JPH07313884A - Catalyst for photolysis of water and production of hydrogen using the same - Google Patents
Catalyst for photolysis of water and production of hydrogen using the sameInfo
- Publication number
- JPH07313884A JPH07313884A JP6133593A JP13359394A JPH07313884A JP H07313884 A JPH07313884 A JP H07313884A JP 6133593 A JP6133593 A JP 6133593A JP 13359394 A JP13359394 A JP 13359394A JP H07313884 A JPH07313884 A JP H07313884A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- compound
- layered compound
- group
- aqueous solution
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000006303 photolysis reaction Methods 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000015843 photosynthesis, light reaction Effects 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000004065 semiconductor Substances 0.000 claims abstract description 27
- 238000005349 anion exchange Methods 0.000 claims abstract description 10
- 238000005341 cation exchange Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 55
- 239000007864 aqueous solution Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 229910004576 Cd1-xZnxS Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- -1 anion compound Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-O octylazanium Chemical compound CCCCCCCC[NH3+] IOQPZZOEVPZRBK-UHFFFAOYSA-O 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FVIZARNDLVOMSU-UHFFFAOYSA-N ginsenoside K Natural products C1CC(C2(CCC3C(C)(C)C(O)CCC3(C)C2CC2O)C)(C)C2C1C(C)(CCC=C(C)C)OC1OC(CO)C(O)C(O)C1O FVIZARNDLVOMSU-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、水の光分解用触媒及び
それを用いた水素の製造方法に関し、特に太陽光によっ
て効率良く水を光分解する触媒及びそれを用いた水素の
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for photodecomposition of water and a method for producing hydrogen using the same, and more particularly to a catalyst for efficiently decomposing water by sunlight and a method for producing hydrogen using the same. .
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】近年、
半導体を電極として用い、水を光分解することにより水
素を製造する方法が見出され、光エネルギーを化学エネ
ルギーに変換する方法が提案されている。このように、
水を水素と酸素に光分解することのできる半導体の代表
的なものとして、ＴｉＯ2 及びＳｒＴｉＯ3 等が知られ
ている。2. Description of the Related Art In recent years,
A method of producing hydrogen by photodecomposing water using a semiconductor as an electrode has been found, and a method of converting light energy into chemical energy has been proposed. in this way,
TiO 2 and SrTiO 3 are known as typical semiconductors capable of photolyzing water into hydrogen and oxygen.
【０００３】しかしながら、それらの半導体はいずれも
３ｅＶ以上の大きいバンドギャップを有するため、太陽
光はほとんど利用できないという問題がある。太陽エネ
ルギーの利用効率の向上のためには、３ｅＶ未満のバン
ドギャップを有する半導体が望まれるが、一般的にバン
ドギャップの小さい半導体は触媒活性が小さく、また溶
液中で溶解しやすいため、化学的な安定性に劣るという
欠点がある。However, since these semiconductors all have a large band gap of 3 eV or more, there is a problem that sunlight can hardly be used. In order to improve the utilization efficiency of solar energy, a semiconductor having a bandgap of less than 3 eV is desired. Generally, a semiconductor having a small bandgap has low catalytic activity and is easily dissolved in a solution. There is a drawback that it is inferior in stability.
【０００４】したがって、本発明の目的は、水溶液中で
安定に働き、しかも太陽光で効率よく水素を製造するこ
とのできる水の光分解用触媒、及びそれを用いた水素製
造方法を提供することである。Therefore, an object of the present invention is to provide a catalyst for photolysis of water which works stably in an aqueous solution and can efficiently produce hydrogen by sunlight, and a hydrogen production method using the same. Is.
【０００５】[0005]
【課題を解決するための手段】上記課題に鑑み鋭意研究
の結果、本発明者は、太陽光によって励起される白金を
担持した半導体を、陽イオン交換性層状化合物又は陰イ
オン交換性層状化合物に包接したものを水の光分解用触
媒として利用すれば、アルカリ化合物又はアルコール等
の水溶液中で安定であるとともに、太陽光によって効率
よく水を光分解し、水素を製造することができることを
発見し、本発明を完成した。As a result of earnest research in view of the above problems, the present inventor has found that a platinum-loaded semiconductor excited by sunlight is converted into a cation-exchangeable layered compound or an anion-exchanged layered compound. It was discovered that if the clathrate is used as a catalyst for photolysis of water, it will be stable in an aqueous solution of an alkali compound or alcohol, and will be able to efficiently photolyze water by sunlight to produce hydrogen. Then, the present invention has been completed.
【０００６】すなわち、本発明の水の光分解用触媒は、
太陽光により励起される半導体を陽イオン交換性層状化
合物又は陰イオン交換性層状化合物に包接してなり、前
記半導体がＰｔを０．０５〜５重量％担持したＣｄ1-X
ＺｎX Ｓ（ただし、０≦Ｘ≦1.0 である。）からなるこ
とを特徴とする。That is, the water photolysis catalyst of the present invention comprises:
Cd 1 -X in which a semiconductor excited by sunlight is included in a cation-exchangeable layered compound or an anion-exchanged layered compound, and the semiconductor carries 0.05 to 5% by weight of Pt.
Zn X S (where 0≤X≤1.0).
