JP5213223B2 - Method for decomposing carbon-containing compound and method for producing carbon microstructure - Google Patents
Method for decomposing carbon-containing compound and method for producing carbon microstructure Download PDFInfo
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- JP5213223B2 JP5213223B2 JP2007220324A JP2007220324A JP5213223B2 JP 5213223 B2 JP5213223 B2 JP 5213223B2 JP 2007220324 A JP2007220324 A JP 2007220324A JP 2007220324 A JP2007220324 A JP 2007220324A JP 5213223 B2 JP5213223 B2 JP 5213223B2
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- carbon
- containing compound
- light
- microstructure
- temperature
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- 239000012298 atmosphere Substances 0.000 description 2
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Carbon And Carbon Compounds (AREA)
Description
本発明は、炭素含有化合物の分解方法及びこれによってカーボンナノ粒子やカーボンナノコイル等のカーボン微小構造体を得るカーボン微小構造体の製造方法に関し、特に、芳香族化合物等の炭素含有有機化合物に光照射して分解することによってカーボン微小構造体を生成する炭素含有化合物の分解方法及びカーボン微小構造体の製造方法に関する。 The present invention relates to a method for decomposing a carbon-containing compound and a method for producing a carbon microstructure such that a carbon microstructure such as carbon nanoparticles and carbon nanocoils is obtained. In particular, the present invention relates to a carbon-containing organic compound such as an aromatic compound. The present invention relates to a method for decomposing a carbon-containing compound that produces a carbon microstructure by irradiation and decomposition, and a method for producing a carbon microstructure.
エレクトロニクスや医療、複合材料、エネルギーなどの幅広い分野で機能性材料としての利用可能性に注目を集めている炭素素材として、フラーレンやカーボンナノチューブ（ＣＮＴ）等のカーボン微小構造体がある。サッカーボール形状のＣ６０を代表とするフラーレンは、１９８５年にH.W. Kroto、F.E. Smalleyらによって発見され、炭素の新しい同素体として定着している（下記非特許文献１参照）。ＣＮＴは、グラファイト構造の炭素が管状に巻いた形態の炭素材料であり、概して、単層構造のもの（ＳＷＣＮＴ）と多層構造のもの（ＭＷＣＮＴ）とに分類される。ＣＮＴの層構造における層間距離は約３．４オングストロームであり、黒鉛における層間距離である３．３５４オングストロームに近い。ＣＮＴの炭素間結合はｓｐ２である上に３次元で構成されているので、その機械特性は材料として極めて強固である（下記非特許文献２参照）。 Carbon materials that are attracting attention as a functional material in a wide range of fields such as electronics, medicine, composite materials, and energy include carbon microstructures such as fullerenes and carbon nanotubes (CNT). Fullerene typified by C 60 soccer ball shape, HW Kroto in 1985, discovered by FE Smalley et al, established as the new allotrope is (see the following Non-Patent Document 1) carbon. CNT is a carbon material in which graphite-structured carbon is rolled into a tube, and is generally classified into a single-layer structure (SWCNT) and a multi-layer structure (MWCNT). The interlayer distance in the layer structure of CNT is about 3.4 angstroms, which is close to the interlayer distance in graphite of 3.354 angstroms. Since the carbon-carbon bond of CNT is sp 2 and is configured in three dimensions, its mechanical properties are extremely strong as a material (see Non-Patent Document 2 below).
フラーレンやＣＮＴの代表的な合成方法として、アーク放電法やレーザーアブレーション法、化学気相成長法（ＣＶＤ）等があり、レーザーアブレーション法はＳＷＣＮＴやナノホーンを製造するのに適し、アーク放電法は表面欠陥が少ないナノチューブが得られ、ＣＶＤ法は生産性が高いといった長所が挙げられる。しかし、何れの方法も、生成温度が６００〜１０００℃以上と非常に高温である。 Typical methods for synthesizing fullerenes and CNTs include arc discharge, laser ablation, and chemical vapor deposition (CVD). Laser ablation is suitable for manufacturing SWCNTs and nanohorns. Nanotubes with few defects can be obtained, and the CVD method has advantages such as high productivity. However, in any of the methods, the generation temperature is as high as 600 to 1000 ° C. or higher.
又、フラーレンやＣＮＴ以外にも、ナノグラファイト構造体、ナノカプセル、カーボンナノオニオン等と称されるグラファイト層で構成された中空構造の炭素材料があり、これらは、緩衝材、潤滑剤、研磨剤や電池電極材料、電子放出素子、ガス貯蔵装置等への応用が期待されている。これらの炭素材料は、アーク放電やレーザーアブレーションによって生じるアモルファス構造のカーボンナノ粒子を、不活性ガス雰囲気中で２０００〜３０００℃という超高温に加熱することによって生成する（下記特許文献１参照）。あるいは、５〜１０気圧の不活性ガス雰囲気中で炭素ターゲットにＣＯ２レーザーを照射して１０００℃以上の原子又はクラスター状炭素を発生させることによっても生成することができる（下記特許文献２参照）。 In addition to fullerenes and CNTs, there are hollow carbon materials composed of graphite layers called nanographite structures, nanocapsules, carbon nano-onions, etc., which are buffer materials, lubricants, abrasives Applications to battery electrode materials, electron-emitting devices, gas storage devices, and the like are expected. These carbon materials are produced by heating carbon nanoparticles having an amorphous structure generated by arc discharge or laser ablation to an ultrahigh temperature of 2000 to 3000 ° C. in an inert gas atmosphere (see Patent Document 1 below). Alternatively, it can be generated by irradiating a carbon target with a CO 2 laser in an inert gas atmosphere of 5 to 10 atm to generate atoms or clustered carbon at 1000 ° C. or higher (see Patent Document 2 below). .
他方、超臨界状態における分子の運動エネルギーの高さに注目し、超臨界流体をキャリア流体として、炭化水素誘導体を金属触媒に作用させて分解することにより炭素固体膜を形成する方法等が提案されている（例えば、下記特許文献３参照）。この方法においては、金属触媒を１６００〜１８００℃に加熱して活性種とし、これを反応に用いている。
上述したような炭素素材を生成する従来の製造方法では、炭素ターゲットを蒸散させて一旦炭素単原子状態とした後に再度グラファイト構造に構成するか、あるいは、アモルファスカーボンナノ粒子に構造変化を生じさせて目的の構造に変換しており、高温度での処理によって炭素間の結合を緩和・解離させている。炭化水素誘導体を用いる方法においても、高温度での処理が用いられている。 In the conventional manufacturing method for generating the carbon material as described above, the carbon target is evaporated to once form a carbon monoatomic state and then formed into a graphite structure again, or the amorphous carbon nanoparticles are changed in structure. It has been converted to the desired structure, and bonds between carbons are relaxed and dissociated by high-temperature treatment. In a method using a hydrocarbon derivative, a treatment at a high temperature is used.
しかし、この様な特有の機能が期待される高機能炭素素材の実用化を進めるには、より安全且つ容易な製造方法の開発が必要であり、より低い温度での製造を実現することが望まれる。 However, it is necessary to develop a safer and easier manufacturing method in order to promote the practical use of high-performance carbon materials that are expected to have such unique functions, and it is desirable to realize manufacturing at a lower temperature. It is.
又、製造原料を炭素ターゲットに限定することなく、廃棄物等から回収される物質を直接利用して高機能炭素素材の製造が可能であれば、供給が高まって利用し易くなり、用途開発も様々な分野に拡げることが可能となると共に、資源の再利用の促進が可能である。 In addition, if high-performance carbon materials can be produced by directly using materials recovered from waste, etc., without limiting the production raw material to carbon targets, the supply will increase and it will be easier to use, and application development will also be possible. It can be expanded to various fields, and reuse of resources can be promoted.
本発明は、構造に起因する機能を様々な用途において発揮することが期待されるカーボン微小構造体を、より安全で消費エネルギーが少ない条件で容易に得られるカーボン微小構造体の製造方法を提供することを課題とする。 The present invention provides a method for producing a carbon microstructure that can easily obtain a carbon microstructure that is expected to exhibit the functions attributable to the structure in various applications under conditions that are safer and consume less energy. This is the issue.
又、本発明は、カーボン微小構造体の製造原料として炭素含有化合物を直接使用することを可能とし、廃棄物等から回収される物質を機能性物質の製造原料として利用して従来より低温でカーボン微小構造体を製造できる炭素含有化合物の分解方法を提供することを課題とする。 In addition, the present invention makes it possible to directly use a carbon-containing compound as a raw material for producing a carbon microstructure, and uses a substance recovered from waste or the like as a raw material for producing a functional substance at a lower temperature than in the past. It is an object of the present invention to provide a method for decomposing a carbon-containing compound capable of producing a microstructure.
上記課題を解決するために、炭素化合物の分解条件を検討したところ、亜臨界〜超臨界の性質を利用することにより、従来より極めて低い温度で炭素含有化合物の分解及びカーボン微小構造体の製造が可能となることを見出した。 In order to solve the above-mentioned problems, the decomposition conditions of the carbon compound were examined. By utilizing the subcritical to supercritical properties, the decomposition of the carbon-containing compound and the production of the carbon microstructure can be performed at an extremely lower temperature than before. I found it possible.
