JP5131726B2 - Fullerene wire manufacturing method - Google Patents
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Ｃ６０、Ｃ７０、原子内包フラーレン、および、それらの誘導体からなるフラーレン分子を構成要素とする、棒状結晶、針状結晶、ひげ結晶、もしくは、繊維であるフラーレン細線の製造方法に関する。 The present invention relates to a method for producing a fullerene fine wire that is a rod-like crystal, needle-like crystal, whisker crystal, or fiber, comprising C 60 , C 70 , atom-encapsulated fullerene, and a fullerene molecule composed of derivatives thereof.
フラーレン分子の粉末の溶解液に光を照射して得たフラーレン分子粉末の飽和溶液に、液−液界面を形成し、これに超音波照射してフラーレン細線を製造方法において、中心波長３０２ｎｍの紫外光をＣ６０飽和ピリジン溶液に照射することは非特許文献１に示すとおり、従来公知である。
しかし、従来の方法では、収率が不十分であったので、本発明は、その収率を著しく向上することを目的とする。 However, since the yield is insufficient in the conventional method, the present invention aims to significantly improve the yield.
本発明は、上記問題を解決するために、照射する光を波長範囲４００ｎｍ−５００ｎｍの青色光としたことを特徴とするものである。
In order to solve the above problems, the present invention is characterized in that the light to be irradiated is blue light having a wavelength range of 400 nm to 500 nm .
前記非特許文献１で示す従来例では、中心波長３０２ｎｍの紫外光を照射したが、この波長では、Ｃ６０細線の析出に適したＣ６０とピリジンとの化合物が十分に生成していなかったものと思われる。
これに対し、本発明では、青色光（４００ｎｍ−５００ｎｍ）を照射した結果、このような問題がなく収率が格段に向上した。
また非特許文献１で示す従来例では、Ｃ６０飽和ピリジンとイソプロピルアルコールの量比を１：９に固定したが、本発明によって、この量比を１：１０から１：６の範囲に拡張した場合も、Ｃ６０細線が生成するという効果を発揮した。
また非特許文献１で示す従来例では、保管温度を１０℃に固定していた。しかし、本発明では、保管温度、５℃、１０℃、１５℃の全てにおいて、再現性良く、Ｃ６０細線が生成するという効果を発揮した。
In the conventional example shown in Non-Patent Document 1, ultraviolet light having a central wavelength of 302 nm was irradiated, but at this wavelength, a compound of C 60 and pyridine suitable for precipitation of C 60 fine wires was not sufficiently formed. I think that the.
On the other hand, in this invention, as a result of irradiating with blue light (400 nm-500 nm), there was no such problem and the yield was remarkably improved.
Further, in the conventional example shown in Non-Patent Document 1, the quantitative ratio of C 60 saturated pyridine and isopropyl alcohol is fixed at 1: 9, but this quantitative ratio is expanded to a range of 1:10 to 1: 6 by the present invention. Again, it was effective as C 60 thin line is produced.
In the conventional example shown in Non-Patent Document 1, the storage temperature is fixed at 10 ° C. However, in the present invention, C 60 fine wires were produced with good reproducibility at all storage temperatures of 5 ° C., 10 ° C., and 15 ° C.
（１）フラーレン溶液の調製
Ｃ６０ （９９．５＋％ ＭＴＲ Ｌｔｄ．）を用いた。Ｃ６０の溶媒として、ピリジン（密度 ０．９８１９ ｇ／ｍｌ）を用いた。Ｃ６０粉末をメノウ乳鉢で粉砕して、ガラスビン（５０ｍＬ）に入れたピリジンに添加し、これを、超音波洗浄装置を用いて、３０分間超音波攪拌して飽和溶液を作った。この溶液を、桐山ロート（２１ｍｍφ、ろ紙Ｎｏ．５Ｃ）を用いて、溶け残ったＣ６０をろ別し、沈殿を除去したＣ６０飽和ピリジン溶液を得た。このビンを、Ｈｅｒａｅｕｓ Ｋｕｌｚｅｒ ＧｍＢＨ社のＴｅｃｈｎｏｔｒａｙ ＣＵを用いて、青色光（波長分布４００ｎｍ〜５００ｎｍ）で、２４時間照射した。また、同様にＣ６０飽和ピリジンのガラスビンを、中心波長３０２ ｎｍ紫外光（光源：ＵＶＰ Ｍｏｄｅｌ ＵＶＭ−５７， ＵＳＡ）で２４時間照射した。
(1) was used for the preparation of fullerene solution C 60 (99.5 +% MTR Ltd. ). Pyridine (density 0.9819 g / ml) was used as the C 60 solvent. C 60 powder was pulverized in an agate mortar and added to pyridine in a glass bottle (50 mL), and this was ultrasonically stirred for 30 minutes using an ultrasonic cleaning device to make a saturated solution. This solution, using a Kiriyama funnel (21Mmfai, filter paper No. 5C), the remaining C 60 dissolved was filtered off, to give a C 60 saturated pyridine solution to remove the precipitate. This bottle was irradiated with blue light (wavelength distribution: 400 nm to 500 nm) for 24 hours using a Technoray CU manufactured by Heraeus Kulzer GmBH. Similarly, a glass bottle of C 60 saturated pyridine was irradiated with ultraviolet light having a central wavelength of 302 nm (light source: UVP Model UVM-57, USA) for 24 hours.
