JPS6256588A - Method for decomposing water by visible radiation - Google Patents
Method for decomposing water by visible radiationInfo
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- JPS6256588A JPS6256588A JP60196467A JP19646785A JPS6256588A JP S6256588 A JPS6256588 A JP S6256588A JP 60196467 A JP60196467 A JP 60196467A JP 19646785 A JP19646785 A JP 19646785A JP S6256588 A JPS6256588 A JP S6256588A
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Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、水を可視光分解し、酸素と水素を得る方法に
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method of decomposing water with visible light to obtain oxygen and hydrogen.
従来ｎ型の半導体電極に光照射して水を分解し、半導体
表面で酸素を、白金などの対極表面で水素を発生させる
ことは知られている。しかし、水中で安定に使用できる
半導体は酸化チタン、酸化亜鉛などのようにバンドギャ
ップ（Ｅｇ＞の人き、）材料に限られ、有効な光は４０
０ｎｍ以下の紫外光領域のみに限られていた。４００〜
８００ｎ＋ｎの可視光領域が利用できるｎ型半導体は全
て水中光照射条件下では不活性化してしまう。この理由
は人別して２つあり、１つはｎ−Ｃｄ５やｎ−ＧａＡｓ
などのように界面に近いいわゆる欠乏層に生ずるホール
が半導体を酸化的に溶解してしまう場合であり、他はｎ
−３ｉのように、ホールが酸化物皮膜を作ってしまい、
不活性化する場合である。このような可視域ｎ型半導体
を如何に安定イヒして使用するかは、この分野の重要な
課題であった。It is conventionally known to irradiate an n-type semiconductor electrode with light to decompose water and generate oxygen on the semiconductor surface and hydrogen on the surface of a counter electrode such as platinum. However, semiconductors that can be stably used underwater are limited to bandgap (Eg>) materials such as titanium oxide and zinc oxide, and effective light is limited to 40
It was limited only to the ultraviolet light region of 0 nm or less. 400～
All n-type semiconductors that can utilize the visible light region of 800n+n are inactivated under underwater light irradiation conditions. There are two reasons for this, one being n-Cd5 and n-GaAs.
In other cases, holes generated in the so-called depletion layer near the interface dissolve the semiconductor in an oxidative manner;
- As in 3i, the holes form an oxide film,
This is a case of inactivation. How to stably use such a visible n-type semiconductor has been an important issue in this field.
したかっ−Ｃ本発明の目的は、可視域ｎ型半導体を用い
て水を可視光分解し、酸素と水素を得る方法を提供する
ことであ゛る。An object of the present invention is to provide a method of decomposing water with visible light using a visible region n-type semiconductor to obtain oxygen and hydrogen.
本発明者は、トリス（２，２“−ビピリジン）ルテニウ
ム（ＩＩ）錯体（以下Ｒｕ（ｂｐＹ）ａ’＋と略す）を
ペンダント基に持つような高分子錯体薄膜を、可視域ｎ
型半導体表面に被覆すると、水中光照射条件下でも半導
体が安定化されることを見出した（参考文献としてラジ
ェシュウォー（Ｒａｊｅｓｈｗａｒ）、金子、山田、ジ
ャーナル・オブ・エレクトロケミカル・ソサエティ（Ｊ
、８１ｅｃｔｒｏｃｈｅｍ、Ｓｏｃ、 ） 、１３０巻
、３８頁（１９８３年〉、ラジェシュウォー（Ｒａｊｅ
ｓｈｗａｒ）、金子、山田、ナウフィ−（Ｎｏｕｆｉ）
、ジャーナル・オブ・フィジカル・ケミストリー（、Ｊ
、 Ｐｈｙｓ、 Ｃｈｅｍ、 ） 、８９巻、８０６頁
（１９８５年）。さらに、鋭意研究の結果、この膜中に
水を酸化するための触媒を共存させて用いると、水の可
視光分解が可能になることを見出し、本発明を完成する
に至った。The present inventor has developed a polymer complex thin film having a tris(2,2"-bipyridine)ruthenium(II) complex (hereinafter abbreviated as Ru(bpY)a'+) as a pendant group in the visible range n
They found that when coated on the surface of a type semiconductor, the semiconductor was stabilized even under underwater light irradiation conditions (References: Rajeshwar, Kaneko, Yamada, Journal of Electrochemical Society (J.