本発明の一態様によれば、炭素含有化合物の分解方法は、炭素含有化合物に光照射して分解する炭素含有化合物の分解方法であって、前記炭素含有化合物は芳香族化合物であり、前記光照射は、前記炭素含有化合物を臨界領域流体又は温度がＴｃ±３°Ｋ以内の臨界近傍流体に調整して可視光域の光を照射することを要旨とする。
更に、本発明の他の態様によれば、炭素含有化合物の分解方法は、炭素含有化合物に光照射して分解する炭素含有化合物の分解方法であって、前記炭素含有化合物は非芳香族系の有機化合物であり、前記光照射は、前記炭素含有化合物を臨界領域流体又は温度がＴｃ±３°Ｋ以内の臨界近傍流体に調整して行い、前記光照射において照射される光は、紫外線波長域の光を含む。
According to one aspect of the present invention, the method for decomposing a carbon-containing compound is a method for decomposing a carbon-containing compound that is decomposed by irradiating the carbon-containing compound with light, wherein the carbon-containing compound is an aromatic compound, The gist of irradiation is to adjust the carbon-containing compound to a critical region fluid or a near critical fluid having a temperature within Tc ± 3 ° K and irradiate light in the visible light region .
Furthermore, according to another aspect of the present invention, the method for decomposing a carbon-containing compound is a method for decomposing a carbon-containing compound that is decomposed by irradiating the carbon-containing compound with light, wherein the carbon-containing compound is non-aromatic. It is an organic compound, and the light irradiation is performed by adjusting the carbon-containing compound to a critical region fluid or a near critical fluid having a temperature within Tc ± 3 ° K, and the light irradiated in the light irradiation is in an ultraviolet wavelength range. Including light.
又、本発明の一態様によれば、カーボン微小構造体の製造方法は、上記記載の炭素含有化合物の分解方法に従って上記炭素含有化合物からカーボン微小構造体を生成することを要旨とする。
更に、本発明の他の態様によれば、カーボン微小構造体の製造方法は、炭素含有化合物として芳香族化合物を亜臨界流体又は臨界領域流体に調整し、紫外線波長域の光を照射することにより、生じる炭素からグラファイト構造の入れ籠形カーボン微小構造体又はアモルファスのコイル状カーボン微小構造体を形成することを要旨とする。
Moreover, according to one aspect of the present invention, the gist of a method for producing a carbon microstructure is to produce a carbon microstructure from the carbon-containing compound according to the carbon-containing compound decomposition method described above.
Furthermore, according to another aspect of the present invention, a method for producing a carbon microstructure includes adjusting an aromatic compound as a carbon-containing compound to a subcritical fluid or a critical region fluid, and irradiating light in an ultraviolet wavelength region. The gist of the present invention is to form a graphite-like carbon microstructure having a graphite structure or an amorphous coiled carbon microstructure from the resulting carbon.
上記炭素含有化合物は、上記カーボン微小構造体の形成核となる金属の共存下で分解することができる。 The carbon-containing compound can be decomposed in the presence of a metal that forms the nucleus of the carbon microstructure.
本発明によれば、従来に比べて非常に低い温度でカーボン微小構造体を製造することが可能となり、カーボンナノ粒子やカーボンナノコイル等の供給の安全性を高めることができる。又、原料を炭素素材に限定することなく、幅広く有機炭素化合物を直接原料として分解してカーボン微小構造体を製造することができるので、廃棄物等から回収される炭素化合物を機能性材料の製造原料として有効利用することが促進される。 According to the present invention, it becomes possible to produce a carbon microstructure at a very low temperature compared to the conventional case, and it is possible to improve the safety of supply of carbon nanoparticles, carbon nanocoils, and the like. In addition, carbon microstructures can be produced by decomposing a wide range of organic carbon compounds directly as raw materials, without limiting the raw materials to carbon materials, so that carbon compounds recovered from waste etc. can be produced as functional materials. Effective utilization as a raw material is promoted.
気−液間の相平衡において、ある温度以上では気体を圧縮しても液体にならず、気体と液体との区別が無くなる臨界点があることが知られており、臨界点における温度及び圧力を臨界温度Ｔｃ及び臨界圧力Ｐｃと称し、この時の流体の密度を臨界密度と言う。臨界点及び超臨界（温度及び／又は圧力が臨界点を超える）の状態では、物質は、気体と液体との中間的な性質を示す高密度の流体となり、臨界圧力前後でその溶解能力が著しく変化することから、通常の抽出では困難とされる特定物質の選択的抽出が可能となったり、分子の運動エネルギーが大きいことから、酸化分解や高分子物質のモノマー化などの化学反応の場として有効であることなどが知られている。又、臨界点より温度が低い範囲において液相と気相とが共存する亜臨界状態も、臨界及び超臨界に準じて分子の運動エネルギーが大きく、界面付近の密度揺らぎが非常に大きい。 In the gas-liquid phase equilibrium, it is known that there is a critical point where the gas does not become liquid when compressed above a certain temperature, and there is no distinction between gas and liquid. It is called a critical temperature T c and a critical pressure P c, and the density of the fluid at this time is called a critical density. In the critical point and supercritical state (temperature and / or pressure exceeds the critical point), the substance becomes a high-density fluid showing intermediate properties between gas and liquid, and its dissolving ability is remarkably around the critical pressure. Because it changes, it becomes possible to selectively extract specific substances that are difficult to obtain by ordinary extraction, and because the kinetic energy of molecules is large, it is used as a place for chemical reactions such as oxidative degradation and monomerization of polymer substances. It is known that it is effective. Further, in the subcritical state where the liquid phase and the gas phase coexist in the range where the temperature is lower than the critical point, the kinetic energy of the molecule is large according to the criticality and supercriticality, and the density fluctuation near the interface is very large.
通常の状態において、有機化合物に光（電磁波）を照射すると、化合物の吸収帯波長の光によって化合物分子が励起されて結合が解離し、解離した原子がより高い結合エネルギーを有する新たな原子と結合しなければ、光照射の停止によって再結合し元に戻る。芳香族化合物は紫外線波長域に吸収帯を有するので、液相状態の芳香族化合物に紫外線を照射すると、分解してアモルファス炭素やグラファイトが生成する。この時、照射強度を高くすると、グラファイト層状炭素で形成された入れ籠状の微小構造体（カーボンナノ粒子）が僅かに生成することが判った。更に、芳香族化合物を亜臨界〜超臨界流体に調整した場合には、紫外線の照射強度を低下させても同様のカーボンナノ粒子が生成することが判明した。これらの結果は、通常状態では生成の可能性が極めて低いカーボン微小構造体を、亜臨界〜超臨界状態で反応させることによって生成し易くすることが可能であることを示している。 Under normal conditions, when an organic compound is irradiated with light (electromagnetic waves), the compound molecule is excited by light of the absorption band wavelength of the compound, the bond is dissociated, and the dissociated atom is bonded to a new atom having a higher binding energy. If not, it will recombine and return to its original state by stopping the light irradiation. Since an aromatic compound has an absorption band in the ultraviolet wavelength region, when an aromatic compound in a liquid phase is irradiated with ultraviolet light, it decomposes to produce amorphous carbon or graphite. At this time, it was found that, when the irradiation intensity was increased, a cage-like microstructure (carbon nanoparticles) formed of graphite layered carbon was slightly generated. Furthermore, it has been found that when the aromatic compound is adjusted to a subcritical to supercritical fluid, similar carbon nanoparticles are produced even if the irradiation intensity of ultraviolet rays is reduced. These results indicate that it is possible to easily generate a carbon microstructure having a very low possibility of generation in a normal state by reacting in a subcritical to supercritical state.
この理由は定かではないが、一因として、亜臨界〜超臨界状態の流体では分子密度及び運動エネルギーが非常に高いことが挙げられる。つまり、亜臨界〜超臨界状態において分子結合が解離すると、運動エネルギーが高いために、解離した元素が他の様々な成分と出合う可能性が高まり、通常の反応状態では得られ難い分子が生成する可能性や、生じ得る生成物の多様性・特殊性が高まるものと考えられる。実際に、臨界流体中に置かれたフラーレン結晶では、流体中へ溶解・分散しないにも拘わらず、網状、シート状、螺旋状等の様々な微小構造体の生成、つまり、形態変化が観察され、このことは、亜臨界〜超臨界領域では運動エネルギーの高さによって原子・分子が運動規制から解放されて移動・再配列の自由度が高まり、通常では得られ難い原子・分子配列の発生の可能性を高め得ることを示している。従って、亜臨界〜超臨界流体の状態は、結合が解離した原子と他の原子とによる新たな結合を形成する際に規則性の高い特定の構造体を生成する確率を高めるには好都合の反応場であると言える。 The reason for this is not clear, but one reason is that the molecular density and kinetic energy are very high in subcritical to supercritical fluids. In other words, when the molecular bond dissociates in the subcritical to supercritical state, the kinetic energy is high, so the possibility of the dissociated element coming into contact with various other components increases, and molecules that are difficult to obtain in the normal reaction state are generated. It is considered that the possibility and the diversity and speciality of the products that can be generated will increase. In fact, in fullerene crystals placed in a critical fluid, the formation of various microstructures such as nets, sheets, and spirals, that is, morphological changes, is observed even though they are not dissolved or dispersed in the fluid. This means that in the subcritical to supercritical region, the high kinetic energy frees atoms / molecules from motion regulation and increases the freedom of movement / rearrangement. It shows that the possibility can be increased. Therefore, the state of subcritical to supercritical fluid is a favorable reaction to increase the probability of generating a specific structure with high regularity when a new bond is formed by an atom from which a bond is dissociated and another atom. It can be said that it is a place.
