JP2010254489A - Device for generating hydrogen using photocatalyst - Google Patents
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 71
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 71
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 230000001699 photocatalysis Effects 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
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- 238000000034 method Methods 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011343 solid material Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000002834 transmittance Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 5
- 230000001133 acceleration Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
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- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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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
-
- 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
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Abstract
Description
本発明は、光触媒を用いて太陽光と水から水素、および酸素を生成せしめるデバイス、装置に係わる発明であり、太陽光利用技術、エネルギー変換技術、水素を生成、製造する技術に関する技術である。 The present invention relates to a device and an apparatus for generating hydrogen and oxygen from sunlight and water using a photocatalyst, and relates to a technology for utilizing sunlight, an energy conversion technology, and a technology for producing and producing hydrogen.
炭酸ガス排出削減、エネルギーのクリーン化の観点から、水素エネルギーシステムが注目されている。水素をエネルギー媒体に使うことにより、燃料電池で電気や熱、直接燃焼で熱や動力として使用できる。この時、最終生成物は無害、安全な水となり、クリーンなエネルギー循環サイクルが創出できる。エネルギー媒体としての水素は、天然にも存在するが、ほとんどは石油や、天然ガスから触媒によるクラッキングにより製造される。また、水を電気分解することにより、水素と酸素を製造することが可能であるが、電気分解する電気エネルギーが必要であり、根本的な解決にならない。ただし、太陽電池により光エネルギーを電気に変え、その電力で電気分解するシステムは可能であるが、太陽電池の製造コスト、エネルギー消費量、蓄電技術を考慮すると、必ずしも有効な製造方法とはいえない。 Hydrogen energy systems are attracting attention from the perspective of reducing carbon dioxide emissions and cleaning energy. By using hydrogen as an energy medium, it can be used as electricity or heat in fuel cells, or as heat or power in direct combustion. At this time, the final product is harmless and safe water, and a clean energy circulation cycle can be created. Hydrogen as an energy medium exists in nature, but most of it is produced from petroleum or natural gas by catalytic cracking. In addition, it is possible to produce hydrogen and oxygen by electrolyzing water, but electric energy to be electrolyzed is necessary, which is not a fundamental solution. However, a system that converts light energy into electricity with a solar cell and electrolyzes it with electricity is possible, but it is not always an effective manufacturing method in consideration of the manufacturing cost, energy consumption, and power storage technology of the solar cell. .
これに対し、光触媒を用いた水素生成は、水と太陽光とから直接水素を製造するシステムであり、太陽光エネルギーを有効に水素エネルギーに変換できる。ただし、代表的な光触媒のアナタース型の酸化チタンを用いても、太陽光変換効率としても、0.5%程度であり、まだまだ効率を向上させる必要がある。酸化チタン光触媒自体が、太陽光の400nm以下の紫外線しか吸収励起しないところに課題があり、材料の可視光化、および可視光応答材料の開発が待たれている(特許文献1)。一方、効率よく水素を製造するセル、デバイス、および装置の検討もされつつある。大きくは、粉末式と電極式に分けられる。
粉末式は、水溶液に直接粉末化した光触媒材料を分散させて、粒子に光を照射することにより、水素と酸素を生成させ、一定量のガスが生成したところで、酸素と水素に分離して取り出す方式である。一方、電極式は、光触媒をITO膜や、導電性基板上に塗布、成膜し、電極化したものと、対極として白金板などの導電体を導線で接続し、光触媒が形成された電極に光を照射し、酸素発生と同時に励起した電子を対極に導き、対極で水素を発生させる。粉末式は構造が簡単、簡便であるが、水素、酸素の分離が困難で、効率が低下する。電極式は、水素と酸素は別々の極で発生させるので、分離は簡単であるが、電極に成形する制約が発生する。
In contrast, hydrogen generation using a photocatalyst is a system that directly produces hydrogen from water and sunlight, and can effectively convert solar energy into hydrogen energy. However, even if anatase type titanium oxide, a typical photocatalyst, is used, the solar conversion efficiency is about 0.5%, and it is still necessary to improve the efficiency. There is a problem in that the titanium oxide photocatalyst itself absorbs and excites only ultraviolet rays of 400 nm or less of sunlight, and the development of a visible light responsive material and a visible light responsive material is awaited (Patent Document 1). On the other hand, cells, devices, and apparatuses that efficiently produce hydrogen are being studied. In general, it can be divided into a powder type and an electrode type.
