JP4035618B2 - Fullerene fine wire manufacturing method - Google Patents
Fullerene fine wire manufacturing method Download PDFInfo
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- JP4035618B2 JP4035618B2 JP2004069597A JP2004069597A JP4035618B2 JP 4035618 B2 JP4035618 B2 JP 4035618B2 JP 2004069597 A JP2004069597 A JP 2004069597A JP 2004069597 A JP2004069597 A JP 2004069597A JP 4035618 B2 JP4035618 B2 JP 4035618B2
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 title claims description 34
- 229910003472 fullerene Inorganic materials 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000002904 solvent Substances 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical group CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- ZDHURYWHEBEGHO-UHFFFAOYSA-N potassiopotassium Chemical compound [K].[K] ZDHURYWHEBEGHO-UHFFFAOYSA-N 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000012047 saturated solution Substances 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- -1 filters Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RFAXLXKIAKIUDT-UHFFFAOYSA-N IPA-3 Chemical compound C1=CC=C2C(SSC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 RFAXLXKIAKIUDT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000459 effect on growth Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Description
本発明は、フラ−レン系炭素材料、特に実用化に適したフラ−レンを構成要素とする長さ１ｍｍ以上のフラ−レン細線の製造方法に関する。
The present invention Hula - Ren-based carbon material, particularly practical Suitable hula - method for producing RenHoso line - length 1mm or more infrastructure to Ren components.
フラーレン細線（フラーレンナノウィスカ、フラーレンナノファイバー）は、内外の研
究所、民間企業、大学で最近注目を集めており、開発競争が激化しつつある。
Fullerene fine wires (fullerene nanowhiskers, fullerene nanofibers) have recently attracted attention in domestic and overseas research institutes, private companies, and universities, and development competition is intensifying.
本発明者らは、先に、液−液界面析出法を用いてフラーレン細線を製造する方法を開発
した（特許文献１、非特許文献１、非特許文献２)。
The present inventors have previously developed a method for producing a fullerene fine wire using a liquid-liquid interface precipitation method (
この方法は、 フラーレンを構成要素とする炭素細線を得るにあたり、（１）フラーレ
ンを溶解している第１溶媒を含む溶液と、前記第１溶媒よりもフラーレンの溶解能が小さ
な第２溶媒とを合わせる工程、（２）前記溶液と前記第２溶媒との間に液−液界面を形成
する工程、及び（３）前記液−液界面にて炭素細線を析出させる工程を含む炭素細線の製
造方法である。また、本発明者らは、フラーレン細線の成長中に可視光を照射することに
よって、著しく成長が促進されることを明らかにして来た（非特許文献３）。
In this method, when obtaining a carbon fine wire having fullerene as a constituent element, (1) a solution containing a first solvent in which fullerene is dissolved, and a second solvent having a lower fullerene solubility than the first solvent. A method of producing a carbon fine wire, including a step of combining, (2) a step of forming a liquid-liquid interface between the solution and the second solvent, and (3) a step of depositing a carbon fine wire at the liquid-liquid interface. It is. Moreover, the present inventors have clarified that growth is remarkably promoted by irradiating visible light during the growth of fullerene fine wires (Non-patent Document 3).
フラ−レン細線は、触媒・フィルタ−・ガス吸着材料、軽量ナノ配線材料、樹脂複合材料、イオン交換樹脂、フラ−レンシェルチュ−ブ用作製材料、発熱細線など幅広い用途がある。本発明はこれらの用途の実用化を加速するために、フラ−レン細線の作製技術を提供することを課題とする。
Fullerene thin wires have a wide range of uses such as catalysts, filters, gas adsorbing materials, lightweight nanowiring materials, resin composite materials, ion exchange resins, fullerene shell tube preparation materials, and heat generating thin wires. An object of the present invention is to provide a technique for producing fullerene fine wires in order to accelerate the practical application of these applications.
本発明者らは、本発明者らが開発した前記の液−液界面析出法を用いてフラーレン細線を製造する際に、光によって著しくフラーレン細線の成長が促進されることを明らかにしたが、前記第１溶媒よりもフラーレンの溶解能が小さな第２溶媒に微量なアルカリ金属やアルカリ土類金属元素の添加も、成長に多大の効果をもたらすことを発見した。この新たな知見に基づき得られた結果として以下の発明を行った。
The present inventors have clarified that the growth of fullerene fine lines is significantly promoted by light when producing fullerene fine lines using the liquid-liquid interface precipitation method developed by the present inventors. It has been discovered that the addition of a trace amount of an alkali metal or alkaline earth metal element to the second solvent having a lower ability to dissolve fullerene than the first solvent has a great effect on growth. The following invention was performed as a result obtained based on this new knowledge .
