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JP2012062222A - Carbon nanostructure - Google Patents

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JP2012062222A
JP2012062222A JP2010207936A JP2010207936A JP2012062222A JP 2012062222 A JP2012062222 A JP 2012062222A JP 2010207936 A JP2010207936 A JP 2010207936A JP 2010207936 A JP2010207936 A JP 2010207936A JP 2012062222 A JP2012062222 A JP 2012062222A
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metal
carbon nanostructure
encapsulated
carbon
crystal
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Nobuyuki Nishi
信之 西
Norikazu Adachi
安達　　紀和
Yasuyuki Oba
保幸 大場
Manabu Yamada
学 山田
Kenichiro Kami
謙一郎 加美
Kazuhiko Mizuuchi
和彦 水内
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Denso Corp
Nippon Steel Chemical and Materials Co Ltd
National Institute of Natural Sciences
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Denso Corp
Nippon Steel Chemical Co Ltd
National Institute of Natural Sciences
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    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Electric Double-Layer Capacitors Or The Like (AREA)
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  • Battery Electrode And Active Subsutance (AREA)

Abstract

【課題】電極材料及び触媒担体などとして使用することのできる、新規な構造の炭素ナノ構造体を提供する。
【解決手段】金属塩を含む溶液に対してメチルアセチレンガスを吹き込み、金属メチルアセチリドのワイヤー状結晶体を作製し、前記棒状結晶体及び／又は前記板状結晶体に第１の加熱処理を施して、前記金属メチルアセチリド中の金属を偏析させるとともに、前記棒状結晶体及び／又は前記板状結晶体中の炭素を偏析させ、炭素を含む棒状体及び／又は板状体が３次元的に結合してなる炭素ナノ構造中間体を得るとともに、この炭素ナノ構造中間体中に前記金属が内包されてなる金属内包炭素ナノ構造体を作製し、前記金属内包炭素ナノ構造体を硝酸と接触させ、前記金属内包炭素ナノ構造物に対して第２の加熱処理を施して、前記金属内包炭素ナノ構造物に内包される前記金属を噴出させ、グラフェン多層膜壁で画定される肺胞状空孔を有する炭素ナノ構造体を得る。
【選択図】図４Disclosed is a carbon nanostructure having a novel structure that can be used as an electrode material and a catalyst support.
Methylacetylene gas is blown into a solution containing a metal salt to produce a metal-methylacetylide wire crystal, and the rod-like crystal and / or the plate-like crystal is subjected to a first heat treatment. And segregating the metal in the metal methyl acetylide and segregating the carbon in the rod-like crystal body and / or the plate-like crystal body, so that the rod-like body and / or the plate-like body containing carbon are three-dimensionally bonded. To obtain a carbon nanostructure intermediate body, and to produce a metal-encapsulated carbon nanostructure in which the metal is encapsulated in the carbon nanostructure intermediate, and contact the metal-encapsulated carbon nanostructure with nitric acid, The metal-encapsulated carbon nanostructure is subjected to a second heat treatment, and the metal encapsulated in the metal-encapsulated carbon nanostructure is ejected to form alveolar pores defined by the graphene multilayer film walls. Obtain a carbon nanostructure.
[Selection] Figure 4

Description

本発明は、炭素ナノ構造体に関する。   The present invention relates to a carbon nanostructure.

炭素材料は、低温型燃料電池、スーパーキャパシタやリチウムイオン２次電池の電極、あるいは液相触媒反応における触媒担持体として用いられ、その重要性と作製コストの廉価性の必要が益々高まっている。電極や触媒担体としての使用に対しては、空孔率が高く気体や液体の流動性の高さが重要となってくる。これに加えて、電極材料としては高い電気伝導特性と電流密度の高さが要求される。   Carbon materials are used as electrodes for low-temperature fuel cells, supercapacitors and lithium ion secondary batteries, or as catalyst carriers in liquid-phase catalytic reactions, and the importance of them and the need for low production costs are increasing. For use as an electrode or a catalyst carrier, high porosity and high fluidity of gas or liquid are important. In addition, the electrode material is required to have high electric conduction characteristics and high current density.

炭素材料を電極材料として使用する一例として、非特許文献１では、プロピレンガスの高温分解法で得られた顆粒状炭素の表面にCVD(Chemical Vapor Deposition)法によって堆積付着させたシリコン・炭素複合物が、20時間放電速度(C/20)に於いて、1,270 mAh/cm-3という高い容量維持率を示し、炭素材の表面に固定しているにもかかわらず、98％以上の充放電効率を得ている。しかしながら、高い電流密度領域では、この容量維持率が著しく低下すること、また、比表面積が十分ではないため空洞内部の空間からの比表面積への寄与が大きく、上記特性を安定して得ることができないという問題があった。 As an example of using a carbon material as an electrode material, Non-Patent Document 1 discloses a silicon-carbon composite deposited and adhered by CVD (Chemical Vapor Deposition) on the surface of granular carbon obtained by a high-temperature decomposition method of propylene gas. Shows a high capacity maintenance rate of 1,270 mAh / cm -3 at a discharge rate of 20 hours (C / 20) and a charge / discharge efficiency of 98% or more despite being fixed on the surface of the carbon material. Have gained. However, in the high current density region, the capacity retention rate is significantly reduced, and since the specific surface area is not sufficient, the contribution to the specific surface area from the space inside the cavity is large, and the above characteristics can be obtained stably. There was a problem that I could not.