【０００７】また、太陽光により励起される半導体を陽
イオン交換性層状化合物又は陰イオン交換性層状化合物
に包接してなる光分解用触媒を水溶液に添加し、前記水
溶液に光を照射することによって分解し、もって水素を
製造する本発明の水素製造方法は、前記水溶液がアルカ
リ化合物及び／又はアルコールを含有し、前記半導体が
Ｐｔを０．０５〜５重量％担持したＣｄ1-X ＺｎX Ｓ
（ただし、０≦Ｘ≦1.0である。）からなり、前記陽イ
オン交換性層状化合物が、Ｈ2 Ｔｉ4 Ｏ9 、Ｈ4Ｎｂ6
Ｏ17、ＨＢｉＮｂ2 Ｏ7 、Ｈ2 Ｌａ2 Ｔｉ3 Ｏ10 及び
ＨＮｂ3 Ｏ8 からなる群から選ばれた少なくとも１種の
化合物からなり、前記陰イオン交換性層状化合物が、
［Ｍ(II)1-Y Ｍ(III) Y （ＯＨ）2 ］（ＣＯ3 ）
Y/2 （ただし、Ｍ(II)は、Ｍｇ2+、Ｚｎ2+、Ｃｕ2+、Ｎ
ｉ2+及びＣｏ2+からなる群から選ばれた少なくとも１種
の金属であり、Ｍ(III) は、Ａｌ3+、Ｃｒ3+及びＦｅ3+
からなる群から選ばれた少なくとも１種の金属であり、
0.17≦Ｙ≦0.33である。）からなることを特徴とする。In addition, a photodecomposition catalyst obtained by clathrating a semiconductor excited by sunlight into a cation-exchangeable layered compound or an anion-exchanged layered compound is added to an aqueous solution, and the aqueous solution is irradiated with light. In the hydrogen production method of the present invention in which hydrogen is decomposed to produce hydrogen, the aqueous solution contains an alkali compound and / or an alcohol, and the semiconductor contains Cd 1-X Zn X S containing 0.05 to 5 wt% of Pt.
(However, 0 ≦ X ≦ 1.0), and the cation-exchangeable layered compound is H 2 Ti 4 O 9 , H 4 Nb 6
O 17 , HBiNb 2 O 7 , H 2 La 2 Ti 3 O 10 and HNb 3 O 8 and at least one compound selected from the group consisting of:
[M (II) 1-Y M (III) Y (OH) 2 ] (CO 3 )
Y / 2 (However, M (II) is Mg 2+ , Zn 2+ , Cu 2+ , N
At least one metal selected from the group consisting of i 2+ and Co 2+ , M (III) being Al 3+ , Cr 3+ and Fe 3+
At least one metal selected from the group consisting of
0.17 ≦ Y ≦ 0.33. ) Consists of.
【０００８】以下、本発明を詳細に説明する。〔１〕光分解用触媒の構成 本発明の光分解用触媒は、太陽光により励起される半導
体(a) を陽イオン交換性層状化合物(b) 又は陰イオン交
換性層状化合物(c) に包接してなる。The present invention will be described in detail below. [1] Structure of photodecomposition catalyst The photodecomposition catalyst of the present invention comprises a semiconductor (a) excited by sunlight in a cation exchange layered compound (b) or an anion exchange layered compound (c). Come into contact.
【０００９】(a) 半導体 半導体は、太陽光により励起されるものであり、具体的
にはＰｔを０．０５〜５重量％担持したＣｄ1-X ＺｎX
Ｓ（ただし、０≦Ｘ≦1.0 である。）からなる。Ｘ＝０
の場合Ｃｄ1-X ＺｎX ＳはＣｄＳであり、Ｘ＝１の場合
ＺｎＳである。好ましいＸの範囲は、0.05〜0.3 であ
る。 (A) Semiconductor The semiconductor is excited by sunlight, and specifically, Cd 1-X Zn X carrying Pt in an amount of 0.05 to 5% by weight.
S (provided that 0 ≦ X ≦ 1.0). X = 0
In the case of, Cd 1-X Zn X S is CdS, and in the case of X = 1, it is ZnS. The preferable range of X is 0.05 to 0.3.
【００１０】上記Ｃｄ1-X ＺｎX Ｓ半導体は、太陽光で
励起され、包接された層状化合物への電子移動が起こ
り、荷電分離が起こることによって、水分解の触媒活性
を示す。Ｃｄ1-X ＺｎX Ｓ半導体にＰｔを担持すること
により、その触媒活性が著しく向上する。Ｐｔを担持し
たＣｄ1-X ＺｎX Ｓ半導体は効率良く水を分解するが、
水溶液に溶解しやすく安定性が低いため、以下説明する
イオン交換性層状化合物の層間に包接する。The Cd 1-x Zn x S semiconductor exhibits a catalytic activity for water splitting when it is excited by sunlight to cause electron transfer to the clathrated layered compound and charge separation. By supporting Pt on the Cd 1-X Zn X S semiconductor, its catalytic activity is significantly improved. The Cd 1-X Zn X S semiconductor supporting Pt efficiently decomposes water,
Since it is easily dissolved in an aqueous solution and has low stability, it is included between the layers of the ion-exchange layered compound described below.
【００１１】(b) 陽イオン交換性層状化合物 陽イオン交換性層状化合物は、層状の格子間に有する陽
イオンを、化合物の外部の陽イオンと交換できればいか
なるものでもよいが、具体的にはＨ2 Ｔｉ4 Ｏ9 、Ｈ4
Ｎｂ6 Ｏ17、ＨＢｉＮｂ2 Ｏ7 、Ｈ2 Ｌａ2 Ｔｉ3 Ｏ10
及びＨＮｂ3Ｏ8 等が好ましく、特にＨ2 Ｔｉ4 Ｏ9
及びＨ4 Ｎｂ6 Ｏ17が好ましい。 (B) Cation-Exchangeable Layered Compound The cation-exchanged layered compound may be any compound as long as it can exchange the cations between the layered lattices with the cations outside the compound. 2 Ti 4 O 9 , H 4
Nb 6 O 17 , HBiNb 2 O 7 , H 2 La 2 Ti 3 O 10
And HNb 3 O 8 and the like are preferable, and particularly H 2 Ti 4 O 9
And H 4 Nb 6 O 17 are preferred.