In the powder type, hydrogen and oxygen are generated by dispersing photocatalytic material directly in an aqueous solution and irradiating the particles with light. When a certain amount of gas is generated, oxygen and hydrogen are separated and taken out. It is a method. On the other hand, in the electrode type, a photocatalyst is applied to an ITO film or a conductive substrate, formed into an electrode, and a conductive material such as a platinum plate is connected as a counter electrode with a conductive wire to the electrode on which the photocatalyst is formed. Irradiates light, guides the excited electrons simultaneously with the generation of oxygen to the counter electrode, and generates hydrogen at the counter electrode. The powder type is simple and simple in structure, but it is difficult to separate hydrogen and oxygen, and the efficiency is lowered. In the electrode type, since hydrogen and oxygen are generated at separate poles, separation is easy, but there are restrictions on forming into electrodes.
さて、電極式の水素生成デバイスを考えた場合、光を受光して電気を作るところは太陽電池と、水との反応を考えた場合、電気分解槽が近い構造体が考えられるが、光触媒水分解反応は、光と水と固体とガスの各々の反応場を考慮したセル構造体、デバイスの設計が必要であった。 Now, when considering an electrode-type hydrogen generation device, the place where light is received to produce electricity is a structure close to the electrolysis tank when considering the reaction between the solar cell and water. In the decomposition reaction, it was necessary to design a cell structure and a device in consideration of each reaction field of light, water, solid and gas.
電極方式の光触媒水素生成デバイスにおいて、水素生成極と酸素生成極を分離して、ガスの混合、再結合を防止する構造が提案されている。しかしながらこの場合、光を受光して触媒反応を起こさせる電極表面で酸素を生成し、その発生気泡が電極に吸着した状態に
なりことにより、光路を妨げたり、また、反応拡散抵抗を大きくしていた。その結果、デバイスの効率の低下をまねいていた。同様に、対極の水素生成極でも、拡散抵抗の上昇をひきおこし、効率を低下させていた。水素生成効率を向上させるには、気泡による光遮断の低減、電極気泡の除去・拡散の促進が必要であり、高効率受光、電極気泡の高拡散化が課題であった。
In an electrode-type photocatalytic hydrogen generation device, a structure has been proposed in which a hydrogen generation electrode and an oxygen generation electrode are separated to prevent gas mixing and recombination. However, in this case, oxygen is generated on the surface of the electrode that receives light and causes a catalytic reaction, and the generated bubbles are adsorbed on the electrode, thereby obstructing the optical path and increasing the reaction diffusion resistance. It was. As a result, the efficiency of the device was reduced. Similarly, the hydrogen generation electrode as a counter electrode also caused an increase in diffusion resistance and reduced efficiency. In order to improve the hydrogen generation efficiency, it is necessary to reduce light blocking by bubbles and promote removal / diffusion of electrode bubbles, and high efficiency light reception and high diffusion of electrode bubbles have been problems.