（２）液−液界面の形成とフラーレン細線の生成
液−液界面を作るガラスビンとして、１０ｍＬ容量のもので、外径が約２１ｍｍの円筒状のものを用いた。このサイズのものが好ましいが、外径４０ｍｍ以下のガラスビンが扱い易い。ガラスビンは、透明でかつ耐食性に優れているので、容器として適している。金属製バット（横４０ｃｍ縦３０ｃｍ深さ１０ｃｍ）の水を、投げ込み式クーラーで攪拌しつつ、水温を５℃に保った。１０ｍＬガラスビンに、Ｃ６０飽和ピリジンを入れ、次いで、イソプロピルアルコール（ＩＰＡ、密度０．７９ ｇ／ｍｌ）を静かに注いで、液−液界面を作った。液−液界面を形成後、このビンに溶媒蒸発を防ぐための蓋をして、氷水を入れた超音波洗浄器で１分間超音波攪拌し、手で振り混ぜ、さらに、１分間超音波攪拌を施して、界面を適度に拡散させた。この液−液界面析出法により、フラーレン細線が自己組織的に生成する。
(2) Formation of liquid-liquid interface and generation of fullerene thin wire As a glass bottle for forming the liquid-liquid interface, a glass bottle having a capacity of 10 mL and an outer diameter of about 21 mm was used. Although this size is preferable, a glass bottle having an outer diameter of 40 mm or less is easy to handle. Glass bottles are suitable as containers because they are transparent and excellent in corrosion resistance. The water temperature was kept at 5 ° C. while stirring water of a metal bat (width 40 cm, length 30 cm, depth 10 cm) with a throw-in cooler. A 10 mL glass bottle was charged with C 60 saturated pyridine and then isopropyl alcohol (IPA, density 0.79 g / ml) was gently poured to create a liquid-liquid interface. After forming the liquid-liquid interface, the bottle is covered with a cap to prevent solvent evaporation, and is ultrasonically stirred for 1 minute with an ultrasonic cleaner containing ice water, shaken by hand, and then ultrasonically stirred for 1 minute. The interface was diffused appropriately. By this liquid-liquid interface precipitation method, fullerene fine wires are self-organized.
（３）フラーレン細線の生成条件
フラーレン細線が生成する条件は、１）フラーレンの純度、２）フラーレンの有機溶液の青色光もしくは紫外光の照射時間、３）２）の作業終了後から液−液界面を形成するまでの経過時間（単に“経過時間”とする）、４）部屋の温度と湿度、５）用いた光の波長、６）第一溶媒（ピリジン）と第二溶媒（ＩＰＡ）の量比（１：１０， １：９， １：８，１：７，１：６，１：５など）、７）低温恒温器の貯蔵温度（１５℃、１０℃、５℃）に依存する。
このときの部屋の温度、湿度は、それぞれ、２３℃〜２６℃、５０％〜７５％の間である。３つの低温恒温器（（ＳＡＮＹＯ ＭＩＲ−１５３）を用い、それぞれ、貯蔵温度（１５℃、１０℃、５℃）に保った。
本研究の結果、青色光（波長範囲４００ｎｍ−５００ｎｍ）を照射したＣ６０のピリジン溶液の方が、紫外線照射（中心波長３０２ｎｍ）したものよりもＣ６０細線の生成量がより多いことが分かった。経過時間は、１時間〜２５時間である。
好ましい条件として、青色光の照射時間は２４時間、Ｃ６０飽和ピリジン溶液／ＩＰＡの比は１：１０、１：９、１：８である。１５℃、１０℃、５℃の貯蔵温度のいずれにおいてもＣ６０細線が生成した。貯蔵温度５℃においては、液−液界面形成後から１〜２日で、Ｃ６０細線の生成が目視で観察され、最良の結果を得ている。
また、１：９と１：８の両方の量比において、青色光照射したものの方がＣ６０細線の生成量が多いことが分かった。
Ｃ６０細線の生成量は、溶液の保管温度にも依存しており、５℃が最も高いことが分かった。１５℃では、Ｃ６０飽和ピリジン溶液／ＩＰＡの比が小さくなるにつれて、生成量が減少した。
(3) Conditions for generating fullerene fine wires The conditions for generating fullerene fine wires are 1) purity of fullerene, 2) irradiation time of blue light or ultraviolet light of an organic solution of fullerene, and 3) liquid-liquid after the completion of 2) work. Elapsed time to form an interface (simply referred to as “elapsed time”), 4) room temperature and humidity, 5) wavelength of light used, 6) first solvent (pyridine) and second solvent (IPA) Quantity ratio (1:10, 1: 9, 1: 8, 1: 7, 1: 6, 1: 5, etc.) 7) Depends on the storage temperature of the low temperature incubator (15 ° C, 10 ° C, 5 ° C) .
