JP2020104088A - Photocatalyst electrode - Google Patents
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 36
- 239000004065 semiconductor Substances 0.000 claims abstract description 49
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 claims description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 claims description 5
- NUJGNDIAVBGFHG-UHFFFAOYSA-N 5,11-dihydroquinolino[3,2-b]quinoline-6,12-dione Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C(=O)C1=CC=CC=C1N2 NUJGNDIAVBGFHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 230000001699 photocatalysis Effects 0.000 description 19
- 238000004544 sputter deposition Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
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- 238000013032 photocatalytic reaction Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
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- 238000003786 synthesis reaction Methods 0.000 description 3
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- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- GBROPGWFBFCKAG-UHFFFAOYSA-N picene Chemical compound C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 102100032912 CD44 antigen Human genes 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 238000005513 bias potential Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- BZCOSCNPHJNQBP-OWOJBTEDSA-N dihydroxyfumaric acid Chemical compound OC(=O)C(\O)=C(/O)C(O)=O BZCOSCNPHJNQBP-OWOJBTEDSA-N 0.000 description 1
- KLPXTHJOAWGMSD-NXVVXOECSA-N dimethyl (Z)-2,3-dianilinobut-2-enedioate Chemical compound C=1C=CC=CC=1N/C(C(=O)OC)=C(C(=O)OC)\NC1=CC=CC=C1 KLPXTHJOAWGMSD-NXVVXOECSA-N 0.000 description 1
- HMPNVUONVWQKFY-ONEGZZNKSA-N dimethyl (e)-2,3-dihydroxybut-2-enedioate Chemical compound COC(=O)C(\O)=C(/O)C(=O)OC HMPNVUONVWQKFY-ONEGZZNKSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 108010069264 keratinocyte CD44 Proteins 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
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- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
Description
本発明は、導電性基板、有機半導体、および金属微粒子から構成される光触媒電極に関する。 The present invention relates to a photocatalytic electrode composed of a conductive substrate, an organic semiconductor, and metal fine particles.
水素は燃料電池自動車の燃料として欠かせない物質であり、今後の需要増大が予想されている。
水素を製造する手法として、メタンを原料とした工業プロセス（水蒸気改質法）が普及しているが、持続可能な社会の実現にむけて、化石燃料に依存しないクリーンな水素製造方法の開発が望まれている。
そこで注目されているのが、光触媒を利用した水分解水素生成法である。酸化チタンなどの半導体に対して、半導体のバンドギャップよりも大きなエネルギーを有する光を照射すると、価電子帯から伝導体への電子遷移が起こる。このとき、伝導体には励起電子が、価電子帯には正孔が、それぞれ生じる。伝導体の励起電子が水に移動すると水分子が還元分解し、水素が発生する。一方、伝導体に生成した正孔が水に移動すると水分子が酸化分解し、酸素が発生する。このような半導体の光触媒反応を利用した水分解は、本多‐藤島効果とよばれる（非特許文献１）。
Hydrogen is an essential substance as a fuel for fuel cell vehicles, and it is expected that demand will increase in the future.
As a method for producing hydrogen, an industrial process using methane as a raw material (steam reforming method) is widespread, but for the realization of a sustainable society, the development of a clean hydrogen production method that does not depend on fossil fuels Is desired.
Therefore, the water splitting hydrogen production method using a photocatalyst is drawing attention. When a semiconductor such as titanium oxide is irradiated with light having an energy larger than the band gap of the semiconductor, electronic transition from the valence band to the conductor occurs. At this time, excited electrons are generated in the conductor and holes are generated in the valence band. When the excited electrons of the conductor move to water, the water molecule undergoes reductive decomposition and hydrogen is generated. On the other hand, when the holes generated in the conductor move to water, water molecules are oxidatively decomposed to generate oxygen. Water splitting using such a photocatalytic reaction of a semiconductor is called the Honda-Fujishima effect (Non-Patent Document 1).
酸化チタンの光触媒反応を利用した水分解には、４００ nmよりも短波長の光を照射する必要がある。しかし、太陽光にはこのような波長域の光がほとんど含まれていないため、太陽光利用率が低いという欠点がある。太陽光利用率の向上にむけて、太陽光に豊富に含まれる可視光（波長がおよそ４００〜８００ nmの光）を利用可能な新たな光触媒（可視光応答型光触媒）の開発が求められている。 Water splitting using the photocatalytic reaction of titanium oxide requires irradiation with light having a wavelength shorter than 400 nm. However, since sunlight hardly contains light in such a wavelength range, there is a drawback that the sunlight utilization rate is low. Development of new photocatalyst (visible light responsive photocatalyst) that can utilize visible light (light with wavelength of approximately 400 to 800 nm), which is abundant in sunlight, is required to improve the utilization rate of sunlight. There is.