また、特許文献１には、活性炭のミクロ孔内に、リチウムと合金を形成できる金属、例えば錫、カルシウム、ストロンチウム、バリウム、イリジウムなどの活物質を担持させることによって、リチウムイオン２次電池の負極を製造する技術が開示されている。しかしながら、上述した活物質の添加量は活性炭を構成する炭素の重量の30％が上限であり、十分な容量維持率を得ることができず、結果として十分な充放電効率を得ることができないという問題がある。   Patent Document 1 discloses a negative electrode of a lithium ion secondary battery by supporting a metal capable of forming an alloy with lithium, such as tin, calcium, strontium, barium, and iridium, in a micropore of activated carbon. Techniques for manufacturing the are disclosed. However, the upper limit of the amount of the active material added is 30% of the weight of carbon constituting the activated carbon, and a sufficient capacity retention rate cannot be obtained, and as a result, sufficient charge / discharge efficiency cannot be obtained. There's a problem.

炭素材料を触媒担体として使用する一例として、特許文献２では、金属を含まない有機材料から成るアモルファス炭素構造体に、イオンビーム励起化学気相堆積法を用いて、触媒金属（ガリウム）を導入し、触媒金属が導入されたアモルファス炭素構造体を５００℃程度に加熱して、触媒金属をアモルファス炭素構造体から排出し、触媒金属を排出したアモルファス炭素構造体を冷却して、細孔を有するカーボン構造体を得、これを触媒担体として使用することが開示されている。しかしながら、このようにして得た触媒担体では細孔の密度が十分でないため、その後に触媒金属を担持させようとした場合において、その量を十分に保持することができないという問題があった。   As an example of using a carbon material as a catalyst carrier, Patent Document 2 introduces a catalyst metal (gallium) into an amorphous carbon structure made of an organic material that does not contain a metal by using an ion beam-excited chemical vapor deposition method. , The amorphous carbon structure into which the catalyst metal is introduced is heated to about 500 ° C., the catalyst metal is discharged from the amorphous carbon structure, the amorphous carbon structure from which the catalyst metal has been discharged is cooled, and carbon having pores It is disclosed that a structure is obtained and used as a catalyst support. However, the catalyst carrier thus obtained has a problem that the density of the pores is not sufficient, so that when the catalyst metal is subsequently supported, the amount cannot be sufficiently maintained.

また、炭素材料を触媒担体に用いる例として、燃料電池の触媒がある。近年、燃料電池の劣化原因のひとつに、炭素材料の酸化消耗が寄与していることが判明しいている。耐酸化性向上のためには黒鉛化度を上げることが有効だが、通常の活性炭では、黒鉛結晶構造が成長する程度まで再熱処理を行うと、肝心の細孔が潰れてしまい、表面積が顕著に低下してしまうという課題がある。   An example of using a carbon material as a catalyst carrier is a fuel cell catalyst. In recent years, it has been found that the oxidation of carbon materials contributes to one of the causes of deterioration of fuel cells. Increasing the degree of graphitization is effective for improving oxidation resistance, but with normal activated carbon, if reheat treatment is performed to the extent that the graphite crystal structure grows, the critical pores are crushed and the surface area becomes noticeable. There is a problem that it decreases.

特許第４０６９４６５号Patent No. 4069465 特開２００９−２０３１２８号JP 2009-203128 A

High-performance lithium-ion anodes using a hierarchical bottom-up approach, A. Magasinski, P. Dixon, B. Hertzberg, A. Kvit, J. Ayala, and G. Yushin, Nature Materials, 9(2010)353-358High-performance lithium-ion anodes using a hierarchical bottom-up approach, A. Magasinski, P. Dixon, B. Hertzberg, A. Kvit, J. Ayala, and G. Yushin, Nature Materials, 9 (2010) 353-358

本発明は、電極材料及び触媒担体などとして使用することのできる、新規な構造の炭素ナノ構造体を提供することを目的とする。   An object of the present invention is to provide a carbon nanostructure having a novel structure that can be used as an electrode material, a catalyst carrier, and the like.

上記目的を達成すべく、本発明は、
金属塩を含む溶液に対してメチルアセチレンガスを吹き込み、金属メチルアセチリドの棒状結晶体及び／又は板状結晶体を作製し、前記棒状結晶体及び／又は前記板状結晶体に第１の加熱処理を施して、前記金属メチルアセチリド中の金属を偏析させるとともに、前記棒状結晶体及び／又は前記板状結晶体中の炭素を偏析させ、炭素を含む棒状体及び／又は板状体が３次元的に結合してなる炭素ナノ構造中間体を得るとともに、この炭素ナノ構造中間体中に前記金属が内包されてなる金属内包炭素ナノ構造体を作製し、前記金属内包炭素ナノ構造体を硝酸と接触させ、前記金属内包炭素ナノ構造物に対して第２の加熱処理を施して、前記金属内包炭素ナノ構造物に内包される前記金属を噴出させて得たことを特徴とする、炭素ナノ構造体に関する。 In order to achieve the above object, the present invention provides:
Methylacetylene gas is blown into the solution containing the metal salt to produce a metal methylacetylide rod-like crystal and / or plate-like crystal, and the rod-like crystal and / or the plate-like crystal is subjected to a first heat treatment. To segregate the metal in the metal methyl acetylide and segregate the carbon in the rod-like crystal body and / or the plate-like crystal body, so that the rod-like body and / or plate-like body containing carbon is three-dimensional. To obtain a carbon nanostructure intermediate bonded to the carbon nanostructure, to produce a metal-encapsulated carbon nanostructure in which the metal is encapsulated in the carbon nanostructure intermediate, and to contact the metal-encapsulated carbon nanostructure with nitric acid A carbon nanostructure obtained by performing a second heat treatment on the metal-encapsulated carbon nanostructure to eject the metal encapsulated in the metal-encapsulated carbon nanostructure Related That.

