錫などの金属元素を含む化合物や混合粉末などを担体上に担持させたものは、カーボンナノチューブやカーボンナノコイルといった材料合成のための触媒として有用であるとされている（例えば、特許文献１〜４参照。）。 A material in which a compound containing a metal element such as iron, nickel, indium, tin or a mixed powder is supported on a carrier is considered to be useful as a catalyst for synthesizing materials such as carbon nanotubes and carbon nanocoils ( For example, see Patent Documents 1 to 4.)
特許文献１、２にはカーボンナノチューブの合成用触媒として、化合物触媒を特定の担体上に担持させたものを用いることで、カーボンナノチューブを効率的に製造することができると記載されている。 Patent Documents 1 and 2 describe that carbon nanotubes can be efficiently produced by using a compound catalyst supported on a specific carrier as a catalyst for carbon nanotube synthesis.
また、カーボンナノコイル合成用触媒としては、特許文献３に、Ｆｅ、Ｃｏ、Ｎｉなどの遷移金属元素及びＳｎ、Ｉｎなどの元素を含む粒子を多孔性担体に担持させたものが提案されており、ナノコイルの径などを均一化し量産化するための有効な手段であると記載されている。さらに、これらの元素の組成比として、Ｆｅ：ＩｎあるいはＦｅ：Ｓｎが３：１である場合が最も高効率にカーボンナノコイルを製造できるとされている。 Further, as a catalyst for carbon nanocoil synthesis, Patent Document 3 proposes a catalyst in which particles containing a transition metal element such as Fe, Co, and Ni and an element such as Sn and In are supported on a porous carrier. It is described as an effective means for making the diameter of the nanocoil uniform and mass-producing it. Furthermore, as a composition ratio of these elements, it is said that the case where Fe: In or Fe: Sn is 3: 1 can produce carbon nanocoils with the highest efficiency.
また、特許文献４には、ＳｎＯ2の凝集体周辺にＦｅ3Ｏ4の凝集体を担持させる構成の触媒を用いることで、高効率にカーボンナノコイルを製造できると記載されている。
カーボンナノコイルの製造技術は飛躍的に進歩しつつあるものの、現在でも最終的に製造されるカーボンナノコイルのコイル径にはバラツキが生じ、そのコイル径の精度の向上は困難であり、製造したカーボンナノコイルの中にはコイル状ではないチューブ状のカーボンも混在する場合がある。このため、製造したカーボンナノコイルから分級などにより不要なカーボンを除く必要があり、生産効率が悪い。 Although the manufacturing technology of carbon nanocoil is making great progress, even now, the coil diameter of the carbon nanocoil that is finally produced varies, and it is difficult to improve the accuracy of the coil diameter. The carbon nanocoil may contain tube-like carbon that is not coiled. For this reason, it is necessary to remove unnecessary carbon from the produced carbon nanocoil by classification or the like, resulting in poor production efficiency.
このカーボンナノコイルのコイル径がばらつく理由としては次のように考えられている。即ち、実際にカーボンナノコイルの成長核となるのは、数ｎｍサイズの複合金属炭化物微粒子であると考えられている。しかしながら、このようなサイズの複合金属炭化物微粒子をあらかじめ作製することは困難であり、現在では、より大きなサイズを持つ複合金属炭化物粒子を担体に担持させて用いるか、あるいは、酸化物材料などを出発点とし、特定の２種以上の微粒子構成元素がコイル生成環境である高温下において化合物化し、それにより生成した複合金属炭化物微粒子を担体に担持させて用いている。この際に用いる複合金属炭化物微粒子の組成は、構成元素である２種以上の微粒子の、ナノサイズ領域での存在比率に依存することとなるが、複数種の微粒子が均一に存在していない場合には、この存在比率に場所依存性が生じるために、それぞれの成長核となる複合金属炭化物微粒子の組成が僅かにずれ、その結果カーボンナノコイルのコイル径が異なる場合や、チューブ状に成長する場合などといった不均一が生じるのではないかと考えられる。また、より大きなサイズを持つ複合金属炭化物粒子を用いる場合では、さらに成長核となる複合金属炭化物粒子の組成のずれが大きくなり、同様の問題が生じると考えられる。 The reason why the coil diameter of the carbon nanocoil varies is considered as follows. That is, it is considered that the composite metal carbide fine particles having a size of several nanometers are actually the growth nuclei of the carbon nanocoil. However, it is difficult to prepare composite metal carbide fine particles of such a size in advance, and at present, composite metal carbide particles having a larger size are supported on a support or used as an oxide material. In particular, two or more kinds of fine particle constituent elements are compounded at a high temperature, which is a coil generation environment, and composite metal carbide fine particles generated thereby are supported on a carrier and used. The composition of the composite metal carbide fine particles used at this time depends on the abundance ratio of two or more kinds of fine particles as constituent elements in the nano-size region, but when plural kinds of fine particles are not uniformly present. In this case, since the abundance ratio depends on the location, the composition of the composite metal carbide fine particles serving as the respective growth nuclei is slightly shifted, and as a result, the carbon nanocoils have different coil diameters or grow in a tube shape. It is thought that non-uniformity such as a case may occur. Further, when using composite metal carbide particles having a larger size, the compositional deviation of the composite metal carbide particles serving as growth nuclei further increases, and it is considered that the same problem occurs.
このように、従来考えられている以上に、各元素の存在場所の均一性を微細に調整する必要があり、このため、カーボンナノコイル生成触媒となり得る複数種の金属元素を含む微粒子を、担体上にいかに均一に担持させるか、いかに均一な混合物又は化合物を製造するか、その均一性をいかにナノサイズレベルにするか、ということが、コイル径が均一なカーボンナノコイルを得るための課題であると考えられる。 In this way, it is necessary to finely adjust the uniformity of the location of each element more than conventionally considered. For this reason, fine particles containing a plurality of types of metal elements that can be a carbon nanocoil generation catalyst are used as a carrier. How to make it uniformly supported on the top, how to produce a uniform mixture or compound, and how to make the uniformity to the nano-size level are the challenges to obtain carbon nanocoils with a uniform coil diameter. It is believed that there is.
しかしながら、各種セラミックスあるいはカーボンなどの担体上に、２種以上の微粒子を均一担持させることは非常に難しく、現状では満足な均一担持体が得られていない。また、特許文献４に記載のように、酸化錫凝集体の周辺に酸化鉄凝集体を担持させる触媒においても、あらかじめ作製された酸化鉄凝集体の分散液に酸化錫凝集体を混合吸着させる方法が用いられており、現状では厳密に担持させることは困難であり、隣り合った場所に同種の化合物が配置されたり、各凝集体が分離してバラバラに存在したりするなど、不均一な状態しか得られていない。 However, it is very difficult to uniformly carry two or more kinds of fine particles on a carrier such as various ceramics or carbon, and a satisfactory uniform carrier is not obtained at present. Further, as described in Patent Document 4, a method for adsorbing tin oxide aggregates in a preliminarily prepared dispersion of iron oxide aggregates even in a catalyst for supporting iron oxide aggregates around tin oxide aggregates In the present situation, it is difficult to carry it strictly, and the same type of compound is placed in an adjacent place, or each aggregate is separated and exists in a non-uniform state. It has only been obtained.
また、担体上に担持させる触媒量が少ない場合には、複数種の微粒子であっても均一に担持させる方法はあるが、この方法ではコイル径の均一なカーボンナノコイルが得られるものの、成長するナノコイルの数が減少し、収率が上がらないという問題が生じる。例えばゾル−ゲル法や、あらかじめ作製したコロイド状粒子を溶液中で担体上に担持させるといった従来の均一担持方法では、その分散性を高めて場所依存性の非常に小さい、均一な担持体を得ることが可能である反面、この方法は担体表面の細孔への化学吸着を利用するものであるために、担持重量が少ない場合には非常に有効な手段であるものの、担体上に隙間無く高含率に担持させることができない。 In addition, when the amount of catalyst supported on the carrier is small, there is a method of uniformly supporting even a plurality of types of fine particles, but this method can produce carbon nanocoils with a uniform coil diameter, but grows. There arises a problem that the number of nanocoils decreases and the yield does not increase. For example, in the sol-gel method or the conventional uniform loading method in which colloidal particles prepared in advance are supported on a carrier in a solution, the dispersibility is increased to obtain a uniform carrier having very little location dependency. However, since this method uses chemical adsorption to the pores on the surface of the support, it is a very effective means when the supported weight is small. It cannot be supported at the content.
以上のように従来は、カーボンナノコイルのコイル径のバラツキを抑え、高効率にカーボンナノコイルを作製すること、及び、そのために必要な複数種の触媒元素を含む微粒子を均一混合させた状態で担体上に担持させた触媒担持体を得ることは困難であった。本発明は、上記問題を解決したもので、気相法によりコイル径の均一なカーボンナノコイルを作製する際に有用なカーボンナノコイル製造用触媒を提供するものである。 As described above, conventionally, the variation in the diameter of the carbon nanocoil is suppressed, the carbon nanocoil is produced with high efficiency, and the fine particles containing a plurality of kinds of catalyst elements necessary for that purpose are uniformly mixed. It was difficult to obtain a catalyst carrier supported on a carrier. The present invention solves the above-described problems and provides a catalyst for producing carbon nanocoils that is useful when producing carbon nanocoils with a uniform coil diameter by a gas phase method.
本発明の第１のカーボンナノコイル製造用触媒は、鉄化合物粒子と錫化合物粒子とを含む混合体、あるいは鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子を含む混合体を担体上に担持させたカーボンナノコイル製造用触媒であって、前記鉄化合物粒子の平均一次粒子径は１〜１０ｎｍであり、前記錫化合物粒子の平均一次粒子径は１〜１００ｎｍであり、前記インジウム化合物粒子の平均一次粒子径は１〜１００ｎｍであり、前記混合体に含有される錫元素及びインジウム元素の合計量は、前記混合体に含有される鉄元素、錫元素及びインジウム元素の合計量に対して、１０〜９０ｍｏｌ％であることを特徴とする。 In the first catalyst for producing carbon nanocoils of the present invention, a mixture containing iron compound particles and tin compound particles or a mixture containing iron compound particles, tin compound particles and indium compound particles is supported on a carrier. A catalyst for producing carbon nanocoils, wherein the iron compound particles have an average primary particle size of 1 to 10 nm, the tin compound particles have an average primary particle size of 1 to 100 nm, and the indium compound particles have an average primary particle size. The diameter is 1 to 100 nm, and the total amount of tin element and indium element contained in the mixture is 10 to 90 mol with respect to the total amount of iron element, tin element and indium element contained in the mixture. %.