可視光応答型光触媒として、これまでにWO３（非特許文献２）、RuO２（非特許文献３）、Cu2O（非特許文献４）、Cu3VS４（特許文献１）などの無機化合物が報告されている。しかし、これらの化合物の合成には３５０℃以上の高温プロセスが必要である。また、このような無機半導体は吸収波長の改変が難しいため、太陽光の限られた領域の波長しか利用できないことが問題である。 As visible light responsive photocatalysts, inorganic materials such as WO 3 (Non-Patent Document 2), RuO 2 (Non-Patent Document 3), Cu 2 O (Non-Patent Document 4), and Cu 3 VS 4 (Patent Document 1) have been used so far. The compound has been reported. However, the synthesis of these compounds requires a high temperature process of 350° C. or higher. Further, since it is difficult to change the absorption wavelength of such an inorganic semiconductor, there is a problem that only wavelengths in a limited region of sunlight can be used.
太陽光の幅広い波長を有効に利用可能な光触媒材料として、非特許文献５ではZスキーム型光触媒材料が報告されている。Zスキーム型光触媒においては、２種類以上の無機半導体を組み合わせて使用することで、利用波長域を増大させている。しかし、複数種の半導体光触媒反応を同時・協奏的に進めるのは容易ではなく、系全体としての光変換効率は１．１％程度にとどまっている。 Non-Patent Document 5 reports a Z scheme type photocatalyst material as a photocatalyst material that can effectively use a wide wavelength range of sunlight. In the Z scheme type photocatalyst, the usable wavelength range is increased by using two or more kinds of inorganic semiconductors in combination. However, it is not easy to simultaneously and cooperatively proceed a plurality of types of semiconductor photocatalytic reactions, and the photoconversion efficiency of the entire system is only about 1.1%.
非特許文献６には、有機半導体としてピセン（C22H14）を利用した光触媒反応が報告されている。また、非特許文献７には可視光応答型の水分解光触媒としてDibenzo[b, g][1,5]naphthyridine-6,12-(5H, 11H)-dione（以下ＥＰＩと記す）が記載されている。これらの有機半導体は、前述の無機半導体にくらべて穏和な温度で合成することが可能である。また、有機半導体は分子構造の改変による吸収波長のコントロールが容易であり、１種類の半導体化合物のみを用いた単純な系でも、太陽光の幅広い波長域を利用可能な光触媒材料が実現できる。 Non-Patent Document 6 reports a photocatalytic reaction using picene (C 22 H 14 ) as an organic semiconductor. Further, Non-Patent Document 7 describes Dibenzo[b, g][1,5]naphthyridine-6,12-(5H, 11H)-dione (hereinafter referred to as EPI) as a visible light responsive water splitting photocatalyst. ing. These organic semiconductors can be synthesized at a milder temperature than the above-mentioned inorganic semiconductors. In addition, the absorption wavelength of an organic semiconductor can be easily controlled by modifying the molecular structure, and a photocatalytic material that can use a wide wavelength range of sunlight can be realized even in a simple system using only one kind of semiconductor compound.
しかし、有機半導体分子には水から水素への還元反応における良好な反応活性点が存在しないため、水分解水素発生の触媒活性に乏しいという欠点がある。 However, since organic semiconductor molecules do not have good reaction active points in the reduction reaction from water to hydrogen, they have a drawback that they have poor catalytic activity for hydrogen generation in water splitting.
従来の無機半導体ベースの光触媒は、吸収波長域の精密制御が困難なことが問題であった。一方、有機半導体ベースの光触媒は、分子構造の改変による吸収波長域の制御が容易であるが、水分解水素発生における反応活性点となる部位が存在しないために、光触媒活性が低いことが問題であった。
本発明では、有機半導体の表面に水素発生の触媒活性点となるサイトを付与することで上記の問題を解決し、水分解水素発生の効率を向上させる方法を提供する。
The conventional inorganic semiconductor-based photocatalyst has a problem that it is difficult to precisely control the absorption wavelength range. On the other hand, the organic semiconductor-based photocatalyst is easy to control the absorption wavelength range by modifying the molecular structure, but it has a problem that the photocatalytic activity is low because there is no site that becomes the reaction active point in the generation of hydrogen from water splitting. there were.
The present invention provides a method for solving the above problems and improving the efficiency of water splitting hydrogen generation by providing sites on the surface of an organic semiconductor that are catalytically active sites for hydrogen generation.