なお、本発明における“ナノ構造体”とは、以下に詳述するように、この構造体を特徴づける構成要素が、ｎｍオーダから数百ｎｍオーダのスケールのものを含むことに由来して名付けられたものである。   The “nanostructure” in the present invention is named after the structural elements that characterize this structure include those on the order of nm to several hundreds of nm, as will be described in detail below. It is what was done.

また、本発明の炭素ナノ構造体は、これまでにない全く新規な製造方法によって製造されたものであるため、以下に詳述する構造体の特徴は、当該構造体が潜在的に含んでいる特徴の内、一部の顕在化した特徴である可能性が大きい。このような観点から、本発明では、発明の対象物が物の発明ではあるが、敢えて製造方法によって規定し、上記炭素ナノ構造体が潜在的に含んでいる総ての構造的特徴を保護するようにしたものである。   In addition, since the carbon nanostructure of the present invention is manufactured by a completely new manufacturing method that has not been heretofore, the characteristics of the structure described in detail below are potentially included in the structure. Among the features, there is a high possibility that some of the features are manifested. From this point of view, in the present invention, although the object of the invention is a product invention, it is intentionally defined by the manufacturing method and protects all structural features potentially contained in the carbon nanostructure. It is what I did.

以上説明したように、本発明によれば、電極材料及び触媒担体などとして使用することのできる、新規な構造の炭素ナノ構造体を提供することができる。   As described above, according to the present invention, it is possible to provide a carbon nanostructure having a novel structure that can be used as an electrode material and a catalyst carrier.

銅メチルアセチリドのワイヤー状結晶体のＳＥＭ写真である。It is a SEM photograph of the wire-like crystal body of copper methyl acetylide. 銅メチルアセチリドのワイヤー状結晶体のＴＥＭ写真である。It is a TEM photograph of a wire crystal of copper methyl acetylide. 本発明の炭素ナノ構造体の一例を示す外観ＳＥＭ写真である。It is an external appearance SEM photograph which shows an example of the carbon nanostructure of this invention. 図１に示す炭素ナノ構造体の表面を拡大して示すＳＥＭ写真である。It is a SEM photograph which expands and shows the surface of the carbon nanostructure shown in FIG. 図１に示す炭素ナノ構造体の表面を拡大して示すＳＥＭ写真である。It is a SEM photograph which expands and shows the surface of the carbon nanostructure shown in FIG. 図１に示す炭素ナノ構造体の一部におけるＴＥＭ写真である。It is a TEM photograph in a part of carbon nanostructure shown in FIG. 実施例における炭素ナノ構造体のＴＧＡ（熱重量測定）の結果を示すグラフである。It is a graph which shows the result of TGA (thermogravimetry) of the carbon nanostructure in an example. 実施例における炭素ナノ構造体のＴＥＭ写真である。It is a TEM photograph of the carbon nanostructure in an example. 実施例における炭素ナノ構造体の電子エネルギー損失スペクトルを示すグラフである。It is a graph which shows the electron energy loss spectrum of the carbon nanostructure in an Example. 実施例における炭素ナノ構造体の小角Ｘ線散乱スペクトルから得られた空孔分布（体積）を示すグラフである。It is a graph which shows the void | hole distribution (volume) obtained from the small angle X-ray-scattering spectrum of the carbon nanostructure in an Example. 実施例における炭素ナノ構造体の窒素の吸・脱着曲線を示すグラフである。It is a graph which shows the adsorption / desorption curve of nitrogen of the carbon nanostructure in an Example.

以下、本発明の詳細、並びにその他の特徴及び利点について説明する。   The details of the present invention as well as other features and advantages are described below.

本発明の炭素ナノ構造体は、次のようにして得ることができる。
最初に、炭素ナノ構造体の前駆体に相当する金属内包炭素ナノ構造体を製造する。金属内包炭素ナノ構造体は、例えば以下の製造工程に基づいて製造することができる。 The carbon nanostructure of the present invention can be obtained as follows.
First, a metal-encapsulated carbon nanostructure corresponding to a precursor of a carbon nanostructure is manufactured. The metal-encapsulated carbon nanostructure can be manufactured, for example, based on the following manufacturing process.

塩化第一銅のアンモニア水溶液にメチルアセチレンガスまたはメチルアセチレンを含む混合ガスを吹き込む。この際、前記溶液の攪拌を激しく行う。これによって、前記溶液中に黄色の銅メチルアセチリドのワイヤー（図１及び図２参照）の沈殿物が生成する。   Methylacetylene gas or a mixed gas containing methylacetylene is blown into an aqueous solution of cuprous chloride. At this time, the solution is vigorously stirred. This produces a precipitate of yellow copper methyl acetylide wire (see FIGS. 1 and 2) in the solution.

次いで、前記沈殿物を大きめのステンレス製耐圧反応管に移し、電気炉に入れ、例えば９０〜１２０℃の温度で例えば１２時間以上脱溶媒処理を行う。これに、例えば水素ガスを０．０１ｋＰａ以下、好ましくは０．００１ｋＰａ以上となるようにして導入し、さらに２１０〜２５０℃に加熱（第１の加熱処理）すると、暫くしてガスが発生し、メタン及びエチレンの気体、炭素及び銅ナノ粒子の固体への偏析反応が起こる。   Next, the precipitate is transferred to a large stainless steel pressure-resistant reaction tube, placed in an electric furnace, and subjected to a solvent removal treatment at a temperature of 90 to 120 ° C., for example, for 12 hours or more. For example, when hydrogen gas is introduced at 0.01 kPa or less, preferably 0.001 kPa or more, and further heated to 210 to 250 ° C. (first heat treatment), gas is generated for a while, Segregation reactions of methane and ethylene gases, carbon and copper nanoparticles into solids occur.

