JP2002159851A - Adsorbent, catalyst, and catalyst carrier comprising single-layer carbon nanohorn - Google Patents
Adsorbent, catalyst, and catalyst carrier comprising single-layer carbon nanohornInfo
- Publication number
- JP2002159851A JP2002159851A JP2000358362A JP2000358362A JP2002159851A JP 2002159851 A JP2002159851 A JP 2002159851A JP 2000358362 A JP2000358362 A JP 2000358362A JP 2000358362 A JP2000358362 A JP 2000358362A JP 2002159851 A JP2002159851 A JP 2002159851A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- swnhs
- walled carbon
- layer carbon
- carbon nanohorn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000002116 nanohorn Substances 0.000 title claims abstract description 38
- 239000003463 adsorbent Substances 0.000 title claims abstract description 17
- 239000002356 single layer Substances 0.000 title claims abstract 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 10
- 230000004913 activation Effects 0.000 abstract description 5
- 239000003863 metallic catalyst Substances 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 84
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 12
- 238000001994 activation Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000002411 thermogravimetry Methods 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001757 thermogravimetry curve Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 201000001424 dextro-looped transposition of the great arteries Diseases 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、単層カー
ボンナノホーンからなる吸着材、触媒および触媒担体に
関するものである。さらに詳しくは、この出願の発明
は、活性化処理を不要とし、吸着容量の極めて大きな単
層カーボンナノホーン吸着材と、アルコールの液相酸化
に有用な単層カーボンナノホーン触媒および金属触媒の
活性を高めることができる単層カーボンナノホーン触媒
担体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adsorbent, a catalyst and a catalyst carrier comprising a single-walled carbon nanohorn. More specifically, the invention of this application eliminates the need for an activation treatment and enhances the activity of a single-walled carbon nanohorn adsorbent having an extremely large adsorption capacity and a single-walled carbon nanohorn catalyst and a metal catalyst useful for liquid-phase oxidation of alcohol. And a single-walled carbon nanohorn catalyst carrier.
【０００２】[0002]
【従来の技術とその課題】最近、この出願の発明者らに
より、炭素原子のみからなる新しい炭素同素体である単
層カーボンナノホーン（ＳＷＮＨ）が発見された。ＳＷ
ＮＨは、単層カーボンナノチューブの一端が円錐形状を
有する管状体であって、各々の円錐部間に働くファンデ
ルワールス力によって、複数のものがチューブ部を中心
側にし円錐部が角のように表面部に突き出るような構成
で集合し、直径８０ｎｍ程度以下の球状の単層カーボン
ナノホーン集合体（ＳＷＮＨｓ）を形成していることも
見出されている。図１（ａ）〜（ｃ）にＳＷＮＨｓのＴ
ＥＭ像を例示した。2. Description of the Related Art Recently, the inventors of the present application have discovered a single-walled carbon nanohorn (SWNH), which is a new carbon allotrope consisting only of carbon atoms. SW
NH is a tubular body having one end of a single-walled carbon nanotube having a conical shape, and a plurality of the single-walled carbon nanotubes are shaped like a corner with the tube portion as the center side by van der Waals force acting between the respective cone portions. It has also been found that they aggregate in a configuration protruding from the surface to form a spherical single-walled carbon nanohorn aggregate (SWNHs) having a diameter of about 80 nm or less. 1A to 1C show the T of SWNHs.
An EM image is exemplified.
【０００３】ＳＷＮＨのチューブ部は、直径約２ｎｍ，
長さ３０〜５０ｎｍ程度であり、円錐部は軸断面の頂角
が平均２０°程度のものである。ＳＷＮＨｓを構成する
隣接した二つのＳＷＮＨの壁間距離は約０．４ｎｍ以下
である。The tube portion of SWNH has a diameter of about 2 nm,
The length is about 30 to 50 nm, and the conical portion has an average apex angle of about 20 ° in the axial cross section. The distance between two adjacent SWNHs constituting SWNHs is about 0.4 nm or less.
【０００４】このようなＳＷＮＨｓは、フラーレン，カ
−ボンナノチュ−ブ等のニューカーボンと同様に、その
機能および特性の発見と、化学工業をはじめとする広い
分野での応用に大きな期待がよせられている。[0004] Like the new carbons such as fullerenes and carbon nanotubes, such SWNHs are greatly expected to find their functions and characteristics and to be applied to a wide range of fields including the chemical industry. I have.
【０００５】しかしなから、これまでＳＷＮＨｓの機能
および特性に関してはほとんど何も知られていないのが
現状である。[0005] However, at present, almost nothing is known about the functions and characteristics of SWNHs.
【０００６】そこで、この出願の発明は、以上の通りの
事情に鑑みてなされたものであり、ＳＷＮＨｓの構造を
基本とし、これまで未知の新しい機能材として、活性化
処理が不要で、吸着容量の極めて大きな単層カーボンナ
ノホーンの吸着材と、単層カーボンナノホーンの触媒お
よび触媒担体を提供することを課題としている。Accordingly, the invention of this application has been made in view of the circumstances described above, and is based on the structure of SWNHs. As a new functional material which has not been known so far, it does not require an activation treatment and has an adsorption capacity. It is an object of the present invention to provide an extremely large single-walled carbon nanohorn adsorbent and a single-walled carbon nanohorn catalyst and catalyst carrier.
