JP2012245469A - Photocatalyst and method for producing hydrogen using the same - Google Patents
Photocatalyst and method for producing hydrogen using the same Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 150000002431 hydrogen Chemical class 0.000 claims abstract 2
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 150000001298 alcohols Chemical class 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 5
- -1 alcohols Chemical class 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002071 nanotube Substances 0.000 description 7
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002109 single walled nanotube Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
Description
本発明は、光触媒およびこれを用いた水素製造方法に関する。 The present invention relates to a photocatalyst and a method for producing hydrogen using the same.
酸化チタン（ＴｉＯ２）に代表される光触媒成分の触媒活性を向上させるために、光触媒成分とともに助触媒成分を用いた光触媒が開発されている。このような光触媒の代表例として、光触媒成分としての酸化チタン（ＴｉＯ２）と、助触媒成分としての白金（Ｐｔ）とを含むＴｉＯ２／Ｐｔ触媒が挙げられる。ＴｉＯ２／Ｐｔ触媒によれば、高い触媒活性を得ることができるが、貴金属である白金を用いているため、高価であるという課題がある。これに対して、特許文献１では、白金に代えて、助触媒成分としてカーボンナノチューブを用いた光触媒が開示されている。特許文献１の光触媒によれば、アルコール類から水素を生成する反応系において、ＴｉＯ２／Ｐｔ触媒と同程度の高い触媒活性を得られることが記載されている。 In order to improve the catalytic activity of a photocatalyst component typified by titanium oxide (TiO 2 ), a photocatalyst using a promoter component together with the photocatalyst component has been developed. A typical example of such a photocatalyst is a TiO 2 / Pt catalyst containing titanium oxide (TiO 2 ) as a photocatalyst component and platinum (Pt) as a promoter component. According to the TiO 2 / Pt catalyst, high catalytic activity can be obtained, but there is a problem that it is expensive because platinum, which is a noble metal, is used. On the other hand, Patent Document 1 discloses a photocatalyst using carbon nanotubes as a promoter component instead of platinum. According to the photocatalyst of Patent Document 1, it is described that a catalytic activity as high as that of a TiO 2 / Pt catalyst can be obtained in a reaction system that generates hydrogen from alcohols.
光触媒成分と助触媒成分とを含む光触媒を用いた水系の光触媒反応においては、光によって励起された電子は、光触媒成分から助触媒成分に受け渡され、さらに、助触媒成分から水分子や水素イオンまたは水素ラジカル（以下、水分子等という）に受け渡される。光触媒の活性を向上させるためには、光触媒成分から助触媒成分への電子の移動速度と、助触媒成分から水分子等への電子の移動速度を向上させる必要がある。前者の電子の移動速度は、光触媒成分と助触媒成分が接触する確率に依存し、後者の電子の移動速度は、助触媒成分と水分子等が接触する確率に依存する。これらの確率を高くすることによって光触媒の活性を向上させる場合には、光触媒成分、助触媒成分、水分子等の量を増やす必要があり、触媒効率の向上に限界があった。 In an aqueous photocatalytic reaction using a photocatalyst containing a photocatalyst component and a cocatalyst component, electrons excited by light are transferred from the photocatalyst component to the cocatalyst component, and water molecules and hydrogen ions are further transferred from the cocatalyst component. Or it is delivered to hydrogen radicals (hereinafter referred to as water molecules). In order to improve the activity of the photocatalyst, it is necessary to improve the transfer rate of electrons from the photocatalyst component to the promoter component and the transfer rate of electrons from the promoter component to water molecules and the like. The former electron moving speed depends on the probability that the photocatalyst component and the promoter component are in contact, and the latter electron moving speed depends on the probability that the promoter component and the water molecule contact. In order to improve the activity of the photocatalyst by increasing these probabilities, it is necessary to increase the amount of the photocatalyst component, the promoter component, the water molecule, etc., and there has been a limit in improving the catalyst efficiency.
本発明者らは、ナノカーボン類の内部では、通常よりも低いエネルギーで物理的化学的現象が起こり得ることに着目し、ナノカーボン類の内部に水分子等を引き込むことによって、助触媒成分から水分子等への電子の移動速度を向上させることができることを見出した。 The present inventors pay attention to the fact that physical and chemical phenomena can occur at a lower energy than usual inside nanocarbons, and by drawing water molecules and the like into nanocarbons, It has been found that the movement speed of electrons to water molecules and the like can be improved.