また、上記加熱処理によって、偏析反応によって生成した炭素を含む棒状体及び／又は板状体が３次元的に結合してなる炭素ナノ構造中間体が得られるとともに、同じく偏析反応によって生成した銅ナノ粒子が炭素ナノ構造中間体中に内包されてなる金属内包炭素ナノ構造体を得る。   In addition, a carbon nanostructure intermediate formed by three-dimensionally bonding a rod-like body and / or a plate-like body containing carbon produced by the segregation reaction is obtained by the heat treatment, and copper nanoparticle produced by the segregation reaction is also obtained. A metal-encapsulated carbon nanostructure in which particles are encapsulated in a carbon nanostructure intermediate is obtained.

なお、水素ガスの導入は反応直後に生じた炭素の末端の酸化を防ぐためである。また、上述のように水素ガス中で加熱処理を行うことによって、比較的低い温度で偏析反応を生ぜしめることができるとともに、金属内包炭素ナノ構造体を得ることができる。また、偏析反応に伴うガスの発生は、金属内包炭素ナノ構造体中に無数の空洞を形成する。したがって、金属内包炭素ナノ構造体は、図３に示すような、多数のミクロンオーダーの空隙がランダムに形成され、棒状体及び／又は板状体が３次元的な網状に連結されて網状構造の一体型構造物（モノリス）となる。   The introduction of hydrogen gas is to prevent oxidation of carbon ends generated immediately after the reaction. Moreover, by performing heat treatment in hydrogen gas as described above, a segregation reaction can be caused at a relatively low temperature, and a metal-encapsulated carbon nanostructure can be obtained. Moreover, the generation | occurrence | production of the gas accompanying a segregation reaction forms innumerable cavity in a metal inclusion carbon nanostructure. Therefore, in the metal-encapsulated carbon nanostructure, a large number of micron-order voids are randomly formed as shown in FIG. 3, and rod-like bodies and / or plate-like bodies are connected in a three-dimensional network form. It becomes an integrated structure (monolith).

本例では、金属内包炭素ナノ構造体を製造するに際し、塩化第一銅のアンモニア水溶液を用い、金属内包炭素ナノ構造体に内包する金属を銅としているが、これは原料である塩化第一銅の準備及び調整を容易に行うことができることに由来するものである。   In this example, when manufacturing the metal-encapsulated carbon nanostructure, an ammonia aqueous solution of cuprous chloride is used, and the metal encapsulated in the metal-encapsulated carbon nanostructure is copper, but this is the raw material cuprous chloride. This is derived from the fact that the preparation and adjustment can be easily performed.

なお、金属内包炭素ナノ構造体自体も金属体を内包しているので高い電気伝導性を呈する。したがって、高い気孔性と高い電気伝導性とを十分に満足した炭素構造体(炭素材料)として機能させることができる。したがって、電極や触媒担持電極等として好適に用いることができる。この場合、上述のように、内包させる金属を銅とすることにより、電気伝導性をより向上させることができる。   The metal-encapsulated carbon nanostructure itself also includes a metal body and exhibits high electrical conductivity. Therefore, it can function as a carbon structure (carbon material) sufficiently satisfying high porosity and high electrical conductivity. Therefore, it can be suitably used as an electrode or a catalyst-carrying electrode. In this case, as described above, the electrical conductivity can be further improved by using copper as the metal to be included.

次に、上述のようにして得た金属内包炭素ナノ構造物に対して硝酸を接触させる。これは、金属内包炭素ナノ構造体内に内包されている上記金属が、これを囲む炭素壁によって強固に保持されているため、上記硝酸によって上記金属を取り囲む炭素壁の一部を溶かし、以下に説明する第２の加熱処理によって上記金属の噴出を容易かつ完全に行うようにし、上記金属除去後の金属内包炭素ナノ構造体に形成される、後の炭素ナノ構造体の空孔に相当する空洞中に上記金属が残留するのを防止するためのものである。   Next, nitric acid is brought into contact with the metal-encapsulated carbon nanostructure obtained as described above. This is because the metal encapsulated in the metal-encapsulated carbon nanostructure is firmly held by the carbon wall surrounding the metal, so that a part of the carbon wall surrounding the metal is dissolved by the nitric acid, which will be described below. In the cavity corresponding to the vacancies of the subsequent carbon nanostructure formed in the metal-encapsulated carbon nanostructure after the removal of the metal, by performing the second heat treatment to eject the metal easily and completely. This is to prevent the above metal from remaining.

なお、金属内包炭素ナノ構造物を硝酸に接触させた際には、この金属内包炭素ナノ構造物中に内包された上記金属の少なくとも一部が溶出する。   When the metal-encapsulated carbon nanostructure is brought into contact with nitric acid, at least a part of the metal encapsulated in the metal-encapsulated carbon nanostructure is eluted.

また、硝酸は、適宜水で薄めて硝酸水溶液として使用することができる。硝酸との接触時間は、用いる硝酸水溶液の濃度などにも依存するが、好ましくは数十時間である。   Nitric acid can be appropriately diluted with water and used as an aqueous nitric acid solution. The contact time with nitric acid is preferably several tens of hours, although it depends on the concentration of the aqueous nitric acid solution used.

次に、第２の加熱処理を施して、前記金属内包炭素ナノ構造物に内包される金属を噴出（昇華脱離）させ、炭素ナノ構造体を得る。この場合、金属の噴出後の空洞が炭素ナノ構造体の空孔を形成する。第２の加熱処理は、例えば真空中、９００℃〜１４００℃の温度において数時間、具体的には５時間〜１０時間行う。   Next, a second heat treatment is performed to eject (sublimate) the metal encapsulated in the metal-encapsulated carbon nanostructure to obtain a carbon nanostructure. In this case, the cavities after the metal ejection form vacancies in the carbon nanostructure. The second heat treatment is performed, for example, in a vacuum at a temperature of 900 ° C. to 1400 ° C. for several hours, specifically 5 hours to 10 hours.

