JP2018083169A - Catalyst substrate for production of carbon nanotube assembly, and method for producing carbon nanotube assembly - Google Patents
Catalyst substrate for production of carbon nanotube assembly, and method for producing carbon nanotube assembly Download PDFInfo
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- JP2018083169A JP2018083169A JP2016228695A JP2016228695A JP2018083169A JP 2018083169 A JP2018083169 A JP 2018083169A JP 2016228695 A JP2016228695 A JP 2016228695A JP 2016228695 A JP2016228695 A JP 2016228695A JP 2018083169 A JP2018083169 A JP 2018083169A
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Abstract
Description
本発明は、カーボンナノチューブ集合体の製造方法に関する。特に、短時間かつ効率的に、高活性を発現する金属触媒微粒子を基材上に高密度に調整する方法を用いた、カーボンナノチューブ集合体の製造方法に関する。 The present invention relates to a method for producing a carbon nanotube aggregate. In particular, the present invention relates to a method for producing an aggregate of carbon nanotubes using a method in which metal catalyst fine particles that exhibit high activity are adjusted to a high density on a substrate in a short time and efficiently.
近時、電子デバイス材料、光学素子材料、導電性材料、及び生体関連材料などの機能性新素材へのカーボンナノチューブ（以下、ＣＮＴとも称する）の展開が期待されており、その用途、品質、及び量産性などに対する検討が精力的に進められている。 Recently, the development of carbon nanotubes (hereinafter also referred to as CNT) to functional new materials such as electronic device materials, optical element materials, conductive materials, and biological materials is expected. Studies on mass productivity are being conducted energetically.
ＣＮＴの製造方法の一つに、化学気相成長法（以下、ＣＶＤ法とも称する）が知られている（特許文献１などを参照されたい）。この方法は、約５００℃以上１２００℃以下の高温雰囲気下で炭素化合物などの原料ガスを触媒微粒子と接触させることを特徴としており、触媒の種類や配置、あるいは原料ガスの種類や、還元性ガス、雰囲気ガス、合成炉や反応条件といった態様を様々に変化させた中でのＣＮＴの製造が可能であり、ＣＮＴの大量生産に適したものとして注目されている。また、このＣＶＤ法は、単層ＣＮＴと多層ＣＮＴのいずれも製造可能である上、触媒を担持した基材を用いることで、基材面に多数のＣＮＴが垂直に配向したＣＮＴ集合体を製造することができる、という利点を備えている。 As one of CNT manufacturing methods, a chemical vapor deposition method (hereinafter also referred to as a CVD method) is known (see Patent Document 1 and the like). This method is characterized in that a raw material gas such as a carbon compound is brought into contact with catalyst fine particles in a high temperature atmosphere of about 500 ° C. or higher and 1200 ° C. or lower. The type and arrangement of the catalyst, the type of the raw material gas, and the reducing gas It is possible to produce CNTs in various forms such as atmospheric gas, synthesis furnace and reaction conditions, and it is attracting attention as being suitable for mass production of CNTs. In addition, this CVD method can produce both single-walled CNTs and multi-walled CNTs, and uses a substrate carrying a catalyst to produce a CNT aggregate in which many CNTs are vertically oriented on the substrate surface. It has the advantage of being able to.
ＣＮＴのなかでも単層ＣＮＴは、電気的特性（極めて高い電流密度）、熱的特性（ダイアモンドに匹敵する熱伝導度）、光学特性（光通信帯波長域での発光）、水素貯蔵能、及び金属触媒担持能などの各種特性に優れている上、半導体と金属との両特性を備えているため、電子デバイス、蓄電デバイスの電極、ＭＥＭＳ部材、及び機能性複合材料のフィラーなどの材料として注目されている。 Among CNTs, single-walled CNTs have electrical properties (very high current density), thermal properties (thermal conductivity comparable to diamond), optical properties (light emission in the optical communication band wavelength region), hydrogen storage capacity, and Excellent in various properties such as metal catalyst support ability, as well as both semiconductor and metal properties, attracts attention as materials for electronic devices, electrodes for power storage devices, MEMS members, and fillers for functional composite materials Has been.
また、金属不純物が少なく、８００ｍ２／ｇ以上の高い比表面積を有する垂直配向したＣＮＴ集合体は、触媒の担持体やエネルギー・物質貯蔵材として有効であり、スーパーキャパシタやアクチュエータなどの用途に好適である。 In addition, vertically aligned CNT aggregates with low metal impurities and a high specific surface area of 800 m 2 / g or more are effective as catalyst carriers and energy / material storage materials, and are suitable for applications such as supercapacitors and actuators. It is.
このような垂直配向したＣＮＴ集合体が創製されれば、ＣＮＴの応用分野が飛躍的に拡大するものと予測されるが、実用化を推進するためには、垂直配向したＣＮＴ集合体の量産性を向上させることが重要である。 If such vertically aligned CNT aggregates are created, the application field of CNTs is expected to expand dramatically. To promote practical application, mass production of vertically aligned CNT aggregates is expected. It is important to improve.
ＣＶＤ法においては、ＣＮＴ集合体、特に単層ＣＮＴ集合体を高効率で合成するためには、微細、かつ高活性を発現する触媒微粒子を、基材上に高密度に配置する必要がある。特許文献２など従来の化学気相成長法では、触媒微粒子を調整するために、フォーメーション工程と呼ばれる以下のような工程が必要だった。即ち、還元ガスをＣＮＴ製造装置外部から供給し、ＣＮＴ製造装置内に配置された基材上の触媒物質に接触させるとともに、触媒物質および還元ガスの少なくともいずれか一つを加熱して、触媒物質を還元、及びまたは微粒子化する工程が必須であった。このフォーメーション工程の後に、不活性ガスで希釈された原料ガスを触媒微粒子に接触させるＣＮＴ成長工程により、ＣＮＴ集合体を製造することができる。 In the CVD method, in order to synthesize a CNT aggregate, particularly a single-walled CNT aggregate with high efficiency, it is necessary to arrange fine and fine catalyst particles exhibiting high activity on a substrate at high density. In the conventional chemical vapor deposition method such as Patent Document 2, in order to adjust the catalyst fine particles, the following process called a formation process is required. That is, a reducing gas is supplied from the outside of the CNT manufacturing apparatus and brought into contact with a catalytic substance on a substrate disposed in the CNT manufacturing apparatus, and at least one of the catalytic substance and the reducing gas is heated to form a catalytic substance. The step of reducing and / or making fine particles was essential. After this formation step, a CNT aggregate can be produced by a CNT growth step in which a raw material gas diluted with an inert gas is brought into contact with catalyst fine particles.
しかしながら、このフォーメーション工程には、以下のような問題がある。第一に、フォーメーション工程において大量に供給された還元性ガスが基材周りに残存した状態では、続くＣＮＴ成長工程において製造装置内に供給される原料ガス（炭化水素）の分解が抑制され、ＣＮＴ成長効率が低下してしまう。残留水素を速やかに基材周りから排除するために、製造装置内から還元性ガスを高速で排出するか、あるいは（特許文献２のように）フォーメーション工程に適した雰囲気にあるチャンバーからＣＮＴ成長工程に適した雰囲気にあるチャンバーまで基材を搬送する必要があるが、いずれも一定の時間が必要となり、製造効率が低下する。第二に、多くの還元性ガスは可燃性や毒性を有しており、このようなガスを大量に使うため、コスト面や安全面からも問題のある工程である。 However, this formation process has the following problems. First, in the state in which the reducing gas supplied in large quantities in the formation process remains around the substrate, decomposition of the raw material gas (hydrocarbon) supplied into the manufacturing apparatus in the subsequent CNT growth process is suppressed, and CNT Growth efficiency will decrease. In order to quickly remove residual hydrogen from around the substrate, the reducing gas is exhausted from the production apparatus at a high speed, or (as in Patent Document 2) a CNT growth process from a chamber in an atmosphere suitable for the formation process. It is necessary to transport the substrate to a chamber in an atmosphere suitable for the above, but both require a certain amount of time and the production efficiency decreases. Secondly, many reducing gases are flammable and toxic. Since such gases are used in large quantities, this is a problematic process in terms of cost and safety.
しかしながら、従来技術では、還元ガスを用いないと、例えば不活性ガス雰囲気中で基材上にある触媒物質を加熱するのみでは、高活性を発現する触媒微粒子を、基材上に高密度に配置することはできず、その後のＣＮＴ合成工程でもカーボンナノチューブは合成できないことが知られていた（非特許文献１）。 However, in the prior art, if a reducing gas is not used, catalyst fine particles that exhibit high activity are arranged on the substrate at high density simply by heating the catalyst material on the substrate in an inert gas atmosphere, for example. It has been known that carbon nanotubes cannot be synthesized even in the subsequent CNT synthesis process (Non-patent Document 1).
本発明は、上記の如き従来技術の問題点を解決するものであって、従来のフォーメーション工程を省いても、なお高効率でカーボンナノチューブを製造する方法を提供する。 The present invention solves the problems of the prior art as described above, and provides a method for producing carbon nanotubes with high efficiency even if the conventional formation process is omitted.
本発明の一実施形態によると、基材と、前記基材の上に設けられた、触媒金属元素と、電子親和力が５０ ｋＪ／ｍｏｌ以上である助触媒金属元素と、加熱時に前記触媒金属元素又は前記助触媒金属元素が凝集することを防ぎ、前記触媒金属元素と前記助触媒金属元素との混合を促進する合金化補助物質とを含む、触媒前駆体層と、を含む、カーボンナノチューブ集合体製造用触媒基材が提供される。 According to one embodiment of the present invention, a base material, a catalytic metal element provided on the base material, a promoter metal element having an electron affinity of 50 kJ / mol or more, and the catalytic metal element during heating Or a catalyst precursor layer containing an alloying auxiliary material that prevents the promoter metal element from agglomerating and promotes mixing of the catalyst metal element and the promoter metal element. A catalyst substrate for production is provided.
前記カーボンナノチューブ集合体製造用触媒基材において、前記合金化補助物質が、前記触媒金属元素と配位する部位を２箇所以上有する高分子有機化合物又は低分子有機化合物であってもよい。 In the catalyst base for producing a carbon nanotube aggregate, the alloying auxiliary substance may be a high molecular organic compound or a low molecular organic compound having two or more sites coordinated with the catalytic metal element.
前記カーボンナノチューブ集合体製造用触媒基材において、前記合金化補助物質は、ポリビニルアルコール、ポリエチレングリコール、ポリビニルピロリドン及びこれらの誘導体、並びにエチレンジアミン、ビピリジン、クエン酸、エチレンジアミン四酢酸、フェナントロリン、クラウンエーテル、ポルフィリン、及びこれらの誘導体、からなる群から選ばれた１つ以上であってもよい。 In the catalyst substrate for producing the carbon nanotube aggregate, the alloying auxiliary substances include polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone and derivatives thereof, and ethylenediamine, bipyridine, citric acid, ethylenediaminetetraacetic acid, phenanthroline, crown ether, porphyrin. And one or more selected from the group consisting of these derivatives.
前記カーボンナノチューブ集合体製造用触媒基材において、前記合金化補助物質が、前記触媒前駆体層中に２重量％以上存在してもよい。 In the catalyst substrate for producing the carbon nanotube aggregate, the alloying auxiliary substance may be present in the catalyst precursor layer in an amount of 2% by weight or more.
前記カーボンナノチューブ集合体製造用触媒基材において、前記触媒前駆体層において、前記触媒金属元素の含有元素数をＭ、前記助触媒金属元素の含有元素数をＮとしたときに、Ｎ／Ｍが０．０１以上２以下であってもよい。 In the catalyst substrate for producing the carbon nanotube aggregate, in the catalyst precursor layer, when the number of elements contained in the catalyst metal element is M and the number of elements contained in the promoter metal element is N, N / M is It may be 0.01 or more and 2 or less.