本発明は、上記課題に鑑み、光透過セルと、水溶液と光触媒電極と、対極とからなる水素生成デバイスにおいて、水溶液を物理的攪拌することを特徴とする、また、水溶液を攪拌する攪拌機を配備することを特徴とする光触媒水素生成デバイスを提案するものであって、攪拌機が、攪拌子またはプロペラ式攪拌機であること、または、汲み上げポンプであること、更に水温の熱対流による攪拌であることを特徴とする。また、水溶液中に微粒子固体物を分散させ物理的攪拌すること、一定表面を保有する光触媒電極、および対極を水平面から傾斜させることを特徴とするデバイスを提供し、具体的には、粒径が10μm以下のシリカ、ゼオライトの固体物を溶液中に、混合比が0.001から20重量%となることを特徴とする光触媒水素生成デバイスを提供するものである。 In view of the above problems, the present invention provides a hydrogen generation device including a light transmission cell, an aqueous solution, a photocatalyst electrode, and a counter electrode, wherein the aqueous solution is physically stirred, and a stirrer for stirring the aqueous solution is provided. Proposing a photocatalytic hydrogen generation device characterized in that the stirrer is a stirrer or a propeller type stirrer, or is a pumping pump, and further agitated by heat convection at a water temperature. Features. Further, the present invention provides a device characterized by dispersing a solid fine particle in an aqueous solution and physically stirring, a photocatalyst electrode having a constant surface, and a counter electrode inclined from a horizontal plane. The present invention provides a photocatalytic hydrogen generation device characterized in that a mixing ratio of silica and zeolite solids of 10 μm or less in a solution is 0.001 to 20% by weight.
水溶液を物理的攪拌して水流をおこさせることにより、また、水溶液中に微粒子固体物を分散させ、物理的に電極に付着した気泡をたたき出すことにより、さらに、一定表面を保有する光触媒電極、および対極を水平面から傾斜させ、固体物質の接触率を向上させることにより、光路の確保と、反応拡散抵抗の低減を図り、高効率受光、電極気泡の高拡散化で、水素生成効率の向上が可能となる。従来にない、高い効率の光触媒水素生成デバイス、および装置を提供できる。 A photocatalytic electrode having a constant surface by physically stirring the aqueous solution, causing fine particles to disperse in the aqueous solution, and physically ejecting bubbles attached to the electrode; and By tilting the counter electrode from the horizontal plane and improving the contact rate of the solid substance, it is possible to secure the optical path and reduce the reaction diffusion resistance, and to improve the hydrogen generation efficiency by high efficiency light reception and high diffusion of electrode bubbles It becomes. An unprecedented highly efficient photocatalytic hydrogen generation device and apparatus can be provided.
以下に、本発明を具体的に説明する。 The present invention will be specifically described below.
本実施形態の水素生成デバイスは、図1に示すように、光透過セル5と、水溶液1と光触媒電極2と、対極3とを有する。この水素生成デバイスにおいて、水溶液1を物理的攪拌することを特徴とする。水溶液1を攪拌する攪拌機12には、攪拌子またはプロペラ式攪拌機を用いたものや、汲み上げポンプを用いたものを提供する。また、水流を起こさせる機構として、水温の熱対流によるものも可能であることを提案している。光透過セルには、太陽光などが良く透過するように、石英、またはパイレックス(登録商標)セル等を用い、光源に疑似太陽光として波長300〜700nmをもつキセノンランプを用いる。水溶液としては、基本的には蒸留水であるが、水分解過電圧を少しでも下げて、生成を促すために、溶液を若干酸性、またはアルカリ性にする。光触媒電極としては、酸化チタン光触媒を、ITO集電体をもったガラス基板上に形成させる。一方、対極3としては、白金薄膜を用い、光触媒電極2と導線で接続することにより水素生成デバイスを形成させることができる。
As shown in FIG. 1, the hydrogen generation device of this embodiment includes a
光触媒電極に光が照射されると、光触媒内部で、電子が励起され、励起された電子が伝導帯に、電子が励起した価電子帯に正孔が生成する。電子は導線を移動し、対極の表面で水素イオンに電子を供与し、水素を生成する。一方、価電子帯の正孔は、光触媒表面の水酸基の電子を受け取り、酸素を発生させる。反応式を下記に示す。
反応式(1)
光触媒電極:4h(正孔)+4OH− → O2 + 2H2O
対極:4e− + 4H+ → 2H2
全体反応 4h + 4e− +2H2O → 2H2 + O2
この反応が進む時、光触媒電極上には酸素が、対極には水素が発生する。しかしながら、いずれかの電極の反応が滞ると、全体反応効率が低下する。滞る原因として、光触媒電極上に酸素が吸着堆積、または対極上に水素が吸着堆積し、各々のガスの拡散不良が考えられる。また、特に光触媒電極上に堆積した酸素層は、光の透過を妨げ、光照射強度を低下させる。高効率に反応させるためには、表面のガスの拡散を促進させることが必要である。
When light is irradiated to the photocatalyst electrode, electrons are excited inside the photocatalyst, and the excited electrons are generated in the conduction band and holes are generated in the valence band where the electrons are excited. The electrons move through the conducting wire and donate electrons to the hydrogen ions on the surface of the counter electrode to generate hydrogen. On the other hand, the holes in the valence band receive the electrons of the hydroxyl group on the surface of the photocatalyst and generate oxygen. The reaction formula is shown below.