第２の加熱処理は、マイクロ波を用いて行うこともできる。この場合、上記のような真空加熱に比較して、コストを抑えることができる。   The second heat treatment can also be performed using microwaves. In this case, the cost can be reduced as compared with the vacuum heating as described above.

なお、金属内包炭素ナノ構造体に内包される前記金属を噴出させた後、前記金属内包炭素ナノ構造体に溶解洗浄を施し、残存した前記金属を除去することができる。空孔内に噴出させるべき金属が残存していると、後に空孔内に金属を担持させて触媒あるいは電極とした場合に、これら金属同士が互いに反応してしまい、目的とする特性を有する触媒あるいは電極を得ることができない場合がある。   In addition, after ejecting the metal encapsulated in the metal-encapsulated carbon nanostructure, the metal-encapsulated carbon nanostructure can be dissolved and washed to remove the remaining metal. If the metal that should be ejected in the pores remains, then when the metal is supported in the pores and used as a catalyst or electrode, these metals react with each other, and the catalyst has the desired characteristics. Or an electrode may not be obtained.

しかしながら、上述のように、金属内包炭素ナノ構造体に溶解洗浄を施し、空洞内、すなわち形成すべき空孔内に残存する金属を除去することによって、上述した不利益を除去することができる。   However, as described above, the disadvantages described above can be eliminated by subjecting the metal-encapsulated carbon nanostructures to dissolution cleaning to remove the metal remaining in the cavities, ie, the vacancies to be formed.

上記溶解洗浄は、例えば金属内包炭素ナノ構造体を４〜８時間熱硝酸に浸漬させることによって行うことができる。   The dissolution cleaning can be performed, for example, by immersing the metal-encapsulated carbon nanostructure in hot nitric acid for 4 to 8 hours.

また、金属内包炭素ナノ構造体に残存する金属を除去するに際しては、金属内包炭素ナノ構造体に対して第３の加熱処理を施して行うこともできる。この場合、第３の加熱処理を例えば５００℃〜１４００℃の範囲で行うことによって、残留した金属を炭素から分離して除去することができる。   Further, when removing the metal remaining in the metal-encapsulated carbon nanostructure, the metal-encapsulated carbon nanostructure can be subjected to a third heat treatment. In this case, by performing the third heat treatment in the range of 500 ° C. to 1400 ° C., for example, the remaining metal can be separated and removed from the carbon.

なお、金属内包炭素ナノ構造体に残存する金属を除去するに際しての溶解洗浄と第３の加熱処理とは、それぞれ単独で用いることもできるし、両者を併合させて用いることもできる。   Note that the dissolution cleaning and the third heat treatment for removing the metal remaining in the metal-encapsulating carbon nanostructure can be used alone or in combination.

以上のような工程を経て得た炭素ナノ構造体は、例えば、図３に示すように、厚紙の束を燃やして炭化させた燃えかすのような形状をしており、多数のミクロンオーダーの孔がランダムに形成され、棒状体及び／又は板状体が３次元的な網状に連結されて網状構造の一体型構造物（モノリス）となっている。また、図４及び図５に示すように、その表面は瘤状の隆起物で覆われている。なお、図３は、上述のようにして得た炭素ナノ構造体の外観ＳＥＭ写真であり、図４及び図５は、図３に示す炭素ナノ構造体の表面を拡大して示すＳＥＭ写真である。   The carbon nanostructure obtained through the above-described steps has a shape like a scum obtained by burning and carbonizing a bundle of cardboard, as shown in FIG. Are formed at random, and rod-like bodies and / or plate-like bodies are connected in a three-dimensional network form to form an integral structure (monolith) having a network structure. Moreover, as shown in FIG.4 and FIG.5, the surface is covered with the knob-like ridge. 3 is an external SEM photograph of the carbon nanostructure obtained as described above, and FIGS. 4 and 5 are enlarged SEM photographs showing the surface of the carbon nanostructure shown in FIG. .

なお、炭素ナノ構造体を構成する棒状体の直径及び前記板状体の幅は約１００ｎｍ以上１０μｍ以下である。   In addition, the diameter of the rod-shaped body which comprises a carbon nanostructure, and the width | variety of the said plate-shaped body are about 100 nm or more and 10 micrometers or less.

図６は、図３に示す炭素ナノ構造体の一部におけるＴＥＭ写真である。図６から明らかなように、上述にようにして得た炭素ナノ構造体は、その内部において３層から１０層分のグラフェン多層膜壁で画定され、互いに３次元的に連通してなる肺胞状の空孔を有することが分かる。また、肺胞状の空孔は、空孔を画定するグラフェン多層膜壁の、任意の層が枝分かれを繰り返し、ある１つの空孔を画定する層がその空孔と隣接する空孔をも画定し、これによって隣接する空孔同士が互いに連通していることが分かる。   FIG. 6 is a TEM photograph of a part of the carbon nanostructure shown in FIG. As is apparent from FIG. 6, the carbon nanostructure obtained as described above is defined by three to ten layers of graphene multilayer film walls and has an alveolar shape that is three-dimensionally connected to each other. It can be seen that it has Alveolar vacancies can also be defined as any layer of the graphene multilayer wall that defines vacancies, and any layer that repeats branching also defines vacancies adjacent to the vacancies. Thus, it can be seen that adjacent holes communicate with each other.

また、図６からも明らかなように、上記空孔は、一般には表皮付近の比較的小さな、例えば空孔径が１ｎｍ以上２０ｎｍ以下の空孔（第１の空孔）と、内部の比較的大きな、例えば空孔径が１０ｎｍ以上８０ｎｍ以下の空孔（第２の空孔）とを含む。   Further, as is apparent from FIG. 6, the vacancies are generally relatively small in the vicinity of the skin, for example, vacancies having a pore diameter of 1 nm or more and 20 nm or less (first vacancies), and a relatively large inside. For example, a hole having a hole diameter of 10 nm to 80 nm (second hole) is included.