前記カーボンナノチューブ集合体製造用触媒基材において、前記基材の表面に、金属酸化物を含む下地層を有してもよい。 The catalyst base material for producing a carbon nanotube aggregate may have a base layer containing a metal oxide on the surface of the base material.
また、本発明の一実施形態によると、前記何れかのカーボンナノチューブ集合体製造用触媒基材を製造し、前記触媒前駆体層を加熱することにより前記触媒金属元素と前記助触媒金属元素とを含んだ金属触媒微粒子を基材上に形成し、炭化水素ガスを前記金属触媒微粒子に接触させて、カーボンナノチューブ集合体を成長させることを含む、カーボンナノチューブ集合体の製造方法が提供される。 According to an embodiment of the present invention, any one of the catalyst base materials for producing a carbon nanotube aggregate is manufactured, and the catalyst metal layer and the promoter metal element are obtained by heating the catalyst precursor layer. There is provided a method for producing a carbon nanotube aggregate, comprising forming the contained metal catalyst fine particles on a substrate, and bringing a hydrocarbon gas into contact with the metal catalyst fine particles to grow the carbon nanotube aggregate.
前記カーボンナノチューブ集合体の製造方法において、前記触媒金属元素を含む金属化合物と、前記助触媒金属元素を含む金属化合物と、前記合金化補助物質と、を溶解させた溶液を基材上に塗布して、乾燥させることにより、前記カーボンナノチューブ集合体製造用触媒基材を製造してもよい。 In the method for producing a carbon nanotube aggregate, a solution in which the metal compound containing the catalytic metal element, the metal compound containing the promoter metal element, and the alloying auxiliary substance are dissolved is applied onto a substrate. The catalyst base for producing the carbon nanotube aggregate may be produced by drying.
前記カーボンナノチューブ集合体の製造方法において、前記触媒前駆体層を加熱することにより前記合金化補助物質が熱分解して、還元性ガスを発生し、前記還元性ガスが前記触媒金属元素を還元し、前記触媒金属元素と前記助触媒金属元素とを合金化及び微粒子化して、前記金属触媒微粒子を形成してもよい。 In the method of manufacturing the carbon nanotube aggregate, the alloying auxiliary substance is thermally decomposed by heating the catalyst precursor layer to generate a reducing gas, and the reducing gas reduces the catalytic metal element. The metal catalyst fine particles may be formed by alloying and micronizing the catalyst metal element and the promoter metal element.
前記カーボンナノチューブ集合体の製造方法において、粒子径が１ｎｍ以上１０ｎｍ以下の範囲にある前記金属触媒微粒子が前記基材上に１×１０１０個／ｃｍ２以上の個数密度で形成されてもよい。 In the method for producing a carbon nanotube aggregate, the metal catalyst fine particles having a particle diameter in the range of 1 nm to 10 nm may be formed on the substrate at a number density of 1 × 10 10 particles / cm 2 or more.
前記カーボンナノチューブ集合体の製造方法において、０．１ｍｇ／ｃｍ2以上の収量でカーボンナノチューブ集合体を前記基材の表面から成長してもよい。 In the method for producing a carbon nanotube aggregate, the carbon nanotube aggregate may be grown from the surface of the substrate with a yield of 0.1 mg / cm 2 or more.
本発明の一実施形態によると、高温下の炉内において、原料ガスおよび触媒賦活物質を、触媒に接触させ、ＣＮＴ集合体を成長させる化学気相成長法において、短時間かつ効率的に、高活性を発現する金属触媒微粒子を基材上に高密度に調製することができるため、従来よりも効率的に、カーボンナノチューブ集合体の製造が可能となる。 According to an embodiment of the present invention, in a chemical vapor deposition method in which a raw material gas and a catalyst activator are brought into contact with a catalyst to grow a CNT aggregate in a furnace at a high temperature, in a short time and efficiently, Since the metal catalyst fine particles exhibiting the activity can be prepared on the base material at a high density, the carbon nanotube aggregate can be produced more efficiently than before.
以下、図面を参照して本発明に係るカーボンナノチューブ集合体製造用触媒基材及びカーボンナノチューブ集合体の製造方法について説明する。なお、本発明のカーボンナノチューブ集合体製造用触媒基材及びカーボンナノチューブ集合体の製造方法は、以下に示す実施の形態及び実施例の記載内容に限定して解釈されるものではない。なお、本実施の形態及び後述する実施例で参照する図面において、同一部分又は同様な機能を有する部分には同一の符号を付し、その繰り返しの説明は省略する。 Hereinafter, a catalyst base material for producing a carbon nanotube aggregate and a method for producing the carbon nanotube aggregate according to the present invention will be described with reference to the drawings. The catalyst base for producing a carbon nanotube aggregate and the method for producing the carbon nanotube aggregate of the present invention are not construed as being limited to the description of the embodiments and examples shown below. Note that in the drawings referred to in this embodiment mode and examples to be described later, the same portions or portions having similar functions are denoted by the same reference numerals, and description thereof is not repeated.
本発明者らは、遷移金属元素である触媒金属元素を含んだ化合物と、電子親和力の高い助触媒金属元素を含んだ化合物とが、分子レベルで混合された触媒前駆体層を形成し、これを加熱することで、加熱時の雰囲気を問わず、ＣＮＴの製造に適した粒子径かつ高密度の金属触媒微粒子を形成できることを見出した。 The inventors of the present invention form a catalyst precursor layer in which a compound containing a catalytic metal element which is a transition metal element and a compound containing a promoter metal element having a high electron affinity are mixed at a molecular level. It was found that the metal catalyst fine particles having a particle diameter and a high density suitable for the production of CNTs can be formed by heating the above, regardless of the atmosphere during heating.
＜触媒金属元素＞
触媒金属元素としては、第ＶＩＩＩＢ族遷移金属からＣＮＴ集合体の合成用触媒として良く用いられる１種類以上を選択することができる。特に、ＣＮＴ集合体の合成用触媒として良く用いられる、鉄、コバルト及びニッケルからなる群から選択される１種類以上が望ましい。
<Catalytic metal element>
As the catalytic metal element, one or more types often used as a catalyst for synthesizing CNT aggregates can be selected from Group VIIIB transition metals. In particular, one or more types selected from the group consisting of iron, cobalt and nickel, which are often used as catalysts for the synthesis of CNT aggregates, are desirable.
＜助触媒金属元素＞
助触媒金属元素は、電子親和力の高いことが望ましい。一実施形態において、助触媒金属元素は、５０ｋＪ／ｍｏｌ以上、望ましくは１００ｋＪ／ｍｏｌ以上の電子親和力を有する。一般的に貴金属元素類に代表される電子親和力の高い金属元素は、プラスの電荷を有した状態にある種々の金属化合物であっても、高温に加熱されると、その雰囲気に依らず、金属単体に分解される。例えば、塩化白金（ＩＩ）（PtCl2）は空気中で加熱されると、白金と塩素に分解する。即ち、PtCl2→Pt + Cl2の化学反応を生じる。このように生じた金属状態にある助触媒金属元素は、酸化状態にある触媒金属元素と接触混合された際に、これの還元を助け、その結果、触媒金属元素と助触媒金属元素からなる合金を形成させる働きを有する。例えば、非特許文献２に依れば、塩化白金と塩化鉄の混合水溶液を嫌気下で加熱分解させることで、鉄-白金の合金相が形成される。
<Cocatalyst metal element>
The promoter metal element preferably has a high electron affinity. In one embodiment, the promoter metal element has an electron affinity of 50 kJ / mol or higher, desirably 100 kJ / mol or higher. In general, metal elements with high electron affinity, represented by noble metal elements, are various metal compounds that have a positive charge. It is disassembled into a single unit. For example, platinum (II) chloride (PtCl 2 ) decomposes into platinum and chlorine when heated in air. That is, a chemical reaction of PtCl 2 → Pt + Cl 2 occurs. The thus-produced cocatalyst metal element in the metal state assists the reduction of the catalytic metal element in the oxidized state when mixed with the catalyst metal element in the oxidized state. Has the function of forming. For example, according to Non-Patent Document 2, an iron-platinum alloy phase is formed by thermally decomposing a mixed aqueous solution of platinum chloride and iron chloride under anaerobic conditions.
特に、助触媒金属元素は、ＣＮＴの触媒として一般的な鉄、コバルト又はニッケルと、合金を形成しうる組成比が広い元素であることが望ましい。例えば、貴金属元素であるプラチナ、ロジウム、イリジウム、パラジウムは、鉄と完全固溶体を形成する。 In particular, the promoter metal element is desirably an element having a wide composition ratio that can form an alloy with iron, cobalt, or nickel, which is a common CNT catalyst. For example, the noble metal elements platinum, rhodium, iridium, and palladium form a complete solid solution with iron.
また、ＣＮＴ製造用の触媒は比較的高温で用いられるため、融点が高い元素であることが望ましく、一実施形態において、助触媒金属元素は、融点が１０００℃以上、望ましくは１５００℃以上、より望ましくは１８００℃以上、さらに望ましくは２０００℃以上である。 Further, since the catalyst for producing CNTs is used at a relatively high temperature, it is desirable that the element has a high melting point. In one embodiment, the promoter metal element has a melting point of 1000 ° C. or higher, preferably 1500 ° C. or higher. Preferably it is 1800 degreeC or more, More preferably, it is 2000 degreeC or more.
このような観点から、助触媒金属元素は、貴金属元素は助触媒金属元素として望ましい元素群である。一実施形態において、助触媒金属元素は、金（Ａｕ、２２３ｋＪ／ｍｏｌ、融点：１０６４℃）、銀（Ａｇ、電子親和力：１２６ｋＪ／ｍｏｌ、融点：９６１℃）、）、白金（Ｐｔ、電子親和力：２０５ｋＪ／ｍｏｌ、融点：１７６９℃）、パラジウム（Ｐｄ、電子親和力：５４ｋＪ／ｍｏｌ、融点：１５５２℃）、ロジウム（Ｒｈ、電子親和力：１１０ｋＪ／ｍｏｌ、融点：１９６０℃）、イリジウム（Ｉｒ、電子親和力：１５０ｋＪ／ｍｏｌ、融点：２４４３℃）、ルテニウム（Ｒｕ、電子親和力：１０１ｋＪ／ｍｏｌ、融点：２２５０℃）、オスミウム（Ｏｓ、電子親和力：１０４ｋＪ／ｍｏｌ、融点：３０４５℃）からなる群から選択されることが望ましい。ただし、銀は鉄とは合金を形成しないため、触媒金属元素として鉄を選択する場合には、助触媒金属元素は銀以外の上記貴金属から選択する。また、異なる一実施形態において、助触媒金属元素は、クロム（Ｃｒ、電子親和力：６４ｋＪ／ｍｏｌ、融点：１８５７℃）、銅（Ｃｕ、電子親和力：１１９ｋＪ／ｍｏｌ、融点：１０８５℃）であっても良い。また一実施形態において、助触媒金属元素は、上記貴金属等から選択する１つ以上の組み合わせであってもよい。なお、本発明に係る助触媒金属元素には、一般的な助触媒として用いられるタングステンやモリブデンは含まれない。 From such a viewpoint, the promoter metal element is a desirable element group as the promoter metal element. In one embodiment, the promoter metal element is gold (Au, 223 kJ / mol, melting point: 1064 ° C.), silver (Ag, electron affinity: 126 kJ / mol, melting point: 961 ° C.), platinum (Pt, electron affinity). : 205 kJ / mol, melting point: 1769 ° C., palladium (Pd, electron affinity: 54 kJ / mol, melting point: 1552 ° C.), rhodium (Rh, electron affinity: 110 kJ / mol, melting point: 1960 ° C.), iridium (Ir, electron Affinity: 150 kJ / mol, melting point: 2443 ° C.), ruthenium (Ru, electron affinity: 101 kJ / mol, melting point: 2250 ° C.), osmium (Os, electron affinity: 104 kJ / mol, melting point: 3045 ° C.) It is desirable that However, since silver does not form an alloy with iron, when iron is selected as the catalytic metal element, the promoter metal element is selected from the noble metals other than silver. In another embodiment, the promoter metal element is chromium (Cr, electron affinity: 64 kJ / mol, melting point: 1857 ° C.), copper (Cu, electron affinity: 119 kJ / mol, melting point: 1085 ° C.) Also good. In one embodiment, the promoter metal element may be one or more combinations selected from the above-mentioned noble metals and the like. The promoter metal element according to the present invention does not include tungsten or molybdenum used as a general promoter.