Reaction formula (1)
Photocatalytic electrode: 4h (hole) + 4OH- → O 2 + 2H 2 O
Counter electrode: 4e− + 4H + → 2H 2
Overall reaction 4h + 4e− + 2H 2 O → 2H 2 + O 2
As this reaction proceeds, oxygen is generated on the photocatalytic electrode and hydrogen is generated on the counter electrode. However, if the reaction of any of the electrodes is delayed, the overall reaction efficiency decreases. As a cause of the stagnation, oxygen is adsorbed and deposited on the photocatalyst electrode, or hydrogen is adsorbed and deposited on the counter electrode, and each gas may have a poor diffusion. In particular, the oxygen layer deposited on the photocatalytic electrode hinders light transmission and reduces the light irradiation intensity. In order to react with high efficiency, it is necessary to promote the diffusion of gas on the surface.
本発明は、この電極上に吸着堆積したガス、気泡を強制的に除去、拡散させることにより、効率を向上させるものである。 The present invention improves efficiency by forcibly removing and diffusing the gas and bubbles adsorbed and deposited on the electrode.
本発明の光触媒電極は、図2に例示するように、基板10の上に、集電体9が形成され、さらにその上に光触媒8が形成されている。図2に示すように、水流拡散を促進させる方法として、攪拌子12やプロペラ、ポンプを用いたものと、水熱の対流を利用する温度差を与える仕組みにより達成している。また、表面に吸着した気泡13を機械的に振動または接触させ、拡散を促進させる手段として、水溶液中に微粒子固体物14を分散させる方法を発明している。ただし、微粒子固体物14は光の進路を阻害する要因になるので、光散乱または、透過できる物質が選ばれる。光を透過、散乱させる物質として、具体的にはシリカ、ゼオライトが相当する。更に、これらの固体物質を効率よく電極に接触させる方法として、一定表面を保有する光触媒電極、および対極を水平面から傾斜させることを発明している。これは固体物質が重力により沈下するエネルギーを有効に利用するためである。従来の電極式セルは設置面積の低減から垂直方向に配備されている。電極を傾斜させることにより、気泡の放出を向上させることができる。
In the photocatalyst electrode of the present invention, as illustrated in FIG. 2, a current collector 9 is formed on a substrate 10, and a photocatalyst 8 is further formed thereon. As shown in FIG. 2, as a method of promoting water flow diffusion, a method using a
本発明の実施の形態で、共通の装置、評価法について示す。光透過セル5としては、5cmx5cmx10cmの石英性の角柱型セルを用い、その透過率は96%程度である。水溶液1は、0.25MのK2SO4を含んだpH6.8の緩衝溶液100ccを用い、光触媒電極2は、1cmx5cmのITOスパッタ導電膜をガラス表面に形成させたものの上に、1cmx3cmx厚さ500nmの酸化チタンをスパッタしたものを用いた。対極3には、厚さ0.25mmのPt薄2.5mmx3cmを用い、接続線には銅線11を用いた。光源4には、疑似太陽光としてキセノンランプを0.1w/cm2の光強度で照射した。
In the embodiment of the present invention, a common apparatus and an evaluation method will be described. As the
水素生成効率の評価は、図3に示すような、光電流計測により行った。これは、光照射を行った時と、照射しない時の電極間に流れる電流差で反応量を評価する方法で、電流量がすなわち、ファラデーの法則に従った水素発生量とするものである。ただし、酸化チタン光触媒を用いる場合、酸化還元の過電圧があるため、バイアス電圧を印加し、水素生成を確認する方法を行った。印加電圧は、電源6によって、光触媒電極側を陽極、対極側を陰極に印加した。室温、光照射、一定バイアス電圧時の電流値を水素発生量として評価した。電流値は、電流計7で測定する。