また、本発明の第２のカーボンナノコイル製造用触媒は、鉄元素及び錫元素を同一結晶内に含む化合物粒子、あるいは、さらにインジウム元素を同一結晶内に含む化合物粒子からなるカーボンナノコイル製造用触媒であって、前記化合物粒子の平均一次粒子径は、１〜１００ｎｍであり、前記化合物粒子に含有される錫元素及びインジウム元素の合計量は、前記化合物粒子に含有される鉄元素、錫元素及びインジウム元素の合計量に対して、１０〜９０ｍｏｌ％であることを特徴とする。 The second catalyst for producing carbon nanocoils of the present invention is for producing carbon nanocoils comprising compound particles containing iron element and tin element in the same crystal, or compound particles containing indium element in the same crystal. It is a catalyst, The average primary particle diameter of the said compound particle is 1-100 nm, The total amount of the tin element and indium element which are contained in the said compound particle is the iron element contained in the said compound particle, a tin element And it is 10-90 mol% with respect to the total amount of an indium element, It is characterized by the above-mentioned.
また、本発明の第１のカーボンナノコイル製造用触媒の製造方法は、錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液とを、攪拌しながら混合して、鉄化合物粒子と錫化合物粒子とを析出させる工程と、前記鉄化合物粒子と前記錫化合物粒子と乾燥して、前記鉄化合物粒子と前記錫化合物粒子との混合体を製造する工程と、前記混合体を担体上に担持させる工程とを含むことを特徴とするか、又は錫イオンを含むアルカリ水溶液と、鉄イオン及びインジウムイオンを含む水溶液とを、攪拌しながら混合して、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子を析出させる工程と、前記鉄化合物粒子、前記錫化合物粒子及び前記インジウム化合物粒子を乾燥して、前記鉄化合物粒子、前記錫化合物粒子及び前記インジウム化合物粒子の混合体を製造する工程と、前記混合体を担体上に担持させる工程とを含むことを特徴とする。 The first method for producing a catalyst for producing carbon nanocoils of the present invention comprises mixing an alkaline aqueous solution containing tin ions and an aqueous solution containing iron ions while stirring to obtain iron compound particles and tin compound particles. Depositing the iron compound particles and the tin compound particles to produce a mixture of the iron compound particles and the tin compound particles; and supporting the mixture on a carrier; Or an aqueous alkaline solution containing tin ions and an aqueous solution containing iron ions and indium ions are mixed with stirring to precipitate iron compound particles, tin compound particles, and indium compound particles. And drying the iron compound particles, the tin compound particles, and the indium compound particles, and the iron compound particles, the tin compound particles, and the indium compound. A step of producing a mixture of the child, the mixture characterized in that it comprises a step of loading on the support.
また、本発明の第２のカーボンナノコイル製造用触媒の製造方法は、錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液又は鉄イオン及びインジウムイオンを含む水溶液とを、攪拌しながら混合して、各金属化合物粒子を析出させて、前記金属化合物粒子を含む懸濁液を作製する工程と、前記懸濁液を１００〜２５０℃の温度範囲で水熱処理して、鉄元素及び錫元素、あるいは、鉄元素、錫元素及びインジウム元素を同一結晶内に含む化合物粒子を製造する工程とを含むことを特徴とするか、又は錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液又は鉄イオン及びインジウムイオンを含む水溶液とを、攪拌しながら混合して、各金属化合物粒子とを析出させる工程と、前記金属化合物粒子を乾燥するとともに、３００〜７００℃の温度範囲で加熱処理して、鉄元素及び錫元素、あるいは、鉄元素、錫元素及びインジウム元素を同一結晶内に含む化合物粒子を製造する工程とを含むことを特徴とする。 The second method for producing a catalyst for producing carbon nanocoils of the present invention comprises mixing an aqueous alkaline solution containing tin ions and an aqueous solution containing iron ions or an aqueous solution containing iron ions and indium ions while stirring. A step of precipitating each metal compound particle to prepare a suspension containing the metal compound particles, and hydrothermally treating the suspension in a temperature range of 100 to 250 ° C. A step of producing compound particles containing iron element, tin element and indium element in the same crystal, or an alkaline aqueous solution containing tin ions and an aqueous solution containing iron ions or iron ions and indium An aqueous solution containing ions is mixed with stirring to precipitate the metal compound particles, and the metal compound particles are dried and 300 to 700 are dried. By heating at a temperature range of, iron and tin element, or, characterized in that it comprises a step of producing a compound particle comprising iron, tin element and indium element in the same crystal.
本発明のカーボンナノコイル製造用触媒を用いることにより、コイル径の均一なカーボンナノコイルを高効率に生産することができる。 By using the catalyst for producing carbon nanocoils of the present invention, carbon nanocoils having a uniform coil diameter can be produced with high efficiency.
（実施形態１）
先ず、本発明の第１のカーボンナノコイル製造用触媒について説明する。本発明の第１のカーボンナノコイル製造用触媒は、鉄化合物粒子と錫化合物粒子とを含む混合体、あるいは鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子を含む混合体を担体上に担持させたカーボンナノコイル製造用触媒であって、前記鉄化合物粒子の平均一次粒子径は１〜１０ｎｍであり、前記錫化合物粒子の平均一次粒子径は１〜１００ｎｍであり、前記インジウム化合物粒子の平均一次粒子径は１〜１００ｎｍであり、前記混合体に含有される錫元素及びインジウム元素の合計量は、前記混合体に含有される鉄元素、錫元素及びインジウム元素の合計量に対して、１０〜９０ｍｏｌ％であることを特徴とする。
(Embodiment 1)
First, the first catalyst for producing carbon nanocoils of the present invention will be described. In the first catalyst for producing carbon nanocoils of the present invention, a mixture containing iron compound particles and tin compound particles or a mixture containing iron compound particles, tin compound particles and indium compound particles is supported on a carrier. A catalyst for producing carbon nanocoils, wherein the iron compound particles have an average primary particle size of 1 to 10 nm, the tin compound particles have an average primary particle size of 1 to 100 nm, and the indium compound particles have an average primary particle size. The diameter is 1 to 100 nm, and the total amount of tin element and indium element contained in the mixture is 10 to 90 mol with respect to the total amount of iron element, tin element and indium element contained in the mixture. %.
上記本発明のカーボンナノコイル製造用触媒を用いることにより、コイル径の均一なカーボンナノコイルを高効率に生産することができる。即ち、上記本発明のカーボンナノコイル製造用触媒では、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子は、いずれもがナノレベルの平均一次粒子径を有し、且つ、これらが均一に混合していることによって、担体上に担持させた際にも、鉄元素、錫元素及びインジウム元素の存在位置をナノレベルで均一化させることが可能である。このため、コイル径の均一なカーボンナノコイルを高効率に生産することができると考えられる。 By using the carbon nanocoil production catalyst of the present invention, carbon nanocoils having a uniform coil diameter can be produced with high efficiency. That is, in the carbon nanocoil production catalyst of the present invention, the iron compound particles, the tin compound particles, and the indium compound particles all have an average primary particle diameter of nano level, and these are uniformly mixed. Therefore, even when it is supported on the carrier, the existence position of the iron element, tin element and indium element can be made uniform at the nano level. For this reason, it is thought that the carbon nanocoil with a uniform coil diameter can be produced with high efficiency.
従って、上記混合体におけるそれぞれの粒子の平均一次粒子径はナノサイズであることが必要である。特に、鉄化合物粒子の平均一次粒子径は１ｎｍ以上１０ｎｍ以下であり、好ましくは１ｎｍ以上８ｎｍ以下である。上記平均一次粒子径が１０ｎｍを超えると、錫化合物粒子周辺に満遍なく鉄化合物粒子を分布させることが困難となる。このような意味で、鉄化合物粒子の粒子径はより微細であることが好ましく、８ｎｍ以下であることがより好ましい。次に、錫化合物粒子及びインジウム化合物粒子の平均一次粒子径は１ｎｍ以上１００ｎｍ以下であり、好ましくは１ｎｍ以上１０ｎｍ以下である。上記平均一次粒子径が１００ｎｍを超えると、錫化合物粒子及びインジウム化合物粒子がいかに一次粒子レベルで均一分散し、鉄化合物粒子が均一に周辺に分布していた場合でも、数百ｎｍサイズのグレインが存在することとなり、カーボンナノコイルの大きさと比較した場合には組成に偏りのある不均一な状態となる。従って、錫化合物粒子及びインジウム化合物粒子の平均一次粒子径の上限値は１００ｎｍ以下とし、より均一な混合分散状態を実現するためにも、１０ｎｍ以下であることがより好ましい。ここで、錫化合物やインジウム化合物はその硬度が低く、担体上に担持させる際に延伸しやすいため、鉄化合物と比較してやや大きい一次粒子径を持つ場合でも均一な混合体を得やすい。また、鉄化合物粒子、錫化合物粒子、インジウム化合物いずれも、その格子定数が約０．５ｎｍ前後であることから、上記平均一次粒子径が０．５ｎｍ未満の化合物粒子を作製することは困難となる。このため、上記各平均一次粒子径の下限値は１ｎｍとする。 Therefore, the average primary particle diameter of each particle in the mixture needs to be nano-sized. In particular, the average primary particle diameter of the iron compound particles is 1 nm to 10 nm, preferably 1 nm to 8 nm. When the average primary particle diameter exceeds 10 nm, it becomes difficult to uniformly distribute the iron compound particles around the tin compound particles. In this sense, the particle diameter of the iron compound particles is preferably finer, and more preferably 8 nm or less. Next, the average primary particle diameter of the tin compound particles and indium compound particles is 1 nm to 100 nm, preferably 1 nm to 10 nm. When the average primary particle diameter exceeds 100 nm, even if the tin compound particles and the indium compound particles are uniformly dispersed at the primary particle level and the iron compound particles are uniformly distributed in the periphery, grains having a size of several hundred nm are formed. Therefore, when compared with the size of the carbon nanocoil, the composition becomes non-uniform and uneven. Therefore, the upper limit of the average primary particle diameter of the tin compound particles and indium compound particles is 100 nm or less, and 10 nm or less is more preferable in order to realize a more uniform mixed dispersion state. Here, tin compounds and indium compounds have low hardness and are easy to be stretched when supported on a carrier. Therefore, even when they have a slightly larger primary particle diameter than iron compounds, it is easy to obtain a uniform mixture. In addition, since all of the iron compound particles, tin compound particles, and indium compounds have a lattice constant of about 0.5 nm, it is difficult to produce compound particles having the average primary particle diameter of less than 0.5 nm. . For this reason, the lower limit of each average primary particle diameter is set to 1 nm.
