JPS5856036B2 - Water splitting device using light energy - Google Patents
Water splitting device using light energyInfo
- Publication number
- JPS5856036B2 JPS5856036B2 JP51107032A JP10703276A JPS5856036B2 JP S5856036 B2 JPS5856036 B2 JP S5856036B2 JP 51107032 A JP51107032 A JP 51107032A JP 10703276 A JP10703276 A JP 10703276A JP S5856036 B2 JPS5856036 B2 JP S5856036B2
- Authority
- JP
- Japan
- Prior art keywords
- type semiconductor
- electrode
- light
- hydrogen
- oxygen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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
Landscapes
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Hybrid Cells (AREA)
Description
【発明の詳細な説明】
本発明は光エネルギーを直接電気エネルギーに変換する
と共に電解液としての水溶液を分解する光電変換装置に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photoelectric conversion device that directly converts light energy into electrical energy and decomposes an aqueous solution as an electrolyte.
この種装置は少くとも一方がＰ型半導体若しくはｎ型半
導体よりなる一対の電極を電解液としての硫酸水溶液或
いは力性カリ水溶液中に浸漬せる横取をなし、上記半導
体電極にその半導体の禁止帯幅以上のエネルギーを有す
る光を照射すれば光起電力効果により、例えば一対の電
極としてＰ型半導体とｎ型半導体とを用いればＰ型半導
体電極では正、ｎ型半導体電極では負の電位が現われ、
又Ｐ型半導体と白金等の金属とを一対の電極に用いれば
Ｐ型半導体電極に正、金属電極に負の電位が、更にｎ型
半導体と金属とを組合せばｎ型半導体電極に負、金属電
極に正の電位が現われ、両極間に起電力を生じると共に
光励起によってもたらされる光電極反応により水の分解
を行い、次式の如く正極においては還元反応により水素
を発生すると共に負極においては酸化反応により酸素を
発生するものである。This type of device has a pair of electrodes, at least one of which is made of a P-type semiconductor or an N-type semiconductor, which is immersed in an aqueous sulfuric acid solution or an aqueous potassium solution as an electrolyte, and the semiconductor electrode has a prohibited band of the semiconductor. If light with energy greater than the width is irradiated, due to the photovoltaic effect, for example, if a P-type semiconductor and an N-type semiconductor are used as a pair of electrodes, a positive potential will appear at the P-type semiconductor electrode and a negative potential at the n-type semiconductor electrode. ,
Also, if a P-type semiconductor and a metal such as platinum are used as a pair of electrodes, the P-type semiconductor electrode will have a positive potential and the metal electrode will have a negative potential, and if an n-type semiconductor and a metal are combined, the n-type semiconductor electrode will have a negative potential and a metal potential. A positive potential appears at the electrode, generating an electromotive force between the two electrodes, and water is decomposed by the photoelectrode reaction brought about by light excitation. Hydrogen is generated by a reduction reaction at the positive electrode, and an oxidation reaction occurs at the negative electrode, as shown in the following equation. This generates oxygen.
即ち、負極においては
なる反応が起り酸素が発生すると共に、一方正極におい
ては、
（Ｐ型半導体電極
或い、よ金属電極）２Ｈ″＋２°−−１・↑なる反応が
起り水素が発生するものである。That is, at the negative electrode, the following reaction occurs and oxygen is generated, and at the positive electrode, (P-type semiconductor electrode or metal electrode), the following reaction occurs and hydrogen is generated. It is.
このように光の照射により光エネルギーを直接電気エネ
ルギーに変換すると共にその変換過程において水を分解
して水素と酸素を得ることができるものであり、従来の
ように適宜エネルギーを電気エネルギーに一旦変換した
のちこの電気エネルギーで水の電気分解を行うものに比
し工程の省略による経済性ははかり知れないほど大きい
。In this way, light energy can be directly converted into electrical energy by irradiation with light, and in the conversion process, water can be decomposed to obtain hydrogen and oxygen. Compared to the method in which water is then electrolyzed using this electrical energy, the economical efficiency due to the omission of the process is immeasurably greater.
本発明は前述せる有意性に着目し、特に半導体電極の光
電極反応による水素或いは酸素発生の過電圧を考慮して
水素及び酸素の発生効率を向上せしめることを目的とす
るものである。The present invention focuses on the above-mentioned significance and aims to improve the efficiency of hydrogen and oxygen generation, particularly taking into account the overvoltage of hydrogen or oxygen generation due to the photoelectrode reaction of a semiconductor electrode.