【００１２】上記陽イオン交換性層状化合物は、Ｋ2 Ｔ
ｉ4 Ｏ9 、Ｋ4 Ｎｂ6 Ｏ17、ＫＢｉＮｂ2 Ｏ7 、Ｋ2 Ｌ
ａ2 Ｔｉ3 Ｏ10 及びＫＮｂ3 Ｏ8 の粉末を0.1 〜10Ｎ
の塩酸等の水溶液中に１〜24時間分散させ、層間のＫ+
をＨ+ にイオン交換することにより得られる。The above cation-exchangeable layered compound is K 2 T
i 4 O 9 , K 4 Nb 6 O 17 , KBiNb 2 O 7 , K 2 L
a 2 Ti 3 O 10 and KNb 3 O 8 powder in an amount of 0.1-10 N
Then the dispersion 1 to 24 hours in an aqueous solution of hydrochloric acid or the like, the interlayer K +
Is obtained by ion-exchange with H + .
【００１３】(c) 陰イオン交換性層状化合物 陰イオン交換性層状化合物は、層状の格子間に有する陰
イオンを、化合物の外部の陰イオンと交換できればいか
なるものでもよいが、具体的には層状複水酸化物である
［Ｍ(II)1-Y Ｍ(III) Y （ＯＨ）2 ］（ＣＯ3 ）
Y/2 （ただし、Ｍ(II)は、Ｍｇ2+、Ｚｎ2+、Ｃｕ2+、Ｎ
ｉ2+及びＣｏ2+からなる群から選ばれた１種の金属であ
り、Ｍ(III) は、Ａｌ3+、Ｃｒ3+及びＦｅ3+からなる群
から選ばれた１種の金属であり、0.17≦Ｙ≦0.33であ
る。）が好ましい。Ｙが0.17未満では、Ｍｇ（ＯＨ）2
やＭｇＣＯ3 が混入し、0.33を超えるとＡｌ（ＯＨ）3
が混入する。[0013] (c) anion-exchange layered compound anion-exchange layered compound, an anion having between laminar lattice, but may be any if exchange with an external anion compound, specifically a layered It is a double hydroxide [M (II) 1-Y M (III) Y (OH) 2 ] (CO 3 ).
Y / 2 (However, M (II) is Mg 2+ , Zn 2+ , Cu 2+ , N
i 2+ and Co 2+ are one kind of metal selected from the group consisting of, and M (III) is one kind of metal selected from the group consisting of Al 3+ , Cr 3+ and Fe 3+. Yes, 0.17 ≦ Y ≦ 0.33. ) Is preferred. When Y is less than 0.17, Mg (OH) 2
And MgCO 3 are mixed, and when it exceeds 0.33, Al (OH) 3
Is mixed in.
【００１４】〔２〕光分解用触媒の製造方法 本発明の光分解用触媒は、以上説明した半導体を、(1)
陽イオン交換性層状化合物に包接させるか、または(2)
陰イオン交換性層状化合物に包接させたあと、白金を担
持してなるが、その具体的な製造方法をそれぞれについ
て説明する。 [2] Method for Producing Photodecomposition Catalyst The photodecomposition catalyst of the present invention comprises the semiconductor described above (1)
Inclusion in a cation-exchange layered compound, or (2)
After being clathrated by the anion-exchange layered compound, platinum is supported, and specific manufacturing methods thereof will be described below.
【００１５】(1) 陽イオン交換性層状化合物への包接 Ｋ2 Ｔｉ4 Ｏ9 、Ｋ4 Ｎｂ6 Ｏ17、ＫＢｉＮｂ2 Ｏ7 、
Ｋ2 Ｌａ2 Ｔｉ3 Ｏ10及びＫＮｂ3 Ｏ8 等の層状化合物
を塩酸等の水溶液中に１〜２４時間分散させて得られた
Ｈ2 Ｔｉ4 Ｏ9 、Ｈ4 Ｎｂ6 Ｏ17、ＨＢｉＮｂ2 Ｏ7 、
Ｈ2 Ｌａ2 Ｔｉ3 Ｏ10 及びＨＮｂ3 Ｏ8 等の陽イオン
交換性層状化合物を、ｎ−ヘキサン等の有機溶媒に分散
させる。次いでｎ−Ｃ8 Ｈ17ＮＨ2 やｎ−Ｃ3 Ｈ7 ＮＨ
2 等のアルキルアミンを添加し、室温以上かつｎ−ヘキ
サン等の有機溶媒の沸点未満の温度下で１時間〜１週間
反応させ、層間のＨ+ をアルキルアンモニウムイオンと
イオン交換する。 (1) Inclusion in a cation-exchangeable layered compound K 2 Ti 4 O 9 , K 4 Nb 6 O 17 , KBiNb 2 O 7 ,
H 2 Ti 4 O 9 , H 4 Nb 6 O 17 , HBiNb 2 obtained by dispersing a layered compound such as K 2 La 2 Ti 3 O 10 and KNb 3 O 8 in an aqueous solution such as hydrochloric acid for 1 to 24 hours. O 7 ,
The H 2 La 2 Ti 3 O 10 and HNb cation exchange layered compounds such as 3 O 8, are dispersed in an organic solvent such as n- hexane. Then n-C 8 H 17 NH 2 and n-C 3 H 7 NH
An alkylamine such as 2 is added, and the reaction is carried out at room temperature or higher and lower than the boiling point of an organic solvent such as n-hexane for 1 hour to 1 week to exchange H + between the layers with an alkylammonium ion.
【００１６】得られた化合物を、Ｃｄ2+及び／又はＺｎ
2+の塩（酢酸塩等）の水溶液に懸濁し、室温以上かつ水
溶液の沸点（約100 ℃）未満の温度下で１時間〜１週間
反応させ、層間のアルキルアンモニウムイオンと、Ｃｄ
2+及び／又はＺｎ2+とをイオン交換する。その化合物を
乾燥させることなく０〜60℃程度の温度下で、0.5 〜２
時間Ｈ2 Ｓと反応させ、層間のＣｄ2+及び／又はＺｎ2+
をＣｄ1-X ＺｎX Ｓ（ただし、０≦Ｘ≦1.0 である。）
とする。なお、Ｘの値は水溶液中のＣｄ2+とＺｎ2+の組
成比を変えることにより調整することができる。The obtained compound was added to Cd 2+ and / or Zn
Suspended in an aqueous solution of 2+ salt (acetate, etc.) and reacted at room temperature or higher and below the boiling point of the aqueous solution (about 100 ° C.) for 1 hour to 1 week.