また、発明1は、フラ−レンを構成要素とする長さ１ｍｍ以上のフラ−レン細線の製造方法であって、（１）フラーレンを溶解している第１溶媒を含む溶液と、前記第１溶媒よりもフラーレンの溶解能が小さな第２溶媒とを合わせる工程、（２）前記溶液と前記第２溶媒との間に液−液界面を形成する工程、及び（３）前記液−液界面にて炭素細線を析出させる工程よりなり、前記第１溶媒が、トルエン、キシレン、ベンゼン、ヘキサン、ペンタン、二硫化炭素及びこれらの誘導体からなる群より選ばれる少なくとも１種の物質からなり、前記第２溶媒が、ペンタノール、ブチルアルコール、イソプロピルアルコール、ｎ−プロピルアルコール、メチルアルコール、エチルアルコール、及び多価アルコールからなる群より選ばれる少なくとも１種のアルコールからなり、 前記第２溶媒に、ナトリウム、カリウム又はカルシウムの水酸化物並びにカリウムのアルコキシドからなる群から選ばれる少なくとも１種を添加し、添加濃度は、１０−４〜１０−７ｍｏｌ／Ｌであることを特徴とする。
本発明の方法によって、C60やC70分子等からなる、ミリメートルからセンチメートルオ
ーダーの長さのフラーレン細線を得ることが可能となる。この方法により、従来技術に比
べて、数倍から一桁以上長いフラーレン細線を作製することができる。
By the method of the present invention consists of C 60 and C 70 molecules, etc., it is possible to obtain the length of fullerene thin wires centimeter order of millimeters. By this method, it is possible to produce a fullerene fine line that is several times to one digit longer than that of the prior art.
本発明者らが開発した前記の液−液界面析出法は下記のとおりである。
フラーレンを構成要素とする炭素細線を得るにあたり、（１）フラーレンを溶解している
第１溶媒を含む溶液と、前記第１溶媒よりもフラーレンの溶解能が小さな第２溶媒とを合
わせる工程、（２）前記溶液と前記第２溶媒との間に液−液界面を形成する工程、及び（
３）前記液−液界面にて炭素細線を析出させる工程を含む。
The liquid-liquid interface deposition method developed by the present inventors is as follows.
(1) A step of combining a solution containing a first solvent in which fullerene is dissolved with a second solvent having a lower ability to dissolve fullerene than the first solvent in obtaining a carbon fine wire having fullerene as a constituent element. 2) forming a liquid-liquid interface between the solution and the second solvent;
3) including a step of precipitating carbon fine wires at the liquid-liquid interface.
本発明は、前記第２溶媒に、アルカリ金属元素、アルカリ土類金属元素、水酸化カリウム
、水酸化ナトリウムなどのアルカリ金属元素の水酸化物、カリウムメトキシドなどのアル
カリ金属アルコキシド、水酸化カルシウムなどのアルカリ土類金属水酸化物、アルカリ土
類金属アルコキシドからなる群から選ばれる少なくとも１種を添加することを特徴とする
。
In the second solvent, alkali metal element, alkaline earth metal element, hydroxide of alkali metal element such as potassium hydroxide and sodium hydroxide, alkali metal alkoxide such as potassium methoxide, calcium hydroxide, etc. characterized alkaline earth metal hydroxide, the addition of at least one selected from alkaline earth metal alkoxy de or Ranaru group.
好ましい添加濃度は、１０−４〜１０−７mol/L、好ましい液温は、５℃〜２５℃の範
囲、好ましい雰囲気は、大気中もしくは不活性ガス中である。長繊維化の最も好ましい条
件は、液温が１５℃〜２５℃、アルカリおよびアルカリ土類金属元素の濃度が、１ｘ１０
−５mol/L〜１ｘ１０−６mol/Lである。前記第２溶媒に、アルカリ金属およびアルカリ土
類金属元素を高濃度に添加すると、C60細線が成長できない。
A preferable addition concentration is 10 −4 to 10 −7 mol / L, a preferable liquid temperature is in the range of 5 ° C. to 25 ° C., and a preferable atmosphere is air or an inert gas. The most preferable conditions for the long fiber are that the liquid temperature is 15 ° C. to 25 ° C., and the concentration of alkali and alkaline earth metal elements is 1 × 10
It is −5 mol / L to 1 × 10 −6 mol / L. When an alkali metal and an alkaline earth metal element are added to the second solvent at a high concentration, C60 fine wires cannot be grown.
