JP6135166B2 - Redox catalyst, electrode material, electrode, solar cell, fuel cell, and nitrogen oxide removal catalyst - Google Patents
Redox catalyst, electrode material, electrode, solar cell, fuel cell, and nitrogen oxide removal catalyst Download PDFInfo
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- JP6135166B2 JP6135166B2 JP2013025111A JP2013025111A JP6135166B2 JP 6135166 B2 JP6135166 B2 JP 6135166B2 JP 2013025111 A JP2013025111 A JP 2013025111A JP 2013025111 A JP2013025111 A JP 2013025111A JP 6135166 B2 JP6135166 B2 JP 6135166B2
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- catalyst
- electrode
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- carbon nanotube
- solar cell
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Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
本発明は、電極用触媒や窒素酸化物除去触媒として有用な酸化還元触媒、この酸化還元触媒を含有する電極材料、この電極材料を用いて得られる電極、この電極を備える太陽電池および燃料電池、前記酸化還元触媒を含有する窒素酸化物除去触媒に関する。 The present invention relates to a redox catalyst useful as an electrode catalyst or a nitrogen oxide removal catalyst, an electrode material containing the redox catalyst, an electrode obtained using the electrode material, a solar cell and a fuel cell including the electrode, The present invention relates to a nitrogen oxide removing catalyst containing the redox catalyst.
近年、炭素系触媒担体の表面に金属粒子が担持されてなる酸化還元触媒が提案されている。
例えば、特許文献１には、炭素系触媒担体とこの炭素系触媒担体の表面に吸着された金属粒子層とを含む触媒、この触媒を含む電極、及びこの電極を備える燃料電池等が記載されている。
In recent years, a redox catalyst in which metal particles are supported on the surface of a carbon-based catalyst carrier has been proposed.
For example,
従来から、酸化還元触媒は、燃料電池等の電極用触媒や、窒素酸化物除去触媒として用いられてきたが、近年においては、酸化還元触媒のさらなる高性能化を図り、近年のエネルギー問題や環境問題を解決することが要望されてきている。 Conventionally, oxidation-reduction catalysts have been used as catalysts for electrodes of fuel cells and the like, and nitrogen oxide removal catalysts. However, in recent years, further improvement in performance of oxidation-reduction catalysts has led to recent energy problems and environmental problems. There is a desire to solve the problem.
本発明は、かかる実情に鑑みてなされたものであり、電極用触媒や窒素酸化物除去触媒として有用な酸化還元触媒、この酸化還元触媒を電極用触媒として含有する電極材料、この電極材料を用いて得られる電極、この電極を備える太陽電池および燃料電池、前記酸化還元触媒を含有する窒素酸化物除去触媒を提供することを目的とする。 The present invention has been made in view of such circumstances, and is a redox catalyst useful as an electrode catalyst or a nitrogen oxide removal catalyst, an electrode material containing this redox catalyst as an electrode catalyst, and using this electrode material It is an object to provide an electrode obtained in this manner, a solar cell and a fuel cell including this electrode, and a nitrogen oxide removal catalyst containing the oxidation-reduction catalyst.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた。その結果、平均直径（Ａｖ）と直径の標準偏差（σ）とが特定の関係にあるカーボンナノチューブに金属ナノ粒子が担持されてなる酸化還元触媒が、電極用触媒や窒素酸化物除去触媒として有用であることを見出し、本発明を完成するに到った。 The present inventors have intensively studied to solve the above problems. As a result, a redox catalyst in which metal nanoparticles are supported on carbon nanotubes having a specific relationship between the average diameter (Av) and the standard deviation (σ) in diameter is useful as an electrode catalyst or a nitrogen oxide removal catalyst. As a result, the present invention has been completed.
かくして本発明によれば、下記（１）〜（３）の酸化還元触媒、（４）の電極材料、（５）の電極、（６）の太陽電池、（７）の燃料電池、及び（８）の窒素酸化物除去触媒が提供される。
（１）カーボンナノチューブに金属ナノ粒子が担持されてなるものであって、前記カーボンナノチューブが、その平均直径（Ａｖ）と直径の標準偏差（σ）が、関係式：０．６０＞３σ／Ａｖ＞０．２０を満たすものであることを特徴とする酸化還元触媒。
（２）金属ナノ粒子が、平均粒径が０．５〜１５ｎｍ、粒径の標準偏差が１．５ｎｍ以下のものである、（１）に記載の酸化還元触媒。
（３）金属ナノ粒子の担持量が、カーボンナノチューブ１００質量部あたり１〜３０，０００質量部である、（１）または（２）に記載の酸化還元触媒。
（４）前記（１）〜（３）のいずれかに記載の酸化還元触媒を電極用触媒として含有する電極材料。
（５）前記（４）に記載の電極材料を用いて得られる電極。
（６）前記（５）に記載の電極を備える太陽電池。
（７）前記（５）に記載の電極を備える燃料電池。
（８）前記（１）〜（３）のいずれかに記載の酸化還元触媒を含有する窒素酸化物除去触媒。
Thus, according to the present invention, the following redox catalysts (1) to (3), an electrode material (4), an electrode (5), a solar cell (6), a fuel cell (7), and (8) ) Nitrogen oxide removal catalyst.
(1) A metal nanoparticle is supported on a carbon nanotube, and the carbon nanotube has an average diameter (Av) and a standard deviation (σ) of the diameter: relational expression: 0.60> 3σ / Av A redox catalyst characterized by satisfying> 0.20.
(2) The redox catalyst according to (1), wherein the metal nanoparticles have an average particle diameter of 0.5 to 15 nm and a standard deviation of the particle diameter of 1.5 nm or less.
(3) The oxidation-reduction catalyst according to (1) or (2), wherein the supported amount of metal nanoparticles is 1 to 30,000 parts by mass per 100 parts by mass of the carbon nanotubes.
(4) An electrode material containing the redox catalyst according to any one of (1) to (3) as an electrode catalyst.
(5) An electrode obtained using the electrode material according to (4).
(6) A solar cell comprising the electrode according to (5).
(7) A fuel cell comprising the electrode according to (5).
(8) A nitrogen oxide removal catalyst containing the oxidation-reduction catalyst according to any one of (1) to (3).
本発明によれば、電極用触媒や窒素酸化物除去触媒として有用な酸化還元触媒、この酸化還元触媒を電極用触媒として含有する電極材料、この電極材料を用いて得られる電極、この電極を備える太陽電池および燃料電池、前記酸化還元触媒を含有する窒素酸化物除去触媒が提供される。 According to the present invention, a redox catalyst useful as an electrode catalyst or a nitrogen oxide removal catalyst, an electrode material containing the redox catalyst as an electrode catalyst, an electrode obtained using the electrode material, and the electrode are provided. A solar cell, a fuel cell, and a nitrogen oxide removal catalyst containing the oxidation-reduction catalyst are provided.
以下、本発明を、１）酸化還元触媒、２）電極材料及び電極、並びに、３）太陽電池、燃料電池、及び窒素酸化物除去触媒、に項分けして詳細に説明する。 Hereinafter, the present invention will be described in detail by dividing it into 1) a redox catalyst, 2) an electrode material and an electrode, and 3) a solar cell, a fuel cell, and a nitrogen oxide removal catalyst.
１）酸化還元触媒
本発明の酸化還元触媒は、カーボンナノチューブに金属ナノ粒子が担持されてなるものであって、前記カーボンナノチューブが、その平均直径（Ａｖ）と直径の標準偏差（σ）が、関係式：０．６０＞３σ／Ａｖ＞０．２０を満たすものであることを特徴とする。
以下、上記関係式を満たすカーボンナノチューブを「カーボンナノチューブ（Ａ）」ということがある。
1) Redox catalyst The redox catalyst of the present invention is formed by supporting metal nanoparticles on carbon nanotubes, and the carbon nanotubes have an average diameter (Av) and a standard deviation (σ) in diameter, It is characterized by satisfying the relational expression: 0.60> 3σ / Av> 0.20.
Hereinafter, a carbon nanotube satisfying the above relational expression may be referred to as “carbon nanotube (A)”.