, 81 electrochem, Soc, ), vol. 130, p. 38 (1983), Rajeshwar
shwar), Kaneko, Yamada, Noufi
, Journal of Physical Chemistry (,J
, Phys, Chem, ), vol. 89, p. 806 (1985). Further, as a result of extensive research, the inventors discovered that visible light decomposition of water becomes possible when a catalyst for oxidizing water is used in the membrane, and the present invention has been completed.
本発明は、可視域ｎ型半導体電極の表面に、トリス（２
，２’−ビピリジン）ルテニウム（ＩＩ）錯体をペンダ
ント基として有する高分子錯体の膜を被覆し、該膜内に
は媒質として周期律表第■族の金属または金属酸化物を
共存せしめ、この修飾した可視域ｎ型半導体電極を電解
質水溶液に浸漬し、電極表面に可視光を照射することに
より水を分解し、半導体電極上で酸素を発生せしめ、対
極上で水素を発生せしめる方法である。In the present invention, Tris (2
, 2'-bipyridine) ruthenium (II) complex as a pendant group is coated, a metal or metal oxide of Group I of the periodic table is allowed to coexist as a medium in the film, and this modification is performed. In this method, a visible region n-type semiconductor electrode is immersed in an aqueous electrolyte solution, and the electrode surface is irradiated with visible light to decompose water, generate oxygen on the semiconductor electrode, and generate hydrogen on the counter electrode.
以下本発明の詳細な説明する。The present invention will be explained in detail below.
半導体を用いて水を可視光分解するためには、半導体の
Ｅｇは３ｅＶ以下でなければならず、かつその価電子帯
、伝導帯の位置が、水の酸化還元電位に適合している必
要がある。このような理由で、水の可視光分解が可能な
半導体は限られており、たとえばｎ型硫化カドミウム（
ＩＩ−ＣｄＳ。In order to decompose water with visible light using a semiconductor, the Eg of the semiconductor must be 3 eV or less, and the positions of its valence band and conduction band must match the redox potential of water. be. For this reason, there are only a limited number of semiconductors that can decompose water with visible light; for example, n-type cadmium sulfide (
II-CdS.
Ｅｇ＝２．４ｅＶ）、ｎ型セレン化カドミウム（ＩＩ−
ＣｄＳｅ、Ｅｇ＝１．７ ｅＶ）、ｎ型リン化ガリウム
（ＩＩ−ＧａＰ、Ｅｇ＝２．２５ ｅＶ） 、ｎ型リン
化インジウム（ＩＩ−）ｎＰ）などに限定される。前述
のごとくこれらの可視域半導体は全て、水中、光照射条
件下では劣化してしまうので、安定化することが必須条
件である。Eg=2.4eV), n-type cadmium selenide (II-
CdSe, Eg=1.7 eV), n-type gallium phosphide (II-GaP, Eg=2.25 eV), n-type indium phosphide (II-)nP), etc. As mentioned above, all of these visible range semiconductors deteriorate under water or under light irradiation conditions, so stabilization is an essential condition.
このような可視域ｎ型半導体を安定化するために膜とし
て被覆する高分子錯体は、Ｒｕ （ｂｐｙ） ｓ ’
” Ｓ昔体構造をペンダント基に有するもので、その代
表的な例は構造式（Ｉ）で表わされる。The polymer complex coated as a film to stabilize such a visible n-type semiconductor is Ru(bpy)s'
It has an S structure as a pendant group, and a typical example thereof is represented by the structural formula (I).