Ion exchange with 2+ and / or Zn 2+ . The compound is dried at a temperature of 0 to 60 ° C. for 0.5 to 2 without drying.
Cd 2+ and / or Zn 2+ between the layers is reacted with H 2 S for a time.
To Cd 1-X Zn X S (where 0 ≦ X ≦ 1.0).
And The value of X can be adjusted by changing the composition ratio of Cd 2+ and Zn 2+ in the aqueous solution.
【００１７】陽イオン交換性層状化合物に包接する半導
体の比率としては、陽イオン交換性層状化合物を100 重
量部としたとき、１〜50重量部が好ましく、特に10〜20
重量部が好ましい。The ratio of the semiconductor included in the cation-exchange layered compound is preferably 1 to 50 parts by weight, particularly 10 to 20 parts by weight, when the cation-exchanged layered compound is 100 parts by weight.
Parts by weight are preferred.
【００１８】(2) 陰イオン交換性層状化合物への包接 ［Ｍ(II)1-Y Ｍ(III) Y （ＯＨ）2 ］（ＣＯ3 ）
Y/2 （ただし、Ｍ(II)は、Ｍｇ2+、Ｚｎ2+、Ｃｕ2+、Ｎ
ｉ2+及びＣｏ2+からなる群から選ばれた１種の金属であ
り、Ｍ(III) は、Ａｌ3+、Ｃｒ3+及びＦｅ3+からなる群
から選ばれた１種の金属であり、0.17≦Ｙ≦0.33であ
る。）等の層状複水酸化物を、450 〜800 ℃で0.1 〜１
時間仮焼し、岩塩構造型酸化物とする。 (2) Inclusion in an anion-exchange layered compound [M (II) 1-Y M (III) Y (OH) 2 ] (CO 3 )
Y / 2 (However, M (II) is Mg 2+ , Zn 2+ , Cu 2+ , N
i 2+ and Co 2+ are one kind of metal selected from the group consisting of, and M (III) is one kind of metal selected from the group consisting of Al 3+ , Cr 3+ and Fe 3+. Yes, 0.17 ≦ Y ≦ 0.33. ) And other layered double hydroxides at 450-800 ° C for 0.1-1
Calcined for a period of time to form a rock salt structure type oxide.
【００１９】得られた酸化物を、Ｃｄ2+及び／又はＺｎ
2+を含むキレート化剤（ＥＤＴＡ等）の水溶液に懸濁
し、約６０℃で１〜24時間撹拌して層間にＣｄ（ＥＤＴ
Ａ）2-及び／又はＺｎ（ＥＤＴＡ）2-をインターカレー
トした層状複水酸化物とする。その化合物を0.5 〜２時
間Ｈ2 Ｓガスと反応させるか、または0.5 〜２時間硫化
アルカリ（Ｎａ2 Ｓ等）の水溶液と反応させ、層間のＣ
ｄ（ＥＤＴＡ）2-及び／又はＺｎ（ＥＤＴＡ）2-をＣｄ
1-X ＺｎX Ｓ（ただし、０≦Ｘ≦1.0 である。）とす
る。なお、Ｘの値は上記水溶液中のＣｄ2+とＺｎ2+の組
成比を変えることにより調整することができる。The obtained oxide was added to Cd 2+ and / or Zn
It is suspended in an aqueous solution of a chelating agent (EDTA, etc.) containing 2+ and stirred at about 60 ° C. for 1 to 24 hours and Cd (EDT
A) A layered double hydroxide obtained by intercalating 2- and / or Zn (EDTA) 2- . The compound is reacted with H 2 S gas for 0.5 to 2 hours, or with an aqueous solution of alkali sulfide (Na 2 S, etc.) for 0.5 to 2 hours, and the C
d (EDTA) 2− and / or Zn (EDTA) 2− is Cd
1−X Zn X S (where 0 ≦ X ≦ 1.0). The value of X can be adjusted by changing the composition ratio of Cd 2+ and Zn 2+ in the aqueous solution.
【００２０】陰イオン交換性層状化合物に包接する半導
体の比率としては、陰イオン交換性層状化合物を１００
重量部としたとき、５〜５０重量部が好ましく、特に１
０〜３０重量部が好ましい。The ratio of the semiconductors included in the anion-exchange layered compound is 100% of the anion-exchange layered compound.
When it is referred to as parts by weight, 5 to 50 parts by weight is preferable, and particularly 1
0 to 30 parts by weight is preferable.
【００２１】(3) Ｐｔの担持 上記(1) 又は(2) で作成した層間包接光触媒をメタノー
ル水溶液に分散した後、Ｐｔ（ＮＨ3 ）4 Ｃｌ2 及び／
又は（ＮＨ4 ）2 ＰｔＣｌ6 と（ＮＨ4 ）2 ＣＯ3 とを
投入して溶解させ、約５０℃程度の温度で浸透させた
後、１００Ｗ前後の水銀灯の波長４００ｎｍ以上の光で
照射して、層間にＰｔを析出させる。Ｐｔの担持量はＣ
ｄ1-X ＺｎX Ｓの０．０５〜５重量％であり、好ましく
は０．５〜２．０重量％である。この方法でＰｔの担持
を行えば、ＰｔがＣｄ1-X ＺｎX Ｓに近接して担持さ
れ、Ｃｄ1-X ＺｎX Ｓの触媒活性を高めることができ
る。 (3) Support of Pt After the interlayer inclusion photocatalyst prepared in (1) or (2) above is dispersed in an aqueous methanol solution, Pt (NH 3 ) 4 Cl 2 and / or
Alternatively, (NH 4 ) 2 PtCl 6 and (NH 4 ) 2 CO 3 are charged and dissolved, allowed to infiltrate at a temperature of about 50 ° C., and then irradiated with light having a wavelength of 400 nm or more from a mercury lamp of about 100 W. , Pt is deposited between the layers. The loading amount of Pt is C
and 0.05 to 5% by weight of d 1-X Zn X S, preferably 0.5 to 2.0 wt%. By performing the loading of Pt in this way, Pt is supported in proximity to the Cd 1-X Zn X S, can enhance the catalytic activity of Cd 1-X Zn X S.