【０００７】[0007]
【課題を解決するための手段】そこで、この出願の発明
は、上記の課題を解決するものとして、以下の通りの発
明を提供する。Accordingly, the invention of this application provides the following invention to solve the above problems.
【０００８】すなわち、まず第１には、この出願の発明
は、単層カーボンナノホーンが球状に集合してなる単層
カーボンナノホーン集合体であって、近接する単層カー
ボンナノホーンの円錐部により形成される空間に被吸着
物を吸着することを特徴とする単層カーボンナノホーン
吸着材を提供する。That is, first of all, the invention of this application is a single-walled carbon nanohorn aggregate in which single-walled carbon nanohorns are aggregated in a spherical shape, and is formed by conical portions of adjacent single-walled carbon nanohorns. The present invention provides a single-walled carbon nanohorn adsorbent characterized by adsorbing an object to be adsorbed in a space.
【０００９】そして第２には、この出願の発明は、上記
第１の発明について、被吸着物が、気体、有機物、錯
体、生体関連物質のいずれか１種または２種以上である
ことを特徴とする単層カーボンナノホーン吸着材を、第
３には、単層カーボンナノホーンが球状に集合してなる
単層カーボンナノホーン集合体を液相反応における酸化
触媒とすることを特徴とする単層カーボンナノホーン触
媒を、第４には、単層カーボンナノホーンが球状に集合
してなる単層カーボンナノホーン集合体の表面に金属触
媒を担持させること特徴とする単層カーボンナノホーン
触媒担体を提供する。Secondly, the invention of this application is characterized in that, in the first invention, the substance to be adsorbed is any one or more of a gas, an organic substance, a complex, and a biological substance. Thirdly, a single-walled carbon nanohorn aggregate comprising a single-walled carbon nanohorn aggregated in a spherical shape is used as an oxidation catalyst in a liquid phase reaction. Fourthly, the present invention provides a single-walled carbon nanohorn catalyst carrier characterized in that a metal catalyst is supported on the surface of a single-walled carbon nanohorn aggregate in which single-walled carbon nanohorns are aggregated in a spherical shape.
【００１０】[0010]
【発明の実施の形態】この出願の発明は、上記の通りの
特徴を持つものであるが、以下にその実施の形態につい
て説明する。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application has the features as described above, and embodiments thereof will be described below.
【００１１】まず、この出願の発明が提供する単層カー
ボンナノホーン吸着材は、単層カーボンナノホーンが球
状に集合してなる単層カーボンナノホーン集合体（ＳＷ
ＮＨｓ）であって、近接する単層カーボンナノホーンの
円錐部により形成される空間に被吸着物を吸着すること
を特徴としている。First, the single-walled carbon nanohorn adsorbent provided by the invention of the present application is a single-walled carbon nanohorn aggregate (SW) in which single-walled carbon nanohorns are aggregated in a spherical shape.
NHs), which is characterized in that an object to be adsorbed is adsorbed in a space formed by a conical portion of the adjacent single-walled carbon nanohorn.
【００１２】ＳＷＮＨｓは、チューブの一端が円錐形状
の管状体からなる単層カーボンナノチューブの複数のも
のが、各々のチューブ部を中心側にし、円錐部が角のよ
うに表面部に突き出るような構成で球状体を形成したも
のであることが知られている。このようなＳＷＮＨｓに
ついて、この出願の発明では、これを吸着材あるいは触
媒や触媒担体としている。ＳＷＮＨｓが吸着材あるいは
触媒や触媒担体としての機能を有することはこれまで全
く知られていないことであって、この出願の発明によっ
てはじめて提示されることになる。The SWNHs have a structure in which a plurality of single-walled carbon nanotubes each having a conical tubular body at one end of the tube are formed so that each tube portion is located on the center side and the conical portion protrudes to the surface like a corner. Is known to form a spherical body. In the invention of this application, such SWNHs are used as an adsorbent, a catalyst, or a catalyst carrier. It has never been known that SWNHs has a function as an adsorbent, a catalyst or a catalyst carrier, and will be presented for the first time by the invention of this application.
【００１３】なお、この出願の発明では、ＳＷＮＨｓに
ついては「球状」に単層カーボンナノホーンが集合した
ものとしているが、この「球状」であることは、真球状
であることに限定されることはない。同様に、「円錐」
との規定についても真円錐に限られないことは言うまで
もない。In the invention of this application, SWNHs are assumed to be a collection of single-walled carbon nanohorns in a “spherical shape”. However, the “spherical shape” is not limited to a true spherical shape. Absent. Similarly, "cone"
Needless to say, the definition is not limited to a true cone.