本発明においては、このような助触媒金属元素の特徴を利用して、触媒金属元素と助触媒金属元素が分子レベルで混合された触媒前駆体層を形成する。一実施形態において、触媒前駆体層は、還元性ガスを使わずとも、電子親和力の高い助触媒金属元素により、触媒金属元素の還元された金属状態を安定化させる効果を有する。これにより、触媒金属−助触媒金属合金が生成され、この合金が基材上で微粒子化することにより、ＣＮＴの製造に好適な金属触媒微粒子を形成することができる。 In the present invention, utilizing such characteristics of the promoter metal element, a catalyst precursor layer in which the catalyst metal element and the promoter metal element are mixed at the molecular level is formed. In one embodiment, the catalyst precursor layer has an effect of stabilizing the reduced metal state of the catalytic metal element by the promoter metal element having a high electron affinity without using a reducing gas. Thereby, a catalyst metal-promoter metal alloy is produced, and the alloy is finely divided on the base material, whereby metal catalyst fine particles suitable for the production of CNT can be formed.
触媒金属元素と助触媒金属元素を分子レベルで混合された触媒前駆体層を形成する手段として、触媒前駆体層において両元素が混合された状態を保持する役割を持つ合金化補助物質を、触媒前駆体層に混入する手法が有効である。これにより、合金が形成されるのに適切な温度まで触媒前駆体層を昇温する過程において、触媒金属元素あるいは助触媒金属元素が単一の粒子として凝集することを防ぐことができる。 As a means of forming a catalyst precursor layer in which a catalytic metal element and a promoter metal element are mixed at a molecular level, an alloying auxiliary substance having a role of maintaining the mixed state of both elements in the catalyst precursor layer is used as a catalyst. A method of mixing in the precursor layer is effective. Thereby, it is possible to prevent the catalytic metal element or the promoter metal element from aggregating as a single particle in the process of raising the temperature of the catalyst precursor layer to a temperature suitable for forming an alloy.
触媒前駆体層において、触媒金属元素に対する助触媒金属元素の含有量は特に限定されない。ただし、助触媒金属元素の含有量が少なすぎると、触媒金属元素の還元及び微粒子化を促進する効果を発揮しない。また、助触媒金属元素の含有量が多すぎると、触媒金属元素が希釈され過ぎてしまい、金属触媒微粒子が十分なＣＮＴの成長活性を示すことが出来なくなる。そのため、助触媒金属元素数／触媒金属元素数の比は０．０１以上２以下、望ましくは０．０１以上０．８以下、より望ましくは０．０１以上０．５以下である。 In the catalyst precursor layer, the content of the promoter metal element with respect to the catalyst metal element is not particularly limited. However, if the content of the promoter metal element is too small, the effect of promoting the reduction and atomization of the catalyst metal element is not exhibited. Moreover, when there is too much content of a promoter metal element, a catalyst metal element will be diluted too much and metal catalyst fine particles will not be able to show sufficient CNT growth activity. Therefore, the ratio of the number of promoter metal elements to the number of catalyst metal elements is 0.01 or more and 2 or less, desirably 0.01 or more and 0.8 or less, and more desirably 0.01 or more and 0.5 or less.
＜触媒原料物質＞
触媒金属元素及び助触媒金属元素は、金属元素のみからなる金属単体だけでなく、金属化合物を触媒原料物質として用いることができる。一実施形態において、触媒原料物質は、塩化物などの金属塩、酸化物、窒化物、硫化物、又はアセチルアセテート錯体などの有機金属化合物を含む形態で存在していてもよい。また、微量であれば、触媒金属を構成する元素以外の金属元素が混ざっていてもよい。
<Catalyst raw material>
As the catalytic metal element and the promoter metal element, not only a simple metal composed of only a metal element but also a metal compound can be used as a catalyst raw material. In one embodiment, the catalyst source material may be present in a form that includes a metal salt such as chloride, an oxide, nitride, sulfide, or an organometallic compound such as an acetyl acetate complex. Moreover, if it is trace amount, metal elements other than the element which comprises a catalyst metal may be mixed.
＜合金化補助物質＞
合金化補助物質は、合金が形成されるのに適切な温度まで触媒前駆体層を昇温した時に、合金化補助物質自体が熱分解するまで、触媒金属元素又は助触媒金属元素が単一の粒子として凝集することを抑える機能を有することが望ましい。このような機能を有する物質として、触媒金属元素と配位できる配位部位を２箇所以上有する高分子有機化合物又は低分子有機化合物であることが望ましい。合金化補助物質として、具体的には、アルコール性の水酸基、カルボニル基、エーテル基など、配位部位として機能する官能基を２つ以上する有機化合物が挙げられる。さらに具体的には、ポリビニルアルコール、ポリエチレングリコール、ポリビニルピロリドンおよびこれらの誘導体からなる群から選択される高分子有機化合物、並びに多座配位子であるエチレンジアミン、ビピリジン、クエン酸、エチレンジアミン四酢酸、フェナントロリン、クラウンエーテル、ポルフィリン、及びこれらの誘導体からなる群から選択される低分子有機化合物が挙げられる。
<Alloying auxiliary material>
The alloying auxiliary material has a single catalytic metal element or co-catalytic metal element until the alloying auxiliary material itself thermally decomposes when the catalyst precursor layer is heated to a temperature suitable for the formation of the alloy. It is desirable to have a function of suppressing aggregation as particles. The substance having such a function is preferably a high molecular organic compound or a low molecular organic compound having two or more coordination sites capable of coordinating with the catalytic metal element. Specific examples of the alloying auxiliary substance include organic compounds having two or more functional groups that function as coordination sites, such as alcoholic hydroxyl groups, carbonyl groups, and ether groups. More specifically, macromolecular organic compounds selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyvinyl pyrrolidone and derivatives thereof, and polydentate ligands such as ethylenediamine, bipyridine, citric acid, ethylenediaminetetraacetic acid, phenanthroline. , Crown ether, porphyrin, and low molecular organic compounds selected from the group consisting of these derivatives.
合金化補助物質の熱分解温度は、特に限定されないが、３００℃以上９００℃以下の範囲が好ましい。３００℃以下では合金化が進行しないため、合金化補助物質が熱分解した後、触媒金属元素又は助触媒金属元素が単一の粒子として凝集が起こりやすい。一方、９００℃以上では、合金化補助物質が分解した後に基材上に調製される大半の金属触媒微粒子が、オストワルド熟成などの現象により高速で消失してしまい、ＣＮＴ合成に適した高個数密度の金属触媒微粒子の調製には不適である。 The thermal decomposition temperature of the alloying auxiliary substance is not particularly limited, but a range of 300 ° C. or higher and 900 ° C. or lower is preferable. Since alloying does not proceed at 300 ° C. or lower, the catalytic metal element or the promoter metal element is likely to aggregate as a single particle after the alloying auxiliary substance is thermally decomposed. On the other hand, at 900 ° C. or higher, most of the metal catalyst fine particles prepared on the base material after decomposition of the alloying auxiliary substance disappear at a high speed due to a phenomenon such as Ostwald ripening, and a high number density suitable for CNT synthesis. It is unsuitable for the preparation of metal catalyst fine particles.
合金化補助物質は、熱分解する際に還元性ガスを発生する物質であることが好ましい。触媒前駆体層内で発生した還元性ガスは、触媒前駆体層内にある触媒原料物質に直ちに接触することができ、触媒原料物質に含まれる触媒金属元素及び助触媒金属元素を還元及び／又は微粒子化することができる。還元性ガスとは、例えば、水素、一酸化炭素、アンモニア、二窒化酸素（Ｎ２Ｏ）、二酸化硫黄（ＳＯ２）等の触媒金属元素及び／又は助触媒金属元素に対して還元作用を有する物質である。例えば、熱分解時に水素ガスを発生する、水素原子を含んだ有機化合物であれば、合金化補助物質として用いることができる。 The alloying auxiliary substance is preferably a substance that generates a reducing gas when pyrolyzing. The reducing gas generated in the catalyst precursor layer can immediately come into contact with the catalyst raw material in the catalyst precursor layer to reduce and / or reduce the catalytic metal element and the promoter metal element contained in the catalyst raw material. Fine particles can be obtained. The reducing gas has, for example, a reducing action on catalytic metal elements such as hydrogen, carbon monoxide, ammonia, oxygen dinitride (N 2 O), sulfur dioxide (SO 2 ), and / or promoter metal elements. It is a substance. For example, any organic compound containing hydrogen atoms that generates hydrogen gas during thermal decomposition can be used as an alloying auxiliary substance.
触媒前駆体層における触媒原料物質に対する合金化補助物質の含有量については、触媒原料物質に含まれる全ての金属元素を配位させる必要もないため、特に限定されない。ただし、ある程度の量があることが触媒金属元素及び助触媒金属元素の凝集を防ぎやすいことから、触媒前駆体層の中に２重量％以上、望ましくは５重量％以上、より望ましくは５０重量％以上含まれる。 The content of the alloying auxiliary material with respect to the catalyst raw material in the catalyst precursor layer is not particularly limited because it is not necessary to coordinate all the metal elements contained in the catalyst raw material. However, since it is easy to prevent aggregation of the catalytic metal element and the promoter metal element when there is a certain amount, it is 2% by weight or more, preferably 5% by weight or more, more preferably 50% by weight in the catalyst precursor layer. Included.
＜触媒前駆体層＞
触媒前駆体層の厚さは、ＣＮＴ集合体の製造に十分な触媒前駆体層が得られる限り、特に限定されない。また、触媒前駆体層全体の厚さについては特に限定されるものではなく、基材全体を被覆している必要もない。ただし、典型的には、触媒前駆体層を熱分解後に得られる金属触媒微粒子の総体積が、１ｎｍ程度の合金膜の体積に相当する触媒前駆体層の膜厚とするため、成膜後の触媒前駆体層としては１０ｎｍ以上、望ましくは１００ｎｍ以上である。
<Catalyst precursor layer>
The thickness of the catalyst precursor layer is not particularly limited as long as a catalyst precursor layer sufficient for the production of the CNT aggregate is obtained. Further, the thickness of the entire catalyst precursor layer is not particularly limited, and it is not necessary to cover the entire substrate. However, typically, the total volume of metal catalyst fine particles obtained after pyrolyzing the catalyst precursor layer is the thickness of the catalyst precursor layer corresponding to the volume of the alloy film of about 1 nm. The catalyst precursor layer is 10 nm or more, preferably 100 nm or more.