The room temperature and humidity at this time are between 23 ° C. and 26 ° C. and 50% to 75%, respectively. Three low temperature incubators ((SANYO MIR-153) were used and kept at storage temperatures (15 ° C., 10 ° C., 5 ° C.), respectively.
As a result of this study, it was found that C 60 pyridine solution irradiated with blue light (wavelength range 400 nm-500 nm) produced more C 60 fine wires than that irradiated with ultraviolet light (center wavelength 302 nm). . The elapsed time is 1 hour to 25 hours.
As preferable conditions, the irradiation time of blue light is 24 hours, and the ratio of C 60 saturated pyridine solution / IPA is 1:10, 1: 9, 1: 8. C 60 fine wires were produced at all storage temperatures of 15 ° C., 10 ° C. and 5 ° C. At a storage temperature of 5 ° C., the formation of C 60 fine wires was visually observed within 1-2 days after the formation of the liquid-liquid interface, and the best results were obtained.
In addition, it was found that the amount of C 60 fine wire produced was greater in the blue light-irradiated product at both 1: 9 and 1: 8 quantitative ratios.
The amount of C 60 fine wire produced was also dependent on the storage temperature of the solution, and it was found that 5 ° C. was the highest. At 15 ° C., the yield decreased as the C 60 saturated pyridine solution / IPA ratio decreased.
約０．１５ｇのＣ６０粉末をメノウ乳鉢で粉砕して、外径４０ｍｍの透明ガラスビン（容量１００ｍＬ）を用いて、５０ｍＬのピリジン（和光純薬工業（株）製、特級）に溶解させ、蓋をして、紫外光（３０２ｎｍ）を２４時間室温で照射し、最後に、ろ過した。
この照射によって、暗紫色の溶液が赤みを帯びた淡紅色に変化した。外径２１ｍｍの透明ガラスビン（１０ｍＬ容量）に、この紫外線照射したＣ６０飽和ピリジン溶液を０．８２ｍＬ入れて、さらに、８．２ｍＬのＩＰＡをピペットを用いてゆっくりと加えて、液−液界面を形成した（図１（ａ））。ここまでの工程は、全て、約５℃に保った水浴で行なった。
次いで、超音波洗浄器（ｉｕｃｈｉ ＶＳ−１５０， １５０Ｗ）の氷水中で、上記ガラスビンに超音波照射した（図１（ｂ））。このビンは蓋をしたままで、低温恒温器で、１０℃で保管した。
以上の方法によって、４０本のサンプルを調製したが、調整時から４〜７日経過後観察したところ、１６本だけのガラスビン中にＣ６０細線が生成し、収率は４０％であった（図２（ａ））。Ｃ６０細線の生成量は、目視では、ビンによってばらつきがあった。
About 0.15 g of C 60 powder is pulverized in an agate mortar and dissolved in 50 mL of pyridine (made by Wako Pure Chemical Industries, Ltd., special grade) using a transparent glass bottle (capacity 100 mL) with an outer diameter of 40 mm, and the lid And irradiated with ultraviolet light (302 nm) for 24 hours at room temperature, and finally filtered.