〔カーボンナノチューブ（Ａ）〕
本発明に用いるカーボンナノチューブ（Ａ）は、その平均直径（Ａｖ）と直径の標準偏差（σ）が、関係式：０．６０＞３σ／Ａｖ＞０．２０を満たすものである。
なお、本発明において、「カーボンナノチューブ（Ａ）」とは、それを構成する所定のカーボンナノチューブの集合の総称であり、「直径」とは当該所定のカーボンナノチューブの外径を意味する。
[Carbon nanotube (A)]
The carbon nanotube (A) used in the present invention has an average diameter (Av) and a standard deviation (σ) of the diameter satisfying a relational expression: 0.60> 3σ / Av> 0.20.
In the present invention, “carbon nanotube (A)” is a general term for a set of predetermined carbon nanotubes constituting the carbon nanotube, and “diameter” means an outer diameter of the predetermined carbon nanotube.
本発明においてカーボンナノチューブ（Ａ）の平均直径（Ａｖ）及び直径の標準偏差（σ）は、それぞれ標本平均値及び標本標準偏差である。それらは、透過型電子顕微鏡での観察下に、無作為に選択されたカーボンナノチューブ１００本の直径を測定した際の平均値及び標準偏差として求められる。前記関係式における３σは得られた標準偏差（σ）に３を乗じたものである。
平均直径（Ａｖ）と標準偏差（σ）とが、関係式：０．６０＞３σ／Ａｖ＞０．２０を満たすカーボンナノチューブ（Ａ）を用いることにより、優れた触媒活性を有する酸化還元触媒を得ることができる。
In the present invention, the average diameter (Av) and the standard deviation (σ) of the diameter of the carbon nanotube (A) are a sample average value and a sample standard deviation, respectively. They are obtained as an average value and a standard deviation when measuring the diameter of 100 randomly selected carbon nanotubes under observation with a transmission electron microscope. In the above relational expression, 3σ is obtained by multiplying the obtained standard deviation (σ) by 3.
By using the carbon nanotube (A) in which the average diameter (Av) and the standard deviation (σ) satisfy the relational expression: 0.60> 3σ / Av> 0.20, a redox catalyst having excellent catalytic activity is obtained. Can be obtained.
ここで、３σ／Ａｖは、カーボンナノチューブ（Ａ）の直径分布を表し、この値が大きいほど直径分布が広いことを意味する。本発明において直径分布は正規分布をとるものが好ましい。 Here, 3σ / Av represents the diameter distribution of the carbon nanotube (A), and the larger the value, the wider the diameter distribution. In the present invention, the diameter distribution is preferably a normal distribution.
カーボンナノチューブ（Ａ）の直径分布は、透過型電子顕微鏡を用いて観察して算出することができる。すなわち、透過型電子顕微鏡での観察下に、無作為に選択された１００本のカーボンナノチューブの直径を測定し、その結果を用いて、横軸に直径、縦軸に頻度を取り、得られたデータをプロットし、ガウシアンで近似することで得られる。異なる製法で得られたカーボンナノチューブなどを複数種類組み合わせることでも３σ／Ａｖの値を大きくすることはできるが、その場合正規分布の直径分布を得ることは難しい。本発明においてカーボンナノチューブ（Ａ）は、単一製法で得られたカーボンナノチューブからなるものであっても、又は当該カーボンナノチューブに、その直径分布に影響しない量の他の製法で得られたカーボンナノチューブを配合してなるものであってもよい。 The diameter distribution of the carbon nanotube (A) can be calculated by observing with a transmission electron microscope. That is, under observation with a transmission electron microscope, the diameter of 100 randomly selected carbon nanotubes was measured, and the results were used to obtain the diameter on the horizontal axis and the frequency on the vertical axis. It is obtained by plotting the data and approximating with Gaussian. The value of 3σ / Av can also be increased by combining a plurality of types of carbon nanotubes obtained by different production methods, but in this case, it is difficult to obtain a normal distribution of diameters. In the present invention, the carbon nanotube (A) is composed of carbon nanotubes obtained by a single production method, or carbon nanotubes obtained by another production method in an amount that does not affect the diameter distribution of the carbon nanotubes. May be blended.
カーボンナノチューブ（Ａ）の平均直径（Ａｖ）は、目的の性能を有する酸化還元触媒を得る観点から、０．５ｎｍ以上、１５ｎｍ以下が好ましい。 The average diameter (Av) of the carbon nanotubes (A) is preferably 0.5 nm or more and 15 nm or less from the viewpoint of obtaining a redox catalyst having target performance.
カーボンナノチューブ（Ａ）の平均長さは、好ましくは０．１μｍ〜１ｃｍである。カーボンナノチューブ（Ａ）の平均長さが上記範囲内であることで、優れた触媒活性を有する酸化還元触媒を形成し易くなる。
カーボンナノチューブ（Ａ）の平均長さは、例えば、透過型電子顕微鏡を用いて、無作為に選択された１００本のカーボンナノチューブを測定することで、算出することができる。
The average length of the carbon nanotube (A) is preferably 0.1 μm to 1 cm. When the average length of the carbon nanotube (A) is within the above range, a redox catalyst having excellent catalytic activity can be easily formed.
The average length of the carbon nanotube (A) can be calculated, for example, by measuring 100 randomly selected carbon nanotubes using a transmission electron microscope.
カーボンナノチューブ（Ａ）の比表面積は、好ましくは１００〜２５００ｍ２／ｇである。カーボンナノチューブ（Ａ）の比表面積が上記範囲内であることで、優れた触媒活性を有する酸化還元触媒を形成し易くなる。
カーボンナノチューブ（Ａ）の比表面積は、窒素ガス吸着法により求めることができる。
The specific surface area of the carbon nanotube (A) is preferably 100 to 2500 m 2 / g. When the specific surface area of the carbon nanotube (A) is within the above range, it becomes easy to form a redox catalyst having excellent catalytic activity.
The specific surface area of the carbon nanotube (A) can be determined by a nitrogen gas adsorption method.
カーボンナノチューブ（Ａ）を構成するカーボンナノチューブは、単層のものであっても、多層のものであってもよい。 The carbon nanotubes constituting the carbon nanotube (A) may be single-walled or multi-layered.
また、カーボンナノチューブ（Ａ）を構成するカーボンナノチューブは、表面にカルボキシル基等の官能基が導入されたものであってもよい。官能基の導入は、過酸化水素や硝酸等を用いる公知の酸化処理法により行うことができる。 Moreover, the carbon nanotube which comprises a carbon nanotube (A) may have a functional group such as a carboxyl group introduced on its surface. The functional group can be introduced by a known oxidation treatment method using hydrogen peroxide, nitric acid or the like.
カーボンナノチューブ（Ａ）は、公知の方法、例えば、表面にカーボンナノチューブ製造用触媒層（以下、「ＣＮＴ製造用触媒層」ということがある。）を有する基材（以下、「ＣＮＴ製造用基材」ということがある。）上に、原料化合物及びキャリアガスを供給して、化学的気相成長法（ＣＶＤ法）によりカーボンナノチューブを合成する際に、系内に微量の酸化剤を存在させることで、ＣＮＴ製造用触媒層の触媒活性を飛躍的に向上させるという方法（スーパーグロース法）により、得ることができる（ＷＯ２００６／０１１６５５号パンフレット）。 The carbon nanotube (A) is a known method, for example, a substrate having a catalyst layer for producing carbon nanotubes (hereinafter sometimes referred to as a “CNT producing catalyst layer”) on the surface (hereinafter, referred to as “CNT producing substrate”). In addition, when a raw material compound and a carrier gas are supplied and carbon nanotubes are synthesized by chemical vapor deposition (CVD), a small amount of oxidant is present in the system. Thus, it can be obtained by a method (super growth method) of dramatically improving the catalytic activity of the catalyst layer for CNT production (WO 2006/011655 pamphlet).