また、上記混合体に含有される錫元素及びインジウム元素の合計量は、混合体に含有される鉄元素、錫元素及びインジウム元素の合計量に対して、１０ｍｏｌ％以上９０ｍｏｌ％以下であり、１５ｍｏｌ％以上５０ｍｏｌ％以下がより好ましい。鉄、錫、インジウムの各元素の割合が少なすぎる場合には、いかに微粒子を作製して混合した場合でも、場所依存性のない均一混合体を作ることが非常に困難となる。 The total amount of tin element and indium element contained in the mixture is 10 mol% or more and 90 mol% or less, and 15 mol with respect to the total amount of iron element, tin element and indium element contained in the mixture. % To 50 mol% is more preferable. When the ratio of each element of iron, tin, and indium is too small, it becomes very difficult to produce a uniform mixture having no place dependency, no matter how fine particles are produced and mixed.
なお、特許文献３にも記載されているように、例えば鉄元素と錫元素とを含む触媒の場合には、錫元素の割合が２５ｍｏｌ％（鉄：錫＝３：１）である場合が最も好ましいと考えられるが、均一なコイル径を持つカーボンナノコイルが得られるという観点では均一な混合体が得られればよく、その意味で各元素の割合は上記範囲となる。 As described in Patent Document 3, for example, in the case of a catalyst containing an iron element and a tin element, the ratio of the tin element is most preferably 25 mol% (iron: tin = 3: 1). Although it is considered preferable, from the viewpoint of obtaining a carbon nanocoil having a uniform coil diameter, it is only necessary to obtain a uniform mixture. In this sense, the ratio of each element is in the above range.
上記鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子としては、不純物となり得る他の金属元素が含まれていなければよく、カーボンナノコイル生成時に鉄、錫及びインジウムの炭化物の形成を阻害しないものであれば特に制限されない。 The iron compound particles, tin compound particles, and indium compound particles need not contain other metal elements that can be impurities, and do not inhibit the formation of carbides of iron, tin, and indium during the formation of carbon nanocoils. There is no particular limitation.
具体的には、上記鉄化合物粒子は、鉄元素とともに、炭素元素、水素元素及び酸素元素から選ばれる少なくとも一つの元素を含み、且つアモルファス構造を有する化合物、又は、ＦｅＯx（１≦ｘ≦２）、ＦｅＯＯＨ及びＦｅ（ＯＨ）y（１≦ｙ≦３）のいずれかの一般式で表される化合物であることが好ましい。特に、鉄元素とともに、炭素元素、水素元素及び酸素元素から選ばれる少なくとも一つの元素を含み、且つアモルファス構造を有する化合物であれば、鉄化合物粒子と錫化合物粒子、さらにはインジウム化合物粒子とを担体に担持させた場合に、各元素が化合物化しやすいため最も好ましい。これは、各元素を含む粒子が独立で存在すれば、必然的にその粒子サイズ分の不均一が生じるため、なるべく微粒子とすることが好ましいが、さらに化合物化させることで、原子レベルで混ざり合うことが可能となり、その場合に最も均一性が高くなるためである。 Specifically, the iron compound particles include, in addition to the iron element, at least one element selected from a carbon element, a hydrogen element, and an oxygen element, and a compound having an amorphous structure, or FeO x (1 ≦ x ≦ 2 ), FeOOH and Fe (OH) y (1 ≦ y ≦ 3) are preferred. In particular, if the compound contains at least one element selected from carbon element, hydrogen element and oxygen element together with iron element and has an amorphous structure, iron compound particles, tin compound particles, and indium compound particles are supported. In the case where it is supported on, it is most preferable because each element is easily compounded. This is because if the particles containing each element exist independently, inevitably nonuniformity of the particle size will occur, so it is preferable to make the particles as small as possible, but by compounding, they mix at the atomic level This is because the uniformity is highest in that case.
上記錫化合物粒子は、錫元素とともに、炭素元素、水素元素及び酸素元素から選ばれる少なくとも一つの元素を含み、且つアモルファス構造を有する化合物、又はＳｎＯm（１≦ｍ≦２）及びＳｎ（ＯＨ）n（２≦ｎ≦４）のいずれかの一般式で表される化合物であることが好ましい。 The tin compound particles contain at least one element selected from a carbon element, a hydrogen element and an oxygen element together with a tin element, and have an amorphous structure, or SnO m (1 ≦ m ≦ 2) and Sn (OH) A compound represented by any one of the general formulas of n (2 ≦ n ≦ 4) is preferable.
上記インジウム化合物粒子は、インジウム元素とともに、炭素元素、水素元素及び酸素元素から選ばれる少なくとも一つの元素を含み、且つアモルファス構造を有する化合物、又はＩｎＯs（１≦ｓ≦２）及びＩｎ（ＯＨ）t（２≦ｔ≦３）のいずれかの一般式で表される化合物であることが好ましい。 The indium compound particles include an indium element and at least one element selected from a carbon element, a hydrogen element, and an oxygen element, and have an amorphous structure, or InO s (1 ≦ s ≦ 2) and In (OH) It is preferably a compound represented by any general formula of t (2 ≦ t ≦ 3).
また、上記鉄化合物粒子の場合と同様の理由で、上記錫化合物粒子及び上記インジウム化合物粒子は、錫元素あるいはインジウム元素とともに、炭素元素、水素元素及び酸素元素から選ばれる少なくとも一つの元素を含み、且つアモルファス構造を有する化合物であることが特に好ましい。 Further, for the same reason as in the case of the iron compound particles, the tin compound particles and the indium compound particles contain at least one element selected from a carbon element, a hydrogen element, and an oxygen element together with a tin element or an indium element, A compound having an amorphous structure is particularly preferable.
また、上記鉄化合物、錫化合物及びインジウム化合物は、それぞれ鉄元素、錫元素あるいはインジウム元素の炭化物であってもよいが、炭化物粒子をナノサイズの微粒子で得ることは、現状では非常に難しい。 The iron compound, tin compound, and indium compound may be carbides of iron element, tin element, or indium element, respectively, but it is very difficult to obtain carbide particles as nano-sized fine particles.
上記担体の材料としては、酸化アルミニウム、酸化ジルコニウム、酸化ケイ素など、１０００℃近い高温においても安定な結晶構造を保ち、周辺の元素と化学反応を起こさない金属酸化物、あるいは、担体そのものも触媒としての機能を発揮する鉄元素を含む合金又はカーボンなどを用いることができる。 As the material of the carrier, a metal oxide such as aluminum oxide, zirconium oxide, silicon oxide, etc. that maintains a stable crystal structure even at a high temperature close to 1000 ° C. and does not cause a chemical reaction with surrounding elements, or the carrier itself as a catalyst An alloy or carbon containing an iron element that exhibits the above function can be used.
上記担体の形状としては、板状あるいは球状などの粒子状を用いることができるが、気相法でカーボンナノコイルを作製する際には、球状の担体粒子を用いることが好ましい。担体として担体粒子を用いる場合には、担体粒子の大きさは、表面に上記化合物粒子を隙間無く担持することができればよく、担体粒子の平均一次粒子径は０．０１μｍ以上１００μｍ以下であることが好ましい。担体粒子の平均一次粒子径が上記範囲より小さい場合には、作製した混合体を構成する粒子と同等の大きさとなり、担体としての役割を果たさなくなる。また、担体粒子の平均一次粒子径が上記範囲より大きい場合には、担体の全表面積が減少するために、触媒としての上記混合体が被覆する面積が減少し、カーボンナノコイルを成長させる際に無駄な担体容積が増大するため、好ましくない。また、これらの担体粒子は、微粒子を表面に被覆できれば表面特性は問わず、細孔の有無に関わり無く用いることができる。 As the shape of the carrier, a plate shape or a particle shape such as a spherical shape can be used, but when producing a carbon nanocoil by a gas phase method, it is preferable to use a spherical carrier particle. When carrier particles are used as the carrier, the carrier particles need only be able to carry the compound particles on the surface without gaps, and the average primary particle diameter of the carrier particles is 0.01 μm or more and 100 μm or less. preferable. When the average primary particle diameter of the carrier particles is smaller than the above range, the carrier particles have the same size as the particles constituting the prepared mixture and do not serve as a carrier. In addition, when the average primary particle diameter of the carrier particles is larger than the above range, the total surface area of the carrier is reduced, so that the area covered by the mixture as a catalyst is reduced, and the carbon nanocoil is grown. Since a useless carrier volume increases, it is not preferable. These carrier particles can be used regardless of the presence or absence of pores, as long as the surface can be coated with fine particles.
本発明おいて、平均一次粒子径は、透過型電子顕微鏡（ＴＥＭ）写真から観察される３００個の一次粒子の直径又は長軸長さの算術平均から求めるものとする。 In this invention, an average primary particle diameter shall be calculated | required from the arithmetic average of the diameter or long-axis length of 300 primary particles observed from a transmission electron microscope (TEM) photograph.
また、本発明のカーボンナノコイル製造用触媒の比表面積は、１ｍ2／ｇ以上であることが好ましい。上記比表面積が大きい方がカーボンナノコイルの成長起点となるサイトの数が増えることとなり、より微細なコイル径の揃ったカーボンナノコイルを得ることができる。 The specific surface area of the catalyst for producing carbon nanocoils of the present invention is preferably 1 m 2 / g or more. When the specific surface area is larger, the number of sites serving as the growth starting points of the carbon nanocoil is increased, so that carbon nanocoils having a finer coil diameter can be obtained.
次に、本発明の第１のカーボンナノコイル製造用触媒の製造方法について説明する。本発明の第１のカーボンナノコイル製造用触媒の製造方法は、錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液とを、攪拌しながら混合して、鉄化合物粒子と錫化合物粒子とを析出させる第１工程と、前記鉄化合物粒子と前記錫化合物粒子とを乾燥して、前記鉄化合物粒子と前記錫化合物粒子との混合体を製造する第２工程と、前記混合体を担体上に担持させる第３工程とを含むことを特徴とする。 Next, the manufacturing method of the 1st catalyst for carbon nanocoil manufacture of this invention is demonstrated. According to the first method for producing a catalyst for producing carbon nanocoils of the present invention, an alkaline aqueous solution containing tin ions and an aqueous solution containing iron ions are mixed with stirring to precipitate iron compound particles and tin compound particles. A first step of drying, a second step of drying the iron compound particles and the tin compound particles to produce a mixture of the iron compound particles and the tin compound particles, and supporting the mixture on a carrier And a third step.
また、上記混合体にさらにインジウム化合物粒子を含ませる場合には、上記鉄イオンを含む水溶液にさらにインジウムイオンを含有させ、上記と同様の工程を行えばよい。 Moreover, when the indium compound particles are further included in the mixture, indium ions may be further included in the aqueous solution containing iron ions, and the same process as described above may be performed.