【００１４】ＳＷＮＨｓは、図２の断面模式図に示した
ように、表面部に突き出た円錐部の間に形成される空間
に、各種の被吸着物を吸着させるようにしている。被吸
着物としては、気体、有機物、錯体、生体関連物質等
の、各種の物質を考慮することができる。具体的には、
たとえば、Ｏ2，Ｎ2，ＣＯ，ＣＯ2，窒素酸化物，イオ
ン酸化物，メタン等の有機物ガス等の気体、アルコー
ル，アルデヒド，ケトン，脂肪族炭化水素，芳香族炭化
水素等の有機物、金属フタロシアニン等の錯体、汚染水
や汚染気流中の有機不純物や生体関連物質等を対象とす
ることができる。As shown in the schematic sectional view of FIG. 2, SWNHs adsorbs various objects to be adsorbed in a space formed between conical portions projecting from the surface. Various substances such as a gas, an organic substance, a complex, and a biological substance can be considered as the substance to be adsorbed. In particular,
For example, gases such as O 2 , N 2 , CO, CO 2 , nitrogen oxides, ion oxides, organic gases such as methane, organic substances such as alcohols, aldehydes, ketones, aliphatic hydrocarbons and aromatic hydrocarbons, and metals Complexes such as phthalocyanine, organic impurities in polluted water and polluted air, and bio-related substances can be targeted.
【００１５】たとえば、通常ＳＷＮＨｓの比表面積は１
００〜３００ｍ2／ｇ程度であるが、その吸着容量は、
超高比表面積カーボンであるＭＡＣＳＯＲＢ（樹脂ベー
スのカーボン，賦活：ＫＯＨ活性，平均細孔径：１ｎｍ
以下，比表面積：２２９０ｍ 2／ｇ）と比較して、エタ
ノール吸着量で約３．５倍という大きなものとなる。エ
タノール分子の大きさはおよそ０．６ｎｍ以上であり、
図２に示したように、エタノール分子は、ＳＷＮＨｓ吸
着材の表面だけではなく、ＳＷＮＨｓを構成する個々の
単層カーボンナノホーンの円錐部の相互の間に形成され
る空間に吸着される。したがって、ＳＷＮＨｓは比表面
積が約７〜２３倍程度の超高比表面積カーボンよりも多
くの被吸着物質を吸着することができるのである。For example, the specific surface area of SWNHs is usually 1
00-300mTwo/ G, but its adsorption capacity is
MACSORB (resin base)
Carbon, activation: KOH activity, average pore diameter: 1 nm
Below, specific surface area: 2290m Two/ G)
It becomes as large as about 3.5 times the amount of adsorbed phenol. D
The size of the molecule is approximately 0.6 nm or more,
As shown in FIG. 2, ethanol molecules absorb SWNHs.
Not only the surface of the material, but also the individual constituents of SWNHs
Formed between the conical parts of the single-walled carbon nanohorn
Adsorbed in the space. Therefore, SWNHs has a specific surface
More than about 7 to 23 times the product of ultra-high specific surface area carbon
It can adsorb many substances to be adsorbed.
【００１６】また、前記の通りの隣接するチューブ壁に
より構成される空間に加えて、ＳＷＮＨｓのチューブ部
の間に形成される空間（図２において、点線の小さな丸
に囲まれた空間）や、さらにはＳＷＮＨｓそのものの内
部空間にも被吸着分子を吸着することが可能である。た
だし、隣接した二つの単層カーボンナノホーンの管状体
の壁間距離は約０．４ｎｍであることから、被吸着分子
としては、このような壁間スペースに入り込むことがで
きる程度に小さいものである。被吸着分子が十分に小さ
い場合には、この出願の発明のＳＷＮＨｓ吸着材の吸着
容量を、さらに大きなものとすることができる。Further, in addition to the space defined by the adjacent tube walls as described above, a space formed between the tube portions of SWNHs (a space surrounded by a small circle with a dotted line in FIG. 2), Further, the molecules to be adsorbed can be adsorbed in the internal space of the SWNHs itself. However, since the distance between the walls of the tubular body of two adjacent single-walled carbon nanohorns is about 0.4 nm, the molecules to be adsorbed are small enough to enter such a space between the walls. . When the molecules to be adsorbed are sufficiently small, the adsorption capacity of the SWNHs adsorbent of the invention of this application can be further increased.
【００１７】さらに、この出願の発明のＳＷＮＨｓ吸着
材は、驚くべきことに、純粋な炭素材料であるにもかか
わらず、いかなる活性化プロセスをも必要とせず、高い
吸着活性を示す。従来より吸着材として広く使用されて
いる活性炭材料は、製造過程において、物理的あるいは
化学低活性化プロセスが必須とされており、この活性化
プロセスは活性炭の吸着特性を高めるのに効果的であ
る。このことは、ＳＷＮＨｓに独特の新規な化学的特性
の発見として画期的である。Furthermore, the SWNHs adsorbent of the invention of this application surprisingly, despite being a pure carbon material, does not require any activation process and exhibits high adsorption activity. Activated carbon materials that have been widely used as adsorbents in the past require a physical or chemical activation process in the manufacturing process, and this activation process is effective in enhancing the adsorption characteristics of activated carbon. . This is a breakthrough in discovering new chemical properties unique to SWNHs.