以下本発明の一実施例を図面に基づき説明する。An embodiment of the present invention will be described below based on the drawings.
第１図は本発明装置の構成図を示し、一対の電極として
Ｐ型半導体とｎ型半導体とを用いた場合を例にとり説明
するに１は酸化チタン（ｎ Ｔ１０２）、チタン酸ス
トロンチウム（ｎ ５ｒＴｉ０３ ）、チタン酸バリ
ウム（ｎ−ＢａＴｉ０３）等のｎ型半導体よりなる負極
、２はリン化ガリウム（Ｐ ＧａＰ）、ガリウム砒素
（Ｐ −ＧａＡｓ ）等のＰ型半導体よりなる正極であ
り、これら各電極は夫々ガラス管３，４の端面に封着さ
れている。FIG. 1 shows a configuration diagram of the device of the present invention, and will be explained by taking as an example a case where a P-type semiconductor and an n-type semiconductor are used as a pair of electrodes. 1 is titanium oxide (n T102), strontium titanate (n 5rTi03 ), 2 is a negative electrode made of an n-type semiconductor such as barium titanate (n-BaTi03), and 2 is a positive electrode made of a p-type semiconductor such as gallium phosphide (PGaP) or gallium arsenide (P-GaAs). are sealed to the end faces of the glass tubes 3 and 4, respectively.
５はＨ状のガラス容器よりなる電槽でありガラスフィル
ター６により負極室７と正極室８とに区画されている。Reference numeral 5 denotes a battery case made of an H-shaped glass container, which is divided into a negative electrode chamber 7 and a positive electrode chamber 8 by a glass filter 6.
９は硫酸水溶液或いは力性カリ水溶液よりなる電解液、
１０゜１１は石英板よりなる受光窓、１２は酸素ガス捕
集管、１３は水素ガス捕集管、１４は前記ガラス管３，
４及びガス捕集管１２．１３を支持する封目板、１５は
各電極より導出せるリード線１６゜１７間に介挿された
外部負荷抵抗、１８は電圧計である。9 is an electrolytic solution consisting of a sulfuric acid aqueous solution or a potassium aqueous solution;
10° 11 is a light receiving window made of a quartz plate, 12 is an oxygen gas collection tube, 13 is a hydrogen gas collection tube, 14 is the glass tube 3,
4 and a sealing plate supporting the gas collection tubes 12 and 13, 15 an external load resistor inserted between lead wires 16 and 17 led out from each electrode, and 18 a voltmeter.
第２図は本発明による改良された半導体電極の部分拡大
断面図を示し、イはｎ型半導体電極の場合であり、１ａ
はｎ型半導体薄板、１ｂはその受光面に形成された酸素
過電圧の小なる金属酸化物層である。FIG. 2 shows a partially enlarged cross-sectional view of the improved semiconductor electrode according to the present invention, where A is an n-type semiconductor electrode, and 1a is the case of an n-type semiconductor electrode;
is an n-type semiconductor thin plate, and 1b is a metal oxide layer with low oxygen overvoltage formed on its light-receiving surface.
このｎ型半導体電極の製法の一例について述べるにｎ型
半導体薄板（ｎ ＴｌＯ２、ｎ−８ｒＴｉＯ３等）の
受光面をサイドペーパー等で粗面化した後、その面に酸
素過電圧の小さい金属、例えばコバルト、ニッケルの希
薄硝酸塩水溶液（１０−２〜１０−３モル濃度）を５０
■／誕塗布し、ついで１００〜１１０℃で熱分解処理し
て極板受光面に酸素過電圧の小なる金属酸化物層を形成
せるｎ型半導体電極を得る。To describe an example of the method for manufacturing this n-type semiconductor electrode, the light-receiving surface of an n-type semiconductor thin plate (nTlO2, n-8rTiO3, etc.) is roughened with side paper, and then a metal with low oxygen overvoltage, such as cobalt, is applied to the surface. , a dilute aqueous solution of nickel nitrate (10-2 to 10-3 molar concentration) at 50%
(2) The n-type semiconductor electrode is coated and then thermally decomposed at 100 to 110 DEG C. to form a metal oxide layer with low oxygen overvoltage on the light-receiving surface of the electrode plate.