なお、本発明における“肺胞状の空孔”とは、空孔を画定するグラフェン多層膜壁の、任意の層が枝分かれを繰り返し、隣接する空孔同士が互いに連通しているような状態をいう。   In the present invention, the term “alveolar vacancies” refers to a state in which any layer of the graphene multilayer wall defining the vacancies repeats branching and adjacent vacancies communicate with each other. .

図６からも明らかなように、炭素ナノ構造体が肺胞状の空孔を有すると、炭素ナノ構造体中に占める空孔の割合が極めて高くなることが分かる。したがって、このようにして形成された空孔に対して触媒金属あるいは電極材料を担持させれば、その担持量を飛躍的に増大させることができるので、炭素ナノ構造体を含む触媒あるいは電極材料において、それぞれの特性を飛躍的に向上させることができる。   As is clear from FIG. 6, it can be seen that when the carbon nanostructure has alveolar vacancies, the proportion of the vacancies in the carbon nanostructure is extremely high. Therefore, if the catalyst metal or the electrode material is supported in the vacancies formed in this way, the supported amount can be drastically increased. Therefore, in the catalyst or electrode material containing the carbon nanostructure, , Each characteristic can be improved dramatically.

また、グラフェン多層膜壁の形成には、上述した第２の加熱処理が寄与していると考えられる。すなわち、上述の金属を囲む炭素をグラフェン化して、寄与し、さらにはグラフェン多層膜壁の任意の層を枝分かれさせて、肺胞状の空孔の形成に寄与する。   In addition, it is considered that the second heat treatment described above contributes to the formation of the graphene multilayer film wall. That is, the carbon surrounding the above-mentioned metal is graphenized to contribute, and further, an arbitrary layer of the graphene multilayer film wall is branched to contribute to the formation of alveolar vacancies.

本例における炭素ナノ構造体は、例えば８０ｍ２／ｇ以上のＢＥＴ比表面積を有し、多くの場合３００ｍ２／ｇ以上のＢＥＴ比表面積を有する。ＢＥＴ比表面積の大小は、例えば炭素ナノ構造体を構成する棒状体及び板状体の直径や、炭素ナノ構造体中に含まれる空孔径に依存する。例えば、棒状体及び板状体の直径が小さいほど、さらには空孔径が小さいほど上記ＢＥＴ比表面積は増大する。 The carbon nanostructure in this example has a BET specific surface area of, for example, 80 m 2 / g or more, and often has a BET specific surface area of 300 m 2 / g or more. The magnitude of the BET specific surface area depends on, for example, the diameters of rod-like bodies and plate-like bodies constituting the carbon nanostructure, and the pore diameter contained in the carbon nanostructure. For example, the BET specific surface area increases as the diameters of the rod-shaped body and the plate-shaped body decrease, and as the pore diameter decreases.

炭素ナノ構造体の空孔および網状構造によって生じるメソ空間の分布は、例えば小角Ｘ線散乱スペクトルによって知ることができる。   The distribution of mesospace caused by the vacancies and the network structure of the carbon nanostructure can be known, for example, by a small angle X-ray scattering spectrum.

（実施例１）
最初に、第一塩化銅を０．１モル/Ｌ（リッター）の濃度で含むアンモニア水溶液（５．５％）をフラスコに用意し、これを激しく攪拌しながら窒素ガスで１０％に希釈したメチルアセチレンガスを１Ｌ の溶液に対し２００ｍＬ／ｍｉｎ の流速で約１２０分間、回転する溶液の底部から吹き込んだ。これによって、溶液中に銅メチルアセチリドの棒状結晶体及び／又は板状結晶体が生じ沈殿を始めた。 Example 1
First, an aqueous ammonia solution (5.5%) containing cuprous chloride at a concentration of 0.1 mol / L (liter) was prepared in a flask, and this was diluted to 10% with nitrogen gas while stirring vigorously. Acetylene gas was blown into the 1 L solution from the bottom of the rotating solution for about 120 minutes at a flow rate of 200 mL / min. As a result, rod-like crystals and / or plate-like crystals of copper methyl acetylide were formed in the solution, and precipitation started.

次いで、前記沈殿物をメンブレンフィルターで濾過し、ろ過の際に、前記棒状結晶体及び／又は板状結晶体の沈殿物をメタノールで洗浄した。反応時間を長くすると、数百ミクロンの長さにまですることができる。この操作を６回繰り返し、黄色のワイヤー結晶水和沈殿物約５０ｇを得た。   Next, the precipitate was filtered with a membrane filter, and the precipitate of the rod-like crystal body and / or plate-like crystal body was washed with methanol during the filtration. Longer reaction times can be as long as several hundred microns. This operation was repeated 6 times to obtain about 50 g of a yellow wire crystal hydrate precipitate.

次いで、前記沈殿物５０ｇを３００mＬの肉厚ビーカーに入れ、これを更に３Ｌの肉厚ビーカーに入れてこれにテフロン（登録商標）の板を置いて蓋とした。テフロン（登録商標）の板は４枚で、それぞれ厚さ１０ｍｍで空気抜けの小さな穴が重ならないように開けてある。これを内径１５５ｍｍ、長さ３００ｍｍの肉厚５ｍｍのステンレス製真空容器に入れ、一度、１００Ｐａ以下に減圧する。この状態で水素ガスを１Ｌ導入し、０．３気圧程度の圧力で、反応容器の温度を２５０℃に３０分かけて昇温させた。   Next, 50 g of the precipitate was placed in a 300 mL thick beaker, which was further placed in a 3 L thick beaker, and a Teflon (registered trademark) plate was placed thereon to form a lid. There are four Teflon (registered trademark) plates, each having a thickness of 10 mm, so that small holes for air removal do not overlap. This is put into a stainless steel vacuum vessel having an inner diameter of 155 mm and a length of 300 mm and a thickness of 5 mm, and once depressurized to 100 Pa or less. In this state, 1 L of hydrogen gas was introduced, and the temperature of the reaction vessel was raised to 250 ° C. over 30 minutes at a pressure of about 0.3 atm.