本発明のカーボンナノコイル製造用触媒に用いる混合体の製造方法としては、均一な混合体が得られれば、共沈法、ゾル−ゲル法、加水分解法などのいずれの方法を用いてもよく、また、別個に作製された各化合物粒子の均一分散液を作製した後、それらを所定の割合で混合してもかまわない。中でも本発明では、最も簡便に均一な微粒子混合体を得られる方法として、上記第１工程と上記第２工程とを用いる。上記第２工程の終了の段階で鉄化合物粒子と錫化合物粒子とが均一混合していない場合には、鉄元素と錫元素の均一な分布状態が得られにくい。この意味で、鉄化合物粒子の乾燥粉末及び錫化合物粒子の乾燥粉末を別個に作製し、後から混合する方法で得られた混合体は、必然的に数十〜数百ｎｍサイズの凝集体同士の混合物となり、本発明のカーボンナノコイル製造用触媒に用いる混合体の製造方法としては好ましくない。 As a method for producing a mixture used for the catalyst for producing carbon nanocoils of the present invention, any method such as a coprecipitation method, a sol-gel method, or a hydrolysis method may be used as long as a uniform mixture is obtained. Alternatively, after preparing a uniform dispersion of each compound particle prepared separately, they may be mixed at a predetermined ratio. Among these, in the present invention, the first step and the second step are used as the most simple method for obtaining a uniform fine particle mixture. If the iron compound particles and the tin compound particles are not uniformly mixed at the end of the second step, it is difficult to obtain a uniform distribution state of the iron element and the tin element. In this sense, a mixture obtained by separately preparing a dry powder of iron compound particles and a dry powder of tin compound particles, and mixing them later is inevitably an aggregate of several tens to several hundreds of nanometers in size. It is not preferable as a method for producing a mixture used for the catalyst for producing carbon nanocoils of the present invention.
上記第１工程では、あらかじめアルカリ水溶液に錫塩を溶解させ、錫イオンを含むアルカリ水溶液を作製する。この際のアルカリ量は、錫塩と鉄塩の総量に対して、当量以上となるように調整する。これとは別に鉄塩を水に溶解させ、鉄イオンを含む水溶液を作製し、この鉄イオンを含む水溶液を錫イオンを含むアルカリ水溶液に攪拌しながら混合する。また、錫イオンを含むアルカリ水溶液と鉄イオンを含む水溶液とを混合させる際には、酸素が１５％以上含まれるガスを錫イオンを含むアルカリ水溶液中にバブリングなどの手段で流通させることが好ましい。鉄の水酸化物又は水酸化酸化物及び錫の水酸化物又は水酸化酸化物が水溶液中に析出する際に、酸素が流通していることにより、より微細な粒子を得ることが可能となる。酸素が１５％以上含まれるガスとしては、酸素以外の含有ガスに不活性ガスを用いたものを用いることができるが、空気を用いることが最も安価で簡便であり、好ましい。 In the first step, a tin salt is dissolved in an alkaline aqueous solution in advance to prepare an alkaline aqueous solution containing tin ions. The amount of alkali at this time is adjusted to be equal to or more than the total amount of tin salt and iron salt. Separately, an iron salt is dissolved in water to prepare an aqueous solution containing iron ions, and this aqueous solution containing iron ions is mixed with an alkaline aqueous solution containing tin ions while stirring. Moreover, when mixing the aqueous alkaline solution containing tin ions and the aqueous solution containing iron ions, it is preferable to circulate a gas containing 15% or more of oxygen in the aqueous alkaline solution containing tin ions by means such as bubbling. When the iron hydroxide or hydroxide oxide and the tin hydroxide or hydroxide precipitate in the aqueous solution, finer particles can be obtained by circulating oxygen. . As a gas containing 15% or more of oxygen, a gas containing an inert gas other than oxygen can be used. However, air is the cheapest, simplest and preferable.
上記第２工程では、鉄化合物粒子及び錫化合物粒子の均一混合粉末を得るために、鉄化合物粒子と錫化合物粒子とを析出させた懸濁液を室温で１５時間以上の時間熟成した後、洗浄、ろ過し、８５〜９５℃で乾燥することが好ましい。 In the second step, in order to obtain a uniform mixed powder of iron compound particles and tin compound particles, the suspension in which iron compound particles and tin compound particles are precipitated is aged at room temperature for 15 hours or more, and then washed. It is preferable to filter, and to dry at 85-95 degreeC.
上記第３工程において混合体を担体上に担持させる方法としては、特に制限はないが、担体の表面に鉄化合物粒子及び錫化合物粒子を隙間無く担持させることができるメカニカルアロイ法が好適に用いられる。より具体的には、担持粒子（鉄化合物粒子、錫化合物粒子）及び担体粒子を、ボールミルなどを用いて１０〜数百時間程度の間、数百〜数千ｒｐｍ程度の回転数で粉砕混合させ、担体の表面に担持体粒子を機械的に且つ一部化学的に担持する。このため、各原料となる鉄化合物粒子及び錫化合物粒子は微細である方が均一に担持させる観点から好ましい。さらに、鉄化合物粒子及び錫化合物粒子は、確固たる結晶構造を持たないアモルファス状であることが、均一な化合物被覆を行うために最も好ましい。この方法を用いて、担体粒子の表面に０．１〜１０μｍ程度の厚みで鉄化合物粒子及び錫化合物粒子を担持させることができる。 The method of supporting the mixture on the support in the third step is not particularly limited, but a mechanical alloy method that can support the iron compound particles and the tin compound particles on the surface of the support without gaps is preferably used. . More specifically, the support particles (iron compound particles, tin compound particles) and carrier particles are pulverized and mixed at a rotational speed of about several hundred to several thousand rpm for about 10 to several hundred hours using a ball mill or the like. The carrier particles are mechanically and partially chemically supported on the surface of the carrier. For this reason, it is preferable that the iron compound particles and tin compound particles used as raw materials are finer from the viewpoint of uniformly supporting them. Furthermore, the iron compound particles and the tin compound particles are most preferably amorphous so as not to have a firm crystal structure in order to perform uniform compound coating. Using this method, iron compound particles and tin compound particles can be supported on the surface of the carrier particles with a thickness of about 0.1 to 10 μm.
以上の製造方法は、インジウム化合物粒子をさらに含む場合にも、同様にして用いることができる。 The above manufacturing method can be used in the same manner even when the indium compound particles are further included.
（実施形態２）
次に、本発明の第２のカーボンナノコイル製造用触媒について説明する。但し、実施形態１で説明した事項と共通する事項の説明は省略する場合がある。本発明の第２のカーボンナノコイル製造用触媒は、鉄元素及び錫元素を同一結晶内に含む化合物粒子、あるいは、さらにインジウム元素を同一結晶内に含む化合物粒子からなるカーボンナノコイル製造用触媒であって、前記化合物粒子の平均一次粒子径は、１〜１００ｎｍであり、前記化合物粒子に含有される錫元素及びインジウム元素の合計量は、前記化合物粒子に含有される鉄元素、錫元素及びインジウム元素の合計量に対して、１０〜９０ｍｏｌ％であることを特徴とする。
(Embodiment 2)
Next, the second catalyst for producing carbon nanocoils of the present invention will be described. However, the description of matters common to those described in the first embodiment may be omitted. The second catalyst for producing carbon nanocoils of the present invention is a catalyst for producing carbon nanocoils comprising compound particles containing iron element and tin element in the same crystal, or further comprising compound particles containing indium element in the same crystal. The average primary particle diameter of the compound particles is 1 to 100 nm, and the total amount of tin element and indium element contained in the compound particles is the iron element, tin element and indium contained in the compound particles. It is characterized by being 10 to 90 mol% with respect to the total amount of elements.
上記本発明のカーボンナノコイル製造用触媒を用いることにより、実施形態１のカーボンナノコイル製造用触媒を用いた場合よりもさらにコイル径の均一なカーボンナノコイルを高効率に生産することができる。即ち、上記本発明のカーボンナノコイル製造用触媒では、鉄元素、錫元素及びインジウム元素は、いずれも同一結晶内で均一に分布していることによって、鉄−錫化合物粒子あるいは鉄−錫−インジウム化合物粒子を担体上に担持させた際にも、鉄元素、錫元素及びインジウム元素の存在位置を原子レベルで均一化させることが可能である。このため、コイル径のより均一なカーボンナノコイルを高効率に生産することができると考えられる。 By using the carbon nanocoil production catalyst of the present invention, carbon nanocoils having a uniform coil diameter can be produced more efficiently than when the carbon nanocoil production catalyst of Embodiment 1 is used. That is, in the catalyst for producing carbon nanocoils of the present invention, the iron element, the tin element, and the indium element are all uniformly distributed in the same crystal, so that iron-tin compound particles or iron-tin-indium Even when the compound particles are supported on the carrier, the positions of the iron element, tin element and indium element can be made uniform at the atomic level. For this reason, it is thought that the carbon nanocoil with a more uniform coil diameter can be produced with high efficiency.
このため、上記化合物粒子の平均一次粒子径はナノサイズであることが必要であり、１ｎｍ以上１００ｎｍ以下であることが必要であり、好ましくは１ｎｍ以上５０ｎｍ以下である。上記平均一次粒子径が１００ｎｍを超えると、鉄元素、錫元素及びインジウム元素が同一結晶内で均一分布していた場合でも、数百ｎｍサイズのグレインが存在することとなり、ナノコイルの大きさと比較した場合には組成に偏りのある不均一な状態であると考えられるからである。また、各種金属化合物の格子定数が約０．５ｎｍ前後であることから、上記平均一次粒子径が０．５ｎｍ未満の化合物粒子を作製することは困難となる。このため、上記化合物粒子の平均一次粒子径の下限値は１ｎｍとする。 For this reason, the average primary particle diameter of the compound particles needs to be nano-sized, needs to be 1 nm or more and 100 nm or less, and preferably 1 nm or more and 50 nm or less. When the average primary particle diameter exceeds 100 nm, even when iron element, tin element, and indium element are uniformly distributed in the same crystal, grains having a size of several hundred nm exist, and compared with the size of the nanocoil. This is because in some cases, it is considered that the composition is uneven and has an uneven state. Moreover, since the lattice constants of various metal compounds are around 0.5 nm, it is difficult to produce compound particles having the average primary particle diameter of less than 0.5 nm. For this reason, the lower limit of the average primary particle diameter of the compound particles is 1 nm.
また、上記化合物粒子に含有される錫元素及びインジウム元素の合計量は、化合物粒子に含有される鉄元素、錫元素及びインジウム元素の合計量に対して、１０ｍｏｌ％以上９０ｍｏｌ％以下であり、１５ｍｏｌ％以上５０ｍｏｌ％以下がより好ましい。各元素の割合が少なすぎる場合には、鉄、錫、インジウムの各元素を同時に含有する複合金属化合物を作製した場合でも、場所依存性のない均一混合体を作ることが非常に困難となるためである。 The total amount of tin element and indium element contained in the compound particles is 10 mol% or more and 90 mol% or less, and 15 mol with respect to the total amount of iron element, tin element and indium element contained in the compound particles. % To 50 mol% is more preferable. If the proportion of each element is too small, it will be very difficult to make a homogeneous mixture without location dependency even when a composite metal compound containing each element of iron, tin, and indium is prepared at the same time. It is.