たゾしここでＭはスチレン、アクリル酸又はその誘４
体、Ｎ−ビニルピロリドン、４〜ビニルピリジンなどの
単量体、ｘ、ｙ、ｚはそれぞれの繰り返し単位のモル分
率で、Ｘは０．０１〜０，９８の′ａｔｍ、、ｙ Ｌｋ
Ｏ〜０．９ （Ｄ範囲、ｚ ハ０〜０．９８ （７）
ＭＷ囲の値を表わし、ｘ＋ｙ＋ ｚ＝ １である。この
高分子錯体は、４−メチル−４′−ビニル−２，２゛−
ビピリジンの単独重合体（Ｚ−０の場合）、または他の
単量体（Ｍ）との共重合体を、ｃｉｓ−Ｒｕ（ｂｐｙ）
２ＣＲ２と反応させることにより合成される。分子遣
は２０００以上のものがよい。Here M is styrene, acrylic acid or its derivative 4
monomer such as N-vinylpyrrolidone, 4-vinylpyridine, x, y, z are the mole fractions of the respective repeating units, X is 0.01 to 0.98'atm, y Lk
O~0.9 (D range, z ha0~0.98 (7)
It represents the value of MW range, and x+y+z=1. This polymer complex is 4-methyl-4'-vinyl-2,2'-
Bipyridine homopolymer (in the case of Z-0) or copolymer with other monomer (M), cis-Ru (bpy)
It is synthesized by reacting with 2CR2. The molecular weight is preferably 2000 or more.
Ｍがスチレンのように水と親和性がない方が、水中で安
定な膜として使えるので良好な結果を与える。Ｍが′ｒ
アクリル酸その透導体、Ｎ−ビニルピロリドン、４〜ビ
ニルピリジンのような水と親和性の強い共重合体の場合
は、膜は水中で溶解し易いが、分子竜をｉｏ、 ０００
以上と高くすれば使用に耐える。Ｒｕ （ｂｐｙ） ３
”＋をペンダント基に持−）このほかの高分子錯体、
たとえばポリスチレンに２．２゛−ビピリジル基を導入
した後錯体化を行なって得られる、下記式（ＩＩ）の組
成を持つ化合物なども膜材料として用いることができる
。If M has no affinity for water, such as styrene, it can be used as a stable film in water, giving better results. M is 'r
In the case of copolymers with strong affinity for water such as acrylic acid, N-vinylpyrrolidone, and 4-vinylpyridine, the membrane is easily dissolved in water, but the molecular weight is io, 000
If it is higher than that, it can withstand use. Ru (bpy) 3
Other polymer complexes (having + as a pendant group -),
For example, a compound having the composition of formula (II) below, which is obtained by introducing a 2.2'-bipyridyl group into polystyrene and then complexing it, can also be used as the membrane material.
た５゛シここでｘ、’ｌｘ Ｚｓ ｗは各繰り返し単
位のモル分率で、Ｘは０．０１〜０．５、ｙは０〜０．
５．２（まＯ〜０．４、Ｗは０．５〜０．９の範囲で、
ｘ十ｙ十ｚ＋ｗ＝１である。Here, x, 'lx Zs w is the mole fraction of each repeating unit, X is 0.01 to 0.5, and y is 0 to 0.
5.2 (Ma O ~ 0.4, W in the range of 0.5 ~ 0.9,
x10y1z+w=1.
上記高分子錯体は、特公昭５９−８３６１号公報記載の
方法により合成することができる。The above-mentioned polymer complex can be synthesized by the method described in Japanese Patent Publication No. 59-8361.
これらの高分子錯体膜を半導体に被覆するには、半導体
を常法によりエツチングした後、高分子錯体の溶液を塗
布Ｉ、て乾繰するいわゆるキャスト法によろか、あるい
はスピンコーティング法など、通常用いられる方法なら
何でもよい３．膜７はｌ Ｌｌ ００へ〜５０μｍ程度
が適当である。本発明においては膜中のＲｕ（ｂｐｙ）
３Ｊ＋錯体部は、？、導体の光励起により界面近くに生
ずるホールと反応することにより、ホールを半導体から
取り出しで水の酸化のための触媒に伝達する、いわゆる
ｌＩｔ荷リレす体と［。To coat semiconductors with these polymer complex films, there are conventional methods such as etching the semiconductor using a conventional method, applying a solution of the polymer complex, and drying by the so-called casting method, or spin coating. Any method that can be used is acceptable3. The appropriate thickness of the film 7 is approximately 50 μm. In the present invention, Ru(bpy) in the film
3J+ complex part? , a so-called lIt charge-releasing body [.