この際、圧力は徐々に上がって来るが、２〜３時間後に急に圧力が１気圧強まで上昇した。これを冷却することによって真空容器内部に約２０ｇの金属内包炭素ナノ構造体を得た。   At this time, although the pressure gradually increased, the pressure suddenly increased to a little over 1 atm after 2 to 3 hours. By cooling this, about 20 g of metal-encapsulated carbon nanostructures were obtained inside the vacuum vessel.

次いで、１Ｌの三角フラスコに、得られた金属内包炭素ナノ構造体の２０ｇを入れ、３０〜４０重量％の硝酸水溶液４００ｍＬを加えると、炭素ナノ構造体は萎むと同時に赤褐色の二酸化窒素ガスを発生し、さらに炭素ナノ構造体中に残留した銅が溶解した。６０℃程度に約３０〜４８時間加熱し、銅の溶解と不安定な炭素を酸化させた。   Next, when 20 g of the obtained metal-encapsulated carbon nanostructure is placed in a 1 L Erlenmeyer flask and 400 mL of 30-40 wt% nitric acid aqueous solution is added, the carbon nanostructure is deflated and at the same time generates reddish brown nitrogen dioxide gas. Furthermore, the copper remaining in the carbon nanostructure was dissolved. Heating to about 60 ° C. for about 30 to 48 hours caused copper to be dissolved and unstable carbon to be oxidized.

これを濾過し、十分に洗浄乾燥させ、石英管に入れて１１００℃で１２時間程度真空加熱を行った。すると石英管の末端の低温部の壁にまず有機物薄膜が、次いで銅が昇華沈着した。炭素部分のみを取り出し、再度、熱硝酸で残留銅を溶解し、これを乾燥の後、アルミナ製タンマン管に入れて１４００℃で１０時間加熱した。   This was filtered, thoroughly washed and dried, placed in a quartz tube, and heated under vacuum at 1100 ° C. for about 12 hours. Then, an organic thin film was first deposited on the wall of the low temperature portion at the end of the quartz tube, and then copper was sublimated. Only the carbon part was taken out, and the residual copper was dissolved again with hot nitric acid. After drying, this was put into an alumina Tamman tube and heated at 1400 ° C. for 10 hours.

この段階で得られた炭素ナノ構造体にＴＧＡ（熱重量測定）を実施した結果、図７に示すようなグラフが得られた。これは、燃焼温度が680℃とグラファイトに近く、残留金属も２重量％以下であった。このもののTEM像を図８に、電子エネルギー損失スペクトルを図９に、小角Ｘ線散乱スペクトルから得られた空孔分布（体積）を図１０に、窒素の吸・脱着曲線を図１１に示した。図１１のデータから得られたＢＥＴ（Brunauer，Emmett，Teller）比表面積は、３００ｍ２／ｇであった。また、図１０に示すグラフから、炭素ナノ構造体の表面近傍では約６ｎｍの小さい空孔が多く（Comp. 1 and 3）、炭素ナノ構造体の内部では約４０ｎｍの大きな空孔が多い（Comp. 2）ことがわかる。 As a result of performing TGA (thermogravimetry) on the carbon nanostructure obtained at this stage, a graph as shown in FIG. 7 was obtained. The combustion temperature was 680 ° C., which was close to graphite, and the residual metal was 2% by weight or less. FIG. 8 shows a TEM image, FIG. 9 shows an electron energy loss spectrum, FIG. 10 shows a vacancy distribution (volume) obtained from the small-angle X-ray scattering spectrum, and FIG. 11 shows a nitrogen adsorption / desorption curve. . The BET (Brunauer, Emmett, Teller) specific surface area obtained from the data of FIG. 11 was 300 m 2 / g. Further, from the graph shown in FIG. 10, there are many small vacancies of about 6 nm near the surface of the carbon nanostructure (Comp. 1 and 3), and there are many large vacancies of about 40 nm inside the carbon nanostructure (Comp 2) I understand.

（実施例２）
実施例１においては、銅ナノ粒子を内包した炭素ナノ構造体を硝酸処理によって銅の除去と空孔どうしの空間結合部の拡大を図っている。本実施例では、１１００℃の真空加熱の代わりに、マイクロ波による加熱を実施した。なお、加熱時間は２時間弱で十分であった。硝酸処理では、空孔同士が結合して、平均径が４０ｎｍという大きな空孔が生じた。 (Example 2)
In Example 1, removal of copper and expansion of a space coupling portion between pores are attempted by treating a carbon nanostructure encapsulating copper nanoparticles with nitric acid. In this example, instead of vacuum heating at 1100 ° C., microwave heating was performed. It should be noted that a heating time of 2 hours was sufficient. In the nitric acid treatment, the vacancies were combined to form large vacancies with an average diameter of 40 nm.

以上、本発明を上記具体例に基づいて詳細に説明したが、本発明は上記具体例に限定されるものではなく、本発明の範疇を逸脱しない限りにおいてあらゆる変形や変更が可能である。   While the present invention has been described in detail based on the above specific examples, the present invention is not limited to the above specific examples, and various modifications and changes can be made without departing from the scope of the present invention.