上記化合物粒子としては、マグネタイト構造の（Ｆｅ，Ｓｎ）3Ｏ4、（Ｆｅ，Ｓｎ，Ｉｎ）3Ｏ4、ヘマタイト構造のα−（Ｆｅ，Ｓｎ）2Ｏ3、α−（Ｆｅ，Ｓｎ，Ｉｎ）2Ｏ3、マグヘマイト構造のγ−（Ｆｅ，Ｓｎ）2Ｏ3、γ−（Ｆｅ，Ｓｎ，Ｉｎ）2Ｏ3、ゲーサイト構造の（Ｆｅ，Ｓｎ）ＯＯＨ、（Ｆｅ，Ｓｎ，Ｉｎ）ＯＯＨなどの化合物を使用できるが、中でもＦｅ−Ｓｎ置換体あるいはＦｅ−Ｓｎ−Ｉｎ置換体を最も簡便に作製することができ、且つ安定に存在し得るマグネタイト構造あるいはヘマタイト構造を有する化合物が最も好ましい。 Examples of the compound particles include magnetite structure (Fe, Sn) 3 O 4 , (Fe, Sn, In) 3 O 4 , hematite structure α- (Fe, Sn) 2 O 3 , α- (Fe, Sn, in) 2 O 3, maghemite structure γ- (Fe, Sn) 2 O 3, γ- (Fe, Sn, in) 2 O 3, goethite structure (Fe, Sn) OOH, ( Fe, Sn, in ) Compounds such as OOH can be used. Among them, the compound having the magnetite structure or hematite structure that can be most easily prepared and can exist stably is the most. preferable.
本実施形態のカーボンナノコイル製造用触媒は、上記化合物粒子そのものを用いてもよいが、上記化合物粒子をさらに担体上に担持させて用いてもよい。担体としては、実施形態１で説明した担体と同様の担体を用いることができる。 The catalyst for producing carbon nanocoils of this embodiment may use the compound particles themselves, or may be used by further supporting the compound particles on a carrier. As the carrier, the same carrier as that described in Embodiment 1 can be used.
次に、本発明の第２のカーボンナノコイル製造用触媒の製造方法について説明する。本発明の第２のカーボンナノコイル製造用触媒の製造方法は、錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液とを、攪拌しながら混合して、鉄化合物粒子と錫化合物粒子とを析出させて、前記鉄化合物粒子と前記錫化合物粒子とを含む懸濁液を作製する第１工程と、前記懸濁液を１００〜２５０℃の温度範囲で水熱処理する第２ａ工程又は前記鉄化合物粒子と前記錫化合物粒子とを乾燥するとともに、３００〜７００℃の温度範囲で加熱処理する第２ｂ工程とを含むことを特徴とする。これにより、鉄元素及び錫元素を同一結晶内に含む鉄−錫化合物粒子を得ることができる。 Next, the manufacturing method of the 2nd catalyst for carbon nano coil manufacture of this invention is demonstrated. According to the second method for producing a catalyst for producing carbon nanocoils of the present invention, an alkaline aqueous solution containing tin ions and an aqueous solution containing iron ions are mixed with stirring to precipitate iron compound particles and tin compound particles. A first step of preparing a suspension containing the iron compound particles and the tin compound particles, and a second step of hydrothermally treating the suspension in a temperature range of 100 to 250 ° C. or the iron compound particles And the tin compound particles are dried, and include a second step (b) in which heat treatment is performed in a temperature range of 300 to 700 ° C. Thereby, the iron-tin compound particle | grains which contain an iron element and a tin element in the same crystal | crystallization can be obtained.
また、上記鉄−錫化合物粒子の同一結晶内にさらにインジウム元素を含有させる場合には、上記鉄イオンを含む水溶液にさらにインジウムイオンを含有させ、上記と同様の工程を行えばよい。 Further, when an indium element is further contained in the same crystal of the iron-tin compound particles, an indium ion is further contained in the aqueous solution containing the iron ion, and the same process as described above may be performed.
さらに、本発明の第２のカーボンナノコイル製造用触媒の製造方法は、前記化合物粒子を担体上に担持させる第３工程をさらに含むこともできる。 Furthermore, the second method for producing a catalyst for producing carbon nanocoils of the present invention may further include a third step of supporting the compound particles on a carrier.
上記第１工程及び上記第３工程は、実施形態１で説明した第１工程及び第３工程と同様に行うことができるので、その説明は省略する。 Since the first step and the third step can be performed in the same manner as the first step and the third step described in the first embodiment, the description thereof is omitted.
上記第２ａ工程を行う場合は、上記第１工程で得られた懸濁液を室温で１５時間以上の時間熟成した後、水の存在下、１００℃以上２５０℃以下で水熱処理を行うことが好ましい。その後、水熱処理後の懸濁液を洗浄、ろ過し、８５〜９５℃で乾燥すればよい。この際、水熱処理の温度が１００℃未満では各元素間で化合物化せず、２５０℃超えると粒子径が大きく成長しすぎる傾向にあり、また装置設備にかかるコストも上昇するため、好ましくない。 In the case of performing the step 2a, the suspension obtained in the first step is aged at room temperature for 15 hours or longer and then hydrothermally treated at 100 ° C. or higher and 250 ° C. or lower in the presence of water. preferable. Then, what is necessary is just to wash | clean and filter the suspension after hydrothermal treatment, and to dry at 85-95 degreeC. At this time, when the temperature of the hydrothermal treatment is less than 100 ° C., no compound is formed between the elements, and when it exceeds 250 ° C., the particle diameter tends to grow too much and the cost for the equipment increases, which is not preferable.
また、上記第２ｂ工程を行う場合は、上記第１工程で得られた懸濁液を室温で１５時間以上の時間熟成した後、ろ過して乾燥して得られた乾燥粉末を窒素中又は空気中で３００℃以上７００℃以下で加熱処理を行うことが好ましい。この場合も同様に、３００℃未満の温度では各元素間で化合物化しないため好ましくなく、７００℃超える温度では粒子同士が焼結し、粗大粒子が生成するために好ましくない。微粒子を得るためには、上記加熱処理よりも上記水熱処理を行うことがより好ましい。 When the step 2b is performed, the suspension obtained in the first step is aged at room temperature for 15 hours or longer, and then filtered and dried to obtain a dry powder in nitrogen or air. Among them, it is preferable to perform the heat treatment at 300 ° C. or more and 700 ° C. or less. Similarly, in this case, a temperature lower than 300 ° C. is not preferable because it does not compound between elements, and a temperature higher than 700 ° C. is not preferable because particles are sintered and coarse particles are generated. In order to obtain fine particles, it is more preferable to perform the hydrothermal treatment than the heat treatment.
以下、実施例により本発明を説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to a following example.
（実施例１）
水酸化ナトリウム６３．５ｇを４Ｌの水に溶解した後、これに塩化スズ（II）四水和物を２０ｇ溶解し、アルカリ−錫混合水溶液を作製した。これとは別に、塩化鉄（III）七水和物１３６ｇを２Ｌの水に溶解し、鉄水溶液を作製した。この鉄水溶液を上記アルカリ−錫混合水溶液に攪拌しながら滴下し、鉄化合物粒子及び錫化合物粒子の混合沈殿物を析出させた。この混合沈殿物が析出した懸濁液を室温で２０時間熟成した後、水洗、ろ過し、錫元素が１４ｍｏｌ％含有された、鉄化合物粒子及び錫化合物粒子の混合体粉末を得た。ここで、錫元素の含有量は蛍光Ｘ線分析（ＸＲＦ）により求めた。また、以下の他の実施例及び比較例でも同様にして各元素の含有量を求めた。
Example 1
After dissolving 63.5 g of sodium hydroxide in 4 L of water, 20 g of tin (II) chloride tetrahydrate was dissolved therein to prepare an alkali-tin mixed aqueous solution. Separately, 136 g of iron (III) chloride heptahydrate was dissolved in 2 L of water to prepare an aqueous iron solution. This iron aqueous solution was added dropwise to the alkali-tin mixed aqueous solution while stirring to precipitate a mixed precipitate of iron compound particles and tin compound particles. The suspension in which this mixed precipitate was deposited was aged at room temperature for 20 hours, then washed with water and filtered to obtain a mixture powder of iron compound particles and tin compound particles containing 14 mol% of tin element. Here, the content of tin element was determined by fluorescent X-ray analysis (XRF). In addition, the content of each element was determined in the same manner in the following other examples and comparative examples.
この混合体粉末の粉末Ｘ線回折スペクトルを測定した。その結果を図１に示す。図１から、非常にブロードなピークが認められ、鉄化合物及び錫化合物に起因するピークは認められず、鉄化合物粒子及び錫化合物粒子のいずれもアモルファス構造をとることが確認された。但し、上記混合体粉末の色が黄色を呈していたため、本実施例の鉄化合物粒子は元々ＦｅＯＯＨに由来する鉄化合物粒子であると考えられる。 The powder X-ray diffraction spectrum of this mixture powder was measured. The result is shown in FIG. From FIG. 1, it was confirmed that a very broad peak was observed, no peaks attributable to the iron compound and the tin compound were observed, and both the iron compound particles and the tin compound particles had an amorphous structure. However, since the color of the mixture powder was yellow, the iron compound particles of this example are considered to be iron compound particles originally derived from FeOOH.
また、上記混合体粉末のＴＥＭ観察により鉄化合物微粒子及び雲状の錫化合物粒子が観測された。図２にそのＴＥＭ写真を示す。図２のＴＥＭ写真からそれらの平均一次粒子径を測定した結果、鉄化合物粒子及び錫化合物粒子の平均一次粒子径は、それぞれ、２．１ｎｍ及び１８．９ｎｍであった。 Further, iron compound fine particles and cloud-like tin compound particles were observed by TEM observation of the powder mixture. The TEM photograph is shown in FIG. As a result of measuring the average primary particle diameter from the TEM photograph of FIG. 2, the average primary particle diameters of the iron compound particles and the tin compound particles were 2.1 nm and 18.9 nm, respectively.