This irradiation changed the dark purple solution to a reddish light red. Place 0.82 mL of this UV-irradiated C 60 saturated pyridine solution into a transparent glass bottle (10 mL capacity) with an outer diameter of 21 mm, and then slowly add 8.2 mL of IPA using a pipette to form a liquid-liquid interface. It was formed (FIG. 1 (a)). All the steps so far were performed in a water bath maintained at about 5 ° C.
Next, the glass bottle was subjected to ultrasonic irradiation in ice water of an ultrasonic cleaner (Iuchi VS-150, 150 W) (FIG. 1B). The bottle was stored at 10 ° C. in a low temperature incubator with the lid on.
Although 40 samples were prepared by the above method, when observed after 4 to 7 days from the time of adjustment, C 60 fine wires were formed in only 16 glass bottles, and the yield was 40% (Fig. 2 (a)). The amount of C 60 fine wire produced varied from bottle to bottle.
様々なＣ６０飽和ピリジン／ＩＰＡの量比について、Ｃ６０細線の生成を検討した（図２（ａ）、（ｂ））。１：９（＝Ｃ６０飽和ピリジン／ＩＰＡ）のビン（それぞれ、Ｃ６０飽和ピリジン０．９ｍＬとＩＰＡ８．１ｍＬを含む）では、２０本のビンのうちで、１０本のビンに、目視でＣ６０細線の生成が観察され、収率は５０％であった。この場合、Ｃ６０細線の生成が確認できるまで、最短で２日、最長で２２日の育成時間を要しており、ごく少量のＣ６０細線が生成した。 The ratio of the various C 60 saturated pyridine / IPA, were examined the generation of C 60 thin line (FIG. 2 (a), (b) ). In 1: 9 (= C 60 saturated pyridine / IPA) bottles (each containing 0.9 mL C 60 saturated pyridine and 8.1 mL IPA), 10 of 20 bottles were visually Production of 60 fine lines was observed and the yield was 50%. In this case, to be confirmed C 60 thin line generation, 2 days at the shortest, longest and takes a development time of 22 days, to produce only a small amount of C 60 thin line.
１：８のビン（Ｃ６０飽和ピリジン１．０ｍＬとＩＰＡ８．０ｍＬ）では、５本のビンのうちで３本のみにごく少量のＣ６０細線が生成し、収率は、６０％であった。この場合、Ｃ６０細線の生成が確認できるまで、最短で２日、最長で２１日の育成時間を要した。 In 1: 8 bottles (1.0 mL C 60 saturated pyridine and 8.0 mL IPA), only 3 out of 5 bottles produced very small C 60 wires and the yield was 60%. . In this case, to be confirmed C 60 thin line of production is 2 days a minimum, required to train time maximum of 21 days.
１：７のビン（Ｃ６０飽和ピリジン１．１ｍＬとＩＰＡ７．７ｍＬ）では、１３本のビンのうちで８本のみにＣ６０細線が生成し、収率は、６０％であった。この場合、Ｃ６０細線の生成が確認できるまで、最短で３日、最長で５日の育成時間を要した。生成したＣ６０細線は極少量から少量であった。 In the 1: 7 bottle (1.1 mL of C 60 saturated pyridine and 7.7 mL of IPA), only 60 of 13 bottles produced C 60 wires, and the yield was 60%. In this case, until it can be confirmed C 60 thin line of generation, the shortest in three days, took the training time of 5 days at the longest. The resulting C 60 thin line was a small amount of very small amounts.
１：６のビン（Ｃ６０飽和ピリジン１．３ｍＬとＩＰＡ７．８ｍＬ）では、５本のビンのうちで１本のみにＣ６０細線が生成し、収率は、２０％であった。この場合、Ｃ６０細線の生成が確認できるまで、８日の育成時間を要した。生成したＣ６０細線は極少量であった。
１：５のビン（Ｃ６０飽和ピリジン０．５ｍＬとＩＰＡ７．５ｍＬ）では、Ｃ６０細線の生成が、目視で確認できなかった。
In the 1: 6 bottle (1.3 mL of C 60 saturated pyridine and 7.8 mL of IPA), only 60 of the 5 bottles produced C 60 wires, and the yield was 20%. In this case, up to C 60 thin line of generation can be confirmed, took the training time of 8 days. The amount of C 60 fine wire produced was very small.
In a 1: 5 bottle (C 60 saturated pyridine 0.5 mL and IPA 7.5 mL), the formation of C 60 fine wires could not be confirmed visually.