又、口はＰ型半導体電極の場合であり２ａはＰ型半導体
薄板、２ｂはその受光面に形成された水素過電圧の小な
る金属層である。In addition, the opening is a P-type semiconductor electrode, 2a is a P-type semiconductor thin plate, and 2b is a metal layer with low hydrogen overvoltage formed on the light receiving surface.
このＰ型半導体電極の製法の一例について述べるにＰ型
半導体薄板（Ｐ−Ｇａｐ、 Ｐ−ＧａＡｓ等）の受光面
をサイドペーパーで粗面化した後、該薄板を水素過電圧
の小さい金属、例えば白金、パラジウムの弱酸性塩化物
水溶液（０，５〜１．０モル濃度）中に１０分間浸漬し
、ついで前記受光面に白金或いはパラジウム金属を無電
解メッキにより析出せしめ水素過電圧の小なる金属層を
形成せるＰ型半導体電極を得る。To describe an example of the method for manufacturing this P-type semiconductor electrode, the light-receiving surface of a P-type semiconductor thin plate (P-Gap, P-GaAs, etc.) is roughened with side paper, and then the thin plate is coated with a metal having a low hydrogen overvoltage, such as platinum. , immersed in a weakly acidic chloride aqueous solution of palladium (0.5 to 1.0 molar concentration) for 10 minutes, and then depositing platinum or palladium metal on the light-receiving surface by electroless plating to form a metal layer with low hydrogen overvoltage. A P-type semiconductor electrode is obtained.
本発明によれば光電変換過程において同時に水分解し水
素・酸素を発生するに際して、カソード反応により水素
を発生するＰ型半導体電極の受光面に水素過電圧の小さ
い金属層を形成したので水素発生を容易にならしめると
共にアノード反応により酸素を発生するｎ型半導体電極
の受光面に酸素過電圧の小さい金属酸化物層を形成した
ので酸素発生を容易にならしめたものであり、水素及び
酸素の発生効率を向上せしめうる。According to the present invention, when simultaneously decomposing water and generating hydrogen and oxygen in the photoelectric conversion process, a metal layer with low hydrogen overvoltage is formed on the light-receiving surface of the P-type semiconductor electrode that generates hydrogen through a cathode reaction, making it easy to generate hydrogen. At the same time, a metal oxide layer with low oxygen overvoltage is formed on the light-receiving surface of the n-type semiconductor electrode that generates oxygen through an anode reaction, making it easier to generate oxygen and increasing the efficiency of hydrogen and oxygen generation. It can be improved.
第３図は本発明により表面処理したＰ型リン化ガリウム
及びｎ型酸化チタンを夫々正極及び負極に用いた場合ａ
と表面未処理のＰ型リン化ガリウム及びｎ型酸化チタン
を夫々正極及び負極に用いた場合すにおける水素（実線
）及び酸素（破線）の発生量比較特性図である。Figure 3 shows a case where P-type gallium phosphide and n-type titanium oxide, which have been surface-treated according to the present invention, are used for the positive and negative electrodes, respectively.
FIG. 3 is a characteristic diagram comparing the amounts of hydrogen (solid line) and oxygen (broken line) generated in cases where surface-untreated P-type gallium phosphide and n-type titanium oxide are used for the positive and negative electrodes, respectively.
図より明白なるように本発明による半導体電極を用いれ
ば各半導体電極の反応（正極での水素発生、負極での酸
素発生）の過電圧を減少せしめたので光による水分解を
より効率よく行うことができるものであり、この種装置
の利用率に資するところ極めて犬なるものである。As is clear from the figure, by using the semiconductor electrode according to the present invention, the overvoltage of each semiconductor electrode reaction (hydrogen generation at the positive electrode, oxygen generation at the negative electrode) is reduced, so water splitting by light can be performed more efficiently. It is possible to do this, and it is extremely important that this type of device contributes to the utilization rate.