次に、以上のようにして得られた鉄化合物−錫化合物混合体粉末を、担体上に担持させた。担体として平均一次粒子径６０μｍのアルミナ粒子４００ｇを用い、これに鉄化合物−錫化合物粒子混合体粉末６ｇを加え、回転数５００ｒｐｍで３０分の間ボールミルで粉砕混合を行い、アルミナ粒子上に鉄化合物−錫化合物混合体粉末を担持させて、本実施例のカーボンナノコイル製造用触媒を得た。 Next, the iron compound-tin compound mixture powder obtained as described above was supported on a carrier. 400 g of alumina particles having an average primary particle diameter of 60 μm are used as a carrier, 6 g of an iron compound-tin compound particle mixture powder is added thereto, and pulverized and mixed with a ball mill for 30 minutes at a rotation speed of 500 rpm. A catalyst for producing carbon nanocoils of this example was obtained by supporting a tin compound mixture powder.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄化合物−錫化合物混合体の被覆厚さは０．５μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は２．４ｍ2／ｇであった。また、担体粒子の表面の元素分析をエネルギー分散型蛍光Ｘ線分析（ＥＤＸ）により行い、同一混合体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率は１１〜１５ｍｏｌ％であることが分かり、同一粒子内で鉄元素及び錫元素がほぼ一様に分布していることが確認された。 The coating thickness of the iron compound-tin compound mixture supported on the support of the obtained catalyst for producing carbon nanocoils is 0.5 μm, and the BET specific surface area determined from nitrogen gas adsorption is 2.4 m 2 / g. Met. In addition, elemental analysis of the surface of the carrier particles was performed by energy dispersive X-ray fluorescence (EDX), and elemental analysis was performed at 10 locations in the same mixture particles. As a result, the ratio of the tin element was found to be 11 to 15 mol%, and it was confirmed that the iron element and the tin element were distributed almost uniformly within the same particle.
（実施例２）
実施例１と同様の方法で、錫元素が２０ｍｏｌ％含有された、鉄化合物粒子及び錫化合物粒子の混合体粉末を得た。
(Example 2)
In the same manner as in Example 1, a mixture powder of iron compound particles and tin compound particles containing 20 mol% of tin element was obtained.
この混合体粉末の粉末Ｘ線回折スペクトルを測定した結果、実施例１と同様のブロードなピークが観測され、鉄化合物粒子及び錫化合物粒子のいずれもアモルファス構造をとることが確認された。また、ＴＥＭ写真により平均一次粒子径を求めたところ、鉄化合物粒子及び錫化合物粒子の平均一次粒子径は、それぞれ、１．９ｎｍ及び１９．３ｎｍであった。 As a result of measuring the powder X-ray diffraction spectrum of this mixture powder, a broad peak similar to that in Example 1 was observed, and it was confirmed that both the iron compound particles and the tin compound particles had an amorphous structure. Moreover, when the average primary particle diameter was calculated | required with the TEM photograph, the average primary particle diameter of the iron compound particle and the tin compound particle was 1.9 nm and 19.3 nm, respectively.
次に、以上のようにして得られた鉄化合物−錫化合物混合体粉末を１５ｇ用いた以外は、実施例１と同様にして、上記鉄化合物−錫化合物混合体粉末を担体上に担持させて本実施例のカーボンナノコイル製造用触媒を得た。 Next, the iron compound-tin compound mixture powder was supported on a carrier in the same manner as in Example 1 except that 15 g of the iron compound-tin compound mixture powder obtained as described above was used. A catalyst for producing carbon nanocoils of this example was obtained.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄化合物−錫化合物混合体の被覆厚さは１．８μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は２．６ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一混合体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率は１７〜２２ｍｏｌ％であることが分かり、同一粒子内で鉄元素及び錫元素がほぼ一様に分布していることが確認された。 The coating thickness of the iron compound-tin compound mixture supported on the support of the obtained catalyst for producing carbon nanocoils is 1.8 μm, and the BET specific surface area determined from nitrogen gas adsorption is 2.6 m 2 / g. Met. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same mixture particles. As a result, it was found that the ratio of the tin element was 17 to 22 mol%, and it was confirmed that the iron element and the tin element were distributed almost uniformly in the same particle.
（実施例３）
水酸化ナトリウム６３．５ｇと塩化スズ（II）四水和物２０ｇとを４Ｌの水に溶解し、アルカリ−錫混合水溶液を作製し、これとは別に塩化鉄（III）七水和物１３６ｇと塩化インジウム（III）六水和物を２Ｌの水に溶解し、鉄−インジウム混合水溶液を作製した以外は、実施例１と同様にして、錫元素が７ｍｏｌ％、インジウム元素が２３ｍｏｌ％（合計３０ｍｏｌ％）含有された、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子の混合体粉末を得た。
(Example 3)
63.5 g of sodium hydroxide and 20 g of tin (II) chloride tetrahydrate are dissolved in 4 L of water to prepare an alkali-tin mixed aqueous solution. Separately, 136 g of iron (III) chloride heptahydrate Except that indium (III) chloride hexahydrate was dissolved in 2 L of water to prepare an iron-indium mixed aqueous solution, 7 mol% of tin element and 23 mol% of indium element (total 30 mol) were obtained in the same manner as in Example 1. %) Contained, a mixed powder of iron compound particles, tin compound particles and indium compound particles was obtained.
この混合体粉末の粉末Ｘ線回折スペクトルを測定した結果、実施例１と同様のブロードなピークが観測され、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子のいずれもアモルファス構造をとることが確認された。また、ＴＥＭ写真により平均一次粒子径を求めたところ、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子の平均一次粒子径は、それぞれ、２．２ｎｍ、１６．７ｎｍ及び１９．１ｎｍであった。 As a result of measuring the powder X-ray diffraction spectrum of this mixed powder, the same broad peak as in Example 1 was observed, and it was confirmed that all of the iron compound particles, tin compound particles and indium compound particles had an amorphous structure. It was. Moreover, when the average primary particle diameter was calculated | required with the TEM photograph, the average primary particle diameter of iron compound particle | grains, a tin compound particle | grain, and an indium compound particle | grain was 2.2 nm, 16.7 nm, and 19.1 nm, respectively.
次に、以上のようにして得られた混合体粉末を用いた以外は、実施例１と同様にして、上記混合体粉末を担体上に担持させて本実施例のカーボンナノコイル製造用触媒を得た。 Next, except that the mixture powder obtained as described above was used, the mixture powder was supported on a carrier in the same manner as in Example 1, and the carbon nanocoil production catalyst of this example was used. Obtained.
得られたカーボンナノコイル製造用触媒の担体上に担持された上記混合体の被覆厚さは０．５μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は２．７ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一混合体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率は５〜８ｍｏｌ％であり、インジウム元素の比率は２０〜２５ｍｏｌ％であることが分かり、同一粒子内で鉄元素、錫元素及びインジウム元素がほぼ一様に分布していることが確認された。 The coating thickness of the mixture supported on the carrier of the obtained catalyst for producing carbon nanocoils was 0.5 μm, and the BET specific surface area determined from nitrogen gas adsorption was 2.7 m 2 / g. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same mixture particles. As a result, the ratio of tin element is 5 to 8 mol%, the ratio of indium element is 20 to 25 mol%, and iron element, tin element and indium element are distributed almost uniformly in the same particle. It was confirmed that
（実施例４）
鉄水溶液をアルカリ−錫混合水溶液に攪拌しながら滴下する際、アルカリ−錫混合水溶液中に空気をバブリングさせながら、鉄化合物粒子及び錫化合物粒子の混合沈殿物を析出させた以外は、実施例１と同様にして、鉄化合物粒子及び錫化合物粒子の混合体粉末を得た。
Example 4
Example 1 When the aqueous iron solution was dropped into the alkali-tin mixed aqueous solution while stirring, Example 1 except that a mixed precipitate of iron compound particles and tin compound particles was precipitated while bubbling air into the alkaline-tin mixed aqueous solution. In the same manner as above, a mixed powder of iron compound particles and tin compound particles was obtained.
この混合体粉末の粉末Ｘ線回折スペクトルを測定した結果、幅の広いα−ＦｅＯＯＨのピーク及び微弱ながらＳｎ（ＯＨ）2のピークが観測された。また、ＴＥＭ写真により平均一次粒子径を求めたところ、鉄化合物粒子及び錫化合物粒子の平均一次粒子径は、それぞれ、１．５ｎｍ及び１３．２ｎｍであった。 As a result of measuring the powder X-ray diffraction spectrum of this mixture powder, a broad α-FeOOH peak and a weakly Sn (OH) 2 peak were observed. Moreover, when the average primary particle diameter was calculated | required with the TEM photograph, the average primary particle diameter of the iron compound particle and the tin compound particle was 1.5 nm and 13.2 nm, respectively.
次に、以上のようにして得られた鉄化合物−錫化合物混合体粉末を用いた以外は、実施例１と同様にして、上記鉄化合物−錫化合物混合体粉末を担体上に担持させて本実施例のカーボンナノコイル製造用触媒を得た。 Next, the above iron compound-tin compound mixture powder was supported on a carrier in the same manner as in Example 1 except that the iron compound-tin compound mixture powder obtained as described above was used. A catalyst for producing carbon nanocoils of the example was obtained.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄化合物−錫化合物混合体の被覆厚さは０．５μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は２．１ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一混合体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率は１１〜１５ｍｏｌ％であることが分かり、同一粒子内で鉄元素及び錫元素がほぼ一様に分布していることが確認された。 The coating thickness of the iron compound-tin compound mixture supported on the carrier of the resulting catalyst for producing carbon nanocoils is 0.5 μm, and the BET specific surface area determined from nitrogen gas adsorption is 2.1 m 2 / g. Met. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same mixture particles. As a result, the ratio of the tin element was found to be 11 to 15 mol%, and it was confirmed that the iron element and the tin element were distributed almost uniformly within the same particle.
（実施例５）
実施例１と同様の方法で、錫元素が２０ｍｏｌ％含有された、鉄化合物粒子及び錫化合物粒子の混合体粉末を得た。次に、この混合粉末を空気中で、６００℃で２時間の加熱処理を行い、鉄−錫化合物粒子の単体粉末を得た。
(Example 5)
In the same manner as in Example 1, a mixture powder of iron compound particles and tin compound particles containing 20 mol% of tin element was obtained. Next, this mixed powder was heat-treated in air at 600 ° C. for 2 hours to obtain a simple powder of iron-tin compound particles.
この単体粉末の粉末Ｘ線回折スペクトルを測定した結果、α−Ｆｅ2Ｏ3及びβ−ＦｅＯＯＨに起因する明確なピークが観測される一方で、結晶化に十分な熱処理を行っているにも関わらず錫に起因するピークは全く観測されず、錫元素が鉄化合物の結晶構造中の鉄元素と置換されていることが確認された。また、ＴＥＭ写真により平均一次粒子径を求めたところ、鉄−錫化合物粒子の平均一次粒子径は、２０．５ｎｍであった。 As a result of measuring the powder X-ray diffraction spectrum of this simple powder, a clear peak due to α-Fe 2 O 3 and β-FeOOH is observed, but the heat treatment is sufficient for crystallization. No peak attributed to tin was observed, and it was confirmed that the tin element was replaced with the iron element in the crystal structure of the iron compound. Moreover, when the average primary particle diameter was calculated | required with the TEM photograph, the average primary particle diameter of the iron-tin compound particle | grains was 20.5 nm.