【００１８】この出願の発明が提供する単層カーボンナ
ノホーン触媒においては、単層カーボンナノホーンが液
相反応における酸化触媒として作用することを一つの特
徴としている。One feature of the single-walled carbon nanohorn catalyst provided by the invention of this application is that the single-walled carbon nanohorn acts as an oxidation catalyst in a liquid phase reaction.
【００１９】たとえば上記発明によりＳＷＮＨｓに吸着
されたエタノールは、熱処理等による脱着の際には、ア
セトアルデヒドおよびＨ2Ｏとして放出される。すなわ
ち、触媒としてのＳＷＮＨｓの作用により、エタノール
はアセトアルデヒドと水とに分解される。さらに、この
アセトアルデヒドは、ＣＯとＣＨ4とに分解することも
可能である。For example, ethanol adsorbed on SWNHs by the above invention is released as acetaldehyde and H 2 O when desorbed by heat treatment or the like. That is, ethanol is decomposed into acetaldehyde and water by the action of SWNHs as a catalyst. Further, this acetaldehyde can be decomposed into CO and CH 4 .
【００２０】また、ＳＷＮＨｓ自体が１８００℃以上の
真空中で極めて不活性であることは知られていたが、さ
らには、Ｃ60やアモルファスカーボンや活性炭等と比較
して３００〜３５０℃の温度範囲での酸化抵抗が高いこ
とが明らかになった。これにより、ＳＷＮＨｓ触媒は、
より多様な環境で利用可能となる。Further, it SWNHs itself is very inert in vacuo at least 1800 ° C. was known, furthermore, the temperature range of the comparison to 300 to 350 ° C. with C 60 and amorphous carbon and activated carbon It was found that the oxidation resistance was high. This allows the SWNHs catalyst to:
It can be used in more diverse environments.
【００２１】そして、このように、ＳＷＮＨｓは触媒機
能を有することが明らかとなり、この出願の発明のＳＷ
ＮＨｓ触媒を用いることで、吸着した分子を分解するこ
とが可能となる。As described above, it has been clarified that SWNHs has a catalytic function.
The use of the NHs catalyst makes it possible to decompose the adsorbed molecules.
【００２２】この出願の発明が提供する単層カーボンナ
ノホーン触媒担体は、単層カーボンナノホーンの表面に
金属触媒を担持させること特徴としている。The single-walled carbon nanohorn catalyst carrier provided by the invention of this application is characterized in that a metal catalyst is supported on the surface of the single-walled carbon nanohorn.
【００２３】工業用用触媒等として多用されている白金
族元素による金属触媒は、白金族金属が炭素担体に担持
されることで、アルコールからアルデヒド、ケトン、カ
ルボン酸への液相酸化反応において、とても高い触媒活
性を示すことが知られている。このように、従来より、
カーボン材料は、金属触媒の活性を高め、金属触媒を高
分散させるための担体として利用されてきた。A metal catalyst based on a platinum group element, which is widely used as an industrial catalyst or the like, is characterized in that a platinum group metal is supported on a carbon carrier, and is used in a liquid phase oxidation reaction from alcohol to aldehyde, ketone and carboxylic acid. It is known to exhibit very high catalytic activity. Thus, conventionally,
Carbon materials have been used as carriers for enhancing the activity of metal catalysts and for highly dispersing metal catalysts.
【００２４】そこで、より大きい吸着容量を有し触媒機
能をも併せ持つＳＷＮＨｓを金属触媒担体として用いる
ことで、より高分散で触媒活性の高い金属触媒を実現す
ることができる。ＳＷＮＨｓへの金属触媒の担持方法は
特に限定されないが、含浸焼成法を利用することが簡便
であると思われる。この出願の発明の単層カーボンナノ
ホーン触媒担体は、アルコールの酸化反応における金属
触媒の担体として用いることが、より効果的な例として
示される。Therefore, by using SWNHs having a larger adsorption capacity and also having a catalytic function as a metal catalyst carrier, a metal catalyst having higher dispersion and higher catalytic activity can be realized. The method for supporting the metal catalyst on SWNHs is not particularly limited, but it is considered to be simple to use the impregnation firing method. It is shown as a more effective example that the single-walled carbon nanohorn catalyst carrier of the invention of this application is used as a metal catalyst carrier in an alcohol oxidation reaction.
【００２５】なお、この出願の発明におけるＳＷＮＨｓ
については、室温，７６０ＴｏｒｒのＡｒ雰囲気中で、
触媒無しのグラファイトをターゲットとするＣＯ2レー
ザーアブレーション法によって製造することができる。The SWNHs in the invention of the present application
At room temperature in an Ar atmosphere of 760 Torr,
It can be produced by a CO 2 laser ablation method targeting graphite without catalyst.
【００２６】以下、添付した図面に沿って実施例を示
し、この発明の実施の形態についてさらに詳しく説明す
る。The embodiments of the present invention will be described below in more detail with reference to the accompanying drawings.