ＣＮＴ製造用基材においてＣＮＴ製造用触媒層を支持するための支持体は、その表面にＣＮＴ製造用触媒層を担持することができるものであれば、特に限定されない。
前記支持体の材質としては、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、白金等の金属；これらの金属を含む合金；前記金属を含む酸化物；シリコン等の半導体；石英、ガラス、マイカ、グラファイト、ダイヤモンド等の非金属；等が挙げられる。
前記支持体の形状としては、平板状、薄膜状、ブロック状等が挙げられる。
The support for supporting the CNT production catalyst layer in the CNT production substrate is not particularly limited as long as it can carry the CNT production catalyst layer on the surface thereof.
Examples of the material of the support include metals such as iron, nickel, chromium, molybdenum, tungsten, titanium, aluminum, manganese, cobalt, copper, silver, gold, and platinum; alloys containing these metals; oxides containing the metals A semiconductor such as silicon; a non-metal such as quartz, glass, mica, graphite, diamond; and the like.
Examples of the shape of the support include a flat plate shape, a thin film shape, and a block shape.
ＣＮＴ製造用触媒層を構成する触媒としては、従来公知のカーボンナノチューブ製造用触媒を用いることができる。具体的には、塩化鉄、鉄、鉄−モリブデン、アルミナ−鉄、アルミナ−コバルト、アルミナ−鉄−モリブデン等の金属触媒が挙げられる。 A conventionally known carbon nanotube production catalyst can be used as the catalyst constituting the CNT production catalyst layer. Specific examples include metal catalysts such as iron chloride, iron, iron-molybdenum, alumina-iron, alumina-cobalt, and alumina-iron-molybdenum.
原料化合物としては、メタン、エタン、プロパン、エチレン、プロピレン、アセチレン等の炭化水素化合物；メタノール、エタノール等のアルコール化合物；アセトン等のケトン化合物；一酸化炭素；等が挙げられる。 Examples of the raw material compound include hydrocarbon compounds such as methane, ethane, propane, ethylene, propylene, and acetylene; alcohol compounds such as methanol and ethanol; ketone compounds such as acetone; carbon monoxide;
キャリアガスとしては、ヘリウム、アルゴン、水素、窒素、ネオン、クリプトン、二酸化炭素、塩素等が挙げられる。
酸化剤としては、水蒸気、酸素、オゾン、硫化水素等が挙げられる。気相中の酸化剤の含有量は、通常、１０ｐｐｍ以上１００００ｐｐｍ以下である。
Examples of the carrier gas include helium, argon, hydrogen, nitrogen, neon, krypton, carbon dioxide, and chlorine.
Examples of the oxidizing agent include water vapor, oxygen, ozone, hydrogen sulfide and the like. The content of the oxidizing agent in the gas phase is usually 10 ppm or more and 10,000 ppm or less.
反応系内の圧力は、好ましくは１０２Ｐａ〜１０７Ｐａ（１００大気圧）である。
カーボンナノチューブ（Ａ）の製造時の反応系内の温度は、触媒、原料化合物、酸化剤に応じて適宜決定することができる。通常は、４００〜１２００℃である。
The pressure in the reaction system is preferably 10 2 Pa to 10 7 Pa (100 atmospheric pressure).
The temperature in the reaction system during the production of the carbon nanotube (A) can be appropriately determined according to the catalyst, the raw material compound, and the oxidizing agent. Usually, it is 400-1200 degreeC.
〔金属ナノ粒子〕
本発明に用いる金属ナノ粒子は、ナノメートルオーダーの粒子径を有する金属粒子である。
金属ナノ粒子の平均粒径は、好ましくは０．５〜１５ｎｍであり、粒径の標準偏差は、好ましくは１．５ｎｍ以下である。
金属ナノ粒子の平均粒径と粒径の標準偏差が上記範囲内であることで、より優れた性能を有する酸化還元触媒が得られ易くなる。
[Metal nanoparticles]
The metal nanoparticles used in the present invention are metal particles having a particle size on the order of nanometers.
The average particle diameter of the metal nanoparticles is preferably 0.5 to 15 nm, and the standard deviation of the particle diameter is preferably 1.5 nm or less.
When the average particle diameter of the metal nanoparticles and the standard deviation of the particle diameter are within the above ranges, a redox catalyst having better performance can be easily obtained.
金属ナノ粒子としては、周期律表第６族〜第１４族の金属のナノ粒子が挙げられる。
周期律表第６族〜第１４族の金属としては、Ｃｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａ、Ｒｕ、Ｒｈ、Ｐｄ、Ａｇ、Ｃｄ、Ｓｎ、Ｓｂ、Ｗ、Ｒｅ、Ｉｒ、Ｐｔ、Ａｕ、Ｐｂ等が挙げられる。なかでも、汎用性の高い酸化還元触媒が得られることから、Ｆｅ、Ｃｏ、Ｎｉ、Ａｇ、Ｗ、Ｒｕ、Ｐｔ、Ａｕ、Ｐｄが好ましい。
上記金属は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
Examples of the metal nanoparticles include metal nanoparticles of Groups 6 to 14 of the periodic table.
The metals in Groups 6 to 14 of the periodic table include Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Ag, Cd, Sn, Sb, W, Re, Ir , Pt, Au, Pb and the like. Among these, Fe, Co, Ni, Ag, W, Ru, Pt, Au, and Pd are preferable because a highly versatile oxidation-reduction catalyst can be obtained.
The said metal can be used individually by 1 type or in combination of 2 or more types.
〔酸化還元触媒〕
本発明の酸化還元触媒は、カーボンナノチューブ（Ａ）に金属ナノ粒子が担持されてなるものである。
[Redox catalyst]
The oxidation-reduction catalyst of the present invention is obtained by supporting metal nanoparticles on carbon nanotubes (A).
本発明の酸化還元触媒においては、金属ナノ粒子の担持量は特に限定されないが、カーボンナノチューブ（Ａ）１００質量部あたり、１質量部以上が好ましい。金属ナノ粒子の担持量が１質量部以上であることで、より優れた触媒活性を有する酸化還元触媒が得られる。金属ナノ粒子の担持量は多ければ多いほど触媒活性は高くなると考えられるが、カーボンナノチューブ（Ａ）の担持能や経済性を考慮すれば、金属ナノ粒子の担持量の上限は、カーボンナノチューブ（Ａ）１００質量部あたり、通常、３０，０００質量部以下である。 In the oxidation-reduction catalyst of the present invention, the amount of metal nanoparticles supported is not particularly limited, but is preferably 1 part by mass or more per 100 parts by mass of the carbon nanotube (A). When the supported amount of the metal nanoparticles is 1 part by mass or more, a redox catalyst having more excellent catalytic activity can be obtained. Although it is considered that the greater the amount of supported metal nanoparticles, the higher the catalytic activity. However, considering the supporting ability and economic efficiency of carbon nanotubes (A), the upper limit of the supported amount of metal nanoparticles is carbon nanotubes (A ) It is usually 30,000 parts by mass or less per 100 parts by mass.
金属ナノ粒子をカーボンナノチューブに担持させる方法は特に限定されない。例えば、カーボンナノチューブ（Ａ）の存在下で、金属前駆体を還元して金属ナノ粒子を生成させる公知の方法を利用して、金属ナノ粒子をカーボンナノチューブに担持させることができる。
具体的には、水、カーボンナノチューブ（Ａ）、及び分散剤を含有する分散液を調製し、次いで金属前駆体を添加後、溶媒を留去し、さらに水素気流下に加熱して金属前駆体を還元することで、生成した金属ナノ粒子がカーボンナノチューブ（Ａ）に担持されてなる金属ナノ粒子担持体を効率よく得ることができる。
The method for supporting the metal nanoparticles on the carbon nanotube is not particularly limited. For example, in the presence of the carbon nanotube (A), the metal nanoparticle can be supported on the carbon nanotube by using a known method of reducing the metal precursor to generate the metal nanoparticle.
Specifically, a dispersion containing water, carbon nanotubes (A), and a dispersant is prepared, and after adding a metal precursor, the solvent is distilled off, and the metal precursor is further heated under a hydrogen stream. By reducing the above, it is possible to efficiently obtain a metal nanoparticle carrier in which the generated metal nanoparticles are supported on the carbon nanotubes (A).