カリウムをＫＯＨの形でイソプロピルアルコ−ルに溶解させて添加した場合、約５×１０−３ｍｏｌ／Ｌ濃度以上になると粒子状のＣ６０析出物が生じてＣ６０細線を得ることができない。図４のＴＥＭ写真に示すように９．９×１０−３ｍｏｌ／Ｌ濃度のＩＰＡを用いて、Ｃ６０のメタキシレン飽和溶液との液−液法により得た析出物は、球状粒子と不定形な棒状の析出物であった。また、１０−８ｍｏｌ／Ｌ以下の濃度では、濃度が小さすぎて効果が観察されない。
When potassium is dissolved in isopropyl alcohol in the form of KOH and added to a concentration of about 5 × 10 −3 mol / L or more, particulate C 60 precipitates are generated and C 60 fine wires cannot be obtained. As shown in the TEM photograph of FIG. 4, the precipitate obtained by the liquid-liquid method with a saturated solution of C 60 metaxylene using IPA having a concentration of 9.9 × 10 −3 mol / L was not separated from spherical particles. It was a regular rod-like precipitate. Also, 10 in the -8 mol / L or less of the concentration, the concentration is not too with effects observed small.
前記第１溶媒がフラーレンの良溶媒であり、前記第２溶媒がフラーレンの貧溶媒である
。前記第１溶媒が非極性溶媒であり、前記第２溶媒が極性溶媒である。前記第１溶媒が炭
化水素系溶媒である。前記炭化水素系溶媒が、トルエン、キシレン、ベンゼン、ヘキサン
、ペンタン、二硫化炭素及びこれらの誘導体からなる群より選ばれる少なくとも１種の物
質からなる。前記第２溶媒がアルコール系溶媒である。前記アルコール系溶媒が、ペンタ
ノール、ブチルアルコール、イソプロピルアルコール、ｎ−プロピルアルコール、メチル
アルコール、エチルアルコール、及び多価アルコールからなる群より選ばれる少なくとも
１種のアルコールからなる。前記第１工程で、金属触媒又は金属酸化物触媒を添加すると
よい。
The first solvent is a good solvent for fullerene, and the second solvent is a poor solvent for fullerene. The first solvent is a nonpolar solvent and the second solvent is a polar solvent. The first solvent is a hydrocarbon solvent. The hydrocarbon solvent is composed of at least one substance selected from the group consisting of toluene, xylene, benzene, hexane, pentane, carbon disulfide, and derivatives thereof. The second solvent is an alcohol solvent. The alcohol solvent comprises at least one alcohol selected from the group consisting of pentanol, butyl alcohol, isopropyl alcohol, n-propyl alcohol, methyl alcohol, ethyl alcohol, and polyhydric alcohol. In the first step, a metal catalyst or a metal oxide catalyst may be added.
<水酸化カリウム（KOH）をカリウム源としたときの例>
表１の(a)〜(e)に示す溶液組成でフラーレン細線を成長させた。C60の飽和トルエン（第
１溶媒）溶液（約2.2gL-1）を、適当な大きさのガラスバイアルビン（望ましくは、容量5
mL〜50mL）に注ぎ込み、室温付近（５℃〜２５℃）で、ほぼ等量のKOHを溶解したイソプ
ロピルアルコール（第２溶媒）を、ピペットを用いて、静かにビン壁を伝わらせるか、滴
下するかして注ぎ込み、C60のメタキシレン溶液とイソプロピルアルコールの液−液界面
を形成させた。このガラスビンを室温付近（１５℃〜２５℃）で、2週間程度以上静置し
た。この間にC60細線（C60ナノウィスカー）が成長した。以上の方法は、C70細線（C70ナ
ノウィスカー）の作製についても同様に実施した。
<Example when potassium hydroxide (KOH) is used as the potassium source>
Fullerene fine wires were grown with the solution compositions shown in (a) to (e) of Table 1. A saturated solution of C 60 in toluene (first solvent) (approximately 2.2 gL −1 ) is added to a suitably sized glass vial (preferably with a volume of 5
pour into isopropyl alcohol (second solvent) with approximately the same amount of KOH at room temperature (5 ° C to 25 ° C) using a pipette, or gently transfer it to the bottle wall. As a result, the mixture was poured to form a liquid-liquid interface between a C 60 metaxylene solution and isopropyl alcohol. The glass bottle was allowed to stand at about room temperature (15 ° C. to 25 ° C.) for about 2 weeks or more. During this time, C 60 wires (C 60 nanowhiskers) grew. Above process was carried out similarly for manufacturing the C 70 thin line (C 70 nanowhiskers).