【００２７】[0027]
【実施例】（実施例１）３００ｍｌの９９．５％エタノ
ールにＳＷＮＨｓ１０ｍｇを入れ、一般的な超音波槽を
用いて３０分間超音波を照射した。なお、使用したＳＷ
ＮＨｓは、波長１０．６μｍのＣＯ2レーザーを、反応
チャンバー（室温，７６０Ｔｏｒｒ，Ａｒ雰囲気）内で
回転しているφ３０×５０ｍｍのグラファイトターゲッ
トにビーム径１０ｍｍで照射して発生させ、収集フィル
ター上に回収したものであり、その構造は次の通りであ
った。EXAMPLES (Example 1) 10 mg of SWNHs was put in 300 ml of 99.5% ethanol, and ultrasonic waves were irradiated for 30 minutes using a general ultrasonic bath. The used SW
NHs is generated by irradiating a CO 2 laser with a wavelength of 10.6 μm to a φ30 × 50 mm graphite target rotating in a reaction chamber (room temperature, 760 Torr, Ar atmosphere) with a beam diameter of 10 mm, and is generated on a collection filter. The structure was as follows.
【００２８】 このようなエタノール処理を施したＳＷＮＨｓ（以下、
エタノール処理ＳＷＮＨｓという）は、溶媒を自然蒸発
させることで溶液から回収した。超高比表面積を有する
ＭＡＣＳＯＲＢに対しても、同様なエタノール処理を施
した。[0028] SWNHs that have been subjected to such ethanol treatment (hereinafter, referred to as SWNHs)
The ethanol-treated SWNHs) were recovered from the solution by evaporating the solvent spontaneously. The same ethanol treatment was applied to MACSORB having an ultra-high specific surface area.
【００２９】エタノール処理ＳＷＮＨｓ、未処理ＳＷＮ
Ｈｓおよびエタノール処理ＭＡＣＳＯＲＢを試料とし、
熱重量分析（ＴＧＡ）を行うことでエタノール吸着量を
測定した。測定にはＴＧＡ２９５０を用い、９９．９９
９９％のＨｅ雰囲気中で、室温〜６００℃の温度範囲を
昇温速度１０℃／ｍｉｎ．で加熱した。Ｈｅガスの流量
は、６０ｍｌ／ｍｉｎ．で一定とした。なお、試料室は
各々の分析前にＨｅガスでパージし、残留酸素の低減を
図った。Ethanol treated SWNHs, untreated SWN
Hs and ethanol-treated MACSORB as a sample,
The amount of ethanol adsorbed was measured by performing thermogravimetric analysis (TGA). TGA2950 was used for the measurement, and 99.99
In a 99% He atmosphere, the temperature range from room temperature to 600 ° C. was increased at a rate of 10 ° C./min. And heated. The flow rate of He gas is 60 ml / min. And was fixed. The sample chamber was purged with He gas before each analysis to reduce residual oxygen.
【００３０】ＴＧＡの結果を、図３に示した。図中のア
ルファベットａ、ｂはそれぞれエタノール処理ＳＷＮＨ
ｓのＴＧＡ曲線とＤＴＧＡ曲線を、ｃはエタノール処理
ＭＡＣＳＯＲＢのＴＧＡ曲線を示している。未処理ＳＷ
ＮＨｓについては、この温度範囲において目立った重量
変化が見られなかったことから図示しなかった。このこ
とから、残留酸素による分析への影響はなかったものと
した。FIG. 3 shows the result of TGA. The alphabets a and b in the figure are ethanol-treated SWNH, respectively.
s shows the TGA curve and DTGA curve, and c shows the TGA curve of ethanol-treated MACSORB. Unprocessed SW
NHs was not shown because no noticeable weight change was observed in this temperature range. From this, it was determined that the residual oxygen had no effect on the analysis.
【００３１】エタノール処理ＳＷＮＨｓの重量の減少は
エタノールの脱離によるものであり、エタノール処理に
よってＳＷＮＨｓに吸着されたエタノール量に一致す
る。このことから、ＳＷＮＨｓのエタノール吸着量は約
２５重量％であった。また、ＴＧＡ曲線およびＤＴＧＡ
曲線から、エタノールの脱離は１００〜５５０℃の範囲
で２段階で連続的に生じていることが分かった。一方の
曲線ｃから、ＭＡＣＳＯＲＢのエタノール吸着量は７重
量％程度であることがわかった。The decrease in the weight of the SWNHs treated with ethanol is due to the desorption of ethanol, which coincides with the amount of ethanol adsorbed on the SWNHs by the ethanol treatment. From this, the ethanol adsorption amount of SWNHs was about 25% by weight. In addition, TGA curve and DTGA
From the curve, it was found that desorption of ethanol occurred continuously in two steps in the range of 100 to 550 ° C. From one curve c, it was found that the amount of ethanol adsorbed on MACSORB was about 7% by weight.