また、亜臨界〜超臨界状態では、分子密度が高いために、反応中に分子間で相互に影響を及ぼし易くなり、解離した原子の配置に何等かの配向性をもたらすことが考えられる。ベンゼン環等の芳香族環の炭素配置及び電子状態は、グラファイト層構造と近似しており、芳香族化合物が存在する反応場では、解離した炭素が芳香族環の炭素配置及び電子状態の影響を受けて、グラファイト構造の配置に配向し易くなり得る。グラファイト層で構成されるＣＮＴ等の生成機構は、結合が解離した炭素がＣ２状態を介して形成されると考えられているが、Ｃ２を介する反応機構でも芳香族化合物の影響によるグラファイト構造への配向は要因となり得る。又、グラファイト層が平板状ではなく入れ籠状に湾曲して粒子を形成し得る点から、他分子の影響による配向であることが考えられる。 Further, in the subcritical to supercritical state, since the molecular density is high, the molecules are likely to influence each other during the reaction, and it is considered that some orientation is brought about in the arrangement of the dissociated atoms. The carbon configuration and electronic state of an aromatic ring such as a benzene ring are similar to those of a graphite layer structure, and in a reaction field where an aromatic compound exists, the dissociated carbon affects the carbon configuration and electronic state of the aromatic ring. In response, it may be easy to orient in the arrangement of the graphite structure. The formation mechanism of CNTs composed of graphite layers is thought to be formed by the dissociated carbon being formed through the C 2 state, but the graphite structure due to the influence of aromatic compounds in the reaction mechanism through C 2 Orientation to can be a factor. In addition, it is considered that the orientation is due to the influence of other molecules from the point that the graphite layer can be bent into a bowl shape instead of a flat plate shape to form particles.
他方、脂肪族化合物は、臨界〜超臨界状態の高温において分解が進行し得るが、ベンゼン環のような配向素因とはなり難いので、脂肪族化合物の分解の場合には、グラファイト層構造への配向性は低く、生成物はアモルファス炭素になる。従って、脂肪族化合物からカーボン微小構造体の生成を容易にするには、配向性を付与する素因となるものを反応場に供給する必要があり、このような素因には、芳香族化合物の共存、電離・分極や励起等による電磁的な偏向などが挙げられるが、臨界状態への光照射によるエネルギー供給が配向性を生じる素因となっていると考えられる。 On the other hand, decomposition of aliphatic compounds can proceed at high temperatures in a critical to supercritical state, but it is difficult to cause orientational orientation such as a benzene ring. The orientation is low and the product is amorphous carbon. Therefore, in order to facilitate the generation of carbon microstructures from aliphatic compounds, it is necessary to supply the reaction field with a predisposing factor for imparting orientation. Electromagnetic deflection by ionization, polarization, excitation, etc. can be mentioned, but it is considered that energy supply by light irradiation to the critical state is a cause of orientation.
本発明は、上記を鑑み、分子・原子の運動エネルギーが高い亜臨界〜超臨界を利用してカーボン微小構造体の製造を行うもので、反応基質とする炭素含有化合物は芳香族化合物や脂肪族化合物を含む有機炭素化合物であり、これを亜臨界〜超臨界状態の流体に調整して光（電磁波）照射することによって分解反応を進行させ、解離した炭素からカーボン微小構造体を製造する。これにより、従来より低い温度でカーボン微小構造体の生成が可能となる。 In view of the above, the present invention manufactures a carbon microstructure using a subcritical to supercritical molecule / atom kinetic energy, and the carbon-containing compound as a reaction substrate is an aromatic compound or an aliphatic compound. An organic carbon compound containing a compound, which is adjusted to a fluid in a subcritical to supercritical state and irradiated with light (electromagnetic waves) to promote a decomposition reaction, and a carbon microstructure is produced from the dissociated carbon. This makes it possible to generate a carbon microstructure at a lower temperature than in the past.
以下に、本発明に係る炭素含有化合物の分解方法及びこれによるカーボン微小構造体の製造方法について詳細に説明する。 Below, the decomposition | disassembly method of the carbon containing compound which concerns on this invention, and the manufacturing method of the carbon microstructure by this are demonstrated in detail.
反応基質とする芳香族化合物は、置換又は非置換の芳香族環を有する化合物であり、芳香族炭化水素に限定されず、酸素、窒素、硫黄、リン、ハロゲン元素等の置換元素を含んでいても良く、水酸基やカルボニル基、カルボキシル基、エーテル結合、アミノ基、イミノ基、ニトロ基、シアノ基、イソシアノ基、チオール基、チオエーテル結合、スルフォ基等の各種官能基や脂肪族炭化水素基を置換基として有していても使用可能である。芳香族環としては、例えば、ベンゼン、トルエン、キシレン、メシチレン、クメン、スチレン、フェニルエタン等の単環の六員環炭化水素や、ナフタレン、アントラセン、フェナレン、フェナントレン、ビフェニル、インデン、ビフェニレン、トリフェニレン等の多環の六員環炭化水素及びこれらの部分水素化物等が挙げられ、このような環状炭化水素に上記置換基や置換元素が導入されたものが置換芳香族環として挙げられる。このような環構造を有する芳香族化合物から１種以上を適宜選択して反応基質として使用でき、単独である必要はなく、複数種の芳香族化合物の混合でもよい。複数種の芳香族化合物を同時に分解するには、供給する照射光が各化合物の吸収帯波長の光を含んでいる必要がある。芳香族化合物と脂肪族化合物との混合であってもよい。低い温度で亜臨界〜超臨界状態に調整できる点では、常温で液状の化合物が好ましい。又、フッ素、塩素、臭素、ヨウ素等でハロゲン置換された芳香族化合物は、ハロゲンの脱離によって炭素化が進行し易いので、反応基質として好ましい。非芳香族系の基質としては、飽和又は不飽和炭化水素、アルコール、エーテル、ケトン、アルデヒド、脂肪酸等の酸素含有炭化水素、アミン、イミン等の窒素含有炭化水素などの脂肪族化合物があり、例えば、アセチレン、エチレン、ジエチルエーテル、アセトン等が挙げられ、１種以上を適宜選択して使用できる。１つの反応基質に他の反応基質や二酸化炭素等のキャリア物質を混合して臨界温度を低下させることが可能であり、これを利用して臨界温度の高い反応基質に対して低めの臨界温度を適用することが可能である。但し、キャリアや非芳香族化合物を用いると解離炭素がアモルファス化し易くなるので、これらの割合は分解条件を勘案して適宜設定する。 The aromatic compound as a reaction substrate is a compound having a substituted or unsubstituted aromatic ring, and is not limited to an aromatic hydrocarbon, but includes a substitution element such as oxygen, nitrogen, sulfur, phosphorus, and a halogen element. Various functional groups such as hydroxyl group, carbonyl group, carboxyl group, ether bond, amino group, imino group, nitro group, cyano group, isocyano group, thiol group, thioether bond, sulfo group and aliphatic hydrocarbon group are substituted. Even if it has as a group, it can be used. Examples of aromatic rings include monocyclic six-membered hydrocarbons such as benzene, toluene, xylene, mesitylene, cumene, styrene, phenylethane, naphthalene, anthracene, phenalene, phenanthrene, biphenyl, indene, biphenylene, triphenylene, and the like. And polycyclic six-membered hydrocarbons, partially hydrides thereof, and the like, and those obtained by introducing the above substituents and substituent elements into such cyclic hydrocarbons are listed as substituted aromatic rings. One or more kinds of aromatic compounds having such a ring structure can be appropriately selected and used as a reaction substrate, and need not be used alone, and may be a mixture of a plurality of kinds of aromatic compounds. In order to decompose a plurality of types of aromatic compounds at the same time, it is necessary that the irradiation light supplied includes light having an absorption band wavelength of each compound. It may be a mixture of an aromatic compound and an aliphatic compound. A compound that is liquid at room temperature is preferable in that it can be adjusted to a subcritical to supercritical state at a low temperature. In addition, an aromatic compound substituted with halogen by fluorine, chlorine, bromine, iodine or the like is preferable as a reaction substrate because carbonization easily proceeds by elimination of halogen. Non-aromatic substrates include aliphatic compounds such as saturated or unsaturated hydrocarbons, oxygen-containing hydrocarbons such as alcohols, ethers, ketones, aldehydes, and fatty acids, and nitrogen-containing hydrocarbons such as amines and imines. Acetylene, ethylene, diethyl ether, acetone, and the like, and one or more can be appropriately selected and used. One reaction substrate can be mixed with another reaction substrate or a carrier substance such as carbon dioxide to lower the critical temperature, and this can be used to lower the critical temperature to a reaction substrate with a higher critical temperature. It is possible to apply. However, when a carrier or a non-aromatic compound is used, the dissociated carbon is likely to become amorphous. Therefore, these ratios are appropriately set in consideration of the decomposition conditions.