本発明は、有機半導体を使用した光触媒電極に関するものである。
光触媒反応を用いた水分解水素発生を実現するにあたって、有機半導体としては以下の３つの要件を満たすものを使用する必要がある。
「１」 最高被占軌道（HOMO）と最低空軌道（LUMO）のエネルギー差が１．２ｅＶ以上であること。
「２」 反応溶液中におけるLUMOのエネルギー準位が、可逆水素電極（ＲＨＥ）に対して０ Ｖよりも卑な電位にあること。
「３」 反応溶液中におけるHOMOのエネルギー準位が、＋１．２Ｖｖｓ.ＲＨＥより貴な電位にあること。
また、可視光の利用を可能とするためには、下記の要件も満たした有機半導体を使用する必要がある。
「４」 HOMOとLUMOのエネルギー差が３ｅＶ以下であること。
The present invention relates to a photocatalytic electrode using an organic semiconductor.
In order to realize water splitting hydrogen generation using a photocatalytic reaction, it is necessary to use an organic semiconductor that satisfies the following three requirements.
“1” The energy difference between the highest occupied orbit (HOMO) and the lowest unoccupied orbit (LUMO) must be 1.2 eV or more.
[2] The LUMO energy level in the reaction solution is at a base potential lower than 0 V with respect to the reversible hydrogen electrode (RHE).
[3] The energy level of HOMO in the reaction solution is at a potential nobler than +1.2 Vvs.RHE.
In order to use visible light, it is necessary to use an organic semiconductor that also satisfies the following requirements.
“4” Energy difference between HOMO and LUMO must be 3 eV or less.
本発明では、上記条件を満たす有機半導体１２０の表面に、水分解水素発生のための触媒活性点として金属微粒子１３０を塗布した光触媒電極１００を提供する。この電極１００においては、有機半導体１２０の支持体として導電性の基板１１０を使用する。
本光触媒電極においては、有機半導体で光励起した電子は、有機半導体表面の金属微粒子に移動する。金属微粒子表面では、この電子を利用した水分子の還元反応が高速に起こるため、有機半導体を単独で用いた系よりも触媒活性が向上する。
The present invention provides the photocatalyst electrode 100 in which the surface of the organic semiconductor 120 satisfying the above conditions is coated with the fine metal particles 130 as the catalytic active sites for the generation of water splitting hydrogen. In this electrode 100, a conductive substrate 110 is used as a support for the organic semiconductor 120.
In the photocatalyst electrode, the electrons photoexcited by the organic semiconductor move to the metal fine particles on the surface of the organic semiconductor. On the surface of the metal fine particles, the reduction reaction of water molecules using the electrons occurs at a high speed, so that the catalytic activity is improved as compared with the system using the organic semiconductor alone.
本発明によれば、有機半導体を利用した光触媒水分解反応における触媒活性を向上させることができる。 According to the present invention, it is possible to improve the catalytic activity in the photocatalytic water splitting reaction using an organic semiconductor.
本発明では、上記の[1]〜[4]の要件を満たす有機半導体として、エピンドリジオン骨格を含有する有機化合物群（図２）を使用する。以下の実施例では、Ｄｉｂｅｎｚｏ［ｂ, ｇ］［１，５］ｎａｐｈｔｈｙｒｉｄｉｎｅ−６,１２−（５Ｈ, １１Ｈ）−ｄｉｏｎｅ（以下、ＥＰＩと記す）と２，８−ｄｉｆｌｕｏｒｏｄｉｂｅｎｚｏ［ｂ, ｇ］［１，５］ｎａｐｈｔｈｙｒｉｄｉｎｅ−６,１２−（5Ｈ, １１Ｈ）−ｄｉｏｎｅ（以下、2Ｆ-ＥＰＩと記す）を使用した例を示すが、本発明はこれらの化合物を用いたものに限定されるものではない。また、本発明の光触媒電極における有機半導体層については、２種類以上の化合物を組み合わせて使用しても良い。 In the present invention, a group of organic compounds containing an epindridione skeleton (FIG. 2) is used as an organic semiconductor satisfying the above requirements [1] to [4]. In the following examples, Dibenzo[b,g][1,5]naphthyridine-6,12-(5H,11H)-dione (hereinafter referred to as EPI) and 2,8-difluorodibenzo[b,g][1 , 5] Naphthyridine-6,12-(5H, 11H)-dione (hereinafter, referred to as 2F-EPI) is shown, but the present invention is not limited to the use of these compounds. .. Further, for the organic semiconductor layer in the photocatalyst electrode of the present invention, two or more kinds of compounds may be used in combination.