【００３２】以上のことから、この出願の発明のＳＷＮ
Ｈｓ吸着材は、例えば、超高比表面積カーボンよりもエ
タノールの吸着容量が約３．５倍というように、吸着容
量の大きいことが示された。 （実施例２）実施例１の熱重量分析（ＴＧＡ）中に発生
したガスを分析するために、エタノール処理ＳＷＮＨｓ
と未処理ＳＷＮＨｓについて、示差熱質量分析計（ＴＧ
−ＭＳ）によるガス測定を行った。測定は、Ｈｅ／Ｏ2
雰囲気（８０／２０、３０ｍｌ／ｍｉｎ．）で、２５〜
９５０℃の温度範囲で昇温速度１０℃／ｍｉｎ．で行な
った。From the above, the SWN of the invention of this application is
It has been shown that the Hs adsorbent has a larger adsorption capacity, for example, an ethanol adsorption capacity of about 3.5 times that of ultra-high specific surface area carbon. Example 2 In order to analyze the gas generated during the thermogravimetric analysis (TGA) of Example 1, ethanol-treated SWNHs were used.
And untreated SWNHs by differential thermal mass spectrometry (TG
-MS). The measurement was performed using He / O 2
In an atmosphere (80/20, 30 ml / min.), 25-
In a temperature range of 950 ° C., the temperature was raised at a rate of 10 ° C./min. Performed in
【００３３】図４（ａ）に、エタノール処理ＳＷＮＨｓ
（実線）および未処理ＳＷＮＨｓ（点線）からの発生ガ
ス（ＣＯ2）の分析結果を示した。両試料ともに２６０
℃付近からＣＯ2ガスが発生することが確認された。エ
タノール未処理ＳＷＮＨｓに関しては少量のＣＯ2ガス
のみが発生したが、エタノール処理ＳＷＮＨｓに関して
は、ＣＯ2の他に、アセトアルデヒド，Ｈ2Ｏ，ＣＯの発
生が確認された。エタノール処理ＳＷＮＨｓからのＣＯ
2以外の発生ガスの分析結果を図４（ｂ）に示した。ア
セトアルデヒドが約１４０℃で発生しはじめ、続いてＨ
2Ｏ，ＣＯがそれぞれ２６０℃，３００℃で発生したこ
とが分かった。ただし、エタノールは検出されなかっ
た。FIG. 4A shows an ethanol-treated SWNHs.
(Solid line) and analysis results of gas (CO 2 ) generated from untreated SWNHs (dotted line). 260 for both samples
It was confirmed that CO 2 gas was generated from around ℃. Although only a small amount of CO 2 gas was generated for SWNHs not treated with ethanol, generation of acetaldehyde, H 2 O, and CO was confirmed in addition to SW 2 for ethanol-treated SWNHs. CO from ethanol-treated SWNHs
FIG. 4B shows the analysis results of the generated gas other than 2 . Acetaldehyde began to evolve at about 140 ° C., followed by H
It was found that 2 O and CO were generated at 260 ° C. and 300 ° C., respectively. However, ethanol was not detected.
【００３４】エタノール処理ＳＷＮＨｓからエタノール
が検出されなかったことと、他のガス種が検出されたこ
とから、エタノール処理ＳＷＮＨｓからの脱着過程にお
いてエタノールが分解反応を起こしたことが示された。
また、アセトアルデヒドが発生する温度範囲（１４０〜
５６０℃）は、実施例１においてエタノールの脱離が観
察された領域と一致した。このことから、１４０℃から
のエタノール脱離では、ＳＷＮＨｓの触媒作用によりエ
タノールがアセトアルデヒドに分解されて脱離したこと
が示された。No ethanol was detected from the ethanol-treated SWNHs, and other gas species were detected, indicating that ethanol had undergone a decomposition reaction during the desorption process from the ethanol-treated SWNHs.
In addition, the temperature range in which acetaldehyde is generated (140 to
560 ° C.) coincided with the region where the desorption of ethanol was observed in Example 1. From this, it was shown that ethanol was decomposed into acetaldehyde and desorbed by the catalytic action of SWNHs in the desorption of ethanol from 140 ° C.
【００３５】さらに高温側ではエタノールの燃焼が起こ
り、その結果として２６０〜５５０℃の温度範囲におい
てＨ2Ｏが発生し、未処理ＳＷＮＨｓと比較してＣＯ2の
発生量が増加したことが確認された。また、ＣＯの発生
は、アセトアルデヒドがＣＯとＣＨ4に分解してできた
のもであると思われる。Further, it was confirmed that ethanol combustion occurred on the high temperature side, and as a result, H 2 O was generated in a temperature range of 260 to 550 ° C., and the amount of generated CO 2 was increased as compared with untreated SWNHs. Was. It is considered that the generation of CO is also caused by the decomposition of acetaldehyde into CO and CH 4 .