The hydrogen production efficiency was evaluated by photocurrent measurement as shown in FIG. This is a method of evaluating the reaction amount by the difference in current flowing between the electrodes when the light irradiation is performed and when the light irradiation is not performed, and the current amount is a hydrogen generation amount in accordance with Faraday's law. However, when a titanium oxide photocatalyst was used, there was an oxidation-reduction overvoltage, so a method of applying a bias voltage and confirming hydrogen generation was performed. The applied voltage was applied by the power source 6 to the anode on the photocatalyst electrode side and to the cathode on the counter electrode side. The current value at room temperature, light irradiation, and constant bias voltage was evaluated as the amount of hydrogen generation. The current value is measured with an
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。
(実施例1)
本実施例は、攪拌子を用いて水流をセル内で発生させ、水素生成効率が向上した事例を示す。攪拌子は、マグネットにより回転し、回転数を制御できる。既述、水素生成デバイスを用い、回転数を250回/分にした時の光照射したとき、印加電圧0Vと0.5V時の
電流値を測定した。
(実施例2)
本実施例は、「回転数を250回/分にした時」を「回転数を500回/分にした時」に変える以外は実施例1と同様にして、電流値を測定した。
(実施例3)
本実施例は、水流ポンプを用いて水流をセル内で発生させ、水素生成効率が向上した事例を示す。水流ポンプを用い、10cc/分で循環させたとき、印加電圧0Vと0.5V時の電流値を測定した。
(実施例4)
本実施例は、「10cc/分で循環させたとき」を「50cc/分で循環させたとき」に変える以外は実施例3と同様にして、電流値を測定した。
(実施例5)
本実施例は、温度差で液流動する作用を用いて水流をセル内で発生させ、水素生成効率が向上した事例を示す。セルを50℃にヒーターで暖め、水溶液を熱流で循環させたとき、印加電圧0Vと0.5V時の電流値を測定した。
(実施例6)
本実施例は、「セルを50℃にヒーターで暖め」を「セルを70℃にヒーターで暖め」に変える以外は実施例5と同様にして、電流値を測定した。
(実施例7)
本実施例は、固体物質を水溶液に拡散させ、水素生成効率が向上した事例を示す。固体物質に粒径0.8μmのシリカ微粒子を水溶液に0.001重量%分散させた水溶液を用い、既述、水素生成デバイスで、攪拌しない状態で、光照射したときの、印加電圧0Vと0.5V時の電流値を測定した。
(実施例8)
本実施例は、「シリカ微粒子を水溶液に0.001重量%分散させた」を「シリカ微粒子を水溶液に0.1重量%分散させた」に変える以外は実施例7と同様にして、電流値を測定した。
(実施例9)
本実施例は、「シリカ微粒子を水溶液に0.001重量%分散させた」を「シリカ微粒子を水溶液に1重量%分散させた」に変える以外は実施例7と同様にして、電流値を測定した。
(実施例10)
本実施例は、「シリカ微粒子を水溶液に0.001重量%分散させた」を「シリカ微粒子を水溶液に20重量%分散させた」に変える以外は実施例7と同様にして、電流値を測定した。
(実施例11)
本実施例は、「粒径0.8μmのシリカ微粒子」を「粒径4μmのシリカ微粒子」に
変える以外は実施例7と同様にして、電流値を測定した。
(実施例12)
本実施例は、「粒径0.8μmのシリカ微粒子」を「粒径63μmのシリカ微粒子」に
変える以外は実施例7と同様にして、電流値を測定した。
(実施例13)
本実施例は、「粒径0.8μmのシリカ微粒子」を「長辺30μm以下のゼオライト」に
変える以外は実施例7と同様にして、電流値を測定した。
(実施例14)