本発明は、炭素の６員環構造を外殻に有しており、少なくとも一端が開放されている管状のナノカーボン類と、光を照射されることによって電子および正孔を生成する光触媒成分とを含む光触媒を提供する。 The present invention includes a tubular nanocarbon having a carbon 6-membered ring structure in the outer shell and having at least one end opened, and a photocatalytic component that generates electrons and holes when irradiated with light. A photocatalyst is provided.
本発明によれば、炭素の６員環構造を外殻に有している管状のナノカーボン類の少なくとも一端が開放されているため、水分子等がその外殻の内側（ナノカーボン類の内部）に引き込まれる。ナノカーボン類の内部で、助触媒成分であるナノカーボン類から水分子等への電子の移動が成されるため、助触媒成分から水分子等への電子の移動速度が向上する。さらに、ナノカーボン類の内部では、その外部よりも低いエネルギーでナノカーボン類から水分子等へ電子が移動するため、助触媒成分から水分子等への電子の移動速度は、より一層向上する。 According to the present invention, since at least one end of tubular nanocarbons having a carbon six-membered ring structure in the outer shell is open, water molecules and the like are inside the outer shell (inside the nanocarbons). ). Electrons are transferred from nanocarbons, which are promoter components, to water molecules and the like inside the nanocarbons, so that the transfer rate of electrons from the promoter components to water molecules and the like is improved. Furthermore, inside the nanocarbons, electrons move from the nanocarbons to water molecules and the like with lower energy than the outside, so that the transfer rate of electrons from the promoter component to the water molecules and the like is further improved.
前記ナノカーボン類は、開放された端部は２つ以上であることが好ましい。 The nanocarbons preferably have two or more open ends.
本発明は、アルコール類等の水素含有有機化合物またはその水溶液に、上記の光触媒を作用させる、水素製造方法を提供することもできる。この場合、光触媒の温度を４５℃以上とすることが好ましい。 The present invention can also provide a hydrogen production method in which the above-mentioned photocatalyst is allowed to act on a hydrogen-containing organic compound such as alcohols or an aqueous solution thereof. In this case, the temperature of the photocatalyst is preferably 45 ° C. or higher.
本発明によれば、水分子等を反応物質または反応中間体として含む光触媒反応において高い活性を示す光触媒を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the photocatalyst which shows high activity in the photocatalytic reaction containing a water molecule etc. as a reactive substance or a reaction intermediate body can be provided.
本願に係る光触媒は、炭素の６員環構造を外殻に有しており、少なくとも一端が開放されている管状のナノカーボン類と、光を照射されることによって電子および正孔を生成する光触媒成分とを含む。本願に係る光触媒は、水分子等を反応物質として含む光触媒反応において高い活性を示す。水分子等（水分子や水素イオンまたは水素ラジカル）を反応物質または反応中間体として含む光触媒反応としては、例えば、アルコール類等の水素含有有機化合物またはその水溶液に光触媒を作用させて、水素を製造する反応が挙げられる。 The photocatalyst according to the present application has a tubular nanocarbon having a carbon six-membered ring structure in the outer shell and at least one end being opened, and a photocatalyst that generates electrons and holes when irradiated with light. And ingredients. The photocatalyst according to the present application exhibits high activity in a photocatalytic reaction containing water molecules as a reactant. For photocatalytic reactions that contain water molecules (water molecules, hydrogen ions, or hydrogen radicals) as reactants or reaction intermediates, for example, hydrogen is produced by allowing a photocatalyst to act on hydrogen-containing organic compounds such as alcohols or aqueous solutions thereof. Reaction.