ての役割を有する。It has the role of
本発明において用いられる触媒としての、周期律表第■
族の金属または金属酸化物としては、Ｐｔ、、ＰｔＯ２
、ＲｕＳＲｕ （、）２、Ｉｒ、、Ｉ＋０２、Ｒｈ、Ｒ
ｈＯ２、Ｎｉ、ＮｉＯ２、Ｆｅ２Ｏ：＋などが挙げられ
る。この触媒は、光照射により半導体表面に生じたホー
ルを受けて、水を酸化して酸素を発生するために用いる
ものである。ＲｕＯ２やＰｔＯ□などの酸化物が特に良
好な結末を与える。As a catalyst used in the present invention, periodic table No.
Group metals or metal oxides include Pt, PtO2
, RuSRu (,)2, Ir, , I+02, Rh, R
Examples include hO2, Ni, NiO2, Fe2O:+, and the like. This catalyst is used to receive holes generated on the semiconductor surface by light irradiation and oxidize water to generate oxygen. Oxides such as RuO2 and PtO□ give particularly good results.
これらの触媒を高分子錯体膜中に共存させるには、予め
半導体表面に該触媒粉末をのせた後、高分子錯体膜を被
覆するか、あるいは高分子錯体溶液に触媒微粉末を懸濁
させて被覆膜を作ってもよい。In order to coexist these catalysts in a polymer complex film, the catalyst powder is placed on the semiconductor surface in advance and then covered with the polymer complex film, or the fine catalyst powder is suspended in a polymer complex solution. A coating film may also be formed.
また、化学反応によってもこれらの触媒を膜中に共存せ
し狛ることができる。たとえば、高分子錯体膜を半導体
上に被覆した後に、Ｒｕ○４水溶液に、たとえば常温で
、２秒〜２０分間浸漬すると、ＲｕＯ２は膜中に吸着さ
れると同時に還元されてＲｕＯ２となり、微粒子として
膜中に分散する。Further, these catalysts can also be made to coexist in the membrane through chemical reactions. For example, if a polymer complex film is coated on a semiconductor and then immersed in a Ru○4 aqueous solution for 2 seconds to 20 minutes at room temperature, RuO2 is adsorbed into the film and simultaneously reduced to RuO2, forming fine particles. Dispersed in the membrane.
触媒量は少量過ぎても効果が低いが、多過ぎると光を吸
収する結果半導体に到達する光量が低下するので、やは
り効率が落ちる。したがって触媒の量は高分子錯体膜中
０．０５〜５重遣％が適当である。If the amount of catalyst is too small, the effect will be low, but if it is too large, the amount of light reaching the semiconductor will decrease as a result of absorbing light, which will also reduce efficiency. Therefore, the appropriate amount of catalyst is 0.05 to 5% by weight in the polymer complex membrane.
本発明に用いられる電解質水溶液としては、電解質とし
て硝酸塩、硫酸塩、過塩泰酸塩等を０．ｏ１〜２Ｍａ度
で含む水溶液が挙げられる。ハロゲン化塩はハロゲンイ
オンが酸化されてしまうので、この場合には水の光分解
ではなく、ハロゲン化水素の光分解ということになる。The electrolyte aqueous solution used in the present invention includes nitrate, sulfate, persalt salt, etc. as an electrolyte. Examples include aqueous solutions containing o1 to 2 Ma degrees. Since the halogen ions of halide salts are oxidized, in this case, the photolysis is not of water but of hydrogen halide.
上記のようにして作製した修飾半導体電極を、電解質水
溶液中に浸漬して作用極とし、対極としては通常白金を
用い、電極電位を制御するためにせコウ、銀−塩化銀な
どの参照上極を用い、いわゆる三極式で光反応を行なう
こよが望ましい。The modified semiconductor electrode prepared as described above is immersed in an aqueous electrolyte solution to serve as a working electrode, the counter electrode is usually platinum, and a reference electrode such as silver or silver-silver chloride is used to control the electrode potential. It is preferable to carry out the photoreaction using a so-called triode system.
光源としては可視光なら何でもよく、太陽光、ケイ光灯
、白熱電灯、ハロゲンランプ、プロジェクタ−、キセノ
ンランプ、水渓支丁ｊ、！、どが挙げられる。Any visible light source can be used as a light source, such as sunlight, fluorescent lamps, incandescent lamps, halogen lamps, projectors, xenon lamps, water lamps, etc. , etc.
用いるセルも特に制限されないが、酸素上ＪｋＪ！ｆ：
を別々に採取する場合は、作用極側と対極側を分離した
二室型セルを用いる。The cell used is not particularly limited, but JkJ! on oxygen! f:
When collecting the cells separately, use a two-chamber cell with separate working and counter electrodes.