上記有機半導体１２０の表面には、金属微粒子１３０を塗布する。塗布する金属は３族から１１族の元素から選択することができる。この金属種については、白金やニッケルなど、水素過電圧の小さな元素から選択することが望ましい。金属微粒子のサイズについては、平均粒子径が５００ｎｍ以下のものを用いることが好ましい。金属微粒子の塗布方法については、直流スパッタリング法や交流スパッタリング法などが使用できるが、塗布された金属の平均粒子径が５００ｎｍ以下という条件を満たせば特に限定されるものではない。 Metal fine particles 130 are applied to the surface of the organic semiconductor 120. The metal to be applied can be selected from elements of groups 3 to 11. This metal species is preferably selected from elements having a small hydrogen overvoltage, such as platinum and nickel. Regarding the size of the metal fine particles, it is preferable to use those having an average particle diameter of 500 nm or less. As a coating method of the metal fine particles, a DC sputtering method or an AC sputtering method can be used, but it is not particularly limited as long as the average particle diameter of the coated metal is 500 nm or less.
上記有機半導体１２０の支持体としては、導電性の基板１１０を用いる。有機半導体に対する光照射効率を高めるため、基板１１０としてはフッ素ドープ酸化スズ膜（FTO）やスズドープ参加インジウム膜（ITO）をコーティングしたガラス基板など、透明の材料を使用することが望ましい。
上記電極１００を用いた光水分解の装置としては、図３のような構造のもの（２００）を使用できる。この装置は、光触媒電極１００、対電極２１０、電解液水溶液２２０、容器２３０から構成される。光触媒電極１００に光２４０を照射することで、電極１００の表面で電解液水溶液２２０が分解し、水素が発生する。また、このとき同時に対電極２１０では電解液水溶液２２０が酸化分解し、酸素が発生する。水素発生の速度を向上させるため、電極１００と電極２１０の間にポテンショスタット２５０を挿入し、電極１００に対してバイアス電圧を印加することもできる。バイアス電圧を制御するために、２２０には参照電極２６０を挿入することができる。
光２４０としては太陽光のほか、水銀灯、キセノンランプ、発光ダイオード（LED）など光源を用いて発生させた可視光を使用することができる。この光については、有機半導体１２０を光励起させるため、有機半導体１２０のバンドギャップよりも大きなエネルギーの光を含んだ光源を使用する必要がある。
A conductive substrate 110 is used as a support for the organic semiconductor 120. In order to increase the light irradiation efficiency of the organic semiconductor, it is desirable to use a transparent material such as a glass substrate coated with a fluorine-doped tin oxide film (FTO) or a tin-doped indium film (ITO) as the substrate 110.
As a device for water splitting using the electrode 100, a device (200) having a structure as shown in FIG. 3 can be used. This device includes a photocatalyst electrode 100, a counter electrode 210, an electrolytic solution 220, and a container 230. By irradiating the photocatalyst electrode 100 with light 240, the electrolytic solution 220 is decomposed on the surface of the electrode 100 to generate hydrogen. At this time, at the same time, the electrolyte solution 220 is oxidized and decomposed in the counter electrode 210 to generate oxygen. In order to improve the rate of hydrogen generation, a potentiostat 250 may be inserted between the electrode 100 and the electrode 210 to apply a bias voltage to the electrode 100. A reference electrode 260 may be inserted at 220 to control the bias voltage.
As the light 240, in addition to sunlight, visible light generated by using a light source such as a mercury lamp, a xenon lamp, or a light emitting diode (LED) can be used. With respect to this light, in order to optically excite the organic semiconductor 120, it is necessary to use a light source containing light having an energy larger than the band gap of the organic semiconductor 120.
以下、本発明の光触媒電極について実施例を用いて説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the photocatalyst electrode of the present invention will be described using examples, but the present invention is not limited to these examples.
本実施例では、導電基板１１０としてＦＴＯ、有機半導体１２０としてＥＰＩ、金属微粒子１３０として白金を使用した光触媒電極の製造方法と、その光触媒電極を用いた水分解反応についての実施例を示す。
＜１−１．ＥＰＩの合成＞
ジヒドロキシフマル酸１３．２６gを無水メタノール７０mLに溶解させた。この溶液に０℃で攪拌しながら塩化チオニル（１３．４ml）を１５分かけて滴下した。滴下終了後、室温でこの溶液4日間攪拌し、その後、吸引ろ過によって固形物を回収した。得られた固形物をメタノール２０mLとイオン交換水８０ｍLで洗浄し、６０℃で真空乾燥することで、ｄｉｍｅｔｈｙｌ ｄｉｈｙｄｒｏｘｙｆｕｍａｒａｔｅ（中間体１）を得た。
In this example, a method for manufacturing a photocatalyst electrode using FTO as the conductive substrate 110, EPI as the organic semiconductor 120, and platinum as the metal fine particles 130, and a water splitting reaction using the photocatalyst electrode will be described.