前記分散液に使用される分散剤としては、カーボンナノチューブ（Ａ）の分散能があれば、低分子、高分子を問わないが、分散性や分散安定性に優れることから高分子であるのが好ましい。高分子の種類としては、合成高分子であっても天然高分子であってもよい。カーボンナノチューブ（Ａ）の分散性に優れることから、イオン性高分子が好ましい。当該イオン性高分子としては、スルホン酸やカルボン酸などのイオン性官能基を持つものが好ましく、中でも、ポリスチレンスルホン酸、コンドロイチン硫酸、ヒアルロン酸、カルボキシメチルセルロースおよびそれらの誘導体がより好ましく、カルボキシメチルセルロースおよびその誘導体が特に好ましい。
低分子からなる分散剤としては、例えば、陽イオン性界面活性剤、両イオン性界面活性剤、陰イオン性界面活性剤、非イオン性界面活性剤、オリゴ糖、およびステロイド誘導体などが挙げられる。
これらの分散剤は、それぞれ単独で、または２種以上を混合して用いることができる。
The dispersant used in the dispersion is not particularly limited as long as it has the ability to disperse the carbon nanotubes (A), but it is a polymer because of its excellent dispersibility and dispersion stability. preferable. The type of polymer may be a synthetic polymer or a natural polymer. Since the dispersibility of the carbon nanotube (A) is excellent, an ionic polymer is preferable. As the ionic polymer, those having an ionic functional group such as sulfonic acid and carboxylic acid are preferable, and among them, polystyrene sulfonic acid, chondroitin sulfate, hyaluronic acid, carboxymethyl cellulose and derivatives thereof are more preferable, carboxymethyl cellulose and Its derivatives are particularly preferred.
Examples of the low molecular weight dispersant include a cationic surfactant, an amphoteric surfactant, an anionic surfactant, a nonionic surfactant, an oligosaccharide, and a steroid derivative.
These dispersants can be used alone or in admixture of two or more.
前記分散液は、本発明の効果を妨げない範囲において、さらに、その他の成分を含有してもよい。その他の成分としては、結着剤や導電助剤などが挙げられる。これらは、公知のものを適宜使用すればよい。 The dispersion may further contain other components as long as the effects of the present invention are not hindered. Examples of other components include a binder and a conductive aid. These may be appropriately known ones.
前記分散液は、溶媒全体の５０質量％以上が水であるのが好ましく、親水性有機溶媒を含有するものであってもよい。
親水性有機溶媒としては、メチルアルコール、エチルアルコール、プロピルアルコール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；テトラヒドロフラン、ジオキサン、ジグライム等のエーテル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン等のアミド類；ジメチルスルホキシド、スルホラン等の含イオウ系溶媒；等が挙げられる。これらの溶媒は１種単独で、あるいは２種以上を組み合わせて用いることができる。
In the dispersion, 50% by mass or more of the entire solvent is preferably water, and may contain a hydrophilic organic solvent.
Examples of hydrophilic organic solvents include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; N, N-dimethylformamide and N, N-dimethyl. And amides such as acetamide, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; and the like. These solvents can be used alone or in combination of two or more.
前記分散液は、カーボンナノチューブ（Ａ）、分散剤および所望によりその他の成分を、水または水含有混合溶媒中で混合し、カーボンナノチューブ（Ａ）を分散させることで得ることができる。 The dispersion can be obtained by dispersing the carbon nanotubes (A) by mixing the carbon nanotubes (A), a dispersant, and optionally other components in water or a water-containing mixed solvent.
混合処理や分散処理は、公知の方法を利用することができる。例えば、ナノマイザー、アルティマイザー、超音波分散機、ボールミル、サンドグラインダー、ダイノミル、スパイクミル、ＤＣＰミル、バスケットミル、ペイントコンディショナー、高速攪拌装置等を用いる方法が挙げられる。 A known method can be used for the mixing process and the dispersion process. Examples thereof include a method using a nanomizer, an optimizer, an ultrasonic disperser, a ball mill, a sand grinder, a dyno mill, a spike mill, a DCP mill, a basket mill, a paint conditioner, a high-speed stirring device, and the like.
カーボンナノチューブ（Ａ）の含有量は、特に限定されないが、分散液全体中、好ましくは０．００１〜１０質量％である。
カーボンナノチューブ（Ａ）の含有量を上記範囲内にすることで、カーボンナノチューブ（Ａ）が高分散された分散液を効率よく調製することができる。
Although content of a carbon nanotube (A) is not specifically limited, Preferably it is 0.001-10 mass% in the whole dispersion liquid.
By setting the content of the carbon nanotube (A) within the above range, a dispersion in which the carbon nanotube (A) is highly dispersed can be efficiently prepared.
分散剤の含有量は、カーボンナノチューブ（Ａ）１００質量部に対して、好ましくは２０〜２５０質量部である。分散剤の含有量を上記範囲内にすることで、カーボンナノチューブ（Ａ）が高分散された分散液を効率よく調製することができる。 The content of the dispersant is preferably 20 to 250 parts by mass with respect to 100 parts by mass of the carbon nanotube (A). By setting the content of the dispersant within the above range, a dispersion in which the carbon nanotubes (A) are highly dispersed can be efficiently prepared.
前記金属前駆体は、還元反応により金属ナノ粒子を形成し得る化合物である。金属前駆体は、目的の金属ナノ粒子が得られ、かつ、用いる溶媒に溶解するものであれば、特に限定されない。
金属前駆体としては、周期律表第６族〜第１４族の金属の塩や錯体が挙げられる。
金属前駆体を構成する配位子等としては、水、一酸化炭素、塩化物イオン、水酸化物イオン、硝酸イオン、酢酸イオン、酸化物イオン、炭酸イオン、アセチルアセトネートイオン、シュウ酸イオン等が挙げられる。
また、前記金属元素が負の電荷を有する錯体中に含まれる場合、金属前駆体には、陽イオンが含まれる。かかる陽イオンとしては、水素イオン；ナトリウム、カリウム等のアルカリ金属イオン；カルシウムイオン等のアルカリ土類金属イオン；アンモニウムイオン；等が挙げられる。
The metal precursor is a compound that can form metal nanoparticles by a reduction reaction. A metal precursor will not be specifically limited if the target metal nanoparticle is obtained and it melt | dissolves in the solvent to be used.
Examples of the metal precursor include salts and complexes of metals in Groups 6 to 14 of the periodic table.
Examples of ligands constituting the metal precursor include water, carbon monoxide, chloride ions, hydroxide ions, nitrate ions, acetate ions, oxide ions, carbonate ions, acetylacetonate ions, oxalate ions, etc. Is mentioned.
When the metal element is contained in a complex having a negative charge, the metal precursor contains a cation. Examples of such cations include hydrogen ions; alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium ions; ammonium ions;
金属前駆体としては、Ｐｔ（ＮＨ３）２（ＮＯ２）２、（ＮＨ４）２［ＲｕＣｌ６］、（ＮＨ４）２［ＲｕＣｌ５（Ｈ２Ｏ）］、Ｈ２ＰｔＣｌ４、Ｈ２ＰｔＣｌ６、Ｋ２ＰｔＣｌ４、Ｋ２ＰｔＣｌ６、Ｈ２［ＡｕＣｌ４］、（ＮＨ４）２［ＡｕＣｌ４］、Ｈ［Ａｕ（ＮＯ３）４］Ｈ２Ｏ等が挙げられる。
金属前駆体は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
Examples of the metal precursor include Pt (NH 3 ) 2 (NO 2 ) 2 , (NH 4 ) 2 [RuCl 6 ], (NH 4 ) 2 [RuCl 5 (H 2 O)], H 2 PtCl 4 , H 2. PtCl 6, K 2 PtCl 4, K 2 PtCl 6, H 2 [AuCl 4], (NH 4) 2 [AuCl 4], H [Au (NO 3) 4] H 2 O , and the like.
A metal precursor can be used individually by 1 type or in combination of 2 or more types.