【００２２】〔３〕水素の製造方法 上記光分解用触媒を使用した本発明の水素の製造方法を
以下説明する。光分解する水溶液としては、アルカリ化
合物の水溶液、アルコール水溶液等を使用するのが好ま
しく、またそれらの混合水溶液を使用してもよい。アル
カリ化合物としては、Ｎａ2 Ｓ、Ｎａ2 ＳＯ3 、Ｎａ2
Ｓ2 Ｏ3 及びＮａＮＯ2 等が好ましく、それらの混合物
であってもよい。濃度は0.1 〜１mol/リットルが好まし
い。また、アルコールとしては、２−アミノエタノー
ル、メタノール、エタノール等が好ましく、それらを混
合したものであってもよい。濃度は0.1 〜１mol/リット
ルが好ましい。 [3] Method for producing hydrogen The method for producing hydrogen of the present invention using the above-mentioned photodecomposition catalyst will be described below. As the aqueous solution for photolysis, it is preferable to use an aqueous solution of an alkaline compound, an aqueous solution of alcohol, or the like, or a mixed aqueous solution thereof. Alkali compounds include Na 2 S, Na 2 SO 3 , Na 2
S 2 O 3 and NaNO 2 are preferable, and a mixture thereof may be used. The concentration is preferably 0.1 to 1 mol / liter. The alcohol is preferably 2-aminoethanol, methanol, ethanol or the like, and may be a mixture thereof. The concentration is preferably 0.1 to 1 mol / liter.
【００２３】上記水溶液に本発明の光分解用触媒を添加
する。光分解用触媒の添加量は、0.5 〜５mg／cm3 が好
ましく、特に１〜３mg／cm3 が好ましい。このように光
分解用触媒を添加した水溶液に光を照射することによっ
て水が分解し、水素が発生する。照射する光の波長は55
0 nm以下が好ましい。太陽光の波長は350 〜2000nm程度
であるため、本発明では太陽光を照射してもよい。ま
た、水溶液の温度は25〜60℃が好ましい。The photodecomposition catalyst of the present invention is added to the above aqueous solution. Amount of light cracking catalyst is preferably 0.5 to 5 mg / cm 3, in particular 1-3 mg / cm 3 preferred. By irradiating the aqueous solution containing the photodecomposition catalyst with light in this manner, water is decomposed and hydrogen is generated. The wavelength of light to irradiate is 55
It is preferably 0 nm or less. Since the wavelength of sunlight is about 350 to 2000 nm, sunlight may be irradiated in the present invention. The temperature of the aqueous solution is preferably 25 to 60 ° C.
【００２４】[0024]
【作用】上述したように、本発明の光分解用触媒は、太
陽光によって励起される半導体を陽イオン交換性層状化
合物又は陰イオン交換性層状化合物に包接してなるの
で、バンドギャップは約2.4 〜3.0 ｅＶであり、400 〜
550 nm程度の波長の光の照射により励起して、水の光分
解に対する高い触媒活性を示す。また、本発明の光分解
用触媒は水溶液中でもほとんど溶解することがなく、化
学的に安定している。As described above, the photodecomposition catalyst of the present invention has a band gap of about 2.4 because the semiconductor excited by sunlight is included in the cation exchange layer compound or the anion exchange layer compound. ~ 3.0 eV, 400 ~
Excited by irradiation with light having a wavelength of about 550 nm, it exhibits high catalytic activity for photolysis of water. Further, the photodecomposition catalyst of the present invention hardly dissolves in an aqueous solution and is chemically stable.
【００２５】[0025]
【実施例】本発明を以下の具体的実施例によりさらに詳
細に説明する。実施例１ 固相法により調製したＫ4 Ｎｂ6 Ｏ17の粉末を１００
℃、１Ｎの塩酸水溶液中に１時間分散させ、陽イオン交
換性層状化合物Ｈ4 Ｎｂ6 Ｏ17を得た。これをｎ−ヘキ
サン中に分散させ、イオン交換量でＨ4 Ｎｂ6 Ｏ17の５
倍の量のｎ−Ｃ8Ｈ17ＮＨ2 を添加し、50℃で３日間反
応させ、層間のＨ+ をオクチルアンモニウムイオンとイ
オン交換した。The present invention will be described in more detail by the following specific examples. Example 1 100 K 4 Nb 6 O 17 powder prepared by the solid phase method was used.
The mixture was dispersed in a 1N aqueous hydrochloric acid solution at 1 ° C. for 1 hour to obtain a cation-exchangeable layered compound H 4 Nb 6 O 17 . This was dispersed in n-hexane, and the ion exchange amount of H 4 Nb 6 O 17 was 5%.
It was added twice the amount of n-C 8 H 17 NH 2 , and reacted for 3 days at 50 ° C., and the H + of the interlayer and octyl ammonium ion and ion exchange.