【００３６】このことから、アルコールの酸化反応等に
有用な、ＳＷＮＨｓ触媒が実現されることが示された。 （実施例３）実施例１におけるＳＷＮＨｓおよび他の炭
素材のＯ2雰囲気における熱安定性をＴＧＡ分析により
調べた。炭素材としては、Ｃ60，グラファイト，ダイヤ
モンド，アモルファスカーボン（ａ−Ｃ），気相成長カ
ーボンファイバー（ＶＧＣＦ０７５），活性炭繊維Ａ−
２０（比表面積：１８００ｍ2／ｇ）およびＭＡＣＳＯ
ＲＢ（比表面積：２２９０ｍ2／ｇ）を用いた。その結
果から、図５に、ＳＷＮＨｓと他の炭素材料のＤＴＧＡ
曲線を示した。From this, it was shown that a SWNHs catalyst useful for alcohol oxidation reaction and the like was realized. Example 3 The thermal stability of SWNHs and other carbon materials in Example 1 in an O 2 atmosphere was examined by TGA analysis. Examples of the carbon material include C 60 , graphite, diamond, amorphous carbon (a-C), vapor-grown carbon fiber (VGCF075), and activated carbon fiber A-.
20 (specific surface area: 1800 m 2 / g) and MACSO
RB (specific surface area: 2290 m 2 / g) was used. From the results, FIG. 5 shows DTGA of SWNHs and other carbon materials.
The curves are shown.
【００３７】ＳＷＮＨｓの酸化は３００℃付近から徐々
に始まり、６２０℃付近でピークとなり、７２０℃で終
了することがわかった。他の炭素材料と比較して、ＳＷ
ＮＨｓの熱安定性は、ＶＧＣＦ０７、グラファイトおよ
びダイヤモンドには劣っていた。しかしながら、６１０
℃以下で完全に燃焼するＣ60、ａ―Ｃや２種の活性炭；
Ａ−２０およびＭＡＣＳＯＲＢよりは安定していた。ま
た、これらの材料よりも、３５０〜５５０℃の温度範囲
でのＳＷＮＨｓの酸化速度が低いことが注目された。す
なわち、ＳＷＮＨｓは、３５０〜５５０℃の温度範囲
で、Ｃ60、ａ―Ｃ、Ａ−２０およびＭＡＣＳＯＲＢ等の
材料よりも高い酸化抵抗特性を有することがわかった。It was found that the oxidation of SWNHs started gradually at around 300 ° C., peaked at around 620 ° C., and ended at 720 ° C. SW compared to other carbon materials
The thermal stability of NHs was inferior to VGCF07, graphite and diamond. However, 610
C 60 , aC and two types of activated carbon that burn completely below ℃;
More stable than A-20 and MACSORB. In addition, attention was paid to the fact that SWNHs has a lower oxidation rate in the temperature range of 350 to 550 ° C. than these materials. That, SWNHs is in the temperature range of 350~550 ℃, C 60, a- C, was found to have high oxidation resistance characteristics than the material, such as A-20 and Macsorb.
【００３８】以上のことから、ＳＷＮＨｓの酸素雰囲気
中における熱安定性は高く、Ｃ60、ａ―Ｃ、２種の活性
炭と比較して３００〜３５０℃の温度範囲で高酸化抵抗
を示すことはＳＷＮＨｓ自体に付加的な価値を与え、単
層カーボンナノホーンからなる吸着材、触媒および触媒
担体が広い範囲で利用できることが示された。From the above, it can be seen that SWNHs has high thermal stability in an oxygen atmosphere and exhibits high oxidation resistance in the temperature range of 300 to 350 ° C. as compared with C 60 , aC, and two types of activated carbon. The SWNHs themselves provide additional value and show that adsorbents, catalysts and catalyst supports consisting of single-walled carbon nanohorns can be used in a wide range.
【００３９】もちろん、この発明は以上の例に限定され
るものではなく、細部については様々な態様が可能であ
ることは言うまでもない。Of course, the present invention is not limited to the above-described example, and it goes without saying that various aspects of the details are possible.
【００４０】[0040]
【発明の効果】以上詳しく説明した通り、この発明によ
って、ＳＷＮＨｓの構造を基本とし、これまで未知の新
しい機能材として、活性化処理が不要で、吸着容量の極
めて大きな単層カーボンナノホーンの吸着材と、単層カ
ーボンナノホーンの触媒および触媒担体が提供される。As described above in detail, according to the present invention, as a new functional material based on the structure of SWNHs, an activation material is unnecessary and an adsorption material for a single-walled carbon nanohorn having an extremely large adsorption capacity is known as a new functional material. And a single-walled carbon nanohorn catalyst and catalyst carrier.
【図１】ＳＷＮＨｓのＴＥＭ像を例示した図である。
（ａ）ＳＷＮＨｓは、直径が８０ｎｍ程度でほぼ均一な
大きさの球状体である。（ｂ）それぞれのＳＷＮＨｓ
は、管状のＳＷＮＨが球状に集合して構成されている。
（ｃ）ＳＷＮＨｓの表面部には、２０ｎｍ程度の長さの
円錐状の突出物が複数認められる。FIG. 1 is a diagram illustrating a TEM image of SWNHs.
(A) SWNHs are spherical bodies having a diameter of about 80 nm and a substantially uniform size. (B) Each SWNHs
Is composed of tubular SWNHs aggregated in a spherical shape.