反応基質は、光照射用の反応容器に収容して臨界圧及び臨界温度まで圧力及び温度を上昇することにより臨界領域となる。臨界温度より５〜１０℃程度低い温度で液相と気相とが共存する状態とすれば亜臨界状態に、温度及び／又は圧力を臨界点より高く設定すれば超臨界状態になる。実施上では、反応容器の容積に基づいて反応容器中の反応基質が臨界密度となる反応基質の質量を決定し、この質量の反応基質を反応容器に収容して封止した後に臨界点温度に加熱すれば、容器内の反応基質は臨界密度及び臨界圧となる。収容する反応基質の質量及び／又は加熱温度を低下すれば亜臨界状態に、増加すれば超臨界状態となる。例えば、ベンゼンの臨界点は、Ｔｃ＝２８９．０℃、Ｐｃ＝４．９０ＭＰａであり、温度２００〜２８９℃において気相と液相とが共存する亜臨界状態の流体に調整できる。他の化合物についても同様であり、複数種の化合物の混合状態の場合は、その組成に応じた臨界点が存在するので、これに基づいて調整される。 The reaction substrate is placed in a reaction container for light irradiation and becomes a critical region by raising the pressure and temperature to the critical pressure and critical temperature. If the liquid phase and the gas phase coexist at a temperature lower by about 5 to 10 ° C. than the critical temperature, the subcritical state is set, and if the temperature and / or pressure is set higher than the critical point, the supercritical state is set. In practice, the mass of the reaction substrate at which the reaction substrate in the reaction vessel has a critical density is determined based on the volume of the reaction vessel, and the mass of the reaction substrate is accommodated in the reaction vessel and sealed, and then the critical point temperature is reached. When heated, the reaction substrate in the container has a critical density and a critical pressure. If the mass of the reaction substrate to be accommodated and / or the heating temperature is lowered, it becomes a subcritical state, and if it is increased, it becomes a supercritical state. For example, the critical points of benzene are Tc = 289.0 ° C. and Pc = 4.90 MPa, and can be adjusted to a subcritical fluid in which a gas phase and a liquid phase coexist at a temperature of 200 to 289 ° C. The same applies to other compounds, and in the case of a mixed state of a plurality of types of compounds, there is a critical point corresponding to the composition, and adjustment is made based on this.
使用する反応容器は、内部へ光照射が供給可能で、加圧及び温度調節が可能な容器であり、具体的には、耐熱耐圧素材で製造された透光セルや、照射窓を有するオートクレーブ等のような耐熱耐圧容器が挙げられる。尚、耐熱耐圧素材は、実質的に反応基質と作用しないように溶剤耐性を有する必要がある。 The reaction vessel to be used is a vessel capable of supplying light irradiation inside and capable of pressurization and temperature adjustment. Specifically, a translucent cell made of a heat and pressure resistant material, an autoclave having an irradiation window, etc. The heat-resistant pressure-resistant container like The heat and pressure resistant material must have solvent resistance so that it does not substantially act on the reaction substrate.
反応容器中で亜臨界〜超臨界状態の流体に調整された反応基質は、光照射装置を用いて照射光を供給することによって分解反応を進行させる。使用する照射光は、反応基質の吸収帯波長の光を含むもので、エネルギー効率の点からレーザー光が好ましいが、集光しない放射光によっても反応の進行は可能であり、太陽光やランプ光等も利用可能である。芳香族化合物は紫外光波長域に吸収帯を有するので、紫外光を含む光を照射することによって好適に分解が進行する。赤外線等の長波長の放射は温度上昇を招くので、反応系の温度制御の容易さから、照射光の波長域は、可視光以下の短波長、つまり、可視〜紫外域の波長域が好ましく、可視光（波長７００〜４００nm程度）から紫外光（４００nm〜１００nm程度）以下の波長域に制限した照射光を利用すると好適である。特に２００nm〜４００nm程度の波長域の光が好ましく、紫外光用として提供されている光源は、反応系の温度制御の点でも好都合である。紫外光の代表的な光源及び光学系として、例えば、Ｎｄ：ＹＡＧレーザー、ＫｒＦエキシマレーザー、ＡｒＦエキシマレーザー等のレーザーシステムが挙げられ、ＹＡＧ−ＴＨＧ（３次高調波：波長３５５nm）、ＹＡＧ−ＦＨＧ（４次高調波：波長２６６nm）、ＫｒＦエキシマ（波長：２４８nm）、ＡｒＦエキシマ（波長：１９３nm）等が挙げられる。可視光としては、例えば、ＹＡＧ−ＳＨＧ（２次高調波：波長５３５nm）等がある。赤外光以上の長波長の放射は、反応系の温度上昇により温度制御を難しくするので実用的に扱い難いが、光照射による反応系の温度上昇を水冷やペルチェ素子を用いた冷却によって実質的に抑制可能であれば赤外域近辺の波長を含んでも良く、パルスレーザー等の断続的照射によって温度調節が可能である場合に限り反応系の状態を保持して反応を進行させることが可能となる。 The reaction substrate adjusted to a subcritical to supercritical fluid in the reaction vessel advances the decomposition reaction by supplying irradiation light using a light irradiation device. The irradiation light to be used includes light of the absorption band wavelength of the reaction substrate, and laser light is preferable from the viewpoint of energy efficiency, but the reaction can proceed even with radiated light that is not collected. Etc. are also available. Since an aromatic compound has an absorption band in the ultraviolet wavelength region, decomposition proceeds suitably by irradiating light containing ultraviolet light. Since long-wavelength radiation such as infrared rays causes an increase in temperature, the wavelength range of irradiation light is preferably a short wavelength below visible light, that is, a visible to ultraviolet wavelength range, from the ease of temperature control of the reaction system. It is preferable to use irradiation light limited to a wavelength range from visible light (wavelength of about 700 to 400 nm) to ultraviolet light (about 400 nm to 100 nm) or less. In particular, light in the wavelength range of about 200 nm to 400 nm is preferable, and a light source provided for ultraviolet light is advantageous in terms of temperature control of the reaction system. As a typical light source and optical system of ultraviolet light, for example, a laser system such as an Nd: YAG laser, a KrF excimer laser, an ArF excimer laser, and the like, YAG-THG (third harmonic: wavelength 355 nm), YAG-FHG (4th harmonic: wavelength 266 nm), KrF excimer (wavelength: 248 nm), ArF excimer (wavelength: 193 nm), and the like. Examples of visible light include YAG-SHG (second harmonic: wavelength 535 nm). Long-wavelength radiation over infrared light is difficult to handle practically because it makes temperature control difficult due to the temperature rise of the reaction system, but the temperature rise of the reaction system due to light irradiation is substantially reduced by water cooling or cooling using a Peltier device. If the temperature can be controlled by intermittent irradiation with a pulse laser or the like, the reaction system can be maintained and the reaction can proceed only when the temperature can be controlled by intermittent irradiation such as a pulsed laser. .