本願に係る光触媒成分は、光を照射されることによって電子および正孔を生成する性質を有する物質として公知の物質を利用することができる。例えば、ＴｉＯ２，ＳｒＴｉＯ３，ＣｄＳ，ＧａＰ，ＺｒＯ２，ＫＴａＯ３，ＫＴａ０．７７，Ｎｂ０．２３Ｏ３，Ｎｂ２Ｏ５，ＺｎＯ，Ｆｅ２Ｏ３，ＷＯ３，ＳｎＯ２，Ｉｎ２Ｏ３，ＭｏＯ３Ｃｕ２Ｏ，ＣｕＦｅＯ２，ＩｎＴａＯ４，ＮｉＯｘ／Ｉｎ０．９Ｎｉ０．１ＴａＯ４等の公知の光を照射されることによって電子および正孔を生成する性質を有する物質を単独または複数組み合わせて用いることができる。ＴｉＯ２は、高活性で実用性が高く、光触媒成分として好ましく、アナターゼ型、ルチル型のいずれも好適に利用できるが、より高活性なアナターゼ型を用いることが特に好ましい。 As the photocatalyst component according to the present application, a known substance can be used as a substance having a property of generating electrons and holes when irradiated with light. For example, TiO 2, SrTiO 3, CdS , GaP, ZrO 2, KTaO 3, KTa 0.77, Nb 0.23 O 3, Nb 2 O 5, ZnO, Fe 2 O 3, WO 3, SnO 2, In 2 Substances having the property of generating electrons and holes when irradiated with known light, such as O 3 , MoO 3 Cu 2 O, CuFeO 2 , InTaO 4 , NiO x / In 0.9 Ni 0.1 TaO 4 Can be used alone or in combination. TiO 2 has high activity and high practicality, and is preferable as a photocatalytic component. Either anatase type or rutile type can be suitably used, but it is particularly preferable to use a higher activity anatase type.
本願に係るナノカーボン類は、グラファイトシート又はグラフェンが管状に丸まった形態を有するナノオーダーのカーボン構造体もしくはその誘導体である。外殻は、グラファイトシートと同様の網目状の炭素の６員環構造を有しており、その一部に５員環、７員環、８員環等を含んでいてもよい。本願に係るナノカーボン類としては、特に限定されないが、外殻が単層の単層ナノチューブ（ＳＷＮＴ）、外殻が多層の多層ナノチューブ（ＭＷＮＴ）、カーボンナノホーンおよびその誘導体を例示することができ、これらを単独でもしくは複数組み合わせて用いることができる。なお、本願に係るナノカーボン類は、２つの端部を有する一連の直管状または曲がり管状であってもよいし、分岐を有して３つ以上の端部を有する形状であってもよい。 The nanocarbons according to the present application are a nano-order carbon structure or a derivative thereof having a form in which a graphite sheet or graphene is rounded into a tubular shape. The outer shell has a network-like carbon 6-membered ring structure similar to the graphite sheet, and a part thereof may include a 5-membered ring, a 7-membered ring, an 8-membered ring, or the like. Examples of the nanocarbons according to the present application include, but are not limited to, single-walled single-walled nanotubes (SWNT) whose outer shell is a single-walled nanotube (MWNT), carbon nanohorns, and derivatives thereof. These can be used alone or in combination. The nanocarbons according to the present application may be a series of straight tubes or bent tubes having two ends, or may have a shape having three or more ends with a branch.
さらに、本願に係るナノカーボン類は、管状の外殻の端部の一部または全部が、開放された状態となっている。例えば、２つの端部を有し、一端から他端に伸びる管状のナノチューブの場合、その一方のみが開放端であってもよいし、両端が開放端であってもよい。特に限定されないが、開放された端部は２つ以上であることが好ましい。 Further, in the nanocarbons according to the present application, part or all of the end portion of the tubular outer shell is in an open state. For example, in the case of a tubular nanotube having two end portions and extending from one end to the other end, only one of them may be an open end or both ends may be open ends. Although not particularly limited, it is preferable that there are two or more open ends.
本願に係る少なくとも一端が開放されているナノカーボン類は、水分子等を外殻の内部に積極的に引き込む性質を有することが知られている。ナノカーボン類の内部では、外部と比べて電子の移動速度が向上する。また、ナノカーボン類の内部に水分子等が内包されて水分子等の移動がある程度拘束されるため、ナノカーボン類から水分子等への電子の引渡しが起こり易くなる。すなわち、本願に係る光触媒によれば、ナノカーボン類から水分子等への電子の移動がナノカーボン類の外殻の内側で行われるため、ナノカーボン類から水分子等への電子の移動が起こり易くなる。このため、本願に係る光触媒は、水分子等を反応物質として含む光触媒反応において高い活性を示す。特許文献１には、カーボンナノチューブを光触媒の助触媒成分として用いることが記載されているが、上記のような端部が開放されたナノカーボン類に特有の性質を利用することは、特許文献１に記載も示唆もされていない。 It is known that nanocarbons having at least one open end according to the present application have a property of actively drawing water molecules and the like into the outer shell. Inside the nanocarbons, the movement speed of electrons is improved compared to the outside. In addition, since water molecules and the like are encapsulated in the nanocarbons and movement of the water molecules is restricted to some extent, electrons are easily transferred from the nanocarbons to the water molecules and the like. That is, according to the photocatalyst according to the present application, electrons move from nanocarbons to water molecules and the like inside the outer shell of the nanocarbons, so electrons move from nanocarbons to water molecules and the like. It becomes easy. For this reason, the photocatalyst according to the present application exhibits high activity in a photocatalytic reaction including water molecules as a reactant. Patent Document 1 describes the use of carbon nanotubes as a cocatalyst component of a photocatalyst. However, the use of the properties unique to nanocarbons having open ends as described above is disclosed in Patent Document 1. Is neither described nor suggested.