(C) A plurality of conical protrusions having a length of about 20 nm are observed on the surface of SWNHs.
【図２】集合体表面に突出しているホーン間の空間に吸
着されたエタノール分子（小さい点群）の様子を例示し
た模式図である。（縮尺等は正確ではない。）FIG. 2 is a schematic view illustrating the state of ethanol molecules (small point group) adsorbed in a space between horns protruding from the surface of the aggregate. (The scale is not accurate.)
【図３】ＴＧＡ分析の結果を例示した図であり、ａ，ｂ
はエタノール処理したＳＷＮＨｓのＴＧＡ曲線とＤＴＧ
Ａ曲線を、また、ｃはエタノール処理したＭＡＣＳＯＲ
ＢのＴＧＡ曲線を示している。FIG. 3 is a diagram exemplifying the results of TGA analysis, wherein a, b
Is the TGA curve and DTG of SWNHs treated with ethanol.
A curve, and c is the MACSOR treated with ethanol.
4 shows the TGA curve of B.
【図４】示差熱質量分析の結果を例示した図であり、
（ａ）は未処理ＳＷＮＨｓおよびエタノール処理ＳＷＮ
ＨｓからのＣＯ2の発生濃度曲線を、（ｂ）はエタノー
ル処理ＳＷＮＨｓからのエタノール、アセトアルデヒ
ド、ＣＯおよびＨ2Ｏの発生濃度曲線を示している。FIG. 4 is a diagram illustrating a result of differential thermal mass spectrometry,
(A) Untreated SWNHs and ethanol-treated SWN
The generation density curve of CO 2 from hs, (b) shows ethanol from ethanol treatment SWNHs, acetaldehyde, the generation density curves of CO and H 2 O.
【図５】酸素雰囲気中のＳＷＮＨｓおよび各種カーボン
材料のＤＴＧＡ曲線を例示した図である。FIG. 5 is a diagram illustrating DTGA curves of SWNHs and various carbon materials in an oxygen atmosphere.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 湯田坂 雅子 茨城県つくば市並木３−17−１ ロイヤル コーポヨコタ503 (72)発明者 小海 文夫 茨城県つくば市梅園２−14−27 (72)発明者 高橋 邦充 千葉県野田市七光台344−１ ファミール 野田514 (72)発明者 ジェイムズ アデレーネ ニーシャ 茨城県つくば市御幸が丘34 ＮＥＣ筑波研 究所内 Ｆターム(参考） 4G046 CB01 CB08 4G066 AA04A AA04B AE19B BA21 BA36 CA01 CA20 CA27 CA28 CA35 CA37 CA51 CA52 CA56 DA02 DA08 FA40 GA01 GA06 4G069 AA01 AA03 AA11 BA08A BA08B CB07 CB19 EA03X EA03Y EA04X EA04Y ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masako Yudasaka 3-17-1 Namiki, Tsukuba, Ibaraki Prefecture Royal Corpo Yokota 503 (72) Inventor Fumio Koumi 2-14-27, Umezono, Tsukuba, Ibaraki Prefecture (72) Inventor Kunimitsu Takahashi 344-1 Nankodai, Noda-shi, Chiba Prefecture 514 Famiel Noda 514 (72) Inventor James Adelene Nisha 34 Miyukigaoka, Tsukuba-shi, Ibaraki Pref. CA27 CA28 CA35 CA37 CA51 CA52 CA56 DA02 DA08 FA40 GA01 GA06 4G069 AA01 AA03 AA11 BA08A BA08B CB07 CB19 EA03X EA03Y EA04X EA04Y
Claims (4)
てなる単層カーボンナノホーン集合体であって、近接す
る単層カーボンナノホーンの円錐部により形成される空
間に被吸着物を吸着することを特徴とする単層カーボン
ナノホーン吸着材。1. A single-walled carbon nanohorn aggregate in which single-walled carbon nanohorns are aggregated in a spherical shape, wherein a substance to be adsorbed is adsorbed to a space formed by a conical portion of adjacent single-walled carbon nanohorns. Single-layer carbon nanohorn adsorbent.
関連物質のいずれか１種または２種以上であることを特
徴とする請求項１記載の単層カーボンナノホーン吸着
材。2. The single-walled carbon nanohorn adsorbent according to claim 1, wherein the substance to be adsorbed is one or more of a gas, an organic substance, a complex, and a biological substance.
てなる単層カーボンナノホーン集合体を液相反応におけ
る酸化触媒とすることを特徴とする単層カーボンナノホ
ーン触媒。3. A single-walled carbon nanohorn catalyst comprising a single-walled carbon nanohorn aggregate formed by spherically assembling single-walled carbon nanohorns as an oxidation catalyst in a liquid phase reaction.
てなる単層カーボンナノホーン集合体の表面に金属触媒
を担持させること特徴とする単層カーボンナノホーン触
媒担体。4. A single-walled carbon nanohorn catalyst carrier, wherein a metal catalyst is supported on the surface of a single-walled carbon nanohorn aggregate in which single-walled carbon nanohorns are aggregated in a spherical shape.
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