紫外光の照射によって、芳香族化合物及び不飽和炭化水素は分解し、臨界〜超臨界状態の加熱は、脂肪族化合物を熱反応によって分解するので、亜臨界〜超臨界状態、特に臨界〜超臨界状態での紫外線照射は、様々な有機炭素化合物の分解が可能である。有機炭素化合物は、水素や官能基の脱離、遊離残基の他分子との結合／反応、再分解などを経てグラファイト又はアモルファスカーボンに至る。光照射を受けた反応基質からカーボン微小構造体が生成する反応において、芳香族環状の炭素配列の存在は、その電子状態によって、遊離炭素がグラファイト状に配列する配向性を場に生じさせ、化合物の崩壊及び炭素の再配置が進行してグラファイト層が積層され、１つの傾向として、入れ籠状等の規則的構造が形成される。亜臨界〜超臨界状態の高密度状態は、炭素の配列に影響を与える点で重要であり、キャリアや媒体を含まない反応基質単独の亜臨界〜超臨界流体である方がカーボン微小構造体を生じ易いことからも、反応系中の芳香族環の濃度が高い方が好ましい。従って、反応基質が芳香族化合物のみで構成される形態や、非芳香族系置換基が少ない／無い芳香族化合物で構成される形態は好適である。又、反応基質の炭素以外の元素から生じる生成物による影響の点から、炭素以外の構成元素が少ない化合物、つまり、分子構造に占める炭素の割合が高い芳香族化合物を反応基質とすることが好ましい。他方、非芳香族化合物の場合は、臨界点近傍における光照射によるエネルギー供給が、無秩序な遊離炭素に配向性を与える何等かの素因となり、特に、臨界点近傍において高強度の光照射（例えば出力３００ｍＷ程度以上）を行うことが好ましい。 Upon irradiation with ultraviolet light, aromatic compounds and unsaturated hydrocarbons are decomposed, and heating in a critical to supercritical state decomposes aliphatic compounds by a thermal reaction, so a subcritical to supercritical state, particularly critical to supercritical. Ultraviolet irradiation in the state can decompose various organic carbon compounds. An organic carbon compound reaches graphite or amorphous carbon through elimination of hydrogen and functional groups, binding / reaction with other molecules of free residues, re-decomposition, and the like. In the reaction in which a carbon microstructure is generated from a reaction substrate that has been irradiated with light, the presence of an aromatic cyclic carbon array causes the orientation of free carbon to be arranged in the form of graphite depending on its electronic state, and the compound The graphite layer is laminated by the progress of the decay of the carbon and the rearrangement of carbon, and as one tendency, a regular structure such as a cage shape is formed. The subcritical to supercritical high density state is important in that it affects the carbon arrangement, and the carbon substructure is better if it is a subcritical to supercritical fluid that contains only the reaction substrate without carriers and media. The higher concentration of the aromatic ring in the reaction system is preferable because it is likely to occur. Therefore, a form in which the reaction substrate is composed only of an aromatic compound or a form composed of an aromatic compound with little or no non-aromatic substituent is preferred. Further, from the viewpoint of the influence of products generated from elements other than carbon of the reaction substrate, it is preferable to use a compound having a small amount of constituent elements other than carbon, that is, an aromatic compound having a high proportion of carbon in the molecular structure. . On the other hand, in the case of non-aromatic compounds, energy supply by light irradiation in the vicinity of the critical point is some predisposition to give orientation to disordered free carbon, and in particular, high-intensity light irradiation (for example, output near the critical point) It is preferable to perform about 300 mW or more.
光照射によって生じる炭素は、反応系の状態によって、容器壁面上に積層して特定構造の薄膜を形成したり、微細に凝集して数十nm〜数十μｍ程度の粒子状やコイル状等のカーボン微小構造体を形成し、単粒子又は粒子集合体などの状態で堆積する。このような薄膜状や粒子状等のカーボン微小構造体は、基板を用いて効率よく積層・凝集させることができ、基板の素材として、例えば、アルミナ、グラファイト、窒化ホウ素、炭化珪素等の無機質材が挙げられる。カーボン微小構造体の大きさは、照射光の波長又は照射エネルギー量の制御によってある程度調整可能であり、供給されるエネルギーの増加によってカーボン微小構造体の生成量及び大きさは増大する。 Depending on the state of the reaction system, the carbon produced by the light irradiation is laminated on the wall surface of the container to form a thin film having a specific structure, or finely aggregated to form particles or coils of several tens of nanometers to several tens of micrometers A carbon microstructure is formed and deposited in a state of single particles or particle aggregates. Such a thin film or particulate carbon microstructure can be efficiently laminated and aggregated using a substrate, and as a material of the substrate, for example, an inorganic material such as alumina, graphite, boron nitride, silicon carbide, etc. Is mentioned. The size of the carbon microstructure can be adjusted to some extent by controlling the wavelength of irradiation light or the amount of irradiation energy, and the amount and size of the carbon microstructure increase as the supplied energy increases.
光照射の際、水素の受容体として作用する物質が反応系に共存すると、反応基質からの水素遊離を容易にするので反応進行上好ましい。この点に関して、金属酸化物は還元により水素を消費するので、反応容器内に存在すると、炭素化を促してカーボン微小構造体の生成促進に有利に作用する。 When light irradiation, a substance acting as a hydrogen acceptor coexists in the reaction system, which facilitates the liberation of hydrogen from the reaction substrate, which is preferable for the progress of the reaction. In this regard, since the metal oxide consumes hydrogen by reduction, if it is present in the reaction vessel, it promotes carbonization and has an advantageous effect on promoting the formation of a carbon microstructure.
カーボン微小構造体には様々な形態があり、例えば、カーボンナノ粒子やカーボンナノチューブ等のグラファイト層で構成されるものや、カーボンナノコイル等のようなアモルファスカーボンが一定形状を成した構造体などがあり、半球又は部分球状のものや、表面に凹部を有するもの、籠状等の中空構造を有するものなども生成する。 There are various forms of carbon microstructures, such as those composed of graphite layers such as carbon nanoparticles and carbon nanotubes, and structures where amorphous carbon such as carbon nanocoils has a fixed shape. There are also produced hemispheres or partial spheres, those having concave portions on the surface, those having a hollow structure such as a bowl.
カーボンナノコイルやカーボンナノチューブに関しては、核となる物質を反応系に共存させることによって生成・伸長を促進することが可能であり、使用可能な成長核物質として、アルミニウム、ニッケル、鉄、コバルト、タングステン、モリブデン、マグネシウム、金、銀、錫、チタン、タンタル、シリコン等の金属単体や、ステンレス、ニッケル基合金、マグネシウム合金等の上記金属の合金、Ｆｅ／ＩＴＯ［酸化インジウム錫］等の金属と金属酸化物との複合体が挙げられ、特にステンレス鋼等のＦｅＮｉＣｒ系合金の使用はカーボンナノコイルの形成に好適である。このような核物質は、基板、ロッド等の形態で反応系に導入すると、その表面からチューブ等の成長が開始されたり、光照射された臨界流体中に微量拡散してコイル末端を形成する核として作用する。 With regard to carbon nanocoils and carbon nanotubes, it is possible to promote generation / elongation by allowing a core substance to coexist in the reaction system, and usable growth core materials include aluminum, nickel, iron, cobalt, and tungsten. , Molybdenum, Magnesium, Gold, Silver, Tin, Titanium, Tantalum, Silicon and other simple metals, Stainless steel, Nickel-based alloys, Magnesium alloys and other metal alloys, Fe / ITO [Indium tin oxide] and other metals and metals Examples include composites with oxides, and the use of FeNiCr-based alloys such as stainless steel is particularly suitable for forming carbon nanocoils. When such a nuclear material is introduced into the reaction system in the form of a substrate, a rod, or the like, the growth of a tube or the like starts from the surface, or a small amount diffuses in the light-irradiated critical fluid to form a coil end. Acts as
アモルファス炭素で形成されるカーボンナノコイルは、炭素がグラファイト構造に配置する必要がない点において、ＣＮＴやナノ粒子等の他のカーボン微小構造体とは異なる。反応系を臨界〜超臨界状態に設定するか、照射強度を高くして、コイル構造を成長させる核物質の共存下で反応を進行させると、好適にコイル状微小構造体を生成できるので、発生する遊離炭素量が多い状況において前述の金属を成長核物質として存在すると、コイル状微小構造体が生じ易い。コイル構造の形成速度（成長速度）は相対的に速く、密度及び均質性が高い流体であることが重要であると考えられる。これに関連して、ＦｅＮｉＣｒ合金から流体中に拡散する金属核は有用で、金属核の拡散においては運動エネルギーが高い臨界〜超臨界状態での紫外線照射が肝要であると考えられる。 Carbon nanocoils formed from amorphous carbon differ from other carbon microstructures such as CNTs and nanoparticles in that carbon does not need to be placed in a graphite structure. When the reaction system is set to a critical to supercritical state, or when the irradiation intensity is increased and the reaction is allowed to proceed in the presence of a nuclear material that grows the coil structure, a coiled microstructure can be suitably generated. When the above-mentioned metal exists as a growth nucleus substance in a situation where the amount of free carbon to be produced is large, a coiled microstructure is likely to be generated. It is considered that the formation speed (growth speed) of the coil structure is relatively fast, and it is important that the fluid has high density and homogeneity. In this connection, metal nuclei that diffuse from the FeNiCr alloy into the fluid are useful, and in the diffusion of metal nuclei, ultraviolet irradiation in a critical to supercritical state with high kinetic energy is considered essential.
光照射によって得られる生成物は、概して、上述のような微小構造体を含む煤様の混合物となる。従って、用途に適した特定構造のカーボン微小構造体を得るには、必要に応じて、生成物から無定形炭素を除去したり、従来公知の精製方法から目的とする微小構造体に適した方法を適宜選択して施すことにより、使用に供することができる。例えば、アモルファス炭素とグラファイトとの構造差や粒子寸法差に起因する耐熱温度（耐焼失温度）の相違を利用した熱処理等を利用して精製できる。 The product obtained by light irradiation is generally a cocoon-like mixture containing the microstructure as described above. Therefore, in order to obtain a carbon microstructure having a specific structure suitable for the application, if necessary, the amorphous carbon is removed from the product, or a method suitable for the target microstructure from a conventionally known purification method. By appropriately selecting and applying, can be used. For example, it can be purified by heat treatment using a difference in heat-resistant temperature (burn-out temperature) caused by a structural difference or particle size difference between amorphous carbon and graphite.