金属前駆体を分散液に添加し、適宜混合する。混合は、分散液を調製するのと同様にして行うことができる。分散液に添加する金属前駆体の添加量は、特に限定されないが、金属ナノ粒子がカーボンナノチューブ（Ａ）に担持されてなる金属ナノ粒子担持体を効率よく得る観点から、金属前駆体を添加した後の分散液中の含有量が、好ましくは１．０×１０−１０〜１．０×１０−８質量％となるように添加するのが好適である。 A metal precursor is added to the dispersion and mixed as appropriate. Mixing can be performed in the same manner as preparing the dispersion. The addition amount of the metal precursor added to the dispersion is not particularly limited, but the metal precursor was added from the viewpoint of efficiently obtaining a metal nanoparticle support in which metal nanoparticles are supported on the carbon nanotubes (A). It is preferable to add so that the content in the subsequent dispersion is preferably 1.0 × 10 −10 to 1.0 × 10 −8 mass%.
金属前駆体を添加した分散液からの溶媒の留去は、たとえば、エバポレーターにより分散液を濃縮乾固することで実施することができる。次いで、得られた乾固物を水素気流下に加熱する。水素気流には、窒素やアルゴン等の不活性ガスを混合しても良い。水素気流中の水素濃度としては特に限定されないが、通常１〜１００％である。加熱温度は、通常１００〜８００℃であり、加熱時間は、通常１０分〜５０時間である。かかる条件で、乾固物を加熱して金属前駆体を還元することにより、金属ナノ粒子担持カーボンナノチューブ（Ａ）を効率よく得ることができる。 The solvent can be distilled off from the dispersion liquid to which the metal precursor has been added, for example, by concentrating and drying the dispersion liquid with an evaporator. Next, the obtained dried product is heated under a hydrogen stream. An inert gas such as nitrogen or argon may be mixed in the hydrogen stream. The hydrogen concentration in the hydrogen stream is not particularly limited, but is usually 1 to 100%. The heating temperature is usually 100 to 800 ° C., and the heating time is usually 10 minutes to 50 hours. Under such conditions, the dried metal is heated to reduce the metal precursor, whereby the metal nanoparticle-supported carbon nanotube (A) can be efficiently obtained.
２）電極材料及び電極
本発明の電極材料は、本発明の酸化還元触媒を電極用触媒として含有するものである。本発明の電極材料は、通常、電極の触媒層の形成に用いられる。
本発明の電極材料は、その効果を阻害しない範囲で、酸化還元触媒の他に、結着剤、導電助剤等を含有してもよい。
2) Electrode material and electrode The electrode material of the present invention contains the oxidation-reduction catalyst of the present invention as an electrode catalyst. The electrode material of the present invention is usually used for forming a catalyst layer of an electrode.
The electrode material of the present invention may contain a binder, a conductive auxiliary agent and the like in addition to the redox catalyst as long as the effect is not impaired.
本発明の電極材料は、例えば、単離した酸化還元触媒と他の成分とを混合することで得ることができる。
本発明の酸化還元触媒の含有量は、電極材料全体中、通常、１〜１００質量％である。
The electrode material of the present invention can be obtained, for example, by mixing an isolated redox catalyst and other components.
Content of the oxidation-reduction catalyst of this invention is 1-100 mass% normally in the whole electrode material.
本発明の電極は、本発明の電極材料を用いて得られるものである。
本発明の電極は、例えば、本発明の電極材料を適当な溶媒に分散させて触媒層形成用分散液を調製し、この触媒層形成用分散液を所定の導電性基材上に塗布し、得られた塗膜を乾燥させて触媒層を形成することで製造することができる。
The electrode of the present invention is obtained using the electrode material of the present invention.
The electrode of the present invention is prepared, for example, by dispersing the electrode material of the present invention in an appropriate solvent to prepare a dispersion for forming a catalyst layer, and applying this dispersion for forming a catalyst layer on a predetermined conductive substrate, It can manufacture by drying the obtained coating film and forming a catalyst layer.
触媒層形成用分散液の調製に用いる溶媒としては、水；メチルアルコール、エチルアルコール、プロピルアルコール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；テトラヒドロフラン、ジオキサン、ジグライム等のエーテル類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、１，３−ジメチル−２−イミダゾリジノン等のアミド類；ジメチルスルホキサイド、スルホラン等の含イオウ系溶媒；等が挙げられる。これらの溶媒は１種単独で、あるいは２種以上を組み合わせて用いることができる。 Solvents used for preparing the dispersion for forming the catalyst layer include water; alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; N, N -Amides such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone; sulfur-containing solvents such as dimethylsulfoxide and sulfolane; Can be mentioned. These solvents can be used alone or in combination of two or more.
触媒層形成用分散液は、本発明の効果を阻害しない範囲で、さらに、分散剤、界面活性剤等を含有してもよい。これらは公知のものを適宜使用すればよい。
触媒層形成用分散液は、前記還元反応に用いる分散液の調製方法と同様の方法により、本発明の電極材料を溶媒中にて分散処理することで得ることができる。
触媒層形成用分散液中のカーボンナノチューブ（Ａ）の含有量は、特に限定されないが、分散液全体中、好ましくは０．００１〜１０質量％である。
The dispersion for forming the catalyst layer may further contain a dispersant, a surfactant, and the like as long as the effects of the present invention are not impaired. These may be appropriately known ones.
The dispersion for forming a catalyst layer can be obtained by dispersing the electrode material of the present invention in a solvent by the same method as the method for preparing the dispersion used for the reduction reaction.
The content of the carbon nanotube (A) in the catalyst layer forming dispersion is not particularly limited, but is preferably 0.001 to 10% by mass in the entire dispersion.
本発明の電極は、本発明の電極材料を用いて得られるものである。
本発明の電極としては、色素増感型太陽電池の対向電極や、燃料電池用の電極が挙げられる。
The electrode of the present invention is obtained using the electrode material of the present invention.
Examples of the electrode of the present invention include a counter electrode of a dye-sensitized solar cell and an electrode for a fuel cell.
本発明の電極（色素増感型太陽電池の対向電極）の一例を図１に示す。
図１に示す色素増感型太陽電池の対向電極（１）は、支持体（２）と、導電膜（３）と、本発明の電極材料を用いて形成された触媒層（４）とを有する。
An example of the electrode of the present invention (a counter electrode of a dye-sensitized solar cell) is shown in FIG.
The counter electrode (1) of the dye-sensitized solar cell shown in FIG. 1 includes a support (2), a conductive film (3), and a catalyst layer (4) formed using the electrode material of the present invention. Have.
支持体（２）は、触媒層（４）を担持する役割を担うものである。触媒層（４）を構成する本発明の酸化還元触媒は、導電性を有するため、支持体（２）と触媒層（４）との間には必ずしも導電膜（３）は必要ではない。より良好な通電を確保する観点から、用いる支持体（２）としては、少なくとも触媒層（４）と接しうる表面部分に導電膜（３）が形成されているものが好ましい。 The support (2) plays a role of supporting the catalyst layer (4). Since the oxidation-reduction catalyst of the present invention constituting the catalyst layer (4) has conductivity, the conductive film (3) is not necessarily required between the support (2) and the catalyst layer (4). From the standpoint of ensuring better energization, the support (2) to be used is preferably one in which the conductive film (3) is formed at least on the surface portion that can be in contact with the catalyst layer (4).
前記導電膜（３）としては、白金、金、銀、銅、アルミニウム、インジウム、チタン等の金属；酸化スズ、酸化亜鉛等の導電性金属酸化物；インジウム−スズ酸化物（ＩＴＯ）、インジウム−亜鉛酸化物（ＩＺＯ）等の複合金属酸化物；カーボンナノチューブ（Ａ）以外のカーボンナノチューブ、フラーレン等の炭素材料；及びこれら２種以上の組み合わせ；等からなるものが挙げられる。 Examples of the conductive film (3) include metals such as platinum, gold, silver, copper, aluminum, indium and titanium; conductive metal oxides such as tin oxide and zinc oxide; indium-tin oxide (ITO) and indium Examples include composite metal oxides such as zinc oxide (IZO), carbon materials other than carbon nanotubes (A), carbon materials such as fullerenes, and combinations of two or more thereof.