触媒前駆体層における触媒原料物質と合金化補助物質との混合状態は、限定されるものではない。即ち、触媒原料物質が微粒子状や膜状などの形態で、合金化補助物質と分離して存在していても構わない。ただし、合金化をより促進するため、合金化補助物質に触媒原料物質を構成する金属元素が配位することにより、触媒前駆体層を構成する物質が分子レベルで混合されていることが望ましい。 The mixed state of the catalyst raw material and the alloying auxiliary material in the catalyst precursor layer is not limited. That is, the catalyst raw material may be present separately from the auxiliary alloying material in the form of fine particles or a film. However, in order to further promote alloying, it is desirable that the material constituting the catalyst precursor layer is mixed at the molecular level by coordination of the metal element constituting the catalyst raw material with the alloying auxiliary material.
＜基材＞
基材は、その表面にＣＮＴを成長させる触媒を担持することのできる部材であり、最低限４００℃以上の高温でも形状を維持できるものであれば適宜のものを用いることができる。基材の形態としては、平板等の平面状の形態が、本発明の効果を用いて、大量のＣＮＴを製造するために好ましい。しかしながら、粉末、または線状体の集合体で、平面状をなす基材でもよい。平面状の基材を用いると、原料ガスと触媒賦活物質を触媒に均一に供給しやすいため好ましい。
<Base material>
The base material is a member capable of supporting a catalyst for growing CNTs on the surface thereof, and any suitable material can be used as long as the shape can be maintained even at a high temperature of 400 ° C. or higher. As a form of the substrate, a planar form such as a flat plate is preferable for producing a large amount of CNTs using the effects of the present invention. However, it may be a base material that is a powder or an aggregate of linear bodies and has a planar shape. The use of a planar substrate is preferable because the raw material gas and the catalyst activator can be easily supplied to the catalyst uniformly.
これまでにＣＮＴの製造に実績のある材質としては、鉄、ニッケル、クロム、モリブデン、タングステン、チタン、アルミニウム、マンガン、コバルト、銅、銀、金、白金、ニオブ、タンタル、鉛、亜鉛、ガリウム、インジウム、ゲルマニウム、砒素、燐、アンチモンなどの金属、並びにこれらの金属を含む合金および酸化物、またはシリコン、石英、マグネシア、スピネル、カルシア、ドロマイト、クロミア、ジルコニア、チタニア、ムライ、ガラス、マイカ、グラファイト、アルミナ、酸化マグネシウム、チタン酸カリウム、酸化ジリコニウム、ゼオライト、シリカ、酸化チタン、ダイヤモンドなどの非金属、並びにセラミックおよびこれらの混合物が挙げられる。金属は、シリコンやセラミックと比較して廉価である点が好ましく、特に、鉄−クロム（Ｆｅ−Ｃｒ）合金、鉄−ニッケル（Ｆｅ−Ｎｉ）合金、および鉄−クロム−ニッケル（Ｆｅ−Ｃｒ−Ｎｉ）合金などが本発明の実施に好適である。 The materials that have been used in the manufacture of CNTs so far include iron, nickel, chromium, molybdenum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, platinum, niobium, tantalum, lead, zinc, gallium, Metals such as indium, germanium, arsenic, phosphorus, antimony, and alloys and oxides containing these metals, or silicon, quartz, magnesia, spinel, calcia, dolomite, chromia, zirconia, titania, mulay, glass, mica, graphite , Non-metals such as alumina, magnesium oxide, potassium titanate, zirconium oxide, zeolite, silica, titanium oxide, diamond, and ceramics and mixtures thereof. The metal is preferably less expensive than silicon or ceramic, and in particular, iron-chromium (Fe-Cr) alloy, iron-nickel (Fe-Ni) alloy, and iron-chromium-nickel (Fe-Cr-). Ni) alloys and the like are suitable for the practice of the present invention.
粉末、または線状体としては、具体的には、板状アルミナ・石英フレーク・石英繊維・セラミック繊維・繊維状酸化チタンなどを例示できる。 Specific examples of the powder or linear body include plate-like alumina, quartz flakes, quartz fibers, ceramic fibers, and fibrous titanium oxide.
＜下地層＞
基材の表面に、金属酸化物を含む下地層を有してもよい。下地層は、触媒層の下地として、基材の表面に配置された層である。下地層は、基材の表面に、既知の金属酸化物を成膜することにより形成することができる。特に長尺な単層ＣＮＴの成長に実績がある、アルミナやＭｇＯが適しているが、これらに限定されるものではない。
<Underlayer>
You may have a base layer containing a metal oxide on the surface of a base material. The underlayer is a layer disposed on the surface of the base material as the underlayer of the catalyst layer. The underlayer can be formed by depositing a known metal oxide on the surface of the substrate. In particular, alumina and MgO, which have a proven track record for growing long single-walled CNTs, are suitable, but are not limited thereto.
＜触媒前駆体層成膜工程＞
図１を参照して、触媒前駆体層成膜工程を説明する。基材１０１の表面に下地層１０２を形成する（図１（Ａ））。下地層１０２は、例えばスパッタリング法により形成することができる。下地層１０２の表面（又は上面）に触媒前駆体層１０６を成膜する（図１（Ｂ））。触媒前駆体層１０６の成膜工程は特に制限はない。塗布法や蒸着法など、選択された触媒原料物質と合金化補助物質の組み合わせによって適時選択してよい。ただし、形成される触媒前駆体層においては、合金化補助物質と触媒原料物質が分子レベルで混合されていることが望ましい。そのため、触媒前駆体層１０６の成膜工程としては、それぞれ少なくとも一部の触媒原料物質および合金化補助物質を溶解させた溶液を基材上に塗布する工程と、基材を乾燥させる工程からなることが望ましい。
<Catalyst precursor layer deposition step>
The catalyst precursor layer film forming step will be described with reference to FIG. A base layer 102 is formed on the surface of the substrate 101 (FIG. 1A). The underlayer 102 can be formed by, for example, a sputtering method. A catalyst precursor layer 106 is formed on the surface (or upper surface) of the base layer 102 (FIG. 1B). The film formation process of the catalyst precursor layer 106 is not particularly limited. Selection may be made in a timely manner depending on the combination of the selected catalyst raw material and the alloying auxiliary material such as coating method and vapor deposition method. However, in the formed catalyst precursor layer, it is desirable that the alloying auxiliary substance and the catalyst raw material are mixed at the molecular level. Therefore, the process for forming the catalyst precursor layer 106 includes a process of applying a solution in which at least a part of the catalyst raw material and the alloying auxiliary substance are dissolved, and a process of drying the base. It is desirable.
前述した触媒前駆体層１０６の成膜工程において、溶液の溶媒は問わないが、触媒原料物質及び合金化補助物質の溶解度が高い溶媒を選択することが望ましい。例えば水やアルコール類を選ぶことができる。 In the above-described film formation step of the catalyst precursor layer 106, the solvent of the solution is not limited, but it is desirable to select a solvent having high solubility of the catalyst raw material and the alloying auxiliary material. For example, water or alcohol can be selected.
溶液内にて溶解した触媒原料物質及び合金化補助物質は、保管された溶液内及び塗布工程の後の乾燥工程においてそれぞれが分離や凝集しないことが望ましい。そのため、合金化補助物質は、イオン状で溶解した触媒金属元素と助触媒金属元素とに溶液内で配位結合している事が望ましい。これによって金属元素同士が接触することが抑えられ、保管された溶液内、ならびに塗布工程後の乾燥工程における触媒金属元素と助触媒金属元素の凝集が抑制される。 It is desirable that the catalyst raw material and the alloying auxiliary material dissolved in the solution do not separate or agglomerate in the stored solution and in the drying step after the coating step. Therefore, it is desirable that the alloying auxiliary substance is coordinated in the solution to the catalytic metal element dissolved in an ionic state and the promoter metal element. As a result, the metal elements are prevented from coming into contact with each other, and aggregation of the catalytic metal element and the promoter metal element in the stored solution and in the drying process after the coating process is suppressed.
塗布する方法も問わないが、スピンコート、デッィプコート、スプレーコート、ブレードコートの他、各種塗工技術や印刷技術が該当する。乾燥工程における条件についても特に限定するものではないが、乾燥温度は合金化補助物質の分解や反応が起こる温度以下であることが望ましい。例えば室温にて真空や大気下で乾燥してもよく、その際、溶液の溶媒が未乾燥のまま残存していても良い。 The coating method is not limited, but various coating techniques and printing techniques are applicable in addition to spin coating, dip coating, spray coating, and blade coating. The conditions in the drying step are not particularly limited, but the drying temperature is preferably equal to or lower than the temperature at which the alloying auxiliary substance is decomposed or reacted. For example, it may be dried at room temperature in a vacuum or in the atmosphere, and in that case, the solvent of the solution may remain undried.
＜金属触媒微粒子形成工程＞
触媒前駆体層１０６を加熱し、金属触媒微粒子１０７を形成する（図１（Ｃ））。触媒前駆体層１０６を加熱し、合金化補助物質が熱分解した後、合金化補助物質に配位していた触媒金属元素と助触媒金属元素が直ちに接触する。触媒前駆体層１０６を加熱すると同時に、触媒原料物質である助触媒金属元素が構成していた化合物の熱分解も進行し、金属状態に還元された助触媒金属元素単体も生成される。触媒金属元素が助触媒金属元素に接触すると、両者の混合が進行する。助触媒金属元素との合金化により触媒金属元素の還元も進行し、基材１０１上で金属触媒微粒子１０７の形成が進行する。
<Metal catalyst fine particle formation process>
The catalyst precursor layer 106 is heated to form metal catalyst fine particles 107 (FIG. 1C). After the catalyst precursor layer 106 is heated and the alloying auxiliary material is thermally decomposed, the catalytic metal element coordinated to the alloying auxiliary material immediately contacts the promoter metal element. Simultaneously with the heating of the catalyst precursor layer 106, the thermal decomposition of the compound composed of the promoter metal element as the catalyst raw material also proceeds, and the promoter metal element alone reduced to the metal state is also generated. When the catalytic metal element contacts the promoter metal element, the mixing of both proceeds. Reduction of the catalytic metal element also proceeds by alloying with the promoter metal element, and the formation of the metal catalyst fine particles 107 proceeds on the substrate 101.
本発明においては、加熱時の雰囲気は問わず、還元性ガス、不活性ガス、酸化性ガスのいずれであってもよい。本工程においては、必要に応じて触媒賦活物質を添加してもよい。還元性ガスとは、例えば水素、アンモニア、一酸化炭素、二窒化酸素（Ｎ２Ｏ）、二酸化硫黄（ＳＯ２）及びそれらの混合ガスである。不活性ガスとは、例えば、ヘリウム、アルゴン、窒素、ネオン、クリプトンなどや、これらの混合ガスが挙げられ、特に窒素、ヘリウム、アルゴン、及びこれらの混合ガスが好適である。酸化性ガスとは酸素、乾燥空気、水蒸気などである。 In the present invention, the atmosphere during heating is not limited, and any of a reducing gas, an inert gas, and an oxidizing gas may be used. In this step, a catalyst activator may be added as necessary. The reducing gas is, for example, hydrogen, ammonia, carbon monoxide, oxygen dinitride (N 2 O), sulfur dioxide (SO 2 ), or a mixed gas thereof. Examples of the inert gas include helium, argon, nitrogen, neon, krypton, and a mixed gas thereof, and nitrogen, helium, argon, and a mixed gas thereof are particularly preferable. The oxidizing gas is oxygen, dry air, water vapor and the like.
金属触媒微粒子形成温度は特に限定されず、ＣＮＴ成長工程と違っていてもよい。ただし、用いた合金化補助物質の熱分解開始温度以上であることが望ましい。低温過ぎると、触媒金属元素と助触媒金属元素が接触できず、合金化が進行しない。 The metal catalyst fine particle formation temperature is not particularly limited, and may be different from the CNT growth step. However, it is desirable that the temperature be equal to or higher than the thermal decomposition starting temperature of the alloying auxiliary substance used. If the temperature is too low, the catalytic metal element and the promoter metal element cannot contact and alloying does not proceed.