炭素含有有機化合物には、臨界温度が５００℃以下であるものが数多くあり、特に炭素数が１２以下の脂肪族炭化水素化合物や芳香族化合物の多くは、５００℃以下の加熱によって亜臨界〜臨界領域に調整できる。ベンゼンの臨界温度（２８９℃）はベンゼン型化合物の中でも低く、３００℃程度の低い温度でカーボン微小構造体を生成するための反応基質として極めて好ましい。この点に関しては、フルオロベンゼン（臨界温度：２８８℃）等も好適である。ベンゼンやモノ又はポリハロゲン化ベンゼン等のベンゼン型化合物は、グラファイト構造の粒子を生成し易く、芳香環の脱水素又は脱ハロゲンと結合多環化とによるグラファイト構造の形成及び伸長が進行し易いと解される。 Many carbon-containing organic compounds have a critical temperature of 500 ° C. or lower, and in particular, many of aliphatic hydrocarbon compounds and aromatic compounds having 12 or less carbon atoms are subcritical to critical by heating at 500 ° C. or lower. Can be adjusted to the area. The critical temperature of benzene (289 ° C.) is low among benzene type compounds, and is extremely preferable as a reaction substrate for producing a carbon microstructure at a temperature as low as about 300 ° C. In this regard, fluorobenzene (critical temperature: 288 ° C.) and the like are also suitable. Benzene-type compounds such as benzene and mono- or polyhalogenated benzene tend to generate graphite-structured particles, and the formation and extension of graphite structures by aromatic ring dehydrogenation or dehalogenation and bond polycyclization are likely to proceed. It is understood.
有機炭素化合物を反応基質として生成する入れ籠状中空粒子のカーボン微小構造体は、グラファイト層で形成された壁部が３次元的に閉じた形状であるので、機械的強度が高く、化学的にも安定である。又、カーボンナノチューブと同様に、金属やガス物質、化学的に不安定な物質等を中空部に貯蔵して酸化及びその他の反応から保護する機能性材料として有望である。 The carbon microstructure of the cage-like hollow particles produced using an organic carbon compound as a reaction substrate has a shape in which the wall portion formed by the graphite layer is three-dimensionally closed, so that it has high mechanical strength and is chemically Is also stable. Further, like carbon nanotubes, it is promising as a functional material that protects metals, gas substances, chemically unstable substances, etc. from oxidation and other reactions by storing them in hollow portions.
上述のようにして炭素含有化合物の分解によって得られるカーボン微小構造体は、その構造に応じて、エネルギーコンバータ、電子エミッタ、ナノインダクタ等の電気・電子デバイス用材料、生体トレーサ等の医療素材、水素吸蔵体等の吸収・吸着材、緻密フィルタ等のろ過材、触媒、潤滑剤、プラスチック成形品や構造材にフィラー又は補強剤として配合される複合材料などとして使用が可能であり、ドラッグデリバリーやナノスプリング、ナノサイズベアリング等のマイクロオペレーションデバイスへの応用など、諸分野における機能性材料として有望である。 Carbon microstructures obtained by decomposing carbon-containing compounds as described above can be used for energy converters, electron emitters, materials for electrical devices such as nanoinductors, medical materials such as biological tracers, hydrogen, etc. It can be used as an absorbent / adsorbent material such as an occlusion body, a filter material such as a dense filter, a catalyst, a lubricant, a composite material blended as a filler or reinforcing agent in a plastic molded product or a structural material, etc. It is promising as a functional material in various fields such as application to micro-operation devices such as springs and nano-sized bearings.
芳香族化合物の分解には紫外波長域の照射が必要であるが、本発明に関して、吸収帯波長ではない可視光によっても芳香族化合物の分解反応が進行し得る状態が臨界点近傍、概してＴｃ±３°Ｋ程度の温度範囲内に存在する。つまり、反応基質の吸収帯に含まれない波長の照射光によって分解する。勿論、基質の吸収帯波長である紫外光を使用する方が反応効率が高く好ましいが、反応基質と照射光波長との対応が必須でないことにより実用的な自由度が高まる。つまり、吸収帯が紫外光域にある化合物を紫外光以外の照射によって反応させることが許容され、複数化合物の混合物を反応基質とした場合に、照射光が各化合物の吸収帯波長の光を全て含む必要がない。 For the decomposition of the aromatic compound, irradiation in the ultraviolet wavelength region is necessary. However, in the present invention, the state in which the decomposition reaction of the aromatic compound can proceed even by visible light that is not the absorption band wavelength is near the critical point, generally Tc ±. It exists in the temperature range of about 3 ° K. That is, it is decomposed by irradiation light having a wavelength not included in the absorption band of the reaction substrate. Of course, it is preferable to use ultraviolet light, which is the absorption band wavelength of the substrate, because the reaction efficiency is high and preferable. However, since the correspondence between the reaction substrate and the irradiation light wavelength is not essential, practical flexibility is increased. In other words, it is allowed to react a compound having an absorption band in the ultraviolet light region by irradiation other than ultraviolet light, and when a mixture of a plurality of compounds is used as a reaction substrate, the irradiation light emits all light in the absorption band wavelength of each compound. There is no need to include.
臨界点近傍において基質の吸収帯波長域以外の波長の光照射によって分解反応が進行する理由は定かではないが、臨界点近傍で見られる特異な性質に起因すると考えられる。臨界点近傍においては、分子の運動エネルギーと分子間の引力とが釣り合って大きな分子クラスターが生じ易くなり、又、分子密度の揺らぎが異常に大きくなり、揺らぎの増大に対応して熱力学的性質（圧縮率、磁化率、熱容量など）が特異性を示すと共に、生じた揺らぎの減衰にも時間を要することが判っている。この様な性質を示す領域は、臨界領域と称される。臨界領域における特異現象の１つに、密度揺らぎによる入射光の散乱強度が異常に増大する現象（臨界蛋白光）があり、この際に流体が暗黒色化する（透過光及び散乱光が極度に減少する）現象も観察され、照射エネルギーによる揺らぎの影響が内部エネルギー（電子状態）にも及ぶと考えられる。可視光による分解及びカーボン微小構造体の生成と流体の暗黒色化現象との符合から、臨界領域においては照射光のエネルギーが流体の電子状態やエネルギー準位に影響を及ぼし、これにより、吸収帯波長以外の照射光で分解が進行すると考えられる。つまり、臨界領域においては、1)分子密度の高さ、特に分子クラスターの生成によって、分子結合と光子との衝突頻度が高く、反応の連鎖・受け渡し等による継続性が高くなり、結合の解離が起こり易くなる、2)運動エネルギー及び密度ゆらぎの高い状態への光照射によって分子結合の分極又は励起傾向が極度に高まって反応し易くなる、等によって分解反応の進行確率が高まると考えられる。 The reason why the decomposition reaction proceeds by irradiation with light having a wavelength other than the absorption band wavelength region of the substrate in the vicinity of the critical point is not clear, but is thought to be due to a unique property observed in the vicinity of the critical point. Near the critical point, the molecular kinetic energy balances with the attractive force between the molecules, and large molecular clusters are likely to occur. In addition, the fluctuation of the molecular density becomes abnormally large, and the thermodynamic properties correspond to the increase of fluctuations. It has been found that (compressibility, magnetic susceptibility, heat capacity, etc.) show peculiarities and that it takes time to attenuate the fluctuations that occur. A region exhibiting such a property is called a critical region. One of the singular phenomena in the critical region is a phenomenon in which the incident light scattering intensity is abnormally increased due to density fluctuations (critical protein light). At this time, the fluid becomes dark black (transmitted light and scattered light are extremely (Decrease) phenomenon is also observed, and the influence of fluctuation due to the irradiation energy is considered to extend to the internal energy (electronic state). In the critical region, the energy of the irradiation light affects the electronic state and energy level of the fluid due to the decomposition of visible light and the formation of the carbon microstructure and the darkening phenomenon of the fluid. It is considered that decomposition proceeds with irradiation light other than the wavelength. In other words, in the critical region, 1) due to the high molecular density, especially the generation of molecular clusters, the frequency of collisions between molecular bonds and photons is high, and the continuity due to reaction chaining / passing, etc. is increased, and bond dissociation occurs. It is considered that the probability of progress of the decomposition reaction increases due to the fact that it tends to occur, 2) the irradiation of light to a state with high kinetic energy and density fluctuations, and the tendency of the polarization or excitation of molecular bonds to become extremely high and the reaction becomes easy.