また、ナノカーボン類の内部では、通常とは異なり、水分子が４５℃程度の低い温度で沸騰し、さらにナノカーボン類の外部に噴出することが知られている。本願に係る光触媒を用いて、４５℃程度以上の温度条件で光触媒反応を行うと、ナノカーボン類の開放した端部からナノカーボン類内に水分子が引き込まれて沸騰し、噴出するという現象が繰り返し発生する。ナノカーボン類から電子を受け取った水分子等が速やかにナノカーボン類の内部から放出されるので、ナノカーボン類から水分子等への電子の移動速度がさらに高くなる。また、ナノカーボン類の内部で水分子は沸騰し、高活性化して電子を受け取り易くなることによっても、ナノカーボン類から水分子等への電子の移動速度がさらに高くなる。すなわち、本願に係る光触媒を用いて、水分子等を反応物質として含む光触媒反応を４５℃程度以上の温度条件で行う場合には、特に高い触媒活性を得ることができる。光触媒反応においては、光触媒に光を照射する必要があり、この光の照射により、反応系の温度が高くなることが多い。このため、反応系を加熱する機構を特に設けなくても、反応系が４５℃程度以上になる場合がある。本願に係る光触媒によれば、反応系を全く加熱することなく、もしくは殆ど加熱することなく、特に高い触媒活性を得ることができる。 In addition, it is known that water molecules boil at a temperature as low as about 45 ° C. inside the nanocarbons, and are ejected outside the nanocarbons. When the photocatalyst reaction is performed under a temperature condition of about 45 ° C. or more using the photocatalyst according to the present application, a phenomenon in which water molecules are drawn into the nanocarbons from the open ends of the nanocarbons, boils and erupts. It occurs repeatedly. Since water molecules and the like that have received electrons from the nanocarbons are quickly released from the inside of the nanocarbons, the transfer rate of electrons from the nanocarbons to the water molecules and the like is further increased. In addition, the water molecules boil inside the nanocarbons and are highly activated to easily receive electrons, so that the transfer rate of electrons from the nanocarbons to water molecules and the like is further increased. That is, when the photocatalyst according to the present application is used and a photocatalytic reaction including water molecules as a reactant is performed at a temperature of about 45 ° C. or higher, particularly high catalytic activity can be obtained. In the photocatalytic reaction, it is necessary to irradiate the photocatalyst with light, and this light irradiation often increases the temperature of the reaction system. For this reason, even if a mechanism for heating the reaction system is not particularly provided, the reaction system may be about 45 ° C. or higher. According to the photocatalyst according to the present application, a particularly high catalytic activity can be obtained without heating the reaction system at all or hardly.
本願に係る少なくとも一端が開放されたナノカーボン類は、例えば、一般的な全ての端部が閉じたナノカーボン類に熱処理や酸処理を行うことによって製造することができることが知られている。ナノチューブを例示して説明すると、一般的な方法でナノチューブを合成すると、その先端は半球状のキャップで覆われて閉じている。この先端のキャップを消失させると、開放型のナノチューブが得られる。開放型ナノチューブは、例えば、ナノチューブを生成させた後に、ナノチューブを熱処理して部分酸化することによって製造できる。熱処理による部分酸化は、例えば、酸素雰囲気内において、所定の温度で所定時間加熱することにより行うことができる。また、硝酸等の酸によってナノチューブを部分酸化することもできる。 It is known that the nanocarbons having at least one end opened according to the present application can be manufactured by, for example, performing heat treatment or acid treatment on general nanocarbons having all ends closed. For example, when nanotubes are synthesized by a general method, their tips are covered with a hemispherical cap and closed. When this cap at the tip is eliminated, an open-type nanotube is obtained. An open-type nanotube can be manufactured, for example, by generating a nanotube and then subjecting the nanotube to a partial oxidation by heat treatment. The partial oxidation by the heat treatment can be performed, for example, by heating at a predetermined temperature for a predetermined time in an oxygen atmosphere. The nanotubes can also be partially oxidized with an acid such as nitric acid.