触媒前駆体層１０６の加熱時間は、特に制限ないが、合金化補助物質の分解を十分に開始させる必要がある。合金化補助物質やその量、また分解温度に依存するが、典型的には１秒以上であることが望ましい。 The heating time of the catalyst precursor layer 106 is not particularly limited, but it is necessary to sufficiently start the decomposition of the alloying auxiliary substance. Although it depends on the alloying auxiliary substance, its amount, and the decomposition temperature, it is typically desirable to be 1 second or longer.
適切な触媒原料物質並びに合金化補助物質の量や混合状態、ならびに加熱温度と時間を選択することにより、基材に直交する向きに配向したＣＮＴ集合体を成長させるのに好適な粒子径や個数密度を有する金属触媒微粒子１０７を基材１０１上に形成することができる。 Particle size and number suitable for growing CNT aggregates oriented in the direction orthogonal to the substrate by selecting appropriate amounts of catalyst raw materials and alloying auxiliary materials, mixing conditions, and heating temperature and time. Metal catalyst fine particles 107 having a density can be formed on the substrate 101.
具体的には、生成する金属触媒微粒子１０７の粒子径は、それぞれ１ｎｍ以上１０ｎｍ以下の範囲にあることが望ましい。より好ましくは、１ｎｍ以上５ｎｍ以下の範囲にあることが望ましい。金属触媒微粒子１０７の個数密度は１×１０１０個／ｃｍ２以上、より好ましくは３×１０１０個／ｃｍ２以上、さらに好ましくは１×１０１１個／ｃｍ２以上であることが望ましい。金属触媒微粒子の個数密度の測定方法としては、例えば金属触媒微粒子形成工程の後で基材をＣＮＴ製造装置から取り出し、基材表面を原子力顕微鏡（ＡＦＭ）で直接測定することができる。あるいは、次のＣＮＴ成長工程で成長したＣＮＴ１０９の直径、及びＣＮＴ集合体の密度とＣＮＴ１０９の直径および層数から以下のようにＣＮＴの本数密度を求め、これが触媒の個数密度と同等であると推定することができる。即ちＣＮＴの本数密度は（ＣＮＴ集合体の重量密度）／（ＣＮＴの線密度）となるが、ＣＮＴ集合体の重量密度はＣＮＴ集合体の重量測定と高さ測定を行うことで算出し、またＣＮＴ線密度は、非特許文献３に記載されるＣＮＴの直径との比例関係から算出することができる。ＣＮＴ１０９の直径はＴＥＭによる直接観察や吸収スペクトルにおける吸収バンドエネルギーから測定することができる。 Specifically, the particle diameters of the generated metal catalyst fine particles 107 are preferably in the range of 1 nm or more and 10 nm or less, respectively. More preferably, it is in the range of 1 nm or more and 5 nm or less. The number density of the metal catalyst fine particles 107 is 1 × 10 10 particles / cm 2 or more, preferably 3 × 10 10 particles / cm 2 or more, and more preferably 1 × 10 11 particles / cm 2 or more. As a method for measuring the number density of the metal catalyst fine particles, for example, after the metal catalyst fine particle formation step, the substrate can be taken out from the CNT manufacturing apparatus, and the surface of the substrate can be directly measured with an atomic force microscope (AFM). Alternatively, the number density of CNTs is obtained from the diameter of CNT 109 grown in the next CNT growth step, the density of CNT aggregates, the diameter of CNT 109, and the number of layers as follows, and this is estimated to be equal to the number density of the catalyst. can do. That is, the number density of CNTs is (CNT aggregate weight density) / (CNT linear density), but the CNT aggregate weight density is calculated by measuring the weight and height of the CNT aggregate, The CNT linear density can be calculated from a proportional relationship with the CNT diameter described in Non-Patent Document 3. The diameter of the CNT 109 can be measured from direct observation with a TEM or absorption band energy in an absorption spectrum.
＜ＣＮＴ成長工程＞
次に、基材１０１に原料ガス（例えばブタンまたはアセチレン等の炭化水素ガス）を含んだ混合ガスを接触させることにより、金属触媒微粒子１０７から高速にかつ高収量で効率良くＣＮＴ集合体１０９が製造される（図１（Ｄ））。前記混合ガスには、雰囲気ガスと、触媒賦活物質（例えば水）とが含まれていても良い。
<CNT growth process>
Next, the base material 101 is brought into contact with a mixed gas containing a raw material gas (for example, a hydrocarbon gas such as butane or acetylene), whereby the CNT aggregate 109 is efficiently produced from the metal catalyst fine particles 107 at high speed and with high yield. (FIG. 1D). The mixed gas may contain an atmospheric gas and a catalyst activation material (for example, water).
＜製造装置＞
上述した金属触媒微粒子形成工程及びＣＮＴ成長工程に用いる装置は特には限定されず、既知の装置を用いることができる。また、金属触媒微粒子形成工程とＣＮＴ成長工程とは、同一温度、同一のキャリアガスで行うことが可能であるため、２つの工程に用いるチャンバーを分けなくてもよい。また、温度やガス流量をそれぞれの工程で適時調整することもできるため、金属触媒微粒子形成工程とＣＮＴ成長工程とでチャンバーを分けてもよい。例えば、金属触媒微粒子形成工程は大気中で加熱するための汎用電気炉を用い、ＣＮＴ成長工程は別の装置を用いても良い。
<Manufacturing equipment>
The apparatus used for the metal catalyst fine particle formation process and the CNT growth process described above is not particularly limited, and a known apparatus can be used. Further, since the metal catalyst fine particle forming step and the CNT growth step can be performed at the same temperature and the same carrier gas, the chambers used for the two steps need not be separated. Moreover, since the temperature and gas flow rate can be adjusted in each step as appropriate, the chamber may be divided between the metal catalyst fine particle forming step and the CNT growth step. For example, the metal catalyst fine particle forming process may use a general-purpose electric furnace for heating in the atmosphere, and the CNT growth process may use another apparatus.
製造装置の一例を図２に示す。図２は、特願２０１０−２７９７２５に記載した本発明の一実施形態に係るＣＮＴ集合体の製造装置１００の模式図である。製造装置１００は、例えば、触媒前駆体層１０６を予め成膜した基材１０１（例えばシリコンウエハ）が基材ホルダ１０５に載置された合成炉１１０を備える。合成炉１１０には、第１ガス流路１４５および第２ガス流路１４７が配設され、触媒前駆体層１０６表面と概して垂直に交わるように基材１０１が配設される。第１ガス流路１４５には、第１ガス供給管１４１を介して原料ガスボンベ１６１、雰囲気ガスボンベ１６３及び還元ガスボンベ１６５が接続する。また、第２ガス流路１４７には、第２ガス供給管１４３を介して、触媒賦活物質ボンベ１６７が接続する。第１ガス供給管１４１には、第１炭素濃度調整手段１７１が配設され、原料ガスボンベ１６１、雰囲気ガスボンベ１６３及び還元ガスボンベ１６５から供給される第１ガスの炭素濃度を調整する。また、第２ガス供給管１４３には、第２炭素濃度調整手段１７３が配設され、触媒賦活物質ボンベ１６７から供給される第２ガスの炭素濃度を調整する。 An example of the manufacturing apparatus is shown in FIG. FIG. 2 is a schematic view of a CNT aggregate manufacturing apparatus 100 according to an embodiment of the present invention described in Japanese Patent Application No. 2010-279725. The manufacturing apparatus 100 includes, for example, a synthesis furnace 110 in which a base material 101 (for example, a silicon wafer) on which a catalyst precursor layer 106 is formed in advance is placed on a base material holder 105. In the synthesis furnace 110, a first gas channel 145 and a second gas channel 147 are disposed, and the substrate 101 is disposed so as to intersect the surface of the catalyst precursor layer 106 generally perpendicularly. A source gas cylinder 161, an atmosphere gas cylinder 163, and a reducing gas cylinder 165 are connected to the first gas flow path 145 through a first gas supply pipe 141. In addition, a catalyst activation material cylinder 167 is connected to the second gas flow path 147 through a second gas supply pipe 143. The first gas supply pipe 141 is provided with a first carbon concentration adjusting means 171 for adjusting the carbon concentration of the first gas supplied from the source gas cylinder 161, the atmospheric gas cylinder 163, and the reducing gas cylinder 165. The second gas supply pipe 143 is provided with a second carbon concentration adjusting means 173 for adjusting the carbon concentration of the second gas supplied from the catalyst activation material cylinder 167.
合成炉１１０には、第１ガス流路１４５および第２ガス流路１４７から供給されたガスを外部へ排出するガス排出管１５０が配設される。また、合成炉１１０には、加熱手段１３０が配設される。第１炭素濃度調整手段１７１、第２炭素濃度調整手段１７３及び加熱手段１３０は、図示しない制御手段により制御することができる。 The synthesis furnace 110 is provided with a gas discharge pipe 150 that discharges the gas supplied from the first gas flow path 145 and the second gas flow path 147 to the outside. The synthesis furnace 110 is provided with heating means 130. The first carbon concentration adjusting unit 171, the second carbon concentration adjusting unit 173, and the heating unit 130 can be controlled by a control unit (not shown).
＜ＣＮＴ集合体製造工程＞
図２を参照しながら説明すると、触媒前駆体層１０６を成膜した基材１０１が基材ホルダ１０５に載置され、合成炉１１０内には、第１ガス供給管１４１から第１ガス流路１４５を介して供給された雰囲気ガス（例えばヘリウム）が満たされている。触媒前駆体層１０６表面と第１ガス流路１４５および第２ガス流路１４７とは概して垂直に交わるように基材１０１を配設し、原料ガスが効率良く触媒に供給されるようにする。
<CNT assembly manufacturing process>
Referring to FIG. 2, the base material 101 on which the catalyst precursor layer 106 is formed is placed on the base material holder 105, and the first gas flow path 141 is connected to the first gas flow path in the synthesis furnace 110. An atmospheric gas (for example, helium) supplied via 145 is filled. The base material 101 is disposed so that the surface of the catalyst precursor layer 106 and the first gas flow path 145 and the second gas flow path 147 are generally perpendicular to each other so that the source gas is efficiently supplied to the catalyst.
この段階で上述した金属触媒微粒子１０７を形成する場合には、合成炉１１０内を所定の温度（例えば７５０℃）に加熱し、その状態を所望の時間保持する。触媒前駆体層１０６および雰囲気ガスの少なくともいずれか一つを加熱して、触媒金属元素並びに助触媒金属元素を還元及び／または微粒子化する。このとき、第１ガス供給管１４１から第１ガス流路１４５を介して合成炉１１０内に雰囲気ガスを供給してもよい。 When the metal catalyst fine particles 107 described above are formed at this stage, the inside of the synthesis furnace 110 is heated to a predetermined temperature (for example, 750 ° C.) and the state is maintained for a desired time. At least one of the catalyst precursor layer 106 and the atmospheric gas is heated to reduce and / or atomize the catalytic metal element and the promoter metal element. At this time, atmospheric gas may be supplied into the synthesis furnace 110 from the first gas supply pipe 141 via the first gas flow path 145.