次に、以上のようにして得られた鉄−錫化合物単体粉末を、担体上に担持させた。担体として平均一次粒子径６０μｍのアルミナ粒子４００ｇを用い、これに鉄−錫化合物単体粉末１０ｇを加え、回転数５００ｒｐｍで３０分の間ボールミルで粉砕混合を行い、アルミナ粒子上に鉄−錫化合物単体粉末を担持させて、本実施例のカーボンナノコイル製造用触媒を得た。 Next, the iron-tin compound simple powder obtained as described above was supported on a carrier. 400 g of alumina particles having an average primary particle size of 60 μm are used as a carrier, 10 g of iron-tin compound powder is added thereto, and pulverized and mixed in a ball mill for 30 minutes at a rotation speed of 500 rpm. The catalyst for producing carbon nanocoils of this example was obtained by supporting the powder.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄−錫化合物単体の被覆厚さは１．２μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は１．２ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一単体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率が１９〜２２ｍｏｌ％であることが分かり、鉄元素及び錫元素がほぼ一様に分布していることが確認された。 The coating thickness of the iron-tin compound alone supported on the support of the obtained catalyst for producing carbon nanocoils was 1.2 μm, and the BET specific surface area obtained from nitrogen gas adsorption was 1.2 m 2 / g. It was. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same single particle. As a result, it was found that the ratio of the tin element was 19 to 22 mol%, and it was confirmed that the iron element and the tin element were distributed almost uniformly.
（実施例６）
実施例１と同様の方法で、錫元素が１０ｍｏｌ％含有された、鉄化合物粒子及び錫化合物粒子の混合沈殿物を析出させた。この混合沈殿物が析出した懸濁液を室温で２０時間熟成し、圧力容器中で１５０℃の水熱処理を４時間行った後、水洗、ろ過し、鉄−錫化合物粒子の単体粉末を得た。
(Example 6)
In the same manner as in Example 1, a mixed precipitate of iron compound particles and tin compound particles containing 10 mol% of tin element was deposited. The suspension in which this mixed precipitate was deposited was aged at room temperature for 20 hours, hydrothermally treated at 150 ° C. for 4 hours in a pressure vessel, then washed with water and filtered to obtain a simple powder of iron-tin compound particles. .
この単体粉末の粉末Ｘ線回折スペクトルを測定した。その結果を図３に示す。図３では、比較のためα−Ｆｅ2Ｏ3の既定ピークも合わせて表示した。図３から、α−Ｆｅ2Ｏ3に起因する明確なピークが観測される一方で、結晶化に十分な水熱処理を行っているにも関わらず錫に起因するピークは全く観測されず、錫元素が鉄化合物の結晶構造中の鉄元素と置換されていることが確認された。また、ＴＥＭ観察によるＴＥＭ写真を図４に示す。図４のＴＥＭ写真から平均一次粒子径を求めたところ、鉄−錫化合物粒子の平均一次粒子径は、１２．８ｎｍであった。 The powder X-ray diffraction spectrum of this simple powder was measured. The result is shown in FIG. In FIG. 3, a predetermined peak of α-Fe 2 O 3 is also shown for comparison. From FIG. 3, while a clear peak attributed to α-Fe 2 O 3 is observed, no peak attributed to tin is observed even though hydrothermal treatment sufficient for crystallization is performed. It was confirmed that the element was substituted with the iron element in the crystal structure of the iron compound. Moreover, the TEM photograph by TEM observation is shown in FIG. When the average primary particle diameter was determined from the TEM photograph of FIG. 4, the average primary particle diameter of the iron-tin compound particles was 12.8 nm.
次に、以上のようにして得られた鉄−錫化合物単体粉末を用いた以外は、実施例５と同様にして、上記鉄−錫化合物単体粉末を担体上に担持させて本実施例のカーボンナノコイル製造用触媒を得た。 Next, in the same manner as in Example 5 except that the iron-tin compound simple substance powder obtained as described above was used, the above-mentioned iron-tin compound simple substance powder was supported on a carrier, and the carbon of this example was used. A catalyst for producing nanocoils was obtained.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄−錫化合物単体の被覆厚さは１．１μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は１．８ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一単体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率が９〜１１ｍｏｌ％であることが分かり、鉄元素及び錫元素がほぼ一様に分布していることが確認された。 The coating thickness of the iron-tin compound alone supported on the carbon nanocoil production catalyst support was 1.1 μm, and the BET specific surface area determined from nitrogen gas adsorption was 1.8 m 2 / g. It was. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same single particle. As a result, it was found that the ratio of the tin element was 9 to 11 mol%, and it was confirmed that the iron element and the tin element were distributed almost uniformly.
（実施例７）
実施例３と同様の方法で、錫元素及びインジウム元素がそれぞれ８ｍｏｌ％ずつ含有された、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子の混合体粉末を得た。次に、この混合体粉末を空気中で、６００℃で２時間の加熱処理を行い、鉄−錫−インジウム化合物粒子の単体粉末を得た。
(Example 7)
In the same manner as in Example 3, a mixture powder of iron compound particles, tin compound particles and indium compound particles each containing 8 mol% of tin element and indium element was obtained. Next, this mixture powder was heat-treated in air at 600 ° C. for 2 hours to obtain a simple powder of iron-tin-indium compound particles.
この単体粉末の粉末Ｘ線回折スペクトルを測定した結果、大部分がα−Ｆｅ2Ｏ3に起因する明確なピークが観測され、微弱ながらβ−ＦｅＯＯＨに起因するピークが観測される一方で、結晶化に十分な熱処理を行っているにも関わらず錫及びインジウムに起因するピークは全く観測されず、錫元素及びインジウム元素が鉄化合物の結晶構造中の鉄元素と置換されていることが確認された。また、ＴＥＭ写真により平均一次粒子径を求めたところ、鉄−錫−インジウム化合物粒子の平均一次粒子径は、２４．７ｎｍであった。 As a result of measuring the powder X-ray diffraction spectrum of this simple powder, a clear peak mostly due to α-Fe 2 O 3 was observed, while a weak peak due to β-FeOOH was observed, In spite of sufficient heat treatment for crystallization, no peaks due to tin and indium were observed, confirming that tin and indium elements were replaced with iron elements in the crystal structure of iron compounds. It was. Moreover, when the average primary particle diameter was calculated | required with the TEM photograph, the average primary particle diameter of the iron-tin-indium compound particle | grains was 24.7 nm.
次に、以上のようにして得られた鉄−錫−インジウム化合物単体粉末を用いた以外は、実施例５と同様にして、上記鉄−錫−インジウム化合物単体粉末を担体上に担持させて本実施例のカーボンナノコイル製造用触媒を得た。 Next, except that the iron-tin-indium compound simple powder obtained as described above was used, the iron-tin-indium compound simple powder was supported on a carrier in the same manner as in Example 5. A catalyst for producing carbon nanocoils of the example was obtained.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄−錫−インジウム化合物単体の被覆厚さは１．２μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は１．４ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一単体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率が６〜９ｍｏｌ％であり、インジウム元素の比率が７〜１０ｍｏｌ％であることが分かり、鉄元素、錫元素及びインジウム元素がほぼ一様に分布していることが確認された。 The coating thickness of the simple iron-tin-indium compound supported on the carrier of the obtained catalyst for producing carbon nanocoils is 1.2 μm, and the BET specific surface area obtained from nitrogen gas adsorption is 1.4 m 2 / g. Met. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same single particle. As a result, it was found that the ratio of tin element was 6 to 9 mol% and the ratio of indium element was 7 to 10 mol%, and it was confirmed that iron element, tin element and indium element were distributed almost uniformly. It was done.
（比較例１）
平均一次粒子径２０ｎｍのα酸化鉄粉末１１．４ｇと、平均一次粒子径１５０ｎｍの酸化錫粉末３．６ｇを混合して、錫元素の含有比率を１４ｍｏｌ％とし、これに平均一次粒子径６０μｍのアルミナ粒子４００ｇを加え、回転数５００ｒｐｍで３０分の間ボールミルで粉砕混合を行い、アルミナ粒子上に酸化鉄粒子及び酸化錫粒子を混合担持させた。担体上に担持された担持体粉末の被覆厚さは２．１μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は０．６５ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一粒子中１０箇所の元素分析を行った。その結果、鉄元素及び錫元素の存在比率にバラつきがあり、錫元素の比率が３〜６０ｍｏｌ％と場所により大きく異なる値が得られた。
(Comparative Example 1)
11.4 g of α iron oxide powder having an average primary particle diameter of 20 nm and 3.6 g of tin oxide powder having an average primary particle diameter of 150 nm are mixed to make the content ratio of tin element 14 mol%, and this has an average primary particle diameter of 60 μm. 400 g of alumina particles were added, and pulverized and mixed with a ball mill for 30 minutes at a rotation speed of 500 rpm, and iron oxide particles and tin oxide particles were mixed and supported on the alumina particles. The coating thickness of the carrier powder carried on the carrier was 2.1 μm, and the BET specific surface area determined from nitrogen gas adsorption was 0.65 m 2 / g. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same particle. As a result, the abundance ratio of the iron element and the tin element varied, and the ratio of the tin element was 3 to 60 mol%, which was greatly different depending on the location.
（比較例２）
実施例１と同様の方法で、錫元素が５ｍｏｌ％含有された、鉄化合物粒子及び錫化合物粒子の混合体粉末を得た。
(Comparative Example 2)
In the same manner as in Example 1, a mixture powder of iron compound particles and tin compound particles containing 5 mol% of tin element was obtained.
この混合体粉末の粉末Ｘ線回折スペクトルを測定した結果、実施例１と同様のブロードなピークが観測され、鉄化合物粒子及び錫化合物粒子のいずれもアモルファス構造をとることが確認された。また、ＴＥＭ写真により平均一次粒子径を求めたところ、鉄化合物粒子及び錫化合物粒子の平均一次粒子径は、それぞれ、２．２ｎｍ及び１９．０ｎｍであった。 As a result of measuring the powder X-ray diffraction spectrum of this mixture powder, a broad peak similar to that in Example 1 was observed, and it was confirmed that both the iron compound particles and the tin compound particles had an amorphous structure. Moreover, when the average primary particle diameter was calculated | required with the TEM photograph, the average primary particle diameter of the iron compound particle and the tin compound particle was 2.2 nm and 19.0 nm, respectively.