図１は、本発明に係る炭素含有化合物の分解方法及びカーボン微小構造体の製造方法を実施可能な装置の一例を示す。この装置は、流体を保持し亜臨界〜超臨界に調整するための耐熱耐圧セル１と、レーザー照射装置３とを有し、耐熱耐圧セル１には、耐熱耐圧セル１を包接するヒーター５と、耐熱耐圧セル１の温度を検出する温度センサー７と、温度センサー７の検出温度に従ってヒーター５を制御する温度コントローラ９とが装備されており、耐熱耐圧セル１内の温度が所望の温度に制御される。この実施形態における耐熱耐圧セル１は、耐熱耐圧ガラスや透明石英等のような透光性で溶剤耐性を備えた耐熱耐圧素材で構成され、耐圧耐熱セル１に投入された基質Ｓに臨界圧以上の圧力を加えて保持し、温度コントローラ９によって制御されたヒーター５によって臨界温度前後に耐圧耐熱セル１を加熱することによって基質Ｓは亜臨界〜超臨界状態となる。所望の状態を維持して、レーザー照射装置３から所定波長のレーザー光を照射すると、照射光は全反射ミラー１１を介して耐圧耐熱セル１内に供給される。 FIG. 1 shows an example of an apparatus capable of performing the method for decomposing a carbon-containing compound and the method for producing a carbon microstructure according to the present invention. This apparatus has a heat-resistant pressure cell 1 for holding a fluid and adjusting it to subcritical to supercritical, and a laser irradiation device 3, and the heat-resistant pressure cell 1 includes a heater 5 that encloses the heat-resistant pressure cell 1. The temperature sensor 7 for detecting the temperature of the heat-resistant pressure cell 1 and the temperature controller 9 for controlling the heater 5 according to the temperature detected by the temperature sensor 7 are provided, and the temperature in the heat-resistant pressure cell 1 is controlled to a desired temperature. Is done. The heat-resistant pressure cell 1 in this embodiment is made of a heat-resistant pressure-resistant material such as heat-resistant pressure-resistant glass or transparent quartz that is transparent and has solvent resistance. The substrate S is brought into a subcritical to supercritical state by heating the pressure-resistant and heat-resistant cell 1 around the critical temperature by the heater 5 controlled by the temperature controller 9. When laser light having a predetermined wavelength is irradiated from the laser irradiation device 3 while maintaining a desired state, the irradiation light is supplied into the pressure-resistant and heat-resistant cell 1 via the total reflection mirror 11.
上記の装置は、小規模のバッチ式処理に適しているが、断続的なフロー処理が可能なようにセル構造及び基質供給に関する構成を変更しても良い。又、耐熱耐圧セル１は、レーザー照射を受ける部分のみを透光性の窓に構成してもよい。 The above apparatus is suitable for small-scale batch processing, but the cell structure and substrate supply configuration may be changed so that intermittent flow processing is possible. Moreover, the heat-resistant pressure | voltage resistant cell 1 may comprise only the part which receives laser irradiation to a translucent window.
以下、実施例にて本発明をさらに説明することとするが、本発明はこの実施例に限定されるものではない。 Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.
図１に示す装置において、耐熱耐圧セル１として、石英製透光窓を有するステンレス製セルを用いて、以下の操作を行った。 In the apparatus shown in FIG. 1, the following operation was performed using a stainless steel cell having a quartz transparent window as the heat and pressure cell 1.
（試料１）
容積３mlの耐熱耐圧セル１中にベンゼン１．５ml（１．３２ｇ）を投入して封止し、ヒーター５によって加熱して温度を２８９℃程度に維持してベンゼンを臨界領域とし（圧力４．９０ＭＰａに相当）、レーザー照射装置３からＮｄ−ＹＡＧ第４高調波（波長２６６nm）の紫外光を出力１００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、耐熱耐圧セル１の温度を室温に戻して圧力を常圧に下げ、セル中に残留するベンゼンを乾枯させたところ、煤状残留物が得られた。これを走査型電子顕微鏡で観察すると、直径が４０nm前後の粒子状であり、透過型電子顕微鏡で観察すると、図２のように多層状の壁部によって中空の入れ籠形を構成する粒子構造であった。又、透過型電子顕微鏡による電子線回折像を測定すると、図３のように多結晶の回折像であるリング状の回折象が得られ、グラファイト層構造を有していた。更に、ラマンスペクトルを測定したところ、図４のように１６００cm−１近辺のピーク強度が１３７０cm−１近辺のピーク強度より強かった。
(Sample 1)
Benzene 1.5 ml (1.32 g) is charged in a heat-resistant pressure cell 1 having a volume of 3 ml, sealed, heated by a heater 5 to maintain the temperature at about 289 ° C., and benzene is brought into a critical region (pressure 4. (Corresponding to 90 MPa), an ultraviolet light of Nd-YAG fourth harmonic (wavelength 266 nm) was irradiated from the laser irradiation device 3 at an output of 100 mW and a repetition rate of 10 Hz for 50000. Thereafter, the temperature of the heat and pressure cell 1 was returned to room temperature, the pressure was lowered to normal pressure, and the benzene remaining in the cell was dried, whereby a soot-like residue was obtained. When this is observed with a scanning electron microscope, it is in the form of particles having a diameter of around 40 nm, and when observed with a transmission electron microscope, it has a particle structure that forms a hollow cage shape with a multilayered wall as shown in FIG. there were. Further, when an electron beam diffraction image was measured with a transmission electron microscope, a ring-shaped diffraction image, which is a polycrystalline diffraction image, was obtained as shown in FIG. 3 and had a graphite layer structure. Furthermore, the measured Raman spectrum, was stronger than the peak intensity of the peak intensity 1370 cm -1 vicinity around 1600 cm -1 as shown in FIG.
（試料２）
耐熱耐圧セル１中にベンゼン１．５mlを投入し、液体状のベンゼンにレーザー照射装置３からＮｄ−ＹＡＧ第４高調波（波長２６６nm）の紫外光を出力１００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、セル中に残留するベンゼンを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が２０〜１００nm前後の粒子状であるが、透過型電子顕微鏡で観察すると、図５のような層構造は見られず、アモルファスカーボン粒子であった。
(Sample 2)
1.5 ml of benzene was put into the heat and pressure cell 1, and 50,000 ultraviolet rays of Nd-YAG fourth harmonic (wavelength 266 nm) were emitted from the laser irradiation device 3 to the liquid benzene at an output of 100 mW and a repetition rate of 10 Hz. . Thereafter, the benzene remaining in the cell was dried to obtain a soot-like residue. When this was observed with a scanning electron microscope, it was in the form of particles having a diameter of about 20 to 100 nm, but when observed with a transmission electron microscope, the layer structure as shown in FIG.
（試料３）
紫外光の出力を３００ｍＷに変更したこと以外は試料２と同様の操作を繰り返し、セル中に残留するベンゼンを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が４０nm前後の粒子状のものがあり、透過型電子顕微鏡での観察において図２と同様の多層状の壁部によって中空の入れ籠形を構成する粒子構造であった。
(Sample 3)
Except that the output of ultraviolet light was changed to 300 mW, the same operation as Sample 2 was repeated, and the benzene remaining in the cell was dried off to obtain a soot-like residue. When this is observed with a scanning electron microscope, there are particles having a diameter of around 40 nm, and in observation with a transmission electron microscope, particles forming a hollow cage shape with a multilayered wall portion similar to FIG. It was a structure.
（試料４）
耐熱耐圧セル１中にステンレス鋼製ロッド（Φ６mm×１５mm）を据え、紫外光の出力を３００ｍＷに変更したこと以外は試料１と同様の条件で、セル中のベンゼンに紫外光を照射した。セルの温度及び圧力を室温及び常圧に下げてセル中のロッドを取り出し、ロッド上に生成した煤状残留物を得た。これを走査型電子顕微鏡で観察したところ、図６のような直径５０〜３００nm程度の条状カーボンが捲回したコイル状であり、コイルの直径は１００nm〜３μｍ程度、長さは約５０μｍ以下であった。又、透過型電子顕微鏡で観察すると、図７のようにアモスファスカーボンによってコイル構造が形成されていることが解った。このカーボンコイルをエネルギー分散型Ｘ線分光（ＥＤＳ）によって観察したところ、コイル末端にニッケル粒の存在を検出し、ニッケルがコイル形成の核となっていることを確認した。
(Sample 4)
The benzene in the cell was irradiated with ultraviolet light under the same conditions as in sample 1 except that a stainless steel rod (Φ6 mm × 15 mm) was placed in the heat and pressure cell 1 and the ultraviolet light output was changed to 300 mW. The temperature and pressure of the cell were lowered to room temperature and normal pressure, and the rod in the cell was taken out. Thus, a soot-like residue formed on the rod was obtained. When this was observed with a scanning electron microscope, it was a coil shape in which strip-like carbon having a diameter of about 50 to 300 nm was wound as shown in FIG. 6, the diameter of the coil being about 100 nm to 3 μm, and the length being about 50 μm or less. there were. Further, when observed with a transmission electron microscope, it was found that the coil structure was formed of amorphous carbon as shown in FIG. When this carbon coil was observed by energy dispersive X-ray spectroscopy (EDS), the presence of nickel particles was detected at the end of the coil, and it was confirmed that nickel was the nucleus of coil formation.