１０−３ｍｏｌ／Ｌ濃度のＫＯＨを溶質としたＩＰＡの系では、Ｃ６０細線が成長しなかったが、１０−５〜１０−６ｍｏｌ／Ｌ濃度のＫＯＨ−ＩＰＡの系では、著しく長く成長したＣ６０細線が得られた。ＣＨ３ＯＫを微量添加した（ｆ）と（ｇ）においても、Ｃ ６０細線が育成された。微量のＫＯＨを添加した（ｄ）と（ｅ）でも、Ｃ６０細線が育成された。
In the IPA system in which 10 −3 mol / L concentration of KOH was used as the solute, C 60 fine wires did not grow, but in the 10 −5 to 10 −6 mol / L concentration of KOH-IPA system, the growth was significantly longer. C 60 fine wire was obtained. Also in (f) and (g) where a small amount of CH 3 OK was added , C 60 fine wires were grown. In KOH was added a trace amount (d) and (e), C 60 thin line is grown.
＜ＣＨ３ＯＫをカリウム源としたときの例＞
表１の（ｆ）〜（ｇ）に示す溶液組成でフラ−レン細線を成長させた。ＣＨ３ＯＫを溶質とし、ＩＰＡ―３ｗｔ％ＣＨ３ＯＨを溶媒とする溶液を調製した。（１）と同様にして、微量のＣＨ３ＯＫを添加したＩＰＡ―３ｗｔ％ＣＨ３ＯＨ溶液とＣ６０飽和トルエンもしくはメタキシレン溶液の系による液―液界面析出法によって、Ｃ６０細線を育成した。
<Example when CH 3 OK is used as potassium source>
Fullerene thin wires were grown with the solution compositions shown in (f) to (g) of Table 1. A solution was prepared using CH 3 OK as a solute and IPA-3 wt% CH 3 OH as a solvent. In the same manner as in (1), C 60 fine wires were grown by liquid-liquid interface deposition using an IPA-3 wt% CH 3 OH solution added with a trace amount of CH 3 OK and a C 60 saturated toluene or meta-xylene solution. .
＜Ｃａ（ＯＨ）２をカルシウム源としたときの例＞
Ｃａ（ＯＨ）２のＩＰＡ溶液を調整し、これとＣ６０のメタキシレン飽和溶液の系による液−液法によって、Ｃ６０細線を成長させた。
<Example when Ca (OH) 2 is a calcium source>
An IPA solution of Ca (OH) 2 was prepared, and a C 60 fine wire was grown by a liquid-liquid method using this and a saturated solution of C 60 metaxylene .
＜ＮａＯＨをナトリウム源としたときの例＞
ＮａＯＨ のＩＰＡ溶液を調製し、これとＣ６０のメタキシレン飽和溶液の系による液−液法によって、Ｃ６０細線を成長させた。
<Example when NaOH is used as the sodium source>
An IPA solution of NaOH was prepared, and C 60 fine wires were grown by a liquid-liquid method using this and a saturated solution of C 60 metaxylene .
<長繊維C60細線の観察例>
図１(a)に、実施例１の（ｂ）のKOHを10-5molL-1溶解したIPAとC60のメタキシレン飽和
溶液とで作製したC60細線、 図１（ｂ）に、実施例３のCa(OH)2を10-5 molL-1溶解した
IPAとC60のメタキシレン飽和溶液とで作製したC60細線、図１（ｃ）に、実施例４のNaOH
を10-5molL-1溶解したIPAとC60のメタキシレン飽和溶液とで作製したC60細線の走査電子
顕微鏡（SEM）像を示す。いずれも、ミリメートルオーダーのC60細線として成長している
ことが分かる。
<Observation example of long fiber C 60 fine wire>
Figure 1 (a), C 60 thin line KOH were prepared in a xylene saturated solution of 10 -5 molL -1 dissolved IPA and C 60 of Example 1 (b), in FIG. 1 (b), carried out 10 -5 molL -1 of Ca (OH) 2 of Example 3 was dissolved
The C 60 fine wire prepared with IPA and a saturated solution of C 60 metaxylene, FIG. 1 (c) shows the NaOH of Example 4.