<1-1. Synthesis of EPI>
13.26 g of dihydroxyfumaric acid was dissolved in 70 mL of anhydrous methanol. Thionyl chloride (13.4 ml) was added dropwise to this solution over 15 minutes while stirring at 0°C. After the dropping was completed, the solution was stirred at room temperature for 4 days, and then a solid substance was collected by suction filtration. The obtained solid matter was washed with 20 mL of methanol and 80 mL of ion-exchanged water, and dried under vacuum at 60° C. to obtain dimethyl dihydroxyfumarate (intermediate 1).
続いて、中間体１を無水メタノール５０ｍＬと濃塩酸０．６５ｍＬの混合液に溶解させた。続いて、アニリン１２．９６ｇを加え、７０℃で１時間還流した。その後、この溶液を５時間かけて室温まで冷却し、固体を析出させた。この固体を吸引ろ過によって回収した。回収物をメタノールで洗浄した後、６０℃で真空乾燥し、Ｄｉｍｅｔｈｙｌ ２，３−ｂｉｓ（ｐｈｅｎｙｌａｍｉｎｏ）ｍａｌｅａｔｅ（中間体２）を得た。
次に、熱媒体ダウサムA（２６０ｍＬ）に中間体２を16.15g加え、260℃で３０分間還流した。その後、この溶液を18時間かけて室温まで冷却し、固体を析出させた。次に、この固体を吸引ろ過しによって回収し、石油エーテル３００ｍＬで洗浄した。さらに60℃で真空乾燥することで、２−Ｍｅｔｈｏｘｙｃａｒｂｏｎｙｌ−３−ｐｈｅｎｙｌａｍｉｎｏ−４−ｑｕｉｎｏｌｏｎｅ（中間体３）を得た。
Subsequently, Intermediate 1 was dissolved in a mixed solution of 50 mL of anhydrous methanol and 0.65 mL of concentrated hydrochloric acid. Subsequently, 12.96 g of aniline was added, and the mixture was refluxed at 70° C. for 1 hour. Then, this solution was cooled to room temperature over 5 hours to precipitate a solid. The solid was collected by suction filtration. The recovered product was washed with methanol and then vacuum dried at 60° C. to obtain Dimethyl 2,3-bis(phenylamino)maleate (Intermediate 2).
Next, 16.15 g of Intermediate 2 was added to heat medium Dowsome A (260 mL), and the mixture was refluxed at 260° C. for 30 minutes. Then, this solution was cooled to room temperature over 18 hours to precipitate a solid. The solid was then collected by suction filtration and washed with 300 mL petroleum ether. Further, it was vacuum dried at 60° C. to obtain 2-Methoxyxycarbonyl-3-phenylamino-4-quinolone (intermediate 3).
次に、中間体３をポリリン酸83.2gに加え、１５０℃で３．５時間攪拌した。その後、液温を５０℃に保ちながらイオン交換水７００ｍＬを加えた。次に、分散液中の固体を吸引ろ過で回収し、イオン交換水約１Ｌとメタノール約５００ｍＬで洗浄した。さらに、この固体を８０℃で真空乾燥し、ＥＰＩの粉末を得た。 Next, the intermediate body 3 was added to 83.2 g of polyphosphoric acid, and it stirred at 150 degreeC for 3.5 hours. Then, 700 mL of ion-exchanged water was added while maintaining the liquid temperature at 50°C. Next, the solid in the dispersion was collected by suction filtration and washed with about 1 L of ion-exchanged water and about 500 mL of methanol. Further, this solid was vacuum dried at 80° C. to obtain EPI powder.
＜１−２．ＥＰＩのＦＴＯ基板への固定化＞
１−１で得られたＥＰＩを、表面にＦＴＯ薄膜を有するガラス基板（以下、ＦＴＯ基板と記載する）上に真空蒸着した。ＥＰＩの酸化を防ぐため、真空蒸着時の装置内は1ｍＰａ以下の圧力に設定した。この際、ＥＰＩの蒸着面積はマスクを用いて１．５ｃｍ×０．８ｃｍに規定した。また、蒸着後のＥＰＩの膜厚が３００ｎｍになるように、蒸着時間を調整した。
<1-2. Immobilization of EPI on FTO substrate>
The EPI obtained in 1-1 was vacuum-deposited on a glass substrate having an FTO thin film on its surface (hereinafter referred to as an FTO substrate). In order to prevent the oxidation of EPI, the pressure inside the apparatus during vacuum deposition was set to 1 mPa or less. At this time, the deposition area of EPI was defined to be 1.5 cm×0.8 cm using a mask. The vapor deposition time was adjusted so that the EPI film thickness after vapor deposition was 300 nm.