比較例１のプロセスを、３０２ｎｍの紫外光の代わりに、２４時間青色光（４００−５００ｎｍ）照射したＣ６０飽和ピリジンを用いて行なった。
この照射によって、Ｃ６０飽和ピリジンは暗紫色から濁った黄褐色の溶液に変化した。この波長の光の照射によって、比較例１の場合に比べて、保管温度１０℃において、より多い量のＣ６０細線がより短い日数で生成した。
The process of Comparative Example 1 was performed using C 60 saturated pyridine irradiated with blue light (400-500 nm) for 24 hours instead of 302 nm ultraviolet light.
This irradiation changed the C 60 saturated pyridine from a dark purple to a cloudy tan solution. By the irradiation of light in this wavelength, as compared with the case of Comparative Example 1, the storage temperature 10 ° C., higher amounts of C 60 thin line was produced in shorter days.
１：１０の溶液を用いた場合は、５０本のビンに生成した。 When a 1:10 solution was used, it was produced in 50 bottles.
１：９のガラスビンにおいては、５０本のビンのうちで、４９本のビンにＣ６０細線の生成が認められ、収率は９８％であった。この場合、界面形成後、最短で１日、最長で１０日で、Ｃ６０細線が生成した。図１（ｃ）にこの条件で生成したＣ６０細線を示す。これは、界面形成後１日経過した様子を示しており、Ｃ６０細線の生成が容易に視認できる。界面形成後２日後（図１（ｄ））には、より多くのＣ６０細線が綿球状に生成している。 In the 1: 9 glass bottle, generation of C 60 fine wires was observed in 49 of the 50 bottles, and the yield was 98%. In this case, C 60 fine lines were generated in 1 day at the shortest and 10 days at the longest after the interface formation. Figure 1 (c) shows a C 60 thin line generated by this condition. This shows a state in which one day has elapsed after the formation of the interface, and the generation of C 60 fine lines can be easily visually confirmed. Two days after the formation of the interface (FIG. 1 (d)), more C 60 fine lines are formed in a cotton ball.
１：８のガラスビンにおいては、収率はかなり高くなり、５３本のビンの全てにおいてＣ６０細線が生成し、１００％の収率となった。 In the 1: 8 glass bottle, the yield was quite high, with C 60 fine lines formed in all 53 bottles, yielding 100%.
１：７（１３本）、１：６（５本）、１：５（５本）のガラスビンにおいては、Ｃ６０細線の生成が確認できなかった。
この結果、Ｃ６０細線の生成には、ピリジンとイソプロピルアルコールの量比が、１：７から１：１０の間が好ましい。
In the glass bottles of 1: 7 (13 bottles), 1: 6 (five bottles), and 1: 5 (five bottles), the generation of C 60 fine wires could not be confirmed.
As a result, the amount ratio of pyridine and isopropyl alcohol is preferably between 1: 7 and 1:10 for the production of C 60 fine wires.
１：１０（Ｃ６０飽和ピリジン／ＩＰＡ）のガラスビン中のＣ６０細線を、生成後２日経過したものにつき、走査型電子顕微鏡（ＳＥＭ、Ｈｉｔａｃｈｉ Ｓ−５５００）で観察したものを図３に示す。
このＣ６０細線の外径は約３１５ｎｍであり、内部が外表面層とは異なった密度を持つ組織で充填された構造を示している。外表面の見かけの壁厚は、約７５ｎｍと約９６ｎｍと測定され、見かけの内径は約１７１ｎｍと測定された。このＣ６０細線は両端が閉じた構造を持っていると考えられ、中空構造部分が、溶媒和したＣ６０で充填されていると推察される。
1:10 C 60 thin line in glass bottle (C 60 saturated pyridine / IPA), per that after two days after production, shown in Figure 3 that observed with a scanning electron microscope (SEM, Hitachi S-5500) .
The outer diameter of the C 60 thin line is about 315 nm, illustrates the inside is filled with tissue having different densities with the outer surface layer structure. The apparent wall thickness of the outer surface was measured at about 75 nm and about 96 nm, and the apparent inner diameter was measured at about 171 nm. The C 60 thin line is considered to have both ends closed structure, hollow structure portion is presumed to have been filled with C 60 solvated.