第１図は本発明半導体電極を用いた光エネルギー利用の
水分解装置の構成国、第２図は本発明半導体電極の受光
面における部分拡大断面図を示し、イはｎ型半導体電極
、口はＰ型半導体電極を夫々示す。
第３図は本発明半導体電極を用いた場合と従来の半導体
電極を用いた場合における水素及び酸素発生量一時間特
性比較図である。
１・・・・・・ｎ型半導体電極、１ａ・・・・・・ｎ型
半導体薄板、１ｂ・・・・・・酸素過電圧の小さい金属
酸化物層、２・・・・・・Ｐ型半導体電極、２ａ・・・
・・・Ｐ型半導体薄板、２ｂ・・・・・・水素過電圧の
小さい金属層、５・・・・・・電槽、９・・・・・・電
解液、１０，１１・・・・・・受光窓、１２・・・・・
・酸素ガス捕集管、１３・・・・・・水素ガス捕集管、
１５・・・・・・外部負荷。Figure 1 shows the constituent countries of a water splitting device using light energy using the semiconductor electrode of the present invention, and Figure 2 shows a partially enlarged cross-sectional view of the light receiving surface of the semiconductor electrode of the present invention, where A is an n-type semiconductor electrode and the mouth is an n-type semiconductor electrode. P-type semiconductor electrodes are shown respectively. FIG. 3 is a comparison diagram of the hourly characteristics of the amounts of hydrogen and oxygen generated when the semiconductor electrode of the present invention is used and when a conventional semiconductor electrode is used. 1... N-type semiconductor electrode, 1a... N-type semiconductor thin plate, 1b... Metal oxide layer with low oxygen overvoltage, 2... P-type semiconductor Electrode, 2a...
... P-type semiconductor thin plate, 2b ... Metal layer with low hydrogen overvoltage, 5 ... Battery container, 9 ... Electrolyte, 10, 11 ...・Light receiving window, 12...
・Oxygen gas collection tube, 13...Hydrogen gas collection tube,
15...External load.
Claims (1)
なる一対の電極を水溶性電解液中に浸漬し、これら半導
体電極にその半導体の禁止帯幅以上のエネルギーを有す
る光を照射せしめ、その光励起反応により水分解するも
のにおいて、前記Ｐ型半導体電極の受光面に水素過電圧
の小なる金属層を形成すると共に前記ｎ型半導体電極の
受光面に酸素過電圧の小なる金属酸化物層を形成せしめ
ることを特徴とする光エネルギー利用の水分解装置。1. A pair of electrodes, at least one of which is made of a P-type semiconductor or an N-type semiconductor, is immersed in an aqueous electrolyte, and these semiconductor electrodes are irradiated with light having an energy greater than the forbidden band width of the semiconductor to induce a photoexcitation reaction. In a device that decomposes water by A water splitting device that uses light energy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51107032A JPS5856036B2 (en) | 1976-09-06 | 1976-09-06 | Water splitting device using light energy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51107032A JPS5856036B2 (en) | 1976-09-06 | 1976-09-06 | Water splitting device using light energy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5331576A JPS5331576A (en) | 1978-03-24 |
| JPS5856036B2 true JPS5856036B2 (en) | 1983-12-13 |
Family
ID=14448778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51107032A Expired JPS5856036B2 (en) | 1976-09-06 | 1976-09-06 | Water splitting device using light energy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5856036B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6350274Y2 (en) * | 1983-11-10 | 1988-12-23 | ||
| JPH0127033B2 (en) * | 1984-03-09 | 1989-05-26 | Kunio Suzuki |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55146486A (en) * | 1979-05-01 | 1980-11-14 | Victor Company Of Japan | Drive circuit for dynamic drive type fluorescent indicator lamp |
| JPS5638380U (en) * | 1979-08-31 | 1981-04-11 | ||
| DE3119034C1 (en) * | 1981-05-13 | 1983-03-10 | Kraftwerk Union AG, 4330 Mülheim | Electromagnetic filter |
| JPS5978393A (en) * | 1982-10-27 | 1984-05-07 | ロ−ム株式会社 | Driver for fluorescent indicator tube |
| WO2013031063A1 (en) * | 2011-08-31 | 2013-03-07 | パナソニック株式会社 | Method for reducing carbon dioxide |
| WO2013031062A1 (en) * | 2011-08-31 | 2013-03-07 | パナソニック株式会社 | Method for reducing carbon dioxide |
| WO2015159348A1 (en) * | 2014-04-14 | 2015-10-22 | 富士通株式会社 | Photosynthetic apparatus |
-
1976
- 1976-09-06 JP JP51107032A patent/JPS5856036B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6350274Y2 (en) * | 1983-11-10 | 1988-12-23 | ||
| JPH0127033B2 (en) * | 1984-03-09 | 1989-05-26 | Kunio Suzuki |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5331576A (en) | 1978-03-24 |
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