本発明によれば、可視域ｎ型゛１ε導体を、水中゛・＋
６照射条件下で安定に使用することができ、可視光を照
射して水を光分解し、酸素お水素を装造１−ることかで
きる。According to the present invention, a visible range n-type 1ε conductor can be
It can be stably used under 6 irradiation conditions, and can photolyze water by irradiating it with visible light to produce oxygen and hydrogen.
以下実施例を以て本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例１
ｎ−ＣｄＳ単結晶（表面積（１０２ｃｎｆ ）の裏面に
Ｇａ−Ｉｎ合金を塗布し、ここに銅線を銀エポ手シで接
着ｉ、てオーミックコンタクトをとる。電極表面以外は
絶縁性エポキシ樹脂で固め、Ｃ（ｉＳ表面は濃塩酸でエ
ツチングする。高分子錯体（１）において、Ｍがスチレ
ン、ｘ＝Ｏ１０４８、ｙ−０、０４７、ｚ＝０．９０５
の組成の化合物をＤ Ｍ Ｆに溶解しくａ度はＲｕ錯体
単位で１ｍＭ＞、この溶液を８μβ／ ｃＪの割合でＣ
ｄＳ上に滴下し、拡げ−ＣＦｆＡ乾した後、温風にて乾
煙し、膜とする。この膜厚は約０゜２８μ［ηとａ１算
される。この被覆Ｃｄ、 Ｓを、５１／ｍβ濃度のＲｕ
Ｏ４水溶液に浸すと、ＲｕＯ＋ が膜に吸着されると
同時に還元され、Ｒｕ Ｏ□微粉末とｆｓって膜中に分
肢される。２このようにして作製した修飾ＣｄＳを７室
型セルに装Ｍ（７、セルには０．５ＭＫＮ○３ と０．
Ｉ ＭＨＮ Ｏｊ を含む水溶液を入れ、対極として
は白金線を、参照電極としてはせコウ電極を装着する。Example 1 A Ga-In alloy is applied to the back side of an n-CdS single crystal (surface area (102 cnf)), and a copper wire is bonded here with a silver epoxy adhesive to make ohmic contact.Other than the electrode surface, insulating epoxy is applied. harden with resin, C (iS surface is etched with concentrated hydrochloric acid. In polymer complex (1), M is styrene, x = O1048, y-0, 047, z = 0.905
A compound with a composition of
Drop it onto dS, spread it, dry it, and dry it with hot air to form a film. This film thickness is calculated as approximately 0°28μ[η and a1. This coated Cd, S was treated with Ru at a concentration of 51/mβ.
When immersed in an O4 aqueous solution, RuO+ is adsorbed to the membrane and reduced at the same time, and is separated into the membrane as fine RuO□ powder. 2 The modified CdS prepared in this way was placed in a seven-chamber cell (7, the cell was filled with 0.5MKN○3 and 0.5MKN○3).
An aqueous solution containing I MHN Oj is introduced, a platinum wire is attached as a counter electrode, and a plaster electrode is attached as a reference electrode.
アルゴンガスを１時間吹き込んでから密閉した後に、電
極電位を−０，４Ｖ （ｖ ｓ、 ５ＣＥ）に保ち、紫
外および赤外光カットフィルターを附した５００〜Ｖキ
セノンランプからの可視光をＣｄＳ表面に照射し、反応
させた。光反応にともなってＣｄＳおよび白金表面上に
気泡が発生ずるのが観察された。After blowing in argon gas for 1 hour and sealing, the electrode potential was maintained at −0.4 V (v s, 5 CE) and visible light from a 500-V xenon lamp equipped with an ultraviolet and infrared light cut filter was applied to the CdS surface. was irradiated and reacted. It was observed that bubbles were generated on the CdS and platinum surfaces as a result of the photoreaction.
光電流は約４００μΔ／ ｃＭの定常値を保った。３時
間反応後に、約Ｔμβの水素と３．５μｌの酸素が発生
した。流れた光電流に対する水分解の効率は７０％であ
った。The photocurrent maintained a steady value of approximately 400 μΔ/cM. After 3 hours of reaction, approximately Tμβ of hydrogen and 3.5 μl of oxygen were evolved. The efficiency of water splitting with respect to the applied photocurrent was 70%.