【００２６】得られた化合物を、Ｃｄ（ＣＨ3 ＣＯＯ）
2 とＺｎ（ＣＨ3 ＣＯＯ）2 の混合水溶液（イオン交換
すべき量の20倍のＣｄ2+とＺｎ2+を含有）に懸濁し、50
℃で３日間反応させて層間のオクチルアンモニウムイオ
ンと、Ｃｄ2+及びＺｎ2+とをイオン交換した。得られた
化合物を乾燥させることなく25℃で１時間Ｈ2 Ｓと反応
させ、Ｃｄ0.8 Ｚｎ0.2 Ｓを層間に包接した光分解用触
媒Ｈ4 Ｎｂ6 Ｏ17／Ｃｄ0.8 Ｚｎ0.2 Ｓを得た。この光
分解用触媒のバンドギャップを測定したところ、2.63ｅ
Ｖであった。この触媒をメタノール水溶液に分散した
後、（ＮＨ4 ）2ＰｔＣｌ6 と（ＮＨ4 ）2 ＣＯ3 とを
投入して溶解させ、約５０℃程度の温度で浸透させた
後、約１００Ｗの水銀灯の波長４００ｎｍ以上の光で照
射して、層間にＰｔを析出させて、Ｃｄ0.8 Ｚｎ0.2 Ｓ
の１重量％担持した。Ｐｔを担持した光分解用触媒Ｈ4
Ｎｂ6 Ｏ17／Ｃｄ0.8 Ｚｎ0.2 Ｓのバンドギャップを測
定したところ、２．９８ｅＶであった。The obtained compound was converted into Cd (CH 3 COO)
Suspended in a mixed aqueous solution of 2 and Zn (CH 3 COO) 2 (containing 20 times the amount of Cd 2+ and Zn 2+ to be ion-exchanged), and
The reaction was carried out at ℃ for 3 days to ion-exchange octyl ammonium ion between the layers with Cd 2+ and Zn 2+ . The obtained compound was reacted with H 2 S at 25 ° C. for 1 hour without drying to obtain a photolysis catalyst H 4 Nb 6 O 17 / Cd 0.8 Zn 0.2 S in which Cd 0.8 Zn 0.2 S was included between layers. It was The band gap of this photolysis catalyst was measured and found to be 2.63e.
It was V. After this catalyst was dispersed in an aqueous methanol solution, (NH 4 ) 2 PtCl 6 and (NH 4 ) 2 CO 3 were added and dissolved to allow the catalyst to permeate at a temperature of about 50 ° C. Irradiation with light having a wavelength of 400 nm or more is performed to precipitate Pt between the layers, and Cd 0.8 Zn 0.2 S
Of 1% by weight. Pt-supported photolysis catalyst H 4
The band gap of Nb 6 O 17 / Cd 0.8 Zn 0.2 S was measured and found to be 2.98 eV.
【００２７】実施例２〜８ 実施例１で得られた光分解用触媒Ｈ4 Ｎｂ6 Ｏ17／Ｃｄ
0.8 Ｚｎ0.2 Ｓ１ｇを、それぞれＮａ2 Ｓ（実施例
２）、Ｎａ2 ＳＯ3 （実施例３）、２−アミノエタノー
ル（実施例４）、Ｎａ2 Ｓ2 Ｏ3 （実施例５）、ＮａＮ
Ｏ2 （実施例６）、メタノール（実施例７）及びエタノ
ール（実施例８）の水溶液（0.1 Ｍの濃度、60℃）400
cm3 に添加し、波長が400nm 以上の100 Ｗ高圧水銀ラン
プの光を照射した。このときの水素生成速度をそれぞれ
表１に示す。 Examples 2 to 8 Photodecomposition catalyst H 4 Nb 6 O 17 / Cd obtained in Example 1
0.8 Zn 0.2 S 1 g was added to Na 2 S (Example 2), Na 2 SO 3 (Example 3), 2-aminoethanol (Example 4), Na 2 S 2 O 3 (Example 5) and NaN, respectively.
An aqueous solution of O 2 (Example 6), methanol (Example 7) and ethanol (Example 8) (0.1 M concentration, 60 ° C.) 400
It was added to cm 3 and irradiated with light from a 100 W high pressure mercury lamp having a wavelength of 400 nm or more. The hydrogen production rates at this time are shown in Table 1.
【００２８】比較例１ バルクのＣｄ0.8 Ｚｎ0.2 Ｓ１ｇを、0.1 ＭのＮａ2 Ｓ
水溶液（60℃）400 cm3 に添加し、実施例２と同様にし
て光を照射した。このときの水素生成速度を表１に示
す。 Comparative Example 1 1 g of bulk Cd 0.8 Zn 0.2 S was added to 0.1 M Na 2 S.
The solution was added to 400 cm 3 of the aqueous solution (60 ° C.) and irradiated with light in the same manner as in Example 2. Table 1 shows the hydrogen production rate at this time.
【００２９】比較例2 実施例１と同様な方法で作成したＨ4 Ｎｂ6 Ｏ17／Ｃｄ
0.8 Ｚｎ0.2 Ｓ１ｇを、0.1 ＭのＮａ2 Ｓ水溶液（60
℃）400 cm3 に添加し、実施例２と同様にして光を照射
した。このときの水素生成速度を表１に示す。 Comparative Example 2 H 4 Nb 6 O 17 / Cd prepared by the same method as in Example 1
0.8 Zn 0.2 S 1 g was added to 0.1 M Na 2 S aqueous solution (60
C.) 400 cm 3 and was irradiated with light in the same manner as in Example 2. Table 1 shows the hydrogen production rate at this time.
【００３０】表１実施例No. 水素生成速度 (mmol /h) 実施例２ １．０５ 実施例３ ０．４３ 実施例４ ０．３５ 実施例５ ０．４２ 実施例６ ０．２９ 実施例７ ０．３５ 実施例８ ０．３０ 比較例１ ０．０２５ 比較例２ ０．２７Table 1 Example No. Hydrogen production rate (mmol / h) Example 2 1.05 Example 3 0.43 Example 4 0.35 Example 5 0.42 Example 6 0.29 Example 7 0.35 Example 8 0.30 Comparative Example 1 0.025 Comparative Example 2 0.27
【００３１】表１から明らかなように、Ｈ4 Ｎｂ6 Ｏ17
の層間にＰｔを担持したＣｄ0.8 Ｚｎ0.2 Ｓを包接した
本発明の光分解用触媒は、従来のバルクのＣｄ0.8 Ｚｎ
0.2Ｓ及びＨ4 Ｎｂ6 Ｏ17／Ｃｄ0.8 Ｚｎ0.2 Ｓと比較
して水の分解効率が高く、安定して水素を生成すること
ができる。As is clear from Table 1, H 4 Nb 6 O 17
The photodecomposition catalyst of the present invention in which Pd-supported Cd 0.8 Zn 0.2 S is clathrated between the layers is a conventional bulk Cd 0.8 Zn
The decomposition efficiency of water is higher than that of 0.2 S and H 4 Nb 6 O 17 / Cd 0.8 Zn 0.2 S, and hydrogen can be stably generated.