支持体（２）の具体例としては、金属、金属酸化物、炭素材料、導電性高分子などを用いて形成された導電性のシートや、樹脂やガラスからなる非導電性のシートが挙げられる。なかでも、支持体（２）としては、軽量で、変換効率に優れる色素増感型太陽電池を効率よく形成することができることから、樹脂やガラスからなる非導電性のシートが好ましく、軽量で、変換効率に優れ、安価な色素増感型太陽電池が得られやすいことから、透明樹脂からなるものがより好ましい。 Specific examples of the support (2) include conductive sheets formed using metals, metal oxides, carbon materials, conductive polymers, and non-conductive sheets made of resin or glass. . Among these, as the support (2), a non-conductive sheet made of a resin or glass is preferable because it is lightweight and can efficiently form a dye-sensitized solar cell excellent in conversion efficiency. Since it is excellent in conversion efficiency and an inexpensive dye-sensitized solar cell can be easily obtained, a transparent resin is more preferable.
透明樹脂としては、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、シンジオタクチックポリスチレン（ＳＰＳ）、ポリフェニレンスルフィド（ＰＰＳ）、ポリカーボネート（ＰＣ）、ポリアリレート（ＰＡｒ）、ポリスルホン（ＰＳＦ）、ポリエステル（ＰＥ）、ポリエーテルスルホン（ＰＥＳ）、ポリエーテルイミド（ＰＥＩ）、シクロオレフィンポリマー（ＣＯＰ）、透明ポリイミド（ＰＩ）等の合成樹脂が挙げられる。 Transparent resins include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyester ( Examples thereof include synthetic resins such as PE), polyethersulfone (PES), polyetherimide (PEI), cycloolefin polymer (COP), and transparent polyimide (PI).
支持体（２）の厚みは、特に限定されないが、通常、１０μｍ〜１００ｍｍである。 Although the thickness of a support body (2) is not specifically limited, Usually, they are 10 micrometers-100 mm.
触媒層（４）は、本発明の電極材料を用いて形成された層である。触媒層（４）の厚みは、好ましくは０．００５〜１００μｍである。
触媒層（４）に含まれる本発明の酸化還元触媒の量は、好ましくは０．１ｍｇ／ｍ２〜２×１０４ｍｇ／ｍ２である。
The catalyst layer (4) is a layer formed using the electrode material of the present invention. The thickness of the catalyst layer (4) is preferably 0.005 to 100 μm.
The amount of the redox catalyst of the present invention contained in the catalyst layer (4) is preferably 0.1 mg / m 2 to 2 × 10 4 mg / m 2 .
本発明の電極を含む構造体（燃料電池用の膜電極接合体）の一例を図２に示す。
図２に示す膜電極接合体（５）は、電解質膜（６）と、電解質膜（６）の一方の側に形成された、カソード触媒層（７）及びカソード側ガス拡散層（８）と、電解質膜（６）のもう一方の側に形成された、アノード触媒層（９）及びアノード側ガス拡散層（１０）とを有する。
An example of a structure (a membrane electrode assembly for a fuel cell) including the electrode of the present invention is shown in FIG.
A membrane electrode assembly (5) shown in FIG. 2 includes an electrolyte membrane (6), a cathode catalyst layer (7) and a cathode side gas diffusion layer (8) formed on one side of the electrolyte membrane (6). And an anode catalyst layer (9) and an anode side gas diffusion layer (10) formed on the other side of the electrolyte membrane (6).
電解質膜（６）としては、パーフルオロカーボンスルホン酸樹脂膜等が挙げられる。
カソード触媒層（７）及び／又はアノード触媒層（９）は、本発明の電極材料を用いて形成された層である。
カソード側ガス拡散層（８）、アノード側ガス拡散層（１０）としては、カーボンペーパー、カーボンクロス、カーボン不織布等の導電性多孔質基材が挙げられる。
Examples of the electrolyte membrane (6) include a perfluorocarbon sulfonic acid resin membrane.
The cathode catalyst layer (7) and / or the anode catalyst layer (9) are layers formed using the electrode material of the present invention.
Examples of the cathode gas diffusion layer (8) and the anode gas diffusion layer (10) include conductive porous substrates such as carbon paper, carbon cloth, and carbon nonwoven fabric.
膜電極接合体（５）は、例えば、カソード触媒層（７）とカソード側ガス拡散層（８）とを有する積層体〔積層体（α）〕と、アノード触媒層（９）とアノード側ガス拡散層（１０）とを有する積層体〔積層体（β）〕を形成し、次いで、積層体（α）と積層体（β）を用いて、それぞれの触媒層が対向するように電解質膜（６）を挟み、これらを圧着させることで製造することができる。 The membrane electrode assembly (5) includes, for example, a laminated body (laminated body (α)) having a cathode catalyst layer (7) and a cathode side gas diffusion layer (8), an anode catalyst layer (9), and an anode side gas. A laminated body (laminated body (β)) having a diffusion layer (10), and then using the laminated body (α) and the laminated body (β), the electrolyte membrane ( It can be manufactured by sandwiching 6) and bonding them together.
３）太陽電池、燃料電池、及び窒素酸化物除去触媒
〔太陽電池〕
本発明の太陽電池は、本発明の電極を備えるものである。
本発明の太陽電池としては、例えば、光電極、電解質層、対向電極がこの順に並んでなる構造を有し、対向電極として本発明の電極を備える色素増感型太陽電池が挙げられる。 かかる色素増感型太陽電池は、光電極、電解質層、対向電極の他に、保護層、反射防止層、ガスバリア層等の機能層を有していてもよい。
3) Solar cell, fuel cell, and nitrogen oxide removal catalyst [solar cell]
The solar cell of the present invention comprises the electrode of the present invention.
Examples of the solar cell of the present invention include a dye-sensitized solar cell having a structure in which a photoelectrode, an electrolyte layer, and a counter electrode are arranged in this order, and including the electrode of the present invention as the counter electrode. Such a dye-sensitized solar cell may have functional layers such as a protective layer, an antireflection layer, and a gas barrier layer in addition to the photoelectrode, the electrolyte layer, and the counter electrode.
本発明の太陽電池は、太陽を光源とするものに限定されず、例えば屋内照明を光源とするものであってもよい。
本発明の太陽電池は、本発明の酸化還元触媒を電極用触媒として含有する電極材料を用いて得られる電極を備えるものであるため、変換効率が高く、耐久性に優れる。
本発明の太陽電池は、これらの特徴が特に活かされることから、携帯型太陽電池や屋内用太陽電池として好ましく用いられる。
The solar cell of the present invention is not limited to one using the sun as a light source, and may be one using indoor lighting as a light source, for example.
Since the solar cell of the present invention includes an electrode obtained using an electrode material containing the redox catalyst of the present invention as an electrode catalyst, the conversion efficiency is high and the durability is excellent.
The solar cell of the present invention is preferably used as a portable solar cell or an indoor solar cell because these features are particularly utilized.
〔燃料電池〕
本発明の燃料電池は、本発明の電極を備えるものである。
本発明の燃料電池としては、本発明の電極を触媒層として有するものであればよく、その種類は特に限定されない。例えば、イオン伝導性を有する固体高分子膜を電解質として用いる固体高分子形燃料電池、アルカリ電解液を電解質とするアルカリ形燃料電池、リン酸塩水溶液を電解質として用いるリン酸形燃料電池などが挙げられる。
〔Fuel cell〕
The fuel cell of the present invention comprises the electrode of the present invention.
As long as it has the electrode of this invention as a catalyst layer as a fuel cell of this invention, the kind is not specifically limited. Examples include solid polymer fuel cells that use an ion conductive solid polymer membrane as an electrolyte, alkaline fuel cells that use an alkaline electrolyte as an electrolyte, and phosphoric acid fuel cells that use an aqueous phosphate solution as an electrolyte. It is done.
本発明の燃料電池の具体例としては、例えば、上記の膜電極接合体（５）とセパレータを備えるものが挙げられる。
本発明の燃料電池は、本発明の酸化還元触媒を電極触媒として含有する電極材料を用いて得られる電極を備えるものであるため、発電効率が高く、耐久性に優れる。
As a specific example of the fuel cell of the present invention, for example, one having the above membrane electrode assembly (5) and a separator can be mentioned.
Since the fuel cell of the present invention comprises an electrode obtained using an electrode material containing the redox catalyst of the present invention as an electrode catalyst, the power generation efficiency is high and the durability is excellent.