本実施例は、「水素生成デバイスで、攪拌しない状態で、光照射したとき」を「水素生成デバイスで、攪拌子の回転数を250回転/分にして、光照射したとき」に変える以外は実施例7と同様にして、電流値を測定した。
(実施例15)
本実施例は、電極を垂直面から傾斜させ設置することにより、水素生成効率が向上した
事例を示す。既述、水素生成デバイスの光触媒電極の設置を、垂直面から傾斜を保持させて設置した時の、印加電圧0Vと0.5V時の電流値を測定した。
(実施例16)
本実施例は、実施例7の光触媒電極の設置を、垂直面から傾斜を保持させて設置した以外、全く実施例7と同様にして、電流値を測定した。
(実施例17)
本実施例は、実施例14の光触媒電極の設置を、垂直面から傾斜を保持させて設置した以外、全く実施例14と同様にして、電流値を測定した。
(実施例18)
本実施例は、実施例15の光触媒電極の設置を、垂直面から傾斜を保持させて設置したところと、対極の設置を、垂直面から傾斜を保持させて設置した以外、全く実施例15と同様にして、電流値を測定した。
(比較例1)
上記、実施例1で「回転数を250回/分にした時」を「回転数を0回/分にした時」にした以外は実施例1と同様の方法で、電流値を測定した。
(比較例2)
本比較例は、「粒径0.8μmのシリカ微粒子」を「粒径100μm以上のシリカ粒子」に
変える以外は実施例7と同様にして、電流値を測定した。
(比較例3)
本比較例は、「シリカ微粒子を水溶液に0.001重量%分散させた」を「シリカ微粒子を水溶液に25重量%分散させた」に変える以外は実施例7と同様にして、電流値を測定した。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
Example 1
In this example, a water flow is generated in a cell using a stirrer, and an example in which hydrogen generation efficiency is improved is shown. The stirrer is rotated by a magnet and the number of rotations can be controlled. As described above, the current value at the applied voltage of 0 V and 0.5 V was measured when the hydrogen generation device was used and the light was irradiated when the rotation speed was 250 times / minute.
(Example 2)
In this example, the current value was measured in the same manner as in Example 1 except that “when the number of revolutions was 250 times / minute” was changed to “when the number of revolutions was 500 times / minute”.
(Example 3)
This example shows an example in which a water flow is generated in a cell using a water flow pump and the hydrogen generation efficiency is improved. When the water flow pump was used to circulate at 10 cc / min, current values at an applied voltage of 0 V and 0.5 V were measured.
Example 4
In this example, the current value was measured in the same manner as in Example 3 except that “when circulated at 10 cc / min” was changed to “when circulated at 50 cc / min”.
(Example 5)
The present embodiment shows an example in which the hydrogen generation efficiency is improved by generating a water flow in the cell by using the action of liquid flow with a temperature difference. When the cell was heated to 50 ° C. with a heater and the aqueous solution was circulated with a heat flow, the current values at an applied voltage of 0 V and 0.5 V were measured.