【００３２】[0032]
【発明の効果】以上詳述したように、本発明の光分解用
触媒は、Ｐｔを担持した半導体を、陽イオン交換性層状
化合物又は陰イオン交換性層状化合物に包接してなるた
め、水溶液中でも安定性に優れるとともに、太陽光によ
って効率よく水を光分解し、水素を製造することができ
る。As described in detail above, the photodecomposition catalyst of the present invention comprises a Pt-supported semiconductor in a cation-exchangeable layered compound or an anion-exchanged layered compound. It is excellent in stability and can efficiently photolyze water by sunlight to produce hydrogen.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉田 清英 埼玉県熊谷市末広四丁目14番１号 株式会 社リケン熊谷事業所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyohide Yoshida 4-1-1 Suehiro, Kumagaya-shi, Saitama Stock company Riken Kumagaya Works
Claims (4)
ン交換性層状化合物又は陰イオン交換性層状化合物に包
接してなる水の光分解用触媒において、前記半導体がＰ
ｔを０．０５〜５重量％担持したＣｄ1-X ＺｎX Ｓ（た
だし、０≦Ｘ≦1.0 である。）からなることを特徴とす
る光分解用触媒。1. A catalyst for photolysis of water, comprising a semiconductor excited by sunlight in a cation-exchangeable layered compound or an anion-exchanged layered compound, wherein the semiconductor is P
A photodecomposition catalyst comprising Cd 1-X Zn X S (where 0 ≦ X ≦ 1.0) supporting t in an amount of 0.05 to 5% by weight.
いて、前記陽イオン交換性層状化合物が、Ｈ2 Ｔｉ4 Ｏ
9 、Ｈ4 Ｎｂ6 Ｏ17、ＨＢｉＮｂ2 Ｏ7 、Ｈ2 Ｌａ2 Ｔ
ｉ3 Ｏ10 及びＨＮｂ3 Ｏ8 からなる群から選ばれた少
なくとも１種の化合物からなり、前記陰イオン交換性層
状化合物が、［Ｍ(II)1-Y Ｍ(III) Y（ＯＨ）2 ］（Ｃ
Ｏ3 ）Y/2 （ただし、Ｍ(II)は、Ｍｇ2+、Ｚｎ2+、Ｃｕ
2+、Ｎｉ2+及びＣｏ2+からなる群から選ばれた少なくと
も１種の金属であり、Ｍ(III)は、Ａｌ3+、Ｃｒ3+及び
Ｆｅ3+からなる群から選ばれた少なくとも１種の金属で
あり、0.17≦Ｙ≦0.33である。）からなることを特徴と
する光分解用触媒。2. The catalyst for photolysis of water according to claim 1, wherein the cation-exchange layered compound is H 2 Ti 4 O.
9 , H 4 Nb 6 O 17 , HBiNb 2 O 7 , H 2 La 2 T
i 3 O 10 and HNb 3 O 8 and at least one compound selected from the group consisting of the anion-exchangeable layered compound [M (II) 1-Y M (III) Y (OH) 2 ] (C
O 3 ) Y / 2 (where M (II) is Mg 2+ , Zn 2+ , Cu
At least one metal selected from the group consisting of 2+ , Ni 2+ and Co 2+ , and M (III) is at least selected from the group consisting of Al 3+ , Cr 3+ and Fe 3+. It is one kind of metal, and 0.17 ≦ Y ≦ 0.33. And a photodecomposition catalyst.
ン交換性層状化合物又は陰イオン交換性層状化合物に包
接してなる光分解用触媒を水溶液に添加し、前記水溶液
に光を照射することによって分解し、もって水素を製造
する水素の製造方法において、前記水溶液がアルカリ化
合物及び／又はアルコールを含有し、前記半導体がＰｔ
を０．０５〜５重量％担持したＣｄ1-X ＺｎX Ｓ（ただ
し、０≦Ｘ≦1.0 である。）からなり、前記陽イオン交
換性層状化合物が、Ｈ2 Ｔｉ4Ｏ9 、Ｈ4 Ｎｂ6 Ｏ17、
ＨＢｉＮｂ2 Ｏ7 、Ｈ2 Ｌａ2 Ｔｉ3 Ｏ10 及びＨＮｂ
3 Ｏ8 からなる群から選ばれた少なくとも１種の化合物
からなり、前記陰イオン交換性層状化合物が、［Ｍ(II)
1-Y Ｍ(III) Y （ＯＨ）2 ］（ＣＯ3 ）Y/2 （ただし、
Ｍ(II)は、Ｍｇ2+、Ｚｎ2+、Ｃｕ2+、Ｎｉ2+及びＣｏ2+
からなる群から選ばれた少なくとも１種の金属であり、
Ｍ(III) は、Ａｌ3+、Ｃｒ3+及びＦｅ3+からなる群から
選ばれた少なくとも１種の金属であり、0.17≦Ｙ≦0.33
である。）からなることを特徴とする方法。3. A photodecomposition catalyst obtained by clathrating a semiconductor excited by sunlight into a cation-exchangeable layered compound or an anion-exchanged layered compound is added to an aqueous solution, and the aqueous solution is irradiated with light. In the method for producing hydrogen, which decomposes to produce hydrogen, the aqueous solution contains an alkaline compound and / or alcohol, and the semiconductor contains Pt.