本願に係る光触媒は、本願に係るナノカーボン類と光触媒成分を混合したものであってもよい。また、本願に係るナノカーボン類を担体として用い、光触媒成分を担持したものであってもよい。さらに、本願に係る光触媒は、基板や基体に固定化されていてもよい。本願に係る光触媒の固定化は、例えば、ナノカーボン類を基板や基体に固定化し、これに光触媒成分を含浸法等によって担持させることによって行うことができる。光触媒成分としてナノカーボン類を生成する反応において触媒活性を有する物質を用いる場合には、光触媒成分を基点としてナノカーボン類を成長させてもよい。 The photocatalyst according to the present application may be a mixture of the nanocarbons according to the present application and a photocatalytic component. Moreover, what carried | supported the photocatalyst component using the nanocarbon concerning this application as a support | carrier may be used. Furthermore, the photocatalyst according to the present application may be immobilized on a substrate or a substrate. The immobilization of the photocatalyst according to the present application can be performed, for example, by immobilizing nanocarbons on a substrate or a substrate and supporting the photocatalyst component thereon by an impregnation method or the like. In the case of using a substance having catalytic activity in the reaction for producing nanocarbons as the photocatalyst component, the nanocarbons may be grown using the photocatalyst component as a base point.
本願に係る光触媒は、本願に係るナノカーボン類以外の助触媒成分をさらに含んでいてもよいし、本願に係るナノカーボン類のみを助触媒成分として含むものであってもよい。本願に係るナノカーボン類以外の助触媒成分としては、例えば、Ｐｔ，Ｎｉ，Ｐｄ，Ａｕ，Ａｇ，Ｒｕ，Ｒｈ，Ｆｅ，Ｃｏ，Ｃｕ，Ｚｎ等の金属成分を好適に用いることができる。上記のＰｔ等の金属成分を助触媒成分としてさらに含有する場合には、光触媒成分と金属成分のうち一方が他方に担持された担持触媒であってもよい。特に、ＴｉＯ２表面にＰｔ等の貴金属の微粒子を担持させた場合には、高い触媒活性を得ることができ、好ましい。光触媒成分と、上記のＰｔ等の助触媒成分とを用いた担持触媒は、含浸法、共沈法、蒸着法等の公知の物理的化学的手法を用いて製造することができる。Ｐｔ等の金属成分を助触媒としてさらに含む光触媒を用いる場合にも、同様に、本願に係るナノカーボン類と混合して用いてもよく、また、本願に係るナノカーボン類に担持して用いてもよい。助触媒成分としての金属成分がナノカーボン類を生成する反応において触媒活性を有する物質を用いる場合には、助触媒成分を基点としてナノカーボン類を成長させてもよい。 The photocatalyst according to the present application may further include a promoter component other than the nanocarbons according to the present application, or may include only the nanocarbons according to the present application as a promoter component. As the promoter component other than the nanocarbons according to the present application, for example, metal components such as Pt, Ni, Pd, Au, Ag, Ru, Rh, Fe, Co, Cu, and Zn can be suitably used. When the metal component such as Pt is further contained as a promoter component, a supported catalyst in which one of the photocatalyst component and the metal component is supported on the other may be used. In particular, when noble metal fine particles such as Pt are supported on the TiO 2 surface, high catalytic activity can be obtained, which is preferable. The supported catalyst using the photocatalyst component and the above-described promoter component such as Pt can be produced using a known physical chemical method such as an impregnation method, a coprecipitation method, or a vapor deposition method. Similarly, when using a photocatalyst further containing a metal component such as Pt as a co-catalyst, it may be used by mixing with the nanocarbons according to the present application, Also good. When using a substance having catalytic activity in the reaction in which the metal component as the promoter component generates nanocarbons, the nanocarbons may be grown using the promoter component as a base point.