Shows a scanning electron microscope (SEM) image of a C 60 fine wire prepared from IPA in which 10 -5 molL -1 is dissolved and a saturated solution of C 60 metaxylene. It can be seen that both have grown as C 60 fine wires on the order of millimeters.
図２に、図１の各試料の拡大図を示す。良好に成長したC60細線が示されている。図３
に、実施例１の（ｄ）のC60のメタキシレン飽和溶液と、KOHを10-5molL-1添加したIPAを
用いて、液−液法により作製したC60細線のX線回折図形を示す。回折図形から明らかなよ
うに、結晶性の良いC60細線が得られている。
FIG. 2 shows an enlarged view of each sample in FIG. It has been shown to favorably grown C 60 thin line. FIG.
An X-ray diffraction pattern of a C 60 thin wire prepared by a liquid-liquid method using a saturated solution of C 60 metaxylene in Example 1 (d) and IPA added with 10 −5 mol L −1 of KOH. Show. As is clear from the diffraction pattern, C 60 fine wires with good crystallinity are obtained.
本発明の方法によって得られる長繊維フラーレン細線は取り扱いやすいことが著しい長
所となり、燃料電池触媒担持材料、光増感太陽電池、フィルター、イオン交換カラム充填
剤、抗菌材料、複合繊維材料、など、エネルギー、環境、繊維、半導体、医薬品産業にお
いて利用されることにより、大きな経済効果を生じると期待される。
The long fiber fullerene fine wire obtained by the method of the present invention is a remarkable advantage that it is easy to handle, such as fuel cell catalyst support material, photosensitized solar cell, filter, ion exchange column filler, antibacterial material, composite fiber material, etc. When used in the environment, textile, semiconductor and pharmaceutical industries, it is expected to produce significant economic effects.
Claims (1)
A method for producing a fullerene fine wire having a length of 1 mm or more comprising fullerene as a constituent element , wherein (1) a solution containing a first solvent dissolving fullerene, and dissolution of fullerene more than the first solvent A step of combining a second solvent having a small capacity, (2) a step of forming a liquid-liquid interface between the solution and the second solvent, and (3) depositing a fine carbon wire at the liquid-liquid interface. And the first solvent comprises at least one substance selected from the group consisting of toluene, xylene, benzene, hexane, pentane, carbon disulfide, and derivatives thereof, and the second solvent is pentanol, At least one alcohol selected from the group consisting of butyl alcohol, isopropyl alcohol, n-propyl alcohol, methyl alcohol, ethyl alcohol, and polyhydric alcohol Rannahli, the second solvent, sodium, adding at least one selected from the group consisting of alkoxides of the hydroxide and potassium potassium or calcium, the addition concentration, at 10 -4 ~10 -7 mol / L A manufacturing method characterized by being.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012132250A1 (en) | 2011-03-30 | 2012-10-04 | ソニー株式会社 | Method for manufacturing organic element, method for bonding organic molecular crystal layer, method for manufacturing fine linear conductor, organic element, and fine linear conductor |
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|---|---|---|---|---|
| JP5099310B2 (en) * | 2006-09-14 | 2012-12-19 | 独立行政法人物質・材料研究機構 | Fullerene wire manufacturing method |
| JP2008091575A (en) * | 2006-09-29 | 2008-04-17 | Dainippon Printing Co Ltd | Organic thin film solar cell element and coating liquid for forming photoelectric conversion layer |
| JP5205672B2 (en) * | 2007-08-29 | 2013-06-05 | 独立行政法人物質・材料研究機構 | Fullerene thin substrate and its manufacturing method |
| JP6422156B2 (en) * | 2014-12-01 | 2018-11-14 | 国立研究開発法人物質・材料研究機構 | Adsorption removal filter and adsorption removal method |
| CN112374489B (en) * | 2020-10-30 | 2022-09-20 | 华中科技大学 | Fullerene nanofiber film, porous carbon fiber film and preparation method of fullerene nanofiber film |
| CN115849344B (en) * | 2022-11-23 | 2024-03-29 | 盐城工学院 | Simultaneous preparation of two differently sized and self-separating fullerenes C 60 Method for preparing nano rod |
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| WO2012132250A1 (en) | 2011-03-30 | 2012-10-04 | ソニー株式会社 | Method for manufacturing organic element, method for bonding organic molecular crystal layer, method for manufacturing fine linear conductor, organic element, and fine linear conductor |
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