Claims (12)

金属塩を含む溶液に対してメチルアセチレンガスを吹き込み、金属メチルアセチリドのワイヤー状結晶体を作製し、前記棒状結晶体及び／又は前記板状結晶体に第１の加熱処理を施して、前記金属メチルアセチリド中の金属を偏析させるとともに、前記棒状結晶体及び／又は前記板状結晶体中の炭素を偏析させ、炭素を含む棒状体及び／又は板状体が３次元的に結合してなる炭素ナノ構造中間体を得るとともに、この炭素ナノ構造中間体中に前記金属が内包されてなる金属内包炭素ナノ構造体を作製し、前記金属内包炭素ナノ構造体を硝酸と接触させ、前記金属内包炭素ナノ構造物に対して第２の加熱処理を施して、前記金属内包炭素ナノ構造物に内包される前記金属を噴出させて得たことを特徴とする、炭素ナノ構造体。   Methyl acetylene gas is blown into a solution containing a metal salt to produce a metal methyl acetylide wire crystal, and the rod crystal and / or the plate crystal is subjected to a first heat treatment, and the metal Carbon formed by segregating metal in methyl acetylide and segregating carbon in the rod-like crystal and / or plate-like crystal so that the rod-like and / or plate containing carbon is three-dimensionally bonded. A nanostructured intermediate is obtained, and a metal-encapsulated carbon nanostructure in which the metal is encapsulated in the carbon nanostructure intermediate is produced, and the metal-encapsulated carbon nanostructure is brought into contact with nitric acid, and the metal-encapsulated carbon A carbon nanostructure obtained by performing a second heat treatment on a nanostructure to eject the metal encapsulated in the metal-encapsulated carbon nanostructure. 前記第１の加熱処理は、減圧下で行うことを特徴とする、請求項１に記載の炭素ナノ構造体。   The carbon nanostructure according to claim 1, wherein the first heat treatment is performed under reduced pressure. 前記第１の加熱処理は、水素雰囲気下で行うことを特徴とする、請求項１又は２に記載の炭素ナノ構造体。   The carbon nanostructure according to claim 1 or 2, wherein the first heat treatment is performed in a hydrogen atmosphere. 前記金属内包炭素ナノ構造体に内包される前記金属を噴出させた後、前記金属内包炭素ナノ構造体に溶解洗浄を施し、残存した前記金属を除去して得たことを特徴とする、請求項１〜３のいずれか一に記載の炭素ナノ構造体。   The metal-encapsulated carbon nanostructure is obtained by ejecting the metal encapsulated in the metal-encapsulated carbon nanostructure, and then dissolving and washing the metal-encapsulated carbon nanostructure to remove the remaining metal. The carbon nanostructure according to any one of 1 to 3. 前記金属内包炭素ナノ構造体に内包される前記金属を噴出させた後、前記金属内包炭素ナノ構造体に第３の加熱処理を施し、残存した前記金属を除去して得たことを特徴とする、請求項１〜４のいずれか一に記載の炭素ナノ構造体。   The metal encapsulated carbon nanostructure is ejected and then the metal-encapsulated carbon nanostructure is subjected to a third heat treatment to remove the remaining metal. The carbon nanostructure according to any one of claims 1 to 4. 前記金属は、銅であることを特徴とする、請求項１〜５のいずれか一に記載の炭素ナノ構造体。   The carbon nanostructure according to claim 1, wherein the metal is copper. 炭素を含む前記棒状体及び／又は前記板状体は３次元的に結合してなり、前記棒状体及び／又は前記板状体中には、グラフェン多層膜壁で画定される肺胞状の空孔が形成されていることを特徴とする、請求項１〜６のいずれか一に記載の炭素ナノ構造体。   The rod-like body and / or the plate-like body containing carbon are three-dimensionally bonded, and in the rod-like body and / or the plate-like body, alveolar pores defined by graphene multilayer film walls The carbon nanostructure according to any one of claims 1 to 6, wherein is formed. 前記炭素ナノ構造体は、３次元網状構造の一体型構造物であることを特徴とする、請求項１〜７のいずれか一に記載の炭素ナノ構造体。   The carbon nanostructure according to any one of claims 1 to 7, wherein the carbon nanostructure is an integrated structure having a three-dimensional network structure. 前記棒状体の直径及び前記板状体の幅が１００ｎｍ以上１０μｍ以下であることを特徴とする、請求項１〜８のいずれか一に記載の炭素ナノ構造体。   The carbon nanostructure according to any one of claims 1 to 8, wherein a diameter of the rod-shaped body and a width of the plate-shaped body are 100 nm or more and 10 µm or less. 前記空孔は、空孔径が１ｎｍ以上２０ｎｍ以下の第１の空孔と、空孔径が１０ｎｍ以上８０ｎｍ以下の第２の空孔とを含むことを特徴とする、請求項１〜９のいずれか一に記載の炭素ナノ構造体。   The said hole contains a 1st hole with a hole diameter of 1 nm or more and 20 nm or less, and a 2nd hole with a hole diameter of 10 nm or more and 80 nm or less, The any one of Claims 1-9 characterized by the above-mentioned. The carbon nanostructure according to 1. 前記炭素ナノ構造体は、ＢＥＴ比表面積が８０ｍ２／ｇ以上であることを特徴とする、請求項１〜１０のいずれか一に記載の炭素ナノ構造体。 The carbon nanostructure according to claim 1, wherein the carbon nanostructure has a BET specific surface area of 80 m 2 / g or more. 前記炭素ナノ構造体は、ＢＥＴ比表面積が３００ｍ２／ｇ以上であることを特徴とする、請求項１１に記載の炭素ナノ構造体。 The carbon nanostructure according to claim 11, wherein the carbon nanostructure has a BET specific surface area of 300 m 2 / g or more.
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