この加熱により、触媒前駆体層１０６が還元され、様々な粒子径を有する金属触媒微粒子１０７になり、ＣＮＴ１０９の触媒として好適な状態に調整される。また、必要に応じて第２ガス供給管１４３から第２ガス流路１４７を介して触媒賦活物質を含む第２ガスを添加してもよい。この工程により、触媒金属元素の還元、ＣＮＴの成長に適合した状態の触媒金属元素を含んだ金属微粒子化促進、および触媒金属元素の活性向上の少なくとも一つの効果が現れる。次いで第１ガス流路１４５からの雰囲気ガスの供給を所望（反応条件）に応じて停止あるいは低減する。 By this heating, the catalyst precursor layer 106 is reduced to become metal catalyst fine particles 107 having various particle sizes, and is adjusted to a state suitable as a catalyst of the CNT 109. Moreover, you may add the 2nd gas containing a catalyst activation material from the 2nd gas supply pipe 143 via the 2nd gas flow path 147 as needed. By this step, at least one of the effects of reducing the catalytic metal element, promoting the formation of fine metal particles containing the catalytic metal element in a state suitable for the growth of CNT, and improving the activity of the catalytic metal element appears. Next, the supply of the atmospheric gas from the first gas flow path 145 is stopped or reduced as desired (reaction conditions).
続いて、原料ガスと触媒賦活物質の各々を、合成炉１１０内に配設された互いに異なる配管から金属触媒微粒子１０７からなる触媒層１０３の近傍のガス混合領域１８０に供給する。すなわち、原料ガス（例えばブタンまたはプロパン）と、雰囲気ガスを含む第１ガスを、第１ガス供給管１４１から第１ガス流路１４５を介して合成炉１１０内に供給し、触媒賦活物質（例えば水）を含む第２ガスを第２ガス供給管１４３から第２ガス流路１４７を介して合成炉１１０内に供給する。第１ガス流路１４５および第２ガス流路１４７から供給されたこれらのガスは、基材１０１の触媒層１０３表面に対して略平行方向に向いたガス流を形成した後に、触媒層１０３の近傍のガス混合領域１８０で混合し、所定量で、基材１０１上の触媒層１０３表面に供給される。 Subsequently, each of the raw material gas and the catalyst activation material is supplied to the gas mixing region 180 in the vicinity of the catalyst layer 103 made of the metal catalyst fine particles 107 from different pipes arranged in the synthesis furnace 110. That is, a raw material gas (for example, butane or propane) and a first gas containing an atmospheric gas are supplied from the first gas supply pipe 141 into the synthesis furnace 110 through the first gas flow path 145, and a catalyst activation material (for example, A second gas containing water is supplied from the second gas supply pipe 143 into the synthesis furnace 110 through the second gas flow path 147. These gases supplied from the first gas flow path 145 and the second gas flow path 147 form a gas flow directed in a direction substantially parallel to the surface of the catalyst layer 103 of the substrate 101, and then the catalyst layer 103. It mixes in the gas mixing area | region 180 of the vicinity, and is supplied to the catalyst layer 103 surface on the base material 101 by predetermined amount.
ＣＮＴの生産終了後、合成炉１１０内に残余する、第１ガスに含まれる原料ガス、第２ガスに含まれる触媒賦活物質、それらの分解物、または合成炉１１０内に存在する炭素不純物等がＣＮＴ集合体へ付着することを抑制するために、第１ガス流路１４５から雰囲気ガスのみを流す。 After the CNT production is completed, the raw material gas contained in the first gas, the catalyst activation material contained in the second gas, the decomposition products thereof, or the carbon impurities existing in the synthesis furnace 110 remain in the synthesis furnace 110. In order to suppress adhesion to the CNT aggregate, only the atmospheric gas is allowed to flow from the first gas flow path 145.
冷却ガス環境下でＣＮＴ集合体、触媒、および基材１０１を、好ましくは４００℃以下、より好ましくは２００℃以下に冷却する。冷却ガスとしては、第２ガス供給管１４３から供給する不活性ガスが好ましく、特に安全性、経済性、およびパージ性などの点から窒素が好ましい。このようにして、ＣＮＴ複合材料に用いるＣＮＴ１０９を製造することができる。 Under a cooling gas environment, the CNT aggregate, the catalyst, and the substrate 101 are preferably cooled to 400 ° C. or lower, more preferably 200 ° C. or lower. As the cooling gas, an inert gas supplied from the second gas supply pipe 143 is preferable, and nitrogen is particularly preferable from the viewpoints of safety, economy, purgeability, and the like. In this way, the CNT 109 used for the CNT composite material can be manufactured.
＜ＣＮＴ集合体＞
製造されたＣＮＴ１０９は、垂直配向体である。ＣＮＴ１０９の長さは、１０μｍ以上であることを特徴とする。より好ましくは、１００μｍ以上であり、より好ましくは３００μｍ以上である。また、ＣＮＴ１０９の層数は得には限定されないが、単層を１０％以上含むことが望ましく、より望ましくは、５０％以上含むことが望ましい。
<CNT aggregate>
The manufactured CNT 109 is a vertical alignment body. The length of the CNT 109 is 10 μm or more. More preferably, it is 100 micrometers or more, More preferably, it is 300 micrometers or more. Further, the number of layers of the CNT 109 is not limited, but it is desirable to include 10% or more of a single layer, and more desirably 50% or more.
（実施例１）
実施例１として、触媒金属元素として鉄を用い、助触媒金属元素としてイリジウムを用い、合金化補助物質としてクエン酸及びポリビニルアルコール（ＰＶＡ）を用いて、ＣＮＴ集合体製造用触媒基材を作製した。まず、基材としてシリコンウエハ（縦４０ｍｍ×横４０ｍｍ）を準備し、シリコンエハの表面に酸化シリコン（ＳｉＯ２）膜を５００ｎｍ形成した。触媒を配置する基材の面のＳｉＯ２膜上にアルミナをスパッタリング法により堆積させ、４０ｎｍ以上の下地層を形成した。下地層を形成した基材をアセントで超音波洗浄した後に、イソプロピルアルコール（ＩＰＡ）で更に超音波洗浄した。その後、触媒前駆体層の塗工性を向上させるため、下地層をＯ２プラズマで処理した。
Example 1
As Example 1, iron was used as the catalytic metal element, iridium was used as the promoter metal element, and citric acid and polyvinyl alcohol (PVA) were used as the alloying auxiliary substances to produce a catalyst base material for CNT aggregate production. . First, a silicon wafer (length 40 mm × width 40 mm) was prepared as a base material, and a silicon oxide (SiO 2 ) film having a thickness of 500 nm was formed on the surface of the silicon wafer. Alumina was deposited on the SiO 2 film on the surface of the base material on which the catalyst was placed by sputtering to form an underlayer of 40 nm or more. The substrate on which the underlayer was formed was ultrasonically cleaned with ascent, and then further ultrasonically cleaned with isopropyl alcohol (IPA). Thereafter, in order to improve the coating of the catalyst precursor layer was treated underlayer by O 2 plasma.
７０ｍＭ ＦｅＣｌ３、１０ｍＭ イリジウム（Ｉｒ）、８０ｍＭ クエン酸及び１ｗｔ％ ＰＶＡを含む塗布溶液を調製した。基材の下地層を形成した面に塗布溶液をスピンコート法により塗布した。その後、基材を２００℃で１分間加熱して、塗布溶液を乾燥させることにより、膜厚１０μｍの触媒前駆体層を形成し、ＣＮＴ集合体製造用触媒基材を作製した。 A coating solution containing 70 mM FeCl 3 , 10 mM iridium (Ir), 80 mM citric acid and 1 wt% PVA was prepared. The coating solution was applied to the surface of the base material on which the base layer was formed by spin coating. Thereafter, the substrate was heated at 200 ° C. for 1 minute to dry the coating solution, thereby forming a catalyst precursor layer having a thickness of 10 μm, and a catalyst substrate for producing a CNT aggregate was produced.
ＣＮＴ集合体製造用触媒基材を合成炉に搬入し、Ｈｅを５００ｓｃｃｍ供給しながら、７５０℃で６分間加熱して、触媒金属元素と助触媒金属元素とを合金化及び微粒子化して、金属触媒微粒子を形成した。 A catalyst base material for producing a CNT aggregate is carried into a synthesis furnace, heated at 750 ° C. for 6 minutes while supplying He at 500 sccm, and alloyed with catalyst metal elements and co-catalyst metal elements to form metal catalysts. Fine particles were formed.
合成炉にＨｅを５００ｓｃｃｍ、２０％ アセチレン（Ｃ２Ｈ２）（ヘリウムで２０％に希釈したアセチレンを１００ｓｃｃｍ導入）を１０ｓｃｃｍ、触媒賦活物質として、窒素でバブリングした水を５０ｓｃｃｍ導入し、ＣＮＴ集合体を合成した。 He introduced 500 sccm of He, 50 sccm of 20% acetylene (C 2 H 2 ) (introducing 100 sccm of acetylene diluted to 20% with helium) into 10 sccm, and 50 sccm of water bubbled with nitrogen as a catalyst activator. Was synthesized.
また、金属触媒微粒子を形成した段階で基材を合成炉から取り出し、基材の表面に形成された金属触媒微粒子を原子間力顕微鏡（ＡＦＭ）により観察した像を図３（Ａ）に示す。粒子径が５ｎｍ、個数密度が２×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 Further, FIG. 3A shows an image obtained by removing the base material from the synthesis furnace at the stage of forming the metal catalyst fine particles and observing the metal catalyst fine particles formed on the surface of the base material with an atomic force microscope (AFM). It was confirmed that metal catalyst fine particles having a particle diameter of 5 nm and a number density of 2 × 10 11 particles / cm 2 were formed.
合成されたＣＮＴ集合体のラマンスペクトルを図３（Ｂ）に示す。ラマンスペクトルは、ラマン分光測定装置（サーモエレクトロン社）を使用して、５３２ｎｍの励起波長を用いた。実施例１のＣＮＴ集合体は、１５６０ｃｍ−１以上１６００ｃｍ−１以下の範囲内での最大のピーク強度をＧ、１３１０ｃｍ−１以上１３５０ｃｍ−１以下の範囲内での最大のピーク強度をＤとしたときに、Ｇ／Ｄ比が２．０であった。また、ＣＮＴ集合体の収量は、０．６２１ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、３４５μｍであった。 FIG. 3B shows the Raman spectrum of the synthesized CNT aggregate. For the Raman spectrum, an excitation wavelength of 532 nm was used using a Raman spectrometer (Thermo Electron). CNT aggregate of Example 1, the maximum peak intensity in the range of 1560 cm -1 or 1600 cm -1 or less G, and maximum peak intensity in the range of 1310cm -1 or 1350 cm -1 or less is represented by D Sometimes the G / D ratio was 2.0. The yield of the CNT aggregate was 0.621 mg / cm 2 , and the average height of the CNT aggregate was 345 μm.
（実施例２）
実施例２として、７０ｍＭ ＦｅＣｌ３、１８ｍＭ イリジウム、８８ｍＭ クエン酸及び１ｗｔ％ ＰＶＡを含む塗布溶液を調製したこと以外は実施例１と同様にＣＮＴ集合体製造用触媒基材を作製した。なお、形成した触媒前駆体層の膜厚は１０μｍであった。
(Example 2)
As Example 2, a catalyst base material for producing a CNT aggregate was prepared in the same manner as in Example 1 except that a coating solution containing 70 mM FeCl 3 , 18 mM iridium, 88 mM citric acid and 1 wt% PVA was prepared. The formed catalyst precursor layer had a thickness of 10 μm.