(Example 6)
In this example, the current value was measured in the same manner as in Example 5 except that “warm the cell to 50 ° C. with a heater” was changed to “warm the cell to 70 ° C. with a heater”.
(Example 7)
This example shows an example in which a solid substance is diffused into an aqueous solution and hydrogen production efficiency is improved. When an aqueous solution in which 0.001% by weight of silica fine particles having a particle diameter of 0.8 μm is dispersed in an aqueous solution is used as a solid substance, the applied voltage is 0 V and 0. The current value at 5V was measured.
(Example 8)
In this example, the current value was changed in the same manner as in Example 7, except that “0.001% by weight of silica fine particles were dispersed in an aqueous solution” was changed to “0.1% by weight of silica fine particles was dispersed in an aqueous solution”. Was measured.
Example 9
In this example, the current value was measured in the same manner as in Example 7 except that “silica fine particles dispersed in 0.001% by weight in aqueous solution” was changed to “silica fine particles dispersed in 1% by weight in aqueous solution”. did.
(Example 10)
In this example, the current value was measured in the same manner as in Example 7 except that “silica fine particles were dispersed in an aqueous solution by 0.001% by weight” was changed to “silica fine particles were dispersed in an aqueous solution by 20% by weight”. did.
(Example 11)
In this example, the current value was measured in the same manner as in Example 7 except that “silica fine particles having a particle diameter of 0.8 μm” was changed to “silica fine particles having a particle diameter of 4 μm”.
(Example 12)
In this example, the current value was measured in the same manner as in Example 7 except that “silica fine particles having a particle diameter of 0.8 μm” was changed to “silica fine particles having a particle diameter of 63 μm”.
(Example 13)
In this example, the current value was measured in the same manner as in Example 7 except that “silica fine particles having a particle diameter of 0.8 μm” was changed to “zeolite having a long side of 30 μm or less”.
(Example 14)
In this example, except that “when the light is irradiated with the hydrogen generating device without stirring” is changed to “when the light is irradiated with the hydrogen generating device with the rotation speed of the stirrer being 250 rpm”. The current value was measured in the same manner as in Example 7.
(Example 15)
This example shows an example in which the hydrogen production efficiency is improved by inclining the electrode from the vertical plane. As described above, when the photocatalytic electrode of the hydrogen generation device was installed while maintaining the inclination from the vertical plane, the current values at the applied voltage of 0 V and 0.5 V were measured.
(Example 16)
In this example, the current value was measured in exactly the same manner as in Example 7, except that the photocatalyst electrode of Example 7 was installed while maintaining the inclination from the vertical plane.
(Example 17)
In this example, the current value was measured in exactly the same manner as in Example 14, except that the photocatalyst electrode of Example 14 was installed while maintaining the inclination from the vertical plane.
(Example 18)
This example is exactly the same as Example 15, except that the photocatalytic electrode of Example 15 was installed with the inclination maintained from the vertical plane, and the counter electrode was installed with the inclination maintained from the vertical plane. Similarly, the current value was measured.
(Comparative Example 1)
The current value was measured in the same manner as in Example 1 except that “when the rotational speed was 250 times / minute” in Example 1 was changed to “when the rotational speed was 0 times / minute”.
(Comparative Example 2)
In this comparative example, the current value was measured in the same manner as in Example 7 except that “silica fine particles having a particle diameter of 0.8 μm” was changed to “silica particles having a particle diameter of 100 μm or more”.
(Comparative Example 3)
In this comparative example, the current value was measured in the same manner as in Example 7 except that “silica fine particles were dispersed in 0.001% by weight in an aqueous solution” was changed to “silica fine particles were dispersed in 25% by weight in an aqueous solution”. did.
表1から明らかなように、本発明の水素生成デバイスは、従来に比べ光電流の向上、すなわち水素生成発生を促進させることがわかった。 As is apparent from Table 1, it was found that the hydrogen generation device of the present invention promotes the improvement of photocurrent, that is, the generation of hydrogen compared to the conventional case.