＜１−３．ＥＰＩ表面への白金微粒子の塗布＞
１−２で得られた基板のＥＰＩ層の表面に白金微粒子を塗布するため、白金板をターゲットとしたスパッタリング処理を行った。この処理には日本電子株式会社製の直流スパッタ装置JEC-3000FC AUTO FINE COATERを用いた。処理時の装置内圧力は２Ｐａに設定した。また、スパッタリング時間は2分間に設定した。
<1-3. Application of platinum fine particles to EPI surface>
In order to coat the platinum fine particles on the surface of the EPI layer of the substrate obtained in 1-2, a sputtering treatment using a platinum plate as a target was performed. A DC sputtering device JEC-3000FC AUTO FINE COATER manufactured by JEOL Ltd. was used for this treatment. The internal pressure of the device during processing was set to 2 Pa. The sputtering time was set to 2 minutes.
＜１−４．光触媒電極を用いた水分解装置の構築とその特性評価＞
１−３で得られた電極を作用電極、銀‐塩化銀電極を参照極、白金メッシュを対極としたガラス製の３電極式電解セルを構築した。この電解セルの内部は、電解液として１ｍｏｌ/Ｌの塩酸を満たした。Ｐｒｉｎｃｅｔｏｎ Ａｐｐｌｉｅｄ Ｒｅｓｅａｒｃｈ社製のポテンショスタット（ＶｅｒｓａＳＴＡＴ ３）を用いて参照極に対する作用極の電位が０Ｖになるようにバイアス電位を印加した条件で、作用極に５００W/m2の疑似太陽光を照射し、光応答電流の測定を行った。疑似太陽光の発生には、株式会社三永電機製作所製のソーラーシミュレータ（ＸＥＳ−４０Ｓ２−ＣＥ）を用いた。
<1-4. Construction of water splitting device using photocatalyst electrode and its characterization>
A three-electrode electrolytic cell made of glass having the working electrode as the electrode obtained in 1-3, the silver-silver chloride electrode as the reference electrode, and the platinum mesh as the counter electrode was constructed. The inside of this electrolytic cell was filled with 1 mol/L hydrochloric acid as an electrolytic solution. A potentiostat (VersaSTAT 3) manufactured by Princeton Applied Research was used to irradiate the working electrode with pseudo-sunlight of 500 W/m 2 under the condition that a bias potential was applied so that the potential of the working electrode with respect to the reference electrode was 0 V. The light response current was measured. A solar simulator (XES-40S2-CE) manufactured by Sanei Electric Co., Ltd. was used to generate the pseudo sunlight.
＜結果＞
本実施例で作成した光触媒電極の性能について、１−４の実験で得られた光応答電流を図４に示す。この測定では光照射のＯＮ／ＯＦＦを周期的に切り替えた。光をＯＮにすると電流値が負側に立ち上がり、光をＯＦＦにすると電流値が正側に戻る様子が観測された。光照射時に発生する負の電流は、光触媒電極上での水素発生に対応したものである。この結果から、本発明の光触媒電極が水分解に利用できることが確認できる。
<Results>
Regarding the performance of the photocatalyst electrode prepared in this example, the photoresponse current obtained in the experiments of 1-4 is shown in FIG. In this measurement, ON/OFF of light irradiation was periodically switched. It was observed that when the light was turned on, the current value rose to the negative side, and when the light was turned off, the current value returned to the positive side. The negative current generated during light irradiation corresponds to hydrogen generation on the photocatalytic electrode. From this result, it can be confirmed that the photocatalytic electrode of the present invention can be used for water decomposition.
金属微粒子の塗布によって光触媒活性が向上することを示すため、実施例１の１−３の操作を除いて、金属微粒子を含まない光触媒電極を作製した。
＜結果＞
得られた光触媒電極の特性については、１−４と同様の方法で評価した。測定結果を図５に示す。本例で作製した光触媒電極の光応答電流（光照射時による水分解水素発生に対応する負の電流）は、実施例１にくらべて小さいことが読み取れる。この実験によって、有機半導体ＥＰＩの光触媒活性の向上に対して白金微粒子の塗布が有効なことが示された。
In order to show that the photocatalytic activity is improved by coating the metal fine particles, a photocatalyst electrode containing no metal fine particles was prepared except for the operations 1-3 in Example 1.
<Results>
The characteristics of the obtained photocatalytic electrode were evaluated in the same manner as in 1-4. The measurement result is shown in FIG. It can be read that the photoresponsive current of the photocatalyst electrode manufactured in this example (a negative current corresponding to the generation of hydrogen in water by light irradiation) is smaller than that in Example 1. This experiment showed that the application of platinum fine particles was effective for improving the photocatalytic activity of the organic semiconductor EPI.