本願に係る光触媒は、アルコール類等の水素含有有機化合物またはその水溶液から水素を製造するための光触媒として好適に利用することができる。この場合、光触媒の温度を４５℃以上とすることが好ましい。本願に係る光触媒を用いた水素製造方法では、例えば、アルコール類等の水素含有有機化合物またはその水溶液からなる溶媒に、本願に係る光触媒を混合し、この混合液に光（例えば紫外線）を照射することによって、水素を製造することができる。この場合、混合液の温度が４５℃以上となる条件で光触媒反応を行えば、より高い触媒活性を得ることができるため、好ましい。光を照射することによって反応系を４５℃程度以上することができる場合には、この混合系を加熱する機構を設置する必要はないが、必要に応じて、加熱機構を用いて光触媒反応を行い、水素を製造してもよい。 The photocatalyst according to the present application can be suitably used as a photocatalyst for producing hydrogen from a hydrogen-containing organic compound such as alcohols or an aqueous solution thereof. In this case, the temperature of the photocatalyst is preferably 45 ° C. or higher. In the hydrogen production method using the photocatalyst according to the present application, for example, the photocatalyst according to the present application is mixed in a solvent comprising a hydrogen-containing organic compound such as alcohol or an aqueous solution thereof, and light (for example, ultraviolet rays) is irradiated to the mixed solution. Thus, hydrogen can be produced. In this case, it is preferable to carry out the photocatalytic reaction under the condition that the temperature of the mixed solution is 45 ° C. or higher because higher catalytic activity can be obtained. If the reaction system can be heated to about 45 ° C. or higher by irradiating light, it is not necessary to install a mechanism for heating the mixed system. Hydrogen may be produced.
以上、本発明の実施形態の一例について詳細に説明したが、これらは例示に過ぎず、特許請求の範囲を限定するものではない。特許請求の範囲に記載の技術には、以上に例示した具体例を様々に変形、変更したものが含まれる。 As mentioned above, although an example of embodiment of the present invention was explained in detail, these are only illustrations and do not limit a claim. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.
本明細書または図面に説明した技術要素は、単独であるいは各種の組合せによって技術的有用性を発揮するものであり、出願時請求項記載の組合せに限定されるものではない。また、本明細書または図面に例示した技術は複数目的を同時に達成し得るものであり、そのうちの一つの目的を達成すること自体で技術的有用性を持つものである。
The technical elements described in this specification or the drawings exhibit technical usefulness alone or in various combinations, and are not limited to the combinations described in the claims at the time of filing. In addition, the technology exemplified in this specification or the drawings can achieve a plurality of objects at the same time, and has technical usefulness by achieving one of the objects.
Claims (4)
光を照射されることによって電子および正孔を生成する光触媒成分とを含む光触媒。 Tubular nanocarbons having a carbon six-membered ring structure in the outer shell and having at least one open end;
A photocatalyst comprising a photocatalyst component that generates electrons and holes when irradiated with light.
The method for producing hydrogen according to claim 3, wherein the temperature of the photocatalyst is 45 ° C or higher.
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| WO2014204200A1 (en) * | 2013-06-18 | 2014-12-24 | 서강대학교산학협력단 | Hydrogen fuel converter provided with photocatalyst and method for preparing hydrogen from methanol using photocatalyst |
| WO2016158806A1 (en) * | 2015-03-27 | 2016-10-06 | 富士化学工業株式会社 | Novel composite of iron compound and graphene oxide |
| WO2017191521A1 (en) * | 2016-05-06 | 2017-11-09 | Sabic Global Technologies B.V. | Photo-thermal reactions of alcohols to hydrogen and organic products over metal oxide photo-thermal catalysts |
| CN109715291A (en) * | 2016-10-05 | 2019-05-03 | 学校法人关西学院 | Metallic compound-graphene oxide complex |
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| WO2014204200A1 (en) * | 2013-06-18 | 2014-12-24 | 서강대학교산학협력단 | Hydrogen fuel converter provided with photocatalyst and method for preparing hydrogen from methanol using photocatalyst |
| WO2016158806A1 (en) * | 2015-03-27 | 2016-10-06 | 富士化学工業株式会社 | Novel composite of iron compound and graphene oxide |
| CN107531489A (en) * | 2015-03-27 | 2018-01-02 | 富士化学工业株式会社 | The complex of new iron compound and graphene oxide |
| JPWO2016158806A1 (en) * | 2015-03-27 | 2018-01-25 | 富士化学工業株式会社 | New iron compound and graphene oxide complex |
| RU2706318C2 (en) * | 2015-03-27 | 2019-11-15 | Квансей Гакуин Эдьюкейшнл Фаундейшн | Novel composite material containing iron compound and graphene oxide |
| WO2017191521A1 (en) * | 2016-05-06 | 2017-11-09 | Sabic Global Technologies B.V. | Photo-thermal reactions of alcohols to hydrogen and organic products over metal oxide photo-thermal catalysts |
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| CN109715291A (en) * | 2016-10-05 | 2019-05-03 | 学校法人关西学院 | Metallic compound-graphene oxide complex |
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