〔窒素酸化物除去触媒〕
本発明の窒素酸化物除去触媒は、本発明の酸化還元触媒を含有するものである。
本発明の窒素酸化物除去触媒は、本発明の酸化還元触媒を用いるものであるため、効率が高く、耐久性に優れる。
[Nitrogen oxide removal catalyst]
The nitrogen oxide removing catalyst of the present invention contains the redox catalyst of the present invention.
Since the nitrogen oxide removing catalyst of the present invention uses the oxidation-reduction catalyst of the present invention, the efficiency is high and the durability is excellent.
本発明の窒素酸化物除去触媒は、粉末状であってもよく、公知の方法により成型されたものであってもよい。また、成型処理をするに際し、成形助剤、補強剤、無機繊維、有機バインダー等を用いることができる。 The nitrogen oxide removal catalyst of the present invention may be in the form of powder or may be molded by a known method. In addition, a molding aid, a reinforcing agent, an inorganic fiber, an organic binder, and the like can be used for the molding process.
本発明の窒素酸化物除去触媒を用いて、窒素酸化物を除去する方法は、特に限定されない。例えば、窒素酸化物含有ガスを、還元剤の存在下、本発明の窒素酸化物除去触媒と接触させる、選択的接触還元法が挙げられる。用いる還元剤としては、アンモニア、水素、一酸化炭素、炭化水素などが挙げられる。 The method for removing nitrogen oxides using the nitrogen oxide removing catalyst of the present invention is not particularly limited. For example, there is a selective catalytic reduction method in which a nitrogen oxide-containing gas is brought into contact with the nitrogen oxide removal catalyst of the present invention in the presence of a reducing agent. Examples of the reducing agent used include ammonia, hydrogen, carbon monoxide, and hydrocarbons.
〔製造例１〕光電極の製造
インジウム−スズ酸化物（ＩＴＯ）をスパッタ処理したポリエチレンナフタレートフィルム（ＩＴＯ−ＰＥＮフィルム、フィルム厚み２００μｍ、ＩＴＯ厚み２００ｎｍ、シート抵抗１５Ω／□）のＩＴＯ面上に、バインダーフリーの酸化チタンペースト（ＰＥＣＣ−Ｃ０１−０６、ペクセル・テクノロジーズ社製）を、ベーカー式アプリケーターを用いて、塗布厚み１５０μｍとなるように塗布した。得られた塗膜を常温で１０分間乾燥させた後、１５０℃の恒温槽中でさらに５分間加熱乾燥して、ＩＴＯ−ＰＥＮフィルムと多孔質半導体微粒子層とからなる積層体を得た。
この積層体を幅１．２ｃｍ、長さ２．０ｃｍの大きさにカットし、さらに積層体の短辺の２ｍｍ内側より、多孔質半導体微粒子層を直径６ｍｍの円になるように成形した。これを増感色素溶液〔増感色素：ルテニウム錯体（Ｎ７１９、ソラロニクス社製）、溶媒：アセトニトリル、ｔｅｒｔ−ブタノール、濃度：０．４ｍＭ〕に、４０℃で２時間浸漬させることで、増感色素を多孔質半導体微粒子層に吸着させた。浸漬処理の後、積層体をアセトニトリルで洗浄し、乾燥させることで光電極を得た。
[Production Example 1] Production of photoelectrode On the ITO surface of a polyethylene naphthalate film (ITO-PEN film, film thickness 200 μm, ITO thickness 200 nm, sheet resistance 15 Ω / □) sputtered with indium-tin oxide (ITO) Then, a binder-free titanium oxide paste (PECC-C01-06, manufactured by Pexel Technologies) was applied using a Baker type applicator so as to have a coating thickness of 150 μm. The obtained coating film was dried at room temperature for 10 minutes, and then further heated and dried in a thermostatic bath at 150 ° C. for 5 minutes to obtain a laminate comprising an ITO-PEN film and a porous semiconductor fine particle layer.
This laminate was cut into a size of 1.2 cm in width and 2.0 cm in length, and the porous semiconductor fine particle layer was formed into a circle having a diameter of 6 mm from the inner side of 2 mm on the short side of the laminate. The sensitizing dye is immersed in a sensitizing dye solution [sensitizing dye: ruthenium complex (N719, manufactured by Solaronics), solvent: acetonitrile, tert-butanol, concentration: 0.4 mM] at 40 ° C. for 2 hours. Was adsorbed on the porous semiconductor fine particle layer. After the immersion treatment, the laminate was washed with acetonitrile and dried to obtain a photoelectrode.
〔製造例２〕電解液の調製
ヨウ素０．０５ｍｏｌ／Ｌ、ヨウ化リチウム０．１ｍｏｌ／Ｌ、ｔ−ブチルピリジン０．５ｍｏｌ／Ｌ、および１，２−ジメチル−３−プロピルイミダゾリウムヨージド０．６ｍｏｌ／Ｌとなるように、これらをメトキシアセトニトリルに溶解して、電解液を得た。
[Production Example 2] Preparation of electrolyte solution Iodine 0.05 mol / L, lithium iodide 0.1 mol / L, t-butylpyridine 0.5 mol / L, and 1,2-dimethyl-3-propylimidazolium iodide 0 These were dissolved in methoxyacetonitrile so as to be 6 mol / L to obtain an electrolytic solution.
〔実施例１〕
三口フラスコに、水５０ｍＬ、カーボンナノチューブ０．０３ｇ、及び１ｍＭのｎ−ドデシル硫酸ナトリウム（関東化学社製）１ｍＬを加えた。
なお、前記カーボンナノチューブは、以下の特性値を有した：
平均直径（Ａｖ）：３．３ｎｍ、直径の標準偏差（σ）：０．６４ｎｍ、３σ／Ａｖ：０．５８、平均長さ：１００μｍ、比表面積：８００ｍ２／ｇ、主に単層。
この三口フラスコの内容物に対して、バス型超音波洗浄機〔ＢＲＡＮＳＯＮ社製、５５１０Ｊ−ＭＴ（４２ｋＨｚ、１８０Ｗ）〕を用いて、超音波を室温にて１０分間照射し、次いで、攪拌子を三口フラスコ内に入れて内容物を攪拌した後、再度、超音波を１０分間照射した。
次いで、得られたカーボンナノチューブの分散液に、ジニトロジアンミン白金（ＩＩ）〔Ｐｔ（ＮＨ３）２（ＮＯ２）２ 〕硝酸水溶液を該化合物濃度が２ｍＭになるように添加、混合して乾固した後、水素気流中にて２６０℃で３０分間加熱し、白金ナノ粒子がカーボンナノチューブに担持してなる酸化還元触媒を得た。
[Example 1]
To the three-necked flask, 50 mL of water, 0.03 g of carbon nanotubes, and 1 mL of 1 mM sodium n-dodecyl sulfate (manufactured by Kanto Chemical Co., Inc.) were added.
The carbon nanotubes had the following characteristic values:
Average diameter (Av): 3.3 nm, diameter standard deviation (σ): 0.64 nm, 3σ / Av: 0.58, average length: 100 μm, specific surface area: 800 m 2 / g, mainly monolayer.
The contents of the three-necked flask were irradiated with ultrasonic waves at room temperature for 10 minutes using a bath-type ultrasonic cleaner [manufactured by BRANSON, 5510J-MT (42 kHz, 180 W)]. The contents were stirred in a three-necked flask and then irradiated again with ultrasonic waves for 10 minutes.
Next, dinitrodiammine platinum (II) [Pt (NH 3 ) 2 (NO 2 ) 2 ] nitric acid aqueous solution was added to the obtained carbon nanotube dispersion so that the concentration of the compound was 2 mM, mixed and dried. Then, the mixture was heated at 260 ° C. for 30 minutes in a hydrogen stream to obtain a redox catalyst in which platinum nanoparticles were supported on carbon nanotubes.