実施例１について、金属微粒子１３０を白金からニッケルに変更した電極を作成した。本実施例の光触媒電極においては、実施例１の１−３の部分を下記の方法に置き換えた手順で作製した。
＜２−１．ＥＰＩ表面へのニッケル微粒子の塗布＞
１−２で得られた基板のＥＰＩ層の表面にニッケル微粒子を塗布するため、ニッケル板をターゲットとしたスパッタリング処理を行った。この処理にはアルバック機構株式会社製の高周波スパッタ装置ＶＴＲ−１５１Ｍ/ＳＲＦを用いた。処理時の装置内雰囲気はアルゴンガス５Ｐａに設定した。スパッタリング時の投入電力は５０Ｗに設定した。また、スパッタリング時間は2分間に設定した。
Regarding Example 1, an electrode was prepared in which the metal fine particles 130 were changed from platinum to nickel. The photocatalyst electrode of this example was produced by a procedure in which the parts 1-3 of Example 1 were replaced by the following method.
<2-1. Application of nickel fine particles to EPI surface>
In order to apply the nickel fine particles to the surface of the EPI layer of the substrate obtained in 1-2, a sputtering process using a nickel plate as a target was performed. A high frequency sputtering apparatus VTR-151M/SRF manufactured by ULVAC CORPORATION was used for this treatment. The atmosphere in the apparatus during processing was set to 5 Pa for argon gas. The input power at the time of sputtering was set to 50W. The sputtering time was set to 2 minutes.
＜結果＞
得られた光触媒電極の特性については、１−４と同様の方法で評価した。測定結果を図６に示す。金属微粒子をニッケルとした本実施例においても、実施例１と類似した光応答電流が観測された。また、この光応答電流の振幅は比較例１よりも大きなものであった。本実験により、金属微粒子として、ニッケルも使用可能なことが確認できた。
<Results>
The characteristics of the obtained photocatalytic electrode were evaluated in the same manner as in 1-4. The measurement result is shown in FIG. Also in this example in which the metal fine particles were nickel, a photoresponse current similar to that in Example 1 was observed. The amplitude of this photo-responsive current was larger than that of Comparative Example 1. By this experiment, it was confirmed that nickel can be used as the metal fine particles.
実施例１について、金属微粒子１３０を白金からチタンに変更した電極を作成した。本実施例の光触媒電極においては、実施例１の１−３の部分を、下記の方法に置き換えた手順で作製した。
＜３−１．ＥＰＩ表面へのチタン微粒子の塗布＞
１−２で得られた基板のＥＰＩ層の表面に白金微粒子を塗布するため、チタン板をターゲットとしたスパッタリング処理を行った。この処理にはアルバック機構株式会社製の高周波スパッタ装置ＶＴＲ−１５１Ｍ/ＳＲＦを用いた。スパッタリング時の投入電力は５０Ｗに設定した。処理時の装置内雰囲気はアルゴンガス５Ｐａに設定した。また、スパッタリング時間は2分間に設定した。
Regarding Example 1, an electrode was prepared in which the metal fine particles 130 were changed from platinum to titanium. In the photocatalyst electrode of this example, the steps 1-3 of Example 1 were replaced by the following method.
<3-1. Application of titanium fine particles to EPI surface>
In order to apply the platinum fine particles to the surface of the EPI layer of the substrate obtained in 1-2, sputtering treatment using a titanium plate as a target was performed. A high frequency sputtering apparatus VTR-151M/SRF manufactured by ULVAC CORPORATION was used for this treatment. The input power at the time of sputtering was set to 50W. The atmosphere in the apparatus during processing was set to 5 Pa for argon gas. The sputtering time was set to 2 minutes.
＜結果＞
得られた光触媒電極の特性については、１−４と同様の方法で評価した。測定結果を図７に示す。金属微粒子をチタンとした本実施例においても、実施例１と類似した光応答電流が観測された。また、この光応答電流の振幅は比較例１よりも大きなものであった。本実験により、金属微粒子として、チタンも使用可能なことが示された
<Results>
The characteristics of the obtained photocatalytic electrode were evaluated in the same manner as in 1-4. The measurement result is shown in FIG. 7. Also in this example in which the metal fine particles were titanium, a photoresponse current similar to that in Example 1 was observed. The amplitude of this photo-responsive current was larger than that of Comparative Example 1. This experiment showed that titanium can also be used as the metal fine particles.