実施例１と同様の条件で、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 Metal catalyst fine particles were formed under the same conditions as in Example 1. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図４（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が４ｎｍ、個数密度が３×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 4A shows an AFM image of the metal catalyst fine particles formed on the catalyst base material for producing the CNT aggregate after the base material is taken out from the synthesis furnace when the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 4 nm and a number density of 3 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した実施例２のＣＮＴ集合体のラマンスペクトルを図４（Ｂ）に示す。実施例２のＣＮＴ集合体のＧ／Ｄ比は２．８であった。このことから、実施例２のＣＮＴ集合体は、グラファイト化度が高く、高品質であることが確認された。また、ＣＮＴ集合体の収量は、０．４８９ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、１４９μｍであった。 The Raman spectrum of the CNT aggregate of Example 2 measured under the same conditions as in Example 1 is shown in FIG. The G / D ratio of the CNT aggregate of Example 2 was 2.8. From this, it was confirmed that the CNT aggregate of Example 2 has a high degree of graphitization and high quality. The yield of the CNT aggregate was 0.489 mg / cm 2 , and the average height of the CNT aggregate was 149 μm.
（実施例３）
実施例３として、７０ｍＭ ＦｅＣｌ３、１０ｍＭ イリジウム及び１ｗｔ％ ＰＶＡを含む塗布溶液を調製したこと以外は実施例１と同様にＣＮＴ集合体製造用触媒基材を作製した。なお、形成した触媒前駆体層の膜厚は１０μｍであった。
(Example 3)
As Example 3, a catalyst substrate for producing a CNT aggregate was produced in the same manner as in Example 1 except that a coating solution containing 70 mM FeCl 3 , 10 mM iridium and 1 wt% PVA was prepared. The formed catalyst precursor layer had a thickness of 10 μm.
実施例１と同様の条件で、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 Metal catalyst fine particles were formed under the same conditions as in Example 1. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図５（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が４ｎｍ、個数密度が４×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 5A shows an AFM image of the metal catalyst fine particles formed on the catalyst substrate for producing the CNT aggregate after the base material is taken out from the synthesis furnace at the stage where the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 4 nm and a number density of 4 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した実施例３のＣＮＴ集合体のラマンスペクトルを図５（Ｂ）に示す。実施例３のＣＮＴ集合体のＧ／Ｄ比は２．３であった。このことから、実施例３のＣＮＴ集合体は、グラファイト化度が高く、高品質であることが確認された。また、ＣＮＴ集合体の収量は、０．４０８ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、９２μｍであった。 A Raman spectrum of the CNT aggregate of Example 3 measured under the same conditions as in Example 1 is shown in FIG. The G / D ratio of the CNT aggregate of Example 3 was 2.3. From this, it was confirmed that the CNT aggregate of Example 3 has a high degree of graphitization and high quality. Moreover, the yield of the CNT aggregate was 0.408 mg / cm 2 , and the average height of the CNT aggregate was 92 μm.
（実施例４）
実施例４として、酸素存在下での金属触媒の微粒子化を行った。実施例４として、実施例２と同様にＣＮＴ集合体製造用触媒基材を作製した。
Example 4
As Example 4, the metal catalyst was atomized in the presence of oxygen. As Example 4, a catalyst base material for producing a CNT aggregate was produced in the same manner as in Example 2.
実施例４のＣＮＴ集合体製造用触媒基材を合成炉に搬入し、酸素（Ｏ２）を５００ｓｃｃｍ、窒素（Ｎ２）を１５００ｓｃｃｍ供給しながら、７５０℃で５分間加熱して、触媒金属元素と助触媒金属元素とを合金化及び微粒子化して、金属触媒微粒子を形成した。 Example The CNT aggregate production catalyst substrate 4 is conveyed to the synthesis reactor, the oxygen (O 2) of 500 sccm, while nitrogen (N 2) and 1500sccm fed, and heated for 5 minutes at 750 ° C., the catalytic metal element And cocatalyst metal element were alloyed and finely divided to form metal catalyst fine particles.
その後、合成炉にＨｅを５００ｓｃｃｍ供給しながら、７５０℃で６分間加熱して、合成炉内から、Ｏ２及びＮ２を除去した。合成炉にＨｅを５００ｓｃｃｍ、２０％ アセチレン（Ｃ２Ｈ２）（ヘリウムで２０％に希釈したアセチレンを１００ｓｃｃｍ導入）を１０ｓｃｃｍ、触媒賦活物質として、窒素でバブリングした水を５０ｓｃｃｍ導入し、ＣＮＴ集合体を合成した。 Thereafter, while supplying 500 sccm of He to the synthesis furnace, heating was performed at 750 ° C. for 6 minutes to remove O 2 and N 2 from the synthesis furnace. He introduced 500 sccm of He, 50 sccm of 20% acetylene (C 2 H 2 ) (introducing 100 sccm of acetylene diluted to 20% with helium) into 10 sccm, and 50 sccm of water bubbled with nitrogen as a catalyst activator. Was synthesized.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図６（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が１．５ｎｍ、個数密度が７×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。したがって、本実施例の結果から、本発明に係るＣＮＴ集合体製造用触媒基材は、酸素存在下においても金属触媒の微粒子化が可能であることが実証された。 FIG. 6A shows an AFM image of the metal catalyst fine particles formed on the catalyst substrate for producing the CNT aggregate after the base material is taken out from the synthesis furnace at the stage where the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 1.5 nm and a number density of 7 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate. Therefore, from the results of this example, it was demonstrated that the catalyst base material for producing a CNT aggregate according to the present invention can be made fine in metal catalyst even in the presence of oxygen.
実施例１と同様の条件で測定した実施例４のＣＮＴ集合体のラマンスペクトルを図６（Ｂ）に示す。実施例４のＣＮＴ集合体のＧ／Ｄ比は３８．０であった。このことから、実施例４のＣＮＴ集合体は、グラファイト化度が高く、高品質であることが確認された。また、ＣＮＴ集合体の収量は、０．００９ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、１６μｍであった。 The Raman spectrum of the CNT aggregate of Example 4 measured under the same conditions as in Example 1 is shown in FIG. The G / D ratio of the CNT aggregate of Example 4 was 38.0. From this, it was confirmed that the CNT aggregate of Example 4 has a high degree of graphitization and high quality. The yield of the CNT aggregate was 0.009 mg / cm 2 , and the average height of the CNT aggregate was 16 μm.
（実施例５）
実施例５として、７０ｍＭ ＦｅＣｌ３、７ｍＭ ルテニウム（Ｒｕ）、７７ｍＭ クエン酸及び１ｗｔ％ ＰＶＡを含む塗布溶液を調製したこと以外は実施例１と同様にＣＮＴ集合体製造用触媒基材を作製した。なお、形成した触媒前駆体層の膜厚は１０μｍであった。
(Example 5)
As Example 5, a catalyst base material for producing a CNT aggregate was produced in the same manner as in Example 1 except that a coating solution containing 70 mM FeCl 3 , 7 mM ruthenium (Ru), 77 mM citric acid and 1 wt% PVA was prepared. The formed catalyst precursor layer had a thickness of 10 μm.
実施例１と同様の条件で、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 Metal catalyst fine particles were formed under the same conditions as in Example 1. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図７（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が２ｎｍ、個数密度が２×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 7A shows an AFM image of the metal catalyst fine particles formed on the catalyst base material for producing the CNT aggregate after taking out the base material from the synthesis furnace when the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 2 nm and a number density of 2 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した実施例５のＣＮＴ集合体のラマンスペクトルを図７（Ｂ）に示す。実施例５のＣＮＴ集合体のＧ／Ｄ比は６．１であった。このことから、実施例５のＣＮＴ集合体は、グラファイト化度が高く、高品質であることが確認された。また、実施例５で製造したＣＮＴ集合体の走査型電子顕微鏡（ＳＥＭ）像を図８に示す。ＣＮＴ集合体の収量は、０．６９４ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、３７０μｍであった。 FIG. 7B shows the Raman spectrum of the CNT aggregate of Example 5 measured under the same conditions as in Example 1. The G / D ratio of the CNT aggregate of Example 5 was 6.1. From this, it was confirmed that the CNT aggregate of Example 5 has a high degree of graphitization and high quality. Moreover, the scanning electron microscope (SEM) image of the CNT aggregate manufactured in Example 5 is shown in FIG. The yield of the CNT aggregate was 0.694 mg / cm 2 , and the average height of the CNT aggregate was 370 μm.
（実施例６）
実施例６として、７０ｍＭ ＦｅＣｌ３、１０ｍＭ イリジウム、８０ｍＭ クエン酸、及び１ｗｔ％ グリセリンを含む塗布溶液を調製したこと以外は実施例１と同様にＣＮＴ集合体製造用触媒基材を作製した。なお、形成した触媒前駆体層の膜厚は約１００ｎｍであった。本実施例において、グリセリンは３００℃以下の低温で蒸発することから、クエン酸のみが合金化補助物質として働いている。
(Example 6)
As Example 6, a catalyst base material for producing a CNT aggregate was produced in the same manner as in Example 1 except that a coating solution containing 70 mM FeCl 3 , 10 mM iridium, 80 mM citric acid, and 1 wt% glycerin was prepared. The formed catalyst precursor layer had a thickness of about 100 nm. In this example, since glycerin evaporates at a low temperature of 300 ° C. or less, only citric acid works as an alloying auxiliary substance.
実施例１と同様の条件で、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 Metal catalyst fine particles were formed under the same conditions as in Example 1. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図９（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が２ｎｍ、個数密度が６×１０１０個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 9A shows an AFM image of the metal catalyst fine particles formed on the catalyst base material for producing the CNT aggregate after the base material is taken out from the synthesis furnace at the stage where the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 2 nm and a number density of 6 × 10 10 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した実施例６のＣＮＴ集合体のラマンスペクトルを図９（Ｂ）に示す。実施例６のＣＮＴ集合体のＧ／Ｄ比は１５．２であった。このことから、実施例６のＣＮＴ集合体は、グラファイト化度が高く、高品質であることが確認された。また、ＣＮＴ集合体の収量は、０．１４２ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、７６μｍであった。 FIG. 9B shows the Raman spectrum of the CNT aggregate of Example 6 measured under the same conditions as in Example 1. The G / D ratio of the CNT aggregate of Example 6 was 15.2. From this, it was confirmed that the CNT aggregate of Example 6 has a high degree of graphitization and high quality. Moreover, the yield of the CNT aggregate was 0.142 mg / cm 2 , and the average height of the CNT aggregate was 76 μm.
（比較例１）
比較例１として、助触媒金属元素を用いずに、ＣＮＴ集合体製造用触媒基材を作製した。比較例１として、７０ｍＭ ＦｅＣｌ３、７０ｍＭ クエン酸及び１ｗｔ％ ＰＶＡを含む塗布溶液を調製したこと以外は実施例１と同様にＣＮＴ集合体製造用触媒基材を作製した。なお、形成した触媒前駆体層の膜厚は１０μｍであった。
(Comparative Example 1)
As Comparative Example 1, a catalyst base material for producing a CNT aggregate was produced without using a promoter metal element. As Comparative Example 1, a catalyst base material for producing a CNT aggregate was produced in the same manner as in Example 1 except that a coating solution containing 70 mM FeCl 3 , 70 mM citric acid and 1 wt% PVA was prepared. The formed catalyst precursor layer had a thickness of 10 μm.
実施例１と同様の条件で、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 Metal catalyst fine particles were formed under the same conditions as in Example 1. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図１０（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が５ｎｍ、個数密度が１×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 10A shows an AFM image of the metal catalyst fine particles formed on the catalyst base material for producing the CNT aggregate after taking out the base material from the synthesis furnace when the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 5 nm and a number density of 1 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した比較例１のＣＮＴ集合体のラマンスペクトルを図１０（Ｂ）に示す。比較例１のＣＮＴ集合体のＧ／Ｄ比は３．３であった。しかし、ＣＮＴ集合体の収量は、０．０２９ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、６μｍとなり、実施例１に比してＣＮＴ合成量が著しく低下した。 A Raman spectrum of the CNT aggregate of Comparative Example 1 measured under the same conditions as in Example 1 is shown in FIG. The G / D ratio of the CNT aggregate of Comparative Example 1 was 3.3. However, the yield of the CNT aggregate was 0.029 mg / cm 2 , and the average height of the CNT aggregate was 6 μm, and the amount of CNT synthesis was significantly reduced as compared with Example 1.