（試料５）
耐熱耐圧セル１中にベンゼン１．５mlを投入して封止し、ヒーター５によって加熱して温度を２８９℃程度に維持してベンゼンを臨界状態とし、レーザー照射装置３からＮｄ−ＹＡＧ第２高調波（波長５３２nm）の可視光を出力３００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、耐熱耐圧セル１の温度を下げて圧力を常圧に戻し、セル中に残留するベンゼンを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が１０〜３０nm前後の粒子状であり、透過型電子顕微鏡で観察したところ、試料１と同様に、グラファイトによる多層状の壁部によって中空の入れ籠形を構成する粒子構造であることが確認された。
(Sample 5)
The heat resistant pressure cell 1 is filled with 1.5 ml of benzene, sealed, heated by the heater 5 to maintain the temperature at about 289 ° C., and the benzene is brought into a critical state. Visible light having a wave (wavelength of 532 nm) was irradiated with 50000 shots at an output of 300 mW and a repetition rate of 10 Hz. After that, the temperature of the heat and pressure cell 1 was lowered to return the pressure to normal pressure, and the benzene remaining in the cell was dried up to obtain a soot-like residue. When this is observed with a scanning electron microscope, it is in the form of particles having a diameter of about 10 to 30 nm. When observed with a transmission electron microscope, a hollow cage shape is formed by a multilayered wall portion made of graphite, similar to Sample 1. It was confirmed that the particle structure of
（試料６）
耐熱耐圧セル１中にベンゼン１．５mlを投入して封止し、ヒーター５によって加熱して温度を２００℃に維持してベンゼンを亜臨界状態とし、レーザー照射装置３からＮｄ−ＹＡＧ第４高調波（波長２６６nm）の紫外光を出力１００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、耐熱耐圧セル１の温度を下げて圧力を常圧に戻し、セル中に残留するベンゼンを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が１０〜３０nm前後の粒子状であり、透過型電子顕微鏡で観察したところ、試料１と同様に、グラファイトによる多層状の壁部によって中空の入れ籠形を構成する粒子構造であることが確認された。
(Sample 6)
The heat resistant pressure cell 1 is filled with 1.5 ml of benzene, sealed, heated by the heater 5 to maintain the temperature at 200 ° C., and the benzene is brought into the subcritical state. Waves (wavelength: 266 nm) of ultraviolet light were irradiated with 50000 shots at an output of 100 mW and a repetition rate of 10 Hz. After that, the temperature of the heat and pressure cell 1 was lowered to return the pressure to normal pressure, and the benzene remaining in the cell was dried up to obtain a soot-like residue. When this is observed with a scanning electron microscope, it is in the form of particles having a diameter of about 10 to 30 nm. When observed with a transmission electron microscope, a hollow cage shape is formed by a multilayered wall portion made of graphite, similar to Sample 1. It was confirmed that the particle structure of
（試料７）
耐熱耐圧セル１中にベンゼン１．５mlを投入して封止し、ヒーター５によって加熱して温度を２９０℃に維持してベンゼンを超臨界状態とし、レーザー照射装置３からＮｄ−ＹＡＧ第４高調波（波長２６６nm）の紫外光を出力１００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、耐熱耐圧セル１の温度を下げて圧力を常圧に戻し、セル中に残留するベンゼンを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が１０〜３０nm前後の粒子状であり、透過型電子顕微鏡で観察したところ、試料１と同様に、グラファイトによる多層状の壁部によって中空の入れ籠形を構成する粒子構造であることが確認された。
(Sample 7)
The heat resistant pressure cell 1 is filled with 1.5 ml of benzene and sealed, and heated by the heater 5 to maintain the temperature at 290 ° C. to bring the benzene into a supercritical state, and from the laser irradiation device 3 to the Nd-YAG fourth harmonic. Waves (wavelength: 266 nm) of ultraviolet light were irradiated with 50000 shots at an output of 100 mW and a repetition rate of 10 Hz. After that, the temperature of the heat and pressure cell 1 was lowered to return the pressure to normal pressure, and the benzene remaining in the cell was dried up to obtain a soot-like residue. When this is observed with a scanning electron microscope, it is in the form of particles having a diameter of about 10 to 30 nm. When observed with a transmission electron microscope, a hollow cage shape is formed by a multilayered wall portion made of graphite, similar to Sample 1. It was confirmed that the particle structure of
（試料８）
レーザー照射装置３から照射する紫外光の出力を３００ｍＷに変更し、耐熱耐圧セル中にステンレス鋼製ロッド（Φ６mm×１５mm）を据えたこと以外は試料７と同様にして、超臨界状態のベンゼンへの照射を行ったところ、セル中に残留するベンゼンを乾枯させた後のロッド上に、図６，７と同様のコイル状カーボンが生成していた。
(Sample 8)
Ultraviolet light output from the laser irradiation device 3 is changed to 300 mW, and a stainless steel rod (Φ6mm × 15mm) is installed in the heat-resistant pressure cell. As a result of the irradiation, coiled carbon similar to that shown in FIGS. 6 and 7 was formed on the rod after the benzene remaining in the cell was dried and dried.
（試料９）
耐熱耐圧セル１中にジエチルエーテル１．５mlを投入して封止し、ヒーター５によって加熱して温度を１９４℃に維持してジエチルエーテルを臨界状態とし、レーザー照射装置３からＮｄ−ＹＡＧ第４高調波（波長２６６nm）の紫外光を出力３００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、耐熱耐圧セル１の温度を下げて圧力を常圧に戻し、セル中に残留するジエチエルエーテルを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が１０〜３０nm前後の粒子状であり、透過型電子顕微鏡で観察したところ、試料１と同様に、グラファイトによる多層状の壁部によって中空の入れ籠形を構成する粒子構造であることが確認された。
(Sample 9)
The heat and pressure cell 1 is filled with 1.5 ml of diethyl ether, sealed, heated by a heater 5 to maintain the temperature at 194 ° C., and diethyl ether is brought into a critical state. Harmonic (wavelength 266 nm) ultraviolet light was irradiated 50000 times at an output of 300 mW and a repetition rate of 10 Hz. Thereafter, the temperature of the heat and pressure cell 1 was lowered to return the pressure to normal pressure, and the diethyl ether remaining in the cell was dried up to obtain a soot-like residue. When this is observed with a scanning electron microscope, it is in the form of particles having a diameter of about 10 to 30 nm. When observed with a transmission electron microscope, a hollow cage shape is formed by a multilayered wall portion made of graphite, similar to Sample 1. It was confirmed that the particle structure of
（試料１０）
耐熱耐圧セル１中にアセトン１．５mlを投入して封止し、ヒーター５によって加熱して温度を２３５℃に維持してアセトンを臨界状態とし、レーザー照射装置３からＮｄ−ＹＡＧ第４高調波（波長２６６nm）の紫外光を出力３００ｍＷ、繰り返し数１０Ｈｚで５００００発照射した。この後、耐熱耐圧セル１の温度を下げて圧力を常圧に戻し、セル中に残留するアセトンを乾枯させて、煤状残留物を得た。これを走査型電子顕微鏡で観察すると、直径が１０〜３０nm前後の粒子状であり、透過型電子顕微鏡で観察したところ、試料１と同様に、グラファイトによる多層状の壁部によって中空の入れ籠形を構成する粒子構造であることが確認された。
(Sample 10)
Acetone 1.5 ml is put into the heat and pressure cell 1 and sealed, heated by the heater 5 to maintain the temperature at 235 ° C., the acetone is brought into a critical state, and the Nd-YAG fourth harmonic from the laser irradiation device 3. Ultraviolet light having a wavelength of 266 nm was irradiated with 50,000 shots at an output of 300 mW and a repetition rate of 10 Hz. Thereafter, the temperature of the heat and pressure cell 1 was lowered to return the pressure to normal pressure, and acetone remaining in the cell was dried and dried to obtain a soot-like residue. When this is observed with a scanning electron microscope, it is in the form of particles having a diameter of about 10 to 30 nm. When observed with a transmission electron microscope, a hollow cage shape is formed by a multilayered wall portion made of graphite, similar to Sample 1. It was confirmed that the particle structure of
１ 耐熱耐圧セル、 ３ レーザー照射装置、 ５ ヒーター、
７ 温度センサー、 ９ 温度コントローラ、 １１ 全反射ミラー
1 heat and pressure cell 3 laser irradiation device 5 heater
7 Temperature sensor, 9 Temperature controller, 11 Total reflection mirror
Claims (7)
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| JP2007220324A JP5213223B2 (en) | 2007-08-27 | 2007-08-27 | Method for decomposing carbon-containing compound and method for producing carbon microstructure |
| US12/675,361 US20100243426A1 (en) | 2007-08-27 | 2008-08-25 | Method for decomposing carbon-containing compound, method for producing carbon nano/microstructure, and method for producing carbon thin film |
| EP08792703.4A EP2186775A4 (en) | 2007-08-27 | 2008-08-25 | METHOD FOR DECOMPOSING COMPOUND WITH CARBON CONTENT, METHOD FOR MANUFACTURING CARBON MICROSTRUCTURE, AND METHOD FOR FORMING CARBON THIN FILM |
| PCT/JP2008/065095 WO2009028451A1 (en) | 2007-08-27 | 2008-08-25 | Method for decomposing carbon-containing compound, method for producing carbon microstructure, and method for forming carbon thin film |
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