ＥＰＩ以外の有機半導体が使用可能なことを示すため、本実施例では、導電基板１１０としてＦＴＯ、有機半導体層１２０としてＥＰＩと２Ｆ−ＥＰＩの積層物、金属微粒子１３０として白金を使用した光触媒電極の製造方法と、その光触媒電極を用いた水分解反応についての実施例を示す。
＜４−１．２Ｆ−ＥＰＩの合成＞
実施例１の１−１について、アニリンを４−フルオロアニリンに置き換えることで２Ｆ−ＥＰＩを合成した。４−フルオロアニリンを用いたことを除いて、１−１との違いはない。
In order to show that an organic semiconductor other than EPI can be used, in the present embodiment, a photocatalyst electrode using FTO as the conductive substrate 110, a laminate of EPI and 2F-EPI as the organic semiconductor layer 120, and platinum as the metal fine particles 130. An example of the production method and the water splitting reaction using the photocatalytic electrode is shown.
<Synthesis of 4-1.2F-EPI>
Regarding 1-1 of Example 1, 2F-EPI was synthesized by replacing aniline with 4-fluoroaniline. There is no difference from 1-1 except that 4-fluoroaniline was used.
＜４−２．２Ｆ−ＥＰＩおよびＥＰＩのＦＴＯ基板への固定化＞
１−２と同様の手順で、ＦＴＯ基板上にＥＰＩ（１−１に記した方法で合成）を厚さ３００ｎｍとなるように真空蒸着した。続けて、このＥＰＩ層の上に、２Ｆ―ＥＰＩを厚さ３００ｎｍになるように真空蒸着した。ＥＰＩおよび２Ｆ―ＥＰＩの蒸着面積は１−２と同様に１．５ｃｍ×０．８ｃｍとした。
<4-2.2 F-EPI and Immobilization of EPI on FTO Substrate>
EPI (synthesized by the method described in 1-1) was vacuum-deposited on the FTO substrate to a thickness of 300 nm by the same procedure as in 1-2. Subsequently, 2F-EPI was vacuum-deposited on the EPI layer to a thickness of 300 nm. The vapor deposition area of EPI and 2F-EPI was 1.5 cm×0.8 cm as in 1-2.
＜２−４．２Ｆ−ＥＰＩ表面への白金微粒子の塗布＞
４−２で得られた基板の２Ｆ−ＥＰＩ層の表面に白金微粒子を塗布するため、白金板をターゲットとしたスパッタリング処理を行った。この処理には日本電子株式会社製の直流スパッタ装置ＪＥＣ−３０００ＦＣ ＡＵＴＯ ＦＩＮＥ ＣＯＡＴＥＲを用いた。処理時の装置内圧力は２Ｐａに設定した。また、スパッタリング時間は2分間に設定した。
<2-4.2 Application of platinum fine particles to the surface of F-EPI>
In order to coat the platinum fine particles on the surface of the 2F-EPI layer of the substrate obtained in 4-2, sputtering treatment using a platinum plate as a target was performed. A DC sputtering device JEC-3000FC AUTO FINE COATER manufactured by JEOL Ltd. was used for this treatment. The internal pressure of the device during processing was set to 2 Pa. The sputtering time was set to 2 minutes.
＜２−４．光触媒電極を用いた水分解装置の構築とその特性評価＞
１−４と同様の評価セルを構築し、光触媒電極としての特性評価を行った。本実験では、測定中に光のＯＮ／ＯＦＦを行わず、光を照射し続けた状態で光電流のモニタリングを行った。
<2-4. Construction of water splitting device using photocatalyst electrode and its characterization>
An evaluation cell similar to 1-4 was constructed and the characteristics of the photocatalyst electrode were evaluated. In this experiment, the photocurrent was monitored while the light was kept being radiated without turning ON/OFF the light during the measurement.
＜結果＞
測定結果を図８に示す。本実施例においても、光照射時に水分解水素発生に由来する応答電流が観測された。光応答電流の大きさは比較例１よりも大きいことがわかる。本実験により、ＥＰＩ以外の有機半導体を用いた有機半導体‐金属微粒子複合系でも光触媒電極として機能することが示された。
<Results>
The measurement result is shown in FIG. Also in this example, a response current derived from water splitting hydrogen generation was observed at the time of light irradiation. It can be seen that the magnitude of the photoresponse current is larger than that in Comparative Example 1. This experiment showed that an organic semiconductor-metal fine particle composite system using an organic semiconductor other than EPI also functions as a photocatalytic electrode.
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| EP3241617A1 (en) * | 2016-05-02 | 2017-11-08 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | A method for light-induced actuation of ph-sensitive assemblies and a composite material therefore |
| US20180027809A1 (en) * | 2016-07-28 | 2018-02-01 | eXion labs Inc. | Antimicrobial photoreactive composition comprising organic and inorganic multijunction composite |
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