（比較例２）
比較例２として、触媒金属元素及び助触媒金属元素をスパッタリング法により成膜して、ＣＮＴ集合体製造用触媒基材を作製した。触媒を配置する基材の面のＳｉＯ２膜上にアルミナをスパッタリング法により堆積させ、４０ｎｍ以上の下地層を形成し後に、鉄（Ｆｅ）をスパッタリング法により２．５ｎｍ堆積させた。さらに、Ｉｒをスパッタリング法により０．４ｎｍ堆積させた。
(Comparative Example 2)
As Comparative Example 2, a catalyst metal element and a promoter metal element were formed into a film by a sputtering method to produce a catalyst base material for producing a CNT aggregate. Alumina was deposited on the SiO 2 film on the surface of the base material on which the catalyst was placed by sputtering to form an underlayer of 40 nm or more, and then iron (Fe) was deposited to 2.5 nm by sputtering. Further, Ir was deposited to a thickness of 0.4 nm by a sputtering method.
実施例１と同様の条件で、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 Metal catalyst fine particles were formed under the same conditions as in Example 1. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図１１（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が０．９ｎｍ、個数密度が６×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 11A shows an AFM image of the metal catalyst fine particles formed on the catalyst substrate for producing the CNT aggregate after the base material is taken out from the synthesis furnace at the stage where the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 0.9 nm and a number density of 6 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した比較例２のＣＮＴ集合体のラマンスペクトルを図１１（Ｂ）に示す。比較例２のＣＮＴ集合体のＧ／Ｄ比は１０．４であった。しかし、ＣＮＴ集合体の収量は、０．００７ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、７μｍとなり、実施例１に比してＣＮＴ合成量が著しく低下した。 FIG. 11B shows the Raman spectrum of the CNT aggregate of Comparative Example 2 measured under the same conditions as in Example 1. The G / D ratio of the CNT aggregate of Comparative Example 2 was 10.4. However, the yield of the CNT aggregate was 0.007 mg / cm 2 , and the average height of the CNT aggregate was 7 μm, and the amount of CNT synthesis was significantly reduced as compared with Example 1.
（比較例３）
比較例３として、助触媒金属元素を用いずに、ＣＮＴ集合体製造用触媒基材を作製し、酸化雰囲気で金属触媒微粒子形成工程を行った。比較例３として、７０ｍＭ ＦｅＣｌ３、７０ｍＭ クエン酸及び１ｗｔ％ ＰＶＡを含む塗布溶液を調製したこと以外は実施例４と同様にＣＮＴ集合体製造用触媒基材を作製した。なお、形成した触媒前駆体層の膜厚は１０μｍであった。
(Comparative Example 3)
As Comparative Example 3, a catalyst base material for producing a CNT aggregate was produced without using a promoter metal element, and a metal catalyst fine particle forming step was performed in an oxidizing atmosphere. As Comparative Example 3, a catalyst base material for producing a CNT aggregate was produced in the same manner as in Example 4 except that a coating solution containing 70 mM FeCl 3 , 70 mM citric acid and 1 wt% PVA was prepared. The formed catalyst precursor layer had a thickness of 10 μm.
実施例４と同様の条件で、金属触媒微粒子を形成した。その後、実施例４と同様の条件で、ＣＮＴ集合体を合成した。 Under the same conditions as in Example 4, metal catalyst fine particles were formed. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 4.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図１２（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上には粒子径１ｎｍ以上の構造が観察できず、金属触媒微粒子の形成は確認できなかった。 FIG. 12A shows an AFM image of the metal catalyst fine particles formed on the catalyst base for producing the CNT aggregate after the base material is taken out from the synthesis furnace at the stage where the metal catalyst fine particles are formed. A structure having a particle diameter of 1 nm or more could not be observed on the catalyst substrate for producing a CNT aggregate, and formation of metal catalyst fine particles could not be confirmed.
実施例４と同様の条件で測定した比較例３のラマンスペクトルを図１２（Ｂ）に示す。比較例３においてはＣＮＴの存在を示すＧバンドのピークが観察されなかった。また、ＣＮＴ集合体の収量は、０ｍｇ／ｃｍ２であった。 The Raman spectrum of Comparative Example 3 measured under the same conditions as in Example 4 is shown in FIG. In Comparative Example 3, no G band peak indicating the presence of CNT was observed. Moreover, the yield of the CNT aggregate was 0 mg / cm 2 .
（参考例１）
参考例１として、従来のＣＮＴ集合体製造用触媒基材を水素で還元して微粒子化した例を示す。参考例１として、ＳｉＯ２膜を５００ｎｍ形成したシリコンエハにアルミナをスパッタリング法により堆積させ、４０ｎｍ以上の下地層を形成した。
(Reference Example 1)
As Reference Example 1, an example in which a conventional catalyst base material for producing a CNT aggregate is reduced to fine particles by hydrogen is shown. As Reference Example 1, alumina was deposited on a silicon wafer having a SiO 2 film of 500 nm formed thereon by a sputtering method to form an underlayer of 40 nm or more.
下地層に鉄（Ｆｅ）をスパッタリング法により１．８ｎｍ堆積させた。 Iron (Fe) was deposited on the underlayer by 1.8 nm by a sputtering method.
ＣＮＴ集合体製造用触媒基材を合成炉に搬入し、水素（Ｈ２）を５００ｓｃｃｍ供給しながら、７５０℃で６分間加熱して、触媒金属元素を微粒子化して、金属触媒微粒子を形成した。その後、実施例１と同様の条件で、ＣＮＴ集合体を合成した。 The catalyst base material for producing CNT aggregates was carried into a synthesis furnace, and heated at 750 ° C. for 6 minutes while supplying 500 sccm of hydrogen (H 2 ), thereby finely dividing the catalytic metal element to form metal catalyst fine particles. Thereafter, a CNT aggregate was synthesized under the same conditions as in Example 1.
金属触媒微粒子を形成した段階で基材を合成炉から取り出し、ＣＮＴ集合体製造用触媒基材に形成された金属触媒微粒子のＡＦＭ像を図１３（Ａ）に示す。ＣＮＴ集合体製造用触媒基材上に、粒子径が２．８ｎｍ、個数密度が６×１０１１個／ｃｍ２の金属触媒微粒子が形成されているのが確認できた。 FIG. 13A shows an AFM image of the metal catalyst fine particles formed on the catalyst substrate for producing the CNT aggregate after the base material is taken out from the synthesis furnace at the stage where the metal catalyst fine particles are formed. It was confirmed that metal catalyst fine particles having a particle diameter of 2.8 nm and a number density of 6 × 10 11 particles / cm 2 were formed on the catalyst substrate for producing the CNT aggregate.
実施例１と同様の条件で測定した参考例１のＣＮＴ集合体のラマンスペクトルを図１３（Ｂ）に示す。参考例１のＣＮＴ集合体のＧ／Ｄ比は８．０であった。このことから、参考例１のＣＮＴ集合体は、グラファイト化度が高く、高品質であることが確認された。また、ＣＮＴ集合体の収量は、２．２０８ｍｇ／ｃｍ２、ＣＮＴ集合体の高さの平均は、９１４μｍであった。この結果から、上述した実施例の示したＣＮＴ集合体製造用触媒基材は、参考例１と同様に、ＣＮＴの合成に有効であることが示された。 FIG. 13B shows the Raman spectrum of the CNT aggregate of Reference Example 1 measured under the same conditions as in Example 1. The G / D ratio of the CNT aggregate of Reference Example 1 was 8.0. From this, it was confirmed that the CNT aggregate of Reference Example 1 has a high degree of graphitization and high quality. The yield of the CNT aggregate was 2.208 mg / cm 2 , and the average height of the CNT aggregate was 914 μm. From this result, it was shown that the catalyst base material for producing CNT aggregates shown in the above-described Examples was effective for the synthesis of CNTs as in Reference Example 1.
１００：製造装置、１０１：基材、１０２：下地層、１０３：触媒層、１０５：基材ホルダ、１０６：触媒前駆体層、１０７：金属触媒微粒子、ＣＮＴ、１１０：合成炉、１４１：第１ガス供給管、１４３：第２ガス供給管、１４５：第１ガス流路、１４７：第２ガス流路、１６１：原料ガスボンベ、１６３：雰囲気ガスボンベ、１６５：還元ガスボンベ、１６７：触媒賦活物質ボンベ、１７１：第１炭素濃度調整手段、１７３：第２炭素濃度調整手段 DESCRIPTION OF SYMBOLS 100: Manufacturing apparatus, 101: Base material, 102: Underlayer, 103: Catalyst layer, 105: Base material holder, 106: Catalyst precursor layer, 107: Metal catalyst fine particle, CNT, 110: Synthesis furnace, 141: 1st Gas supply pipe, 143: second gas supply pipe, 145: first gas flow path, 147: second gas flow path, 161: raw material gas cylinder, 163: atmosphere gas cylinder, 165: reducing gas cylinder, 167: catalyst activation substance cylinder, 171: First carbon concentration adjusting means, 173: Second carbon concentration adjusting means
Claims (11)
前記基材の上に設けられた、触媒金属元素と、電子親和力が５０ ｋＪ／ｍｏｌ以上である助触媒金属元素と、加熱時に前記触媒金属元素又は前記助触媒金属元素が凝集することを防ぎ、前記触媒金属元素と前記助触媒金属元素との混合を促進する合金化補助物質とを含む、触媒前駆体層と、
を含む、カーボンナノチューブ集合体製造用触媒基材。 A substrate;
The catalyst metal element provided on the substrate, the promoter metal element having an electron affinity of 50 kJ / mol or more, and the catalyst metal element or the promoter metal element are prevented from agglomerating during heating, A catalyst precursor layer comprising an alloying auxiliary material that promotes mixing of the catalytic metal element and the promoter metal element;
A catalyst base material for producing a carbon nanotube aggregate.
前記触媒前駆体層を加熱することにより前記触媒金属元素と前記助触媒金属元素とを含んだ金属触媒微粒子を基材上に形成し、
炭化水素ガスを前記金属触媒微粒子に接触させて、カーボンナノチューブ集合体を成長させることを含む、カーボンナノチューブ集合体の製造方法。 Producing a catalyst base material for producing a carbon nanotube aggregate according to any one of claims 1 to 6,
By heating the catalyst precursor layer, metal catalyst fine particles containing the catalyst metal element and the promoter metal element are formed on a substrate,
A method for producing a carbon nanotube aggregate, comprising growing a carbon nanotube aggregate by bringing a hydrocarbon gas into contact with the metal catalyst fine particles.
前記還元性ガスが前記触媒金属元素を還元し、前記触媒金属元素と前記助触媒金属元素とを合金化及び微粒子化して、前記金属触媒微粒子を形成する、請求項８に記載のカーボンナノチューブ集合体の製造方法。 The alloying auxiliary substance is thermally decomposed by heating the catalyst precursor layer to generate a reducing gas,
9. The aggregate of carbon nanotubes according to claim 8, wherein the reducing gas reduces the catalytic metal element, and alloying and finely pulverizing the catalytic metal element and the promoter metal element to form the metallic catalyst fine particles. Manufacturing method.
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| CN115228483A (en) * | 2022-07-12 | 2022-10-25 | 远景动力技术(江苏)有限公司 | Catalyst for synthesizing carbon nano-tube and its application |
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