なお、本実施例では、光透過セルとして、5cmx5cmx10cmの石英性の角柱型セルを用いた例を示したが、光を透過するセルであれば、パイレックス(登録商標)でもよいし、サイズを規定するものでもない。また、水溶液は、0.25MのK2SO4を含んだpH6.8の緩衝溶液を用いた事例を示したが、水溶液としては純水でも良いし、電極が溶解しない水溶液であるならば、KOHのアルカリ溶液でも、HClの酸性水溶液でも良い。本実施例では、光触媒電極に、1cmx5cmのITOスパッタ導電膜をガラス表面に形成させたものの上に、1cmx3cmx厚さ500nmの酸化チタンをスパッタしたものを用いたが、光触媒としては、SrTiO3、WO3、TaONなど、光励起する光触媒材料であれば良く、電極集電体もITO以外でも、FTOや、金属基板で合っても良い。また、寸法や成膜方法は、塗布法でも、電解析出法でも良いし、膜厚、寸法も規定するものではない。対極には、厚さ0.25mmのPt薄2.5mmx3cmを用いたが、対極の材料としては、銀や銅でも可能であり、寸法も規定するものではない。本実施例では、光源に、疑似太陽光としてキセノンランプを0.1w/cm2の光強度のものを用いたが、可視光を含む光であれば、太陽光でももちろん良いし、蛍光灯や、LEDも可能で、光強度も規定するものではない。また、水素生成効率の評価では、光電流計測により行ったが、実際の発生
量を直接測定するものでも良いし、バイアス印加電圧も水の分解電圧(1.23V)以内であれば、いくらでも良く、周囲温度も規定するものではない。
In this embodiment, an example in which a 5 cm × 5 cm × 10 cm quartz prismatic cell is used as the light transmitting cell, but Pyrex (registered trademark) may be used as long as the cell transmits light, and the size is specified. It's not something to do. In addition, an example in which a buffer solution having a pH of 6.8 containing 0.25 M K2SO4 was used as the aqueous solution was used. However, the aqueous solution may be pure water, or an alkaline solution of KOH if the electrode does not dissolve. It may be a solution or an acidic aqueous solution of HCl. In this embodiment, the photocatalyst electrode, an ITO sputtering conductive film 1cmx5cm on what was formed on the glass surface, but was used as the sputtering titanium oxide 1cmx3cmx thickness 500 nm, as a photocatalyst, SrTiO 3, WO 3. Any photocatalytic material that can be photoexcited, such as TaON, may be used, and the electrode current collector may be other than ITO, FTO, or a metal substrate. The dimensions and film forming method may be a coating method or an electrolytic deposition method, and the film thickness and dimensions are not specified. As the counter electrode, Pt thin 2.5 mm × 3 cm having a thickness of 0.25 mm was used, but the material of the counter electrode can be silver or copper, and the size is not specified. In this example, a xenon lamp having a light intensity of 0.1 w / cm 2 was used as the pseudo-sunlight as the light source. However, as long as the light includes visible light, sunlight may be used. LEDs are also possible, and the light intensity is not specified. The hydrogen generation efficiency was evaluated by photocurrent measurement. However, the actual generation amount may be directly measured, and any amount may be used as long as the bias applied voltage is within the water decomposition voltage (1.23 V). Also, the ambient temperature is not specified.
本発明は、例えば太陽光から水素を生成するデバイス、および装置、水溶液中の光触媒反応セルに有用である。 The present invention is useful for, for example, a device that generates hydrogen from sunlight, an apparatus, and a photocatalytic reaction cell in an aqueous solution.
1 水溶液
2 光触媒電極
3 対極
4 光源
5 光透過セル
6 電源
7 電流計
8 光触媒
9 集電体
10 基板
11 導線
12 攪拌機
13 気泡
14 固体物質
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