実施例２
実施例１において、ｎ−Ｃｄ５の代りにｎ−ＣｄＳｅを
用い、５００Ｗキセノンランプの代りに直射太陽光を用
いた他は実施例１と全く同様に光反応を行ない、２５時
間反応後に１０μβの水素と５μＲの酸素を（号だ。Example 2 A photoreaction was carried out in the same manner as in Example 1, except that n-CdSe was used instead of n-Cd5 and direct sunlight was used instead of the 500W xenon lamp. After 25 hours of reaction, 10μβ of hydrogen and 5μR of oxygen (No.
実施例３
実施例１において、Ｒｕ○４水溶液の還元法による代り
にＣｄＳ電極の表面にＲｕ Ｏ，粉末を強くこすりつけ
てのせ、その上に実施例１と同様に高分子錯体膜を被覆
した電極を用い、０．５Ｍ ＫＮＯ３のみを含む水溶液
を用いたほかは実施例１と全く同様に光反応を行ない、
１０時間反応後に１６μβの水素と８μβの酸素を得た
。Example 3 In Example 1, instead of using the Ru○4 aqueous reduction method, RuO powder was strongly rubbed onto the surface of the CdS electrode, and then a polymer complex film was coated on top of it in the same manner as in Example 1. The photoreaction was carried out in exactly the same manner as in Example 1, except that an aqueous solution containing only 0.5M KNO3 was used.
After 10 hours of reaction, 16 μβ of hydrogen and 8 μβ of oxygen were obtained.
実施例４
実施例１において、表面積０．５ ｃｍのローＧａＰを
用い、Ｉｎにより銅線とオーミック接触をとり、エツチ
ングは塩酸−硝酸混液にて行ない、高分子錯体としでは
弐ＩＩＩ）においてｘ ＝ ０．０４、ｙ−０，０１、
ｚ＝０．２１、ｗ＝０．７４の組成のものを用い、クロ
ロホルム溶液（ａ度はＲｕ錯体単位でｌ ｍＭ）を１６
μ！／ ｃｉの割合で用いて被覆膜を作製した以外は実
施例１と全く同様に光反応させ、５時間後に水素１０μ
β、酸素５μβを得た。Example 4 In Example 1, low GaP with a surface area of 0.5 cm was used, ohmic contact was made with the copper wire by In, etching was performed with a hydrochloric acid-nitric acid mixture, and x = 0.04,y-0,01,
Using a composition with z = 0.21 and w = 0.74, a chloroform solution (a degree is 1 mM in Ru complex unit) was added to 16
μ! A photoreaction was carried out in the same manner as in Example 1 except that a coating film was prepared using hydrogen at a ratio of
β, oxygen 5μβ was obtained.
実施例５
実施例１に４．５いて、高分子錯体（１）としてＭがメ
チルメタクリレート、ｘ ＝ ０．１、ｙ＝ｏ、Ｚ−０
，９のものを用い、電解質水溶液として１ＭＫ２Ｓ Ｏ
，と０．０１Ｍ）１２ｓ○４を含む水溶液を用い、電極
電位をＯＶ （ｖｓ、５ＣＥ）にして１５０Ｗハロゲン
ランプを用いたほかは実施例１と全く同様に光反応を行
ない、１０時間反応後に水素１８μβ、酸素ＩＪμβを
得た。Example 5 4.5 in Example 1, M is methyl methacrylate as the polymer complex (1), x = 0.1, y = o, Z-0
, 9 was used, and 1MK2SO was used as the electrolyte aqueous solution.
, and 0.01M) 12s○4, the photoreaction was carried out in the same manner as in Example 1, except that the electrode potential was set to OV (vs, 5CE) and a 150W halogen lamp was used. After 10 hours of reaction, 18μβ of hydrogen and IJμβ of oxygen were obtained.
実施例６
実施例３において、ｎ−Ｃｄ５としてＯ１２Ｃｎ？の表
面積のものを用い、ＲｕＯ２の代りにＰｔＯ２粉末を用
いたほかは実施例３と同様に光反応を行ない、５時間反
応後に水素４８μβと酸素２４μβを得た。Example 6 In Example 3, O12Cn? as n-Cd5? The photoreaction was carried out in the same manner as in Example 3, except that PtO2 powder was used instead of RuO2, and after 5 hours of reaction, 48 μβ of hydrogen and 24 μβ of oxygen were obtained.