Of Cd 1 -X Zn X S (provided that 0 ≦ X ≦ 1.0) is carried by 0.05 to 5% by weight, and the cation-exchangeable layered compound is H 2 Ti 4 O 9 , H 4 Nb 6 O 17 ,
HBiNb 2 O 7 , H 2 La 2 Ti 3 O 10 and HNb
The anion-exchange layered compound consisting of at least one compound selected from the group consisting of 3 O 8 and [M (II)
1-Y M (III) Y (OH) 2 ] (CO 3 ) Y / 2 (however,
M (II) is Mg 2+ , Zn 2+ , Cu 2+ , Ni 2+ and Co 2+
At least one metal selected from the group consisting of
M (III) is at least one metal selected from the group consisting of Al 3+ , Cr 3+ and Fe 3+ , and 0.17 ≦ Y ≦ 0.33
Is. ) Consisting of.
て、前記アルカリ化合物が、Ｎａ2 Ｓ、Ｎａ2 ＳＯ3 、
Ｎａ2 Ｓ2 Ｏ3 及びＮａＮＯ2 からなる群から選ばれた
少なくとも１種の化合物からなり、前記アルコールが、
２−アミノエタノール、メタノール及びエタノールから
なる群から選ばれた少なくとも１種のアルコールからな
ることを特徴とする方法。4. The method for producing hydrogen according to claim 3, wherein the alkaline compound is Na 2 S, Na 2 SO 3 ,
The alcohol comprises at least one compound selected from the group consisting of Na 2 S 2 O 3 and NaNO 2 .
A method comprising at least one alcohol selected from the group consisting of 2-aminoethanol, methanol and ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6133593A JPH07313884A (en) | 1994-05-24 | 1994-05-24 | Catalyst for photolysis of water and production of hydrogen using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6133593A JPH07313884A (en) | 1994-05-24 | 1994-05-24 | Catalyst for photolysis of water and production of hydrogen using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07313884A true JPH07313884A (en) | 1995-12-05 |
Family
ID=15108441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6133593A Pending JPH07313884A (en) | 1994-05-24 | 1994-05-24 | Catalyst for photolysis of water and production of hydrogen using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07313884A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998015352A1 (en) * | 1996-10-07 | 1998-04-16 | Korea Research Institute Of Chemical Technology | NOVEL ZnS PHOTOCATALYST, PREPARATION THEREFOR AND METHOD FOR PRODUCING HYDROGEN BY USE OF THE SAME |
| KR100342856B1 (en) * | 2000-02-22 | 2002-07-02 | 김충섭 | CdZnMS photocatalyst added with cation for water decomposition and preparation there for and method for producing hydrogen by use of the same |
| WO2002062467A1 (en) * | 2001-02-07 | 2002-08-15 | Japan Science And Technology Corporation | Oxysulfide photocatalyst for use in decomposition of water by visible light |
| JP2002249031A (en) * | 2001-02-22 | 2002-09-03 | Denaro:Kk | Hydrogen supply stand |
| WO2003078061A1 (en) * | 2002-03-18 | 2003-09-25 | Nittetsu Mining Co., Ltd. | Photocatalyst and process for producing the same |
| JP2003311155A (en) * | 2002-03-27 | 2003-11-05 | Council Scient Ind Res | New preparation method of layered double hydroxide exchanged with diisopropylamide which can be used for c-c bond forming reaction |
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1994
- 1994-05-24 JP JP6133593A patent/JPH07313884A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1108866C (en) * | 1996-10-07 | 2003-05-21 | 韩国化学研究所 | ZnS photocatalyst, preparation thereof and use thereof the producing hydrogen |
| WO1998015352A1 (en) * | 1996-10-07 | 1998-04-16 | Korea Research Institute Of Chemical Technology | NOVEL ZnS PHOTOCATALYST, PREPARATION THEREFOR AND METHOD FOR PRODUCING HYDROGEN BY USE OF THE SAME |
| KR100342856B1 (en) * | 2000-02-22 | 2002-07-02 | 김충섭 | CdZnMS photocatalyst added with cation for water decomposition and preparation there for and method for producing hydrogen by use of the same |
| WO2002062467A1 (en) * | 2001-02-07 | 2002-08-15 | Japan Science And Technology Corporation | Oxysulfide photocatalyst for use in decomposition of water by visible light |
| JP2002249031A (en) * | 2001-02-22 | 2002-09-03 | Denaro:Kk | Hydrogen supply stand |
| US7704914B2 (en) | 2002-03-18 | 2010-04-27 | Nittetsu Mining Co., Ltd. | Photocatalyst and process for producing the same |
| WO2003078061A1 (en) * | 2002-03-18 | 2003-09-25 | Nittetsu Mining Co., Ltd. | Photocatalyst and process for producing the same |
| JP2003311155A (en) * | 2002-03-27 | 2003-11-05 | Council Scient Ind Res | New preparation method of layered double hydroxide exchanged with diisopropylamide which can be used for c-c bond forming reaction |
| JP4494703B2 (en) * | 2002-03-27 | 2010-06-30 | カウンシル オブ サイエンティフィク アンド インダストリアル リサーチ | Method for preparing novel diisopropylamide exchanged stacked dihydroxides that can be used in CC bond formation reactions |
| EA009448B1 (en) * | 2002-06-25 | 2007-12-28 | Ниттецу Майнинг Ко., Лтд. | Highly active photocatalyst and process for producing the same |
| US7608557B2 (en) | 2002-06-25 | 2009-10-27 | Nittetsu Mining Co., Ltd. | Highly active photocatalyst and process for producing the same |
| WO2004000459A1 (en) * | 2002-06-25 | 2003-12-31 | Nittetsu Mining Co., Ltd. | Highly active photocatalyst and process for producing the same |
| CN113083326A (en) * | 2021-03-30 | 2021-07-09 | 宁德师范学院 | Novel bonded zinc indium sulfide/niobic acid heterojunction photocatalyst and preparation method and application thereof |
| CN113083326B (en) * | 2021-03-30 | 2022-06-10 | 宁德师范学院 | Novel bonded zinc indium sulfide/niobic acid heterojunction photocatalyst and preparation method and application thereof |
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