次に、以上のようにして得られた鉄化合物−錫化合物混合体粉末を６ｇ用いた以外は、実施例１と同様にして、上記鉄化合物−錫化合物混合体粉末を担体上に担持させて本実施例のカーボンナノコイル製造用触媒を得た。 Next, the iron compound-tin compound mixture powder was supported on a carrier in the same manner as in Example 1 except that 6 g of the iron compound-tin compound mixture powder obtained as described above was used. A catalyst for producing carbon nanocoils of this example was obtained.
得られたカーボンナノコイル製造用触媒の担体上に担持された鉄化合物−錫化合物混合体の被覆厚さは０．５μｍであり、窒素ガス吸着から求められるＢＥＴ比表面積は２．５ｍ2／ｇであった。また、担体粒子の表面の元素分析をＥＤＸにより行い、同一混合体粒子中１０箇所の元素分析を行った。その結果、錫元素の比率が０．５ｍｏｌ％以下である点が２箇所確認され、残り８箇所では３〜８ｍｏｌ％であることが分かり、一様に分布していないことが確認された。 The coating thickness of the iron compound-tin compound mixture supported on the carrier of the resulting catalyst for producing carbon nanocoils is 0.5 μm, and the BET specific surface area determined from nitrogen gas adsorption is 2.5 m 2 / g. Met. Further, elemental analysis of the surface of the carrier particles was performed by EDX, and elemental analysis was performed at 10 locations in the same mixture particles. As a result, two points where the ratio of the tin element was 0.5 mol% or less were confirmed, and it was found that the remaining 8 points were 3 to 8 mol%, and it was confirmed that they were not uniformly distributed.
以上の実施例１〜７及び比較例１、２の結果を表１にまとめて示す。 The results of Examples 1 to 7 and Comparative Examples 1 and 2 are summarized in Table 1.
表１の結果から、実施例１〜３で得られた各化合物混合体を担持体原料として用いた場合には、担持体原料の各元素比率と、最終的に得られた担持体粒子の表面における元素比率とがほぼ同じとなり、担持体粒子の表面において各元素がほぼ一様に分布していることが分かる。これは、実施例１〜３においては、各化合物粒子の平均一次粒子径を微細化したこと、及び、担持体原料としてアモルファス粒子を用いたことによるためと考えられる。また、各化合物の混合沈殿物を析出させる際に空気をバブリングさせた実施例４では、実施例１〜３に比べて、担持体粒子の粒径をさらに微細化することができたことが分かる。また、実施例５〜７で得られた酸化鉄構造を持つ化合物粒子を担持体として用いた場合には、実施例１〜３と比較しても、担持体粒子の表面において各元素がさらに一様に分布していることが分かる。 From the results in Table 1, when each compound mixture obtained in Examples 1 to 3 is used as a carrier material, the ratio of each element of the carrier material and the surface of the finally obtained carrier particles It can be seen that the element ratios in the graph are almost the same, and each element is distributed almost uniformly on the surface of the carrier particles. This is considered to be because in Examples 1 to 3, the average primary particle diameter of each compound particle was refined and amorphous particles were used as the support material. Moreover, in Example 4 which bubbled air when depositing the mixed deposit of each compound, compared with Examples 1-3, it turned out that the particle size of the carrier particle | grain was able to be refined | miniaturized further. . Further, when the compound particles having an iron oxide structure obtained in Examples 5 to 7 are used as the support, each element is further added on the surface of the support particles even when compared with Examples 1 to 3. It can be seen that the distribution is similar.
一方、比較例１においては、作製した鉄化合物−錫化合物混合体の錫元素の含有比率を実施例１と同様に１４ｍｏｌ％としたが、各化合物粒子の粒子径が大きいために、担持体粒子とした場合の表面元素比率にバラツキが生じ、最大では錫元素の含有比率が６０ｍｏｌ％にまで達する箇所があることが分かる。また、比較例２については、作製した鉄化合物−錫化合物混合体の錫元素の含有比率が５ｍｏｌと少ないために、均一混合することが非常に難しく、結果的に得られた担持体粒子表面に、錫元素の含有率が０．５ｍｏｌ％を下回り錫元素がほとんど分布していない箇所が存在することが分かる。 On the other hand, in Comparative Example 1, the content ratio of tin element in the prepared iron compound-tin compound mixture was 14 mol% as in Example 1. However, since the particle diameter of each compound particle is large, the carrier particles It can be seen that there is a variation in the surface element ratio in the case where the content ratio of tin element is 60 mol% at the maximum. Moreover, about the comparative example 2, since the content ratio of the tin element of the produced iron compound-tin compound mixture is as small as 5 mol, it is very difficult to uniformly mix, and as a result, the obtained support particle surface It can be seen that there are places where the content of tin element is less than 0.5 mol% and the tin element is hardly distributed.
以上のように、本発明は、鉄元素及び錫元素が均一に分布したカーボンナノコイル製造用触媒を提供するものであり、気相法でカーボンナノコイルを作製する際に、コイル径の均一なカーボンナノコイルを高効率に生産することができる。 As described above, the present invention provides a catalyst for producing carbon nanocoils in which iron elements and tin elements are uniformly distributed. When producing carbon nanocoils by a vapor phase method, the coil diameter is uniform. Carbon nanocoils can be produced with high efficiency.
Claims (21)
前記鉄化合物粒子の平均一次粒子径は、１〜１０ｎｍであり、
前記錫化合物粒子の平均一次粒子径は、１〜１００ｎｍであり、
前記混合体に含有される錫元素の量は、前記混合体に含有される鉄元素及び錫元素の合計量に対して、１０〜９０ｍｏｌ％であることを特徴とするカーボンナノコイル製造用触媒。 A catalyst for producing a carbon nanocoil in which a mixture containing iron compound particles and tin compound particles is supported on a carrier,
The average primary particle diameter of the iron compound particles is 1 to 10 nm,
The average primary particle diameter of the tin compound particles is 1 to 100 nm,
The amount of tin element contained in the mixture is 10 to 90 mol% with respect to the total amount of iron element and tin element contained in the mixture.
前記化合物粒子の平均一次粒子径は、１〜１００ｎｍであり、
前記化合物粒子に含有される錫元素の量は、前記化合物粒子に含有される鉄元素及び錫元素の合計量に対して、１０〜９０ｍｏｌ％であることを特徴とするカーボンナノコイル製造用触媒。 A catalyst for producing carbon nanocoils composed of compound particles containing iron element and tin element in the same crystal,
The average primary particle diameter of the compound particles is 1 to 100 nm,
The catalyst for producing carbon nanocoils, wherein the amount of tin element contained in the compound particles is 10 to 90 mol% with respect to the total amount of iron element and tin element contained in the compound particles.
錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液とを、攪拌しながら混合して、鉄化合物粒子と錫化合物粒子とを析出させる工程と、
前記鉄化合物粒子と前記錫化合物粒子とを乾燥して、前記鉄化合物粒子と前記錫化合物粒子との混合体を製造する工程と、
前記混合体を担体上に担持させる工程とを含むことを特徴とするカーボンナノコイル製造用触媒の製造方法。 A method for producing a catalyst for producing carbon nanocoils according to any one of claims 1 to 5,
Mixing an aqueous alkaline solution containing tin ions and an aqueous solution containing iron ions while stirring to precipitate iron compound particles and tin compound particles;
Drying the iron compound particles and the tin compound particles to produce a mixture of the iron compound particles and the tin compound particles;
A method for producing a catalyst for producing carbon nanocoils, comprising a step of supporting the mixture on a carrier.
錫イオンを含むアルカリ水溶液と、鉄イオン及びインジウムイオンを含む水溶液とを、攪拌しながら混合して、鉄化合物粒子、錫化合物粒子及びインジウム化合物粒子を析出させる工程と、
前記鉄化合物粒子、前記錫化合物粒子及び前記インジウム化合物粒子を乾燥して、前記鉄化合物粒子、前記錫化合物粒子及び前記インジウム化合物粒子の混合体を製造する工程と、
前記混合体を担体上に担持させる工程とを含むことを特徴とするカーボンナノコイル製造用触媒の製造方法。 It is a manufacturing method of the catalyst for carbon nanocoil manufacture in any one of Claims 6-8,
Mixing an aqueous alkaline solution containing tin ions and an aqueous solution containing iron ions and indium ions while stirring to precipitate iron compound particles, tin compound particles and indium compound particles;
Drying the iron compound particles, the tin compound particles and the indium compound particles to produce a mixture of the iron compound particles, the tin compound particles and the indium compound particles;
A method for producing a catalyst for producing carbon nanocoils, comprising a step of supporting the mixture on a carrier.
錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液又は鉄イオン及びインジウムイオンを含む水溶液とを、攪拌しながら混合して、各金属化合物粒子を析出させて、前記金属化合物粒子を含む懸濁液を作製する工程と、
前記懸濁液を１００〜２５０℃の温度範囲で水熱処理して、鉄元素及び錫元素、あるいは、鉄元素、錫元素及びインジウム元素を同一結晶内に含む化合物粒子を製造する工程とを含むことを特徴とするカーボンナノコイル製造用触媒の製造方法。 A method for producing a catalyst for producing carbon nanocoils according to claim 9 or 10,
An aqueous alkaline solution containing tin ions and an aqueous solution containing iron ions or an aqueous solution containing iron ions and indium ions are mixed with stirring to precipitate each metal compound particle, and the suspension containing the metal compound particle A step of producing
Hydrothermally treating the suspension in a temperature range of 100 to 250 ° C. to produce compound particles containing iron element and tin element, or iron element, tin element and indium element in the same crystal. A method for producing a catalyst for producing carbon nanocoils.
錫イオンを含むアルカリ水溶液と、鉄イオンを含む水溶液又は鉄イオン及びインジウムイオンを含む水溶液とを、攪拌しながら混合して、各金属化合物粒子を析出させる工程と、
前記金属化合物粒子を乾燥するとともに、３００〜７００℃の温度範囲で加熱処理して、鉄元素及び錫元素、あるいは、鉄元素、錫元素及びインジウム元素を同一結晶内に含む化合物粒子を製造する工程とを含むことを特徴とするカーボンナノコイル製造用触媒の製造方法。 A method for producing a catalyst for producing carbon nanocoils according to claim 9 or 10,
Mixing an aqueous alkali solution containing tin ions and an aqueous solution containing iron ions or an aqueous solution containing iron ions and indium ions while stirring to precipitate each metal compound particle;
A step of drying the metal compound particles and heat-treating them in a temperature range of 300 to 700 ° C. to produce compound particles containing iron element and tin element, or iron element, tin element and indium element in the same crystal. The manufacturing method of the catalyst for carbon nanocoil manufacture characterized by including these.
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