約０．１５ｇのＣ６０粉末をメノウ乳鉢で粉砕して、外径４０ｍｍの透明ガラスビン（容量１００ｍＬ）を用いて、５０ｍＬのピリジン（和光純薬工業（株）製、特級）に溶解させ、蓋をして、青色光（４００ｎｍ−５００ｎｍ）を２４時間室温で照射し、最後に、ろ過した。外径２１ｍｍの透明ガラスビン（１０ｍＬ容量）に、この青色光を照射したＣ６０飽和ピリジン溶液を入れて、さらに、ＩＰＡをピペットを用いてゆっくりと加えて、液−液界面を形成した。ここまでの工程は、全て、約５℃に保った水浴で行なった。
次いで、超音波洗浄器（ｉｕｃｈｉ ＶＳ−１５０， １５０Ｗ）の氷水中で、上記ガラスビンに超音波照射した。このビンは蓋をしたままで、低温恒温器で１０℃で保管した。
この結果、１：１０（２０本）、１：９（２０本）、１：８（２０本）、１：７（１０本）のいずれのガラスビンにおいてもＣ６０細線が生成した。また、潜伏期（＝液−液界面形成直後から目視でＣ６０細線の生成が確認されるまでの期間）は、それぞれ、１日、１日〜２日、 １日〜４日、７日〜１７日であった（図２（ｂ））。潜伏期の逆数を、Ｃ６０細線の生成速度と定義すると、潜伏期が短いほど、生成速度は大きい。
About 0.15 g of C 60 powder is pulverized in an agate mortar and dissolved in 50 mL of pyridine (made by Wako Pure Chemical Industries, Ltd., special grade) using a transparent glass bottle (capacity 100 mL) with an outer diameter of 40 mm, and the lid And irradiated with blue light (400 nm-500 nm) for 24 hours at room temperature and finally filtered. The C 60 saturated pyridine solution irradiated with the blue light was put into a transparent glass bottle (10 mL capacity) having an outer diameter of 21 mm, and IPA was slowly added using a pipette to form a liquid-liquid interface. All the steps so far were performed in a water bath maintained at about 5 ° C.
Next, the glass bottle was irradiated with ultrasonic waves in ice water of an ultrasonic cleaner (Iuchi VS-150, 150 W). The bottle was stored at 10 ° C. in a low temperature incubator with the lid on.
As a result, C 60 fine wires were generated in any of the glass bottles of 1:10 (20), 1: 9 (20), 1: 8 (20), and 1: 7 (10). In addition, the incubation period (= period from immediately after the formation of the liquid-liquid interface until the formation of the C 60 fine line is visually confirmed) is 1 day, 1 day to 2 days, 1 day to 4 days, and 7 days to 17 days, respectively. Day (FIG. 2B). When the reciprocal of the incubation period is defined as the generation rate of the C 60 thin line, the generation rate is larger as the incubation period is shorter.
Ｃ６０細線の生成量は、１：１０、１：９、１：８で、ほぼ等量であったが、１：７では生成量は減少した。しかし、保管温度５℃の例のみではあるが、１：７のビンにおいても、青色光で照射したＣ６０を用いることにより、Ｃ６０細線が生成したことは注目に値する。 The production amount of C 60 fine wire was 1:10, 1: 9, and 1: 8, which were almost equal, but the production amount decreased at 1: 7. However, although it is only an example at a storage temperature of 5 ° C., it is notable that a C 60 fine line was generated by using C 60 irradiated with blue light even in a 1: 7 bottle.
Ｃ６０飽和ピリジン溶液のガラスビンを、３０２ｎｍの紫外光に代えて、青色光（４００ｎｍ−５００ｎｍ）で２４時間照射したものを用いて、保管温度１５℃にて、Ｃ６０細線の生成実験を行なった。
この条件では、より短い時間で、より高いＣ６０ピリジン飽和溶液／ＩＰＡの比において、より多くのＣ６０細線が得られた（図２（ａ））。
Using a glass bottle of C 60 saturated pyridine solution irradiated with blue light (400 nm-500 nm) for 24 hours instead of 302 nm ultraviolet light, a C 60 fine wire generation experiment was conducted at a storage temperature of 15 ° C. .
Under this condition, more C 60 fine wires were obtained in a shorter time and at a higher C 60 pyridine saturated solution / IPA ratio (FIG. 2 (a)).
１：１０のガラスビンにおいては、液−液界面形成から１〜４日の潜伏期間で、１０本のガラスビン全てに、Ｃ６０細線が生成した（収率１００％）。 In the 1:10 glass bottle, C 60 fine wires were formed in all 10 glass bottles in the incubation period of 1 to 4 days from the formation of the liquid-liquid interface (yield 100%).
１：９のガラスビンにおいては、液−液界面形成から２〜１５日の潜伏期間で、１０本のガラスビン全てに、Ｃ６０細線が生成した（収率１００％）。 In the 1: 9 glass bottle, C 60 fine wires were formed in all 10 glass bottles (yield 100%) in the incubation period of 2 to 15 days from the formation of the liquid-liquid interface.