Claims (1)
ピリジン）ルテニウム（II）錯体をペンダント基として
有する高分子錯体の膜を被覆し、該膜内には媒質として
周期律表第VIII族の金属または金属酸化物を共存せしめ
、この修飾した可視域ｎ型半導体電極を電解質水溶液に
浸漬し、電極表面に可視光を照射することにより水を分
解し、半導体電極上で酸素を発生せしめ、対極上で水素
を発生せしめる方法。The surface of an n-type semiconductor electrode in the visible range is coated with a film of a polymer complex having a tris(2,2'-bipyridine)ruthenium(II) complex as a pendant group. This modified visible-range n-type semiconductor electrode is immersed in an aqueous electrolyte solution, and the electrode surface is irradiated with visible light to decompose water and generate oxygen on the semiconductor electrode. , a method of generating hydrogen on the opposite electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60196467A JPS6256588A (en) | 1985-09-05 | 1985-09-05 | Method for decomposing water by visible radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60196467A JPS6256588A (en) | 1985-09-05 | 1985-09-05 | Method for decomposing water by visible radiation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6256588A true JPS6256588A (en) | 1987-03-12 |
| JPH0235037B2 JPH0235037B2 (en) | 1990-08-08 |
Family
ID=16358285
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60196467A Granted JPS6256588A (en) | 1985-09-05 | 1985-09-05 | Method for decomposing water by visible radiation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6256588A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005084A1 (en) * | 1996-07-26 | 1998-02-05 | The Broken Hill Proprietary Company Limited | Photoelectrochemical cell |
| WO2006095916A1 (en) * | 2005-03-10 | 2006-09-14 | Ibaraki University | Photophysicochemical cell |
| JP2009014605A (en) * | 2007-07-06 | 2009-01-22 | Ibaraki Univ | Biophotochemistry cell and its application method |
| JP2011017545A (en) * | 2009-07-07 | 2011-01-27 | Institute Of Biophotochemonics Co Ltd | Electrode for photo-electrochemical measurement |
| CN108588738A (en) * | 2018-06-08 | 2018-09-28 | 东北石油大学 | A method of being electrically coupled the efficient hydrogen manufacturing of degradation of polypropylene and lighter hydrocarbons using solar heat- |
| CN110628036A (en) * | 2018-06-21 | 2019-12-31 | 潍坊学院 | High-conductivity covalent-organic framework material |
-
1985
- 1985-09-05 JP JP60196467A patent/JPS6256588A/en active Granted
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998005084A1 (en) * | 1996-07-26 | 1998-02-05 | The Broken Hill Proprietary Company Limited | Photoelectrochemical cell |
| WO2006095916A1 (en) * | 2005-03-10 | 2006-09-14 | Ibaraki University | Photophysicochemical cell |
| US8188362B2 (en) | 2005-03-10 | 2012-05-29 | Ibaraki University | Photophysicochemical cell |
| JP5374704B2 (en) * | 2005-03-10 | 2013-12-25 | 国立大学法人茨城大学 | Photophysical chemical battery |
| JP2009014605A (en) * | 2007-07-06 | 2009-01-22 | Ibaraki Univ | Biophotochemistry cell and its application method |
| JP2011017545A (en) * | 2009-07-07 | 2011-01-27 | Institute Of Biophotochemonics Co Ltd | Electrode for photo-electrochemical measurement |
| CN108588738A (en) * | 2018-06-08 | 2018-09-28 | 东北石油大学 | A method of being electrically coupled the efficient hydrogen manufacturing of degradation of polypropylene and lighter hydrocarbons using solar heat- |
| CN108588738B (en) * | 2018-06-08 | 2019-06-14 | 东北石油大学 | A method of the efficient hydrogen manufacturing of degradation of polypropylene and lighter hydrocarbons are electrically coupled using solar heat- |
| CN110628036A (en) * | 2018-06-21 | 2019-12-31 | 潍坊学院 | High-conductivity covalent-organic framework material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0235037B2 (en) | 1990-08-08 |
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