〔顕微鏡観察〕
前記酸化還元触媒をエタノールと混合し、室温下での超音波処理（４２ｋＨｚ、１８０Ｗ、１０分間）により分散させることで顕微鏡観察用試料を得た。電界放射型透過電子顕微鏡（ＦＥ−ＴＥＭ）を用いて酸化還元触媒を観察し、無作為に選択された１００個の白金ナノ粒子の画像から、白金ナノ粒子の平均粒径と粒径の標準偏差を求めた。白金ナノ粒子の平均粒径は３ｎｍ、粒径の標準偏差は１ｎｍであった。また、酸化還元触媒における、白金ナノ粒子によるカーボンナノチューブ表面の被覆率は８０％であった。
[Microscopic observation]
The oxidation-reduction catalyst was mixed with ethanol and dispersed by ultrasonic treatment (42 kHz, 180 W, 10 minutes) at room temperature to obtain a sample for microscope observation. The redox catalyst was observed using a field emission transmission electron microscope (FE-TEM), and from the images of 100 randomly selected platinum nanoparticles, the average particle diameter of the platinum nanoparticles and the standard deviation of the particle diameters. Asked. The average particle diameter of the platinum nanoparticles was 3 nm, and the standard deviation of the particle diameter was 1 nm. Moreover, the coverage of the carbon nanotube surface with platinum nanoparticles in the redox catalyst was 80%.
〔密着性〕
上記方法によりエタノールに分散させた酸化還元触媒に対し、再度、室温下での超音波処理（４２ｋＨｚ、１８０Ｗ、１０分間）を行った。この分散液を試料として用いて、ＦＥ−ＴＥＭで酸化還元触媒を観察し、再度の超音波処理の前後における白金ナノ粒子によるカーボンナノチューブ表面の被覆状態の変化を調べた。
観察の結果、白金ナノ粒子の被覆状態が実質的に変わらなかったことから、本発明の酸化還元触媒は、白金ナノ粒子が強固に担持されているものであることが確認された。
[Adhesion]
The oxidation-reduction catalyst dispersed in ethanol by the above method was again subjected to ultrasonic treatment (42 kHz, 180 W, 10 minutes) at room temperature. Using this dispersion as a sample, the redox catalyst was observed with FE-TEM, and the change in the coating state of the carbon nanotube surface with the platinum nanoparticles before and after the ultrasonic treatment was examined again.
As a result of observation, the covering state of the platinum nanoparticles was not substantially changed, and thus it was confirmed that the redox catalyst of the present invention is one in which platinum nanoparticles are firmly supported.
〔色素増感型太陽電池〕
（ａ）色素増感型太陽電池の製造
３０ｍＬのガラス容器に、水５ｇ、エタノール１ｇ、及び、上記酸化還元触媒０．００２５ｇを加えた。
このガラス容器の内容物に対して、バス型超音波洗浄機（ＢＲＡＮＳＯＮ社製、５５１０Ｊ−ＭＴ（４２ｋＨｚ、１８０Ｗ）を用いて、室温にて２時間分散処理を行い、分散液を得た。
[Dye-sensitized solar cell]
(A) Production of dye-sensitized solar cell 5 g of water, 1 g of ethanol, and 0.0025 g of the oxidation-reduction catalyst were added to a 30 mL glass container.
The contents of this glass container were subjected to a dispersion treatment at room temperature for 2 hours using a bath type ultrasonic cleaner (manufactured by BRANSON, 5510J-MT (42 kHz, 180 W) to obtain a dispersion.
インジウム−スズ酸化物（ＩＴＯ）をスパッタ処理したポリエチレンナフタレートフィルム（ＩＴＯ−ＰＥＮフィルム、フィルム厚み２００μｍ、ＩＴＯ厚み２００ｎｍ、シート抵抗１５Ω／□）のＩＴＯ面上に、前記分散液を、バーコーター（テスター産業社製、ＳＡ−２０３、Ｎｏ．１０）を用いて、塗布厚み２２．９μｍとなるように塗布した。得られた塗膜を、２３℃、６０％（相対湿度）で２時間乾燥させて、対向電極を得た。 On the ITO surface of a polyethylene naphthalate film (ITO-PEN film, film thickness 200 μm, ITO thickness 200 nm, sheet resistance 15 Ω / □) sputter-treated with indium-tin oxide (ITO), the dispersion is applied to a bar coater ( Using Tester Sangyo Co., Ltd., SA-203, No. 10), the coating thickness was 22.9 μm. The obtained coating film was dried at 23 ° C. and 60% (relative humidity) for 2 hours to obtain a counter electrode.
サーリン（登録商標）フィルム（厚み２５μｍ、デュポン社製）を、１４ｍｍ四方に切り取り、さらに中心部を直径９ｍｍにくり抜き、スペーサーフィルムを作製した。前記対向電極と製造例１で得た光電極とを、このスペーサーフィルムをはさんで導電面が内側になるように対向させて貼り合せ、１１０℃に加熱したホットプレートの上で１分間熱圧着させた。
放冷後、対向電極に穴をあけ、この穴から製造例２で得た電解液を注液した。電解液を注液後、サーリンフィルム（厚み２５μｍ、デュポン社製）を用いて、電解液の注入に用いた穴を封じることで色素増感型太陽電池を得た。
A Surlyn (registered trademark) film (thickness 25 μm, manufactured by DuPont) was cut into 14 mm squares, and the center portion was cut out to a diameter of 9 mm to prepare a spacer film. The counter electrode and the photoelectrode obtained in Production Example 1 were bonded together with the spacer film sandwiched so that the conductive surface was on the inside, and thermocompression bonded for 1 minute on a hot plate heated to 110 ° C. I let you.
After allowing to cool, a hole was made in the counter electrode, and the electrolytic solution obtained in Production Example 2 was injected from this hole. After injecting the electrolytic solution, a dye-sensitized solar cell was obtained by sealing the hole used for injecting the electrolytic solution using a Surlyn film (thickness 25 μm, manufactured by DuPont).
（ｂ）色素増感型太陽電池の評価
光源として、１５０Ｗキセノンランプ光源にＡＭ１．５Ｇフィルタを装着した擬似太陽光照射装置（ＰＥＣ−Ｌ１１型、ペクセル・テクノロジーズ社製）光源を用いた。光量は、１ｓｕｎ（ＡＭ１．５Ｇ、１００ｍＷｃｍ−２（ＪＩＳ−Ｃ−８９１２のクラスＡ））に調整した。上記方法により得られた色素増感型太陽電池をソースメータ（２４００型ソースメータ、Ｋｅｉｔｈｌｅｙ社製）に接続した。
電流電圧特性は、１ｓｕｎの光照射下、バイアス電圧を、０Ｖから０．８Ｖまで、０．０１Ｖ単位で変化させながら出力電流を測定した。出力電流の測定は、各電圧ステップにおいて、電圧を変化後、０．０５秒後から０．１５秒後の値を積算することで行った。バイアス電圧を、逆方向に０．８Ｖ〜０Ｖまでステップさせる測定も行い、順方向と逆方向の測定の平均値を光電流とした。
上記測定を行って算出したエネルギー変換効率は、４．２％であった。
(B) Evaluation of dye-sensitized solar cell As a light source, a pseudo-sun irradiation device (PEC-L11 type, manufactured by Pexel Technologies) light source in which an AM1.5G filter is attached to a 150 W xenon lamp light source was used. The amount of light was adjusted to 1 sun (AM1.5G, 100 mWcm −2 (JIS-C-8912 class A)). The dye-sensitized solar cell obtained by the above method was connected to a source meter (2400 type source meter, manufactured by Keithley).
For the current-voltage characteristics, the output current was measured while changing the bias voltage from 0 V to 0.8 V in units of 0.01 V under 1 sun light irradiation. The output current was measured by integrating the values from 0.05 seconds to 0.15 seconds after changing the voltage in each voltage step. Measurement was also performed by stepping the bias voltage in the reverse direction from 0.8 V to 0 V, and the average value of the measurement in the forward direction and the reverse direction was defined as the photocurrent.
The energy conversion efficiency calculated by performing the above measurement was 4.2%.
１・・・対向電極
２・・・支持体
３・・・導電膜
４・・・触媒層
５・・・膜電極接合体
６・・・電解質膜
７・・・カソード触媒層
８・・・カソード側ガス拡散層
９・・・アノード触媒層
１０・・・アノード側ガス拡散層
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