１：８のガラスビンにおいては、液−液界面形成から４〜５日の潜伏期間で、２０本のガラスビンのうちの５本に、Ｃ６０細線が生成した（収率２５％）。 In the 1: 8 glass bottle, C 60 fine wires were formed in 5 of 20 glass bottles in a latent period of 4 to 5 days from the formation of the liquid-liquid interface (yield 25%).
１：７のガラスビンにおいては、Ｃ６０細線が全く生成しなかった。
よって、本実施例では、１：１０から１：８が好ましい割合である。
1: In 7 vial, C 60 thin line was not generated at all.
Therefore, in this embodiment, 1:10 to 1: 8 is a preferable ratio.
図４に、１：１０の溶液を用いて、８日間育成したＣ６０細線の走査型電子顕微鏡（ＳＥＭ）による二次電子像を示す。Ｃ６０細線の直径には、ばらつきがあり、矢印で示すように、１２５ｎｍから５００ｎｍの直径の範囲のＣ６０細線が観察されている。図５に示す走査透過電子像（ＳＴＥＭ像， Ｓ−５５００）では、Ｃ６０細線は中空な構造となっており、Ｃ６０ナノチューブが生成したことが分かる。
図中、ひとつの矢印で示したＣ６０細線の直径は約１２５ｎｍ、２つの矢印で示したＣ６０細線の直径は約５００ｎｍである。
図５のＣ６０ナノチューブの壁厚は、約３０ｎｍの非常に薄い厚さの壁から、１２６ｎｍの厚い壁まで、異なった厚さの壁が観察されている。また、Ｃ６０ナノチューブの内径は、４０ｎｍから２００ｎｍまで、広く分布している。（ａ）と（ｂ）のいずれの例においても、壁厚が一様でない。
図６では、Ｃ６０飽和ピリジン溶液とＩＰＡの比が１：８の溶液を用いて、９日間育成した例（二次電子像）を示す。このＣ６０細線は約１７０ｎｍの直径を持ち、中空構造となっていない。これは、中空なＣ６０細線は、有限の壁厚を持っているため、ある外径以下のものは、中空構造を取りえないためである。
図７の外径２２０ｎｍ、内径６４ｎｍのＣ６０細線は中空であり、ほぼ一様な壁厚と小さな内径の孔を持っているＣ６０ナノチューブである。図６のＣ６０細線よりも、より大きな外径を持つ場合は、中空構造を取りえることが分かる。
4 1:10 solution using a shows a secondary electron image by a scanning electron microscope of C 60 thin line was grown for 8 days (SEM). The diameter of the C 60 fine line varies, and as indicated by the arrows, a C 60 fine line having a diameter in the range of 125 nm to 500 nm is observed. Scanning transmission electron image shown in FIG. 5 (STEM image, S-5500) In, C 60 thin line has a hollow structure, it can be seen that C 60 nanotubes are produced.
In the drawing, the diameter of the C 60 thin line indicated by one arrow is about 125 nm, and the diameter of the C 60 thin line indicated by two arrows is about 500 nm.
C 60 nanotube wall of FIG. 5, a very thin wall thickness of about 30 nm, to the thick walls of 126 nm, the wall of different thicknesses are observed. The inner diameter of the C 60 nanotubes, from 40nm to 200 nm, are widely distributed. In both examples (a) and (b), the wall thickness is not uniform.
FIG. 6 shows an example (secondary electron image) grown for 9 days using a solution in which the ratio of C 60 saturated pyridine solution to IPA is 1: 8. The C 60 thin line has a diameter of about 170 nm, not a hollow structure. This is because a hollow C 60 thin wire has a finite wall thickness, and a hollow C 60 wire having a certain outer diameter cannot take a hollow structure.
The C 60 thin wire having an outer diameter of 220 nm and an inner diameter of 64 nm in FIG. 7 is hollow, and is a C 60 nanotube having a substantially uniform wall thickness and a small inner diameter hole. C 60 than thin line in FIG. 6, when having a larger outer diameter, it can be seen that can take a hollow structure.
以上の実施例１から３をまとめると、潜伏期間は、保管温度が低いほど短くなり、生成量はより多くなることが分かった。また、紫外光よりも青色光を照射したＣ６０ピリジン溶液を用いた方が、生成量が多くなることが判明した。 When the above Examples 1 to 3 were put together, it was found that the incubation period was shorter as the storage temperature was lower, and the generation amount was larger. Further, preferable to use a C 60 pyridine solution was irradiated with blue light than ultraviolet light is, the amount that increases were found.
（実施例からの予測性）
非特許文献２から、Ｃ６０をＣ７０に置換しても、同様な作用効果を発揮させ得ることは容易に類推できる。さらに、Ｃ８２などのより高次のフラーレンや原子内包フラーレンに、Ｃ６０を置換しても、同様な作用効果を発揮させ得ることは容易に類推できる。
また、非特許文献３に示したように、（h２-Ｃ６０）Ｐｔ（ＰＰｈ３）２のようなフラーレンの誘導体を、Ｃ６０を置換しても、同様な作用効果を発揮させ得ることは容易に類推できる。
(Predictability from examples)
From Non-Patent Document 2, it can be easily analogized that even if C 60 is replaced with C 70 , the same effect can be exhibited. Furthermore, the higher order fullerenes and atoms encapsulated fullerene such as C 82, be replaced with C 60, can be easily inferred that may be exhibited the same effect.
In addition, as shown in Non-Patent Document 3, even if C 60 is substituted with a fullerene derivative such as (h 2 -C 60 ) Pt (PPh 3 ) 2 , the same effect can be exhibited. Can be easily inferred.
フラーレンの良溶媒としては、実施例に示したピリジンの他に、トルエン、キシレン、二硫化炭素などを用いることができる。また、アルコールは、非特許文献４からも明らかなとおり、イソプロピルアルコールの他に、ｎ−プロピルアルコール、イソブチルアルコールなどのアルコール類一般を用いることができるので、イソプロピルアルコールを他のアルコール類に置換しても、同様な作用効果を発揮させ得ることは容易に類推できる。 As a good solvent for fullerene, toluene, xylene, carbon disulfide and the like can be used in addition to pyridine shown in the examples. As is clear from Non-Patent Document 4, alcohols such as n-propyl alcohol and isobutyl alcohol can be used in addition to isopropyl alcohol, so that isopropyl alcohol can be replaced with other alcohols. However, it can be easily analogized that similar effects can be achieved.
上記実施例における合成は、大気中と冷却水中で行なっているが、乾燥窒素などの不活性ガス中で行なうことも可能である。また、温度コントロールは冷却水を用いずとも、冷却板など冷却できる装置であれば何でも良い。これらの理由によって、実施例の雰囲気を不活性ガスに置換しても、冷却水を、冷却装置に置換しても、同様な作用効果を発揮させ得ることは容易に類推できる。
The synthesis in the above examples is performed in the atmosphere and cooling water, but can also be performed in an inert gas such as dry nitrogen. The temperature control may be anything as long as it can be cooled without using cooling water, such as a cooling plate. For these reasons, it can be easily analogized that even if the atmosphere of the embodiment is replaced with an inert gas or the cooling water is replaced with a cooling device, the same effect can be exhibited.
Ｃ６０細線は半導体である。実施例として、Ｃ６０細線を用いた電界効果トランジスタが作製されている。（非特許文献６を参照）
また、半導体として、メモリ、太陽電池素子、の用途がある。熱処理することによって、導電性繊維とすることにより、燃料電池やリチウムイオン電池の電極としての利用も可能である。図５に示すように、中空なＣ６０細線（＝Ｃ６０ナノチューブ）は、ナノ流路、ナノシリンジ、ナノマテリアル担持材料、化学合成テンプレート、重金属回収媒体、各種触媒担体など、多様な用途を持つ。
C 60 fine wire is a semiconductor. As an example, the field effect transistors are fabricated using a C 60 thin line. (See Non-Patent Document 6)
Further, as semiconductors, there are applications of memories and solar cell elements. By making the conductive fiber by heat treatment, it can be used as an electrode of a fuel cell or a lithium ion battery. As shown in FIG. 5, hollow C 60 thin wires (= C 60 nanotubes) have various uses such as nanochannels, nanosyringes, nanomaterial support materials, chemical synthesis templates, heavy metal recovery media, and various catalyst supports. .
Claims (1)
In the method for producing a fullerene fine wire by forming a liquid-liquid interface in a saturated solution of fullerene molecule powder obtained by irradiating light to a solution of fullerene molecule powder and irradiating it with ultrasonic waves, the irradiated light A fullerene fine wire manufacturing method characterized in that blue light having a wavelength range of 400 nm to 500 nm is used .
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