JPS6265743A - Zinc compound having photocatalytic activity - Google Patents
Zinc compound having photocatalytic activityInfo
- Publication number
- JPS6265743A JPS6265743A JP60203865A JP20386585A JPS6265743A JP S6265743 A JPS6265743 A JP S6265743A JP 60203865 A JP60203865 A JP 60203865A JP 20386585 A JP20386585 A JP 20386585A JP S6265743 A JPS6265743 A JP S6265743A
- Authority
- JP
- Japan
- Prior art keywords
- mixture
- mortar
- added
- photocatalytic activity
- sulfidation
- 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.)
- Granted
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 8
- 150000003752 zinc compounds Chemical class 0.000 title claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011701 zinc Substances 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 9
- 238000011282 treatment Methods 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 9
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004570 mortar (masonry) Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 abstract description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000005486 sulfidation Methods 0.000 abstract 3
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- -1 arsenic anion Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002611 lead compounds Chemical class 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- OKPZIQOBDZDBRW-UHFFFAOYSA-N [Pt].[K] Chemical compound [Pt].[K] OKPZIQOBDZDBRW-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000001495 arsenic compounds Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔利用分野〕
本発明は光触媒活性を有する亜鉛化合物に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION [Field of Application] The present invention relates to a zinc compound having photocatalytic activity.
酸化亜鉛を主体とする金属酸化物触媒を用いて、アルカ
リ金属の硫化物あるいは亜硫酸塩のような被酸ｆヒ性陰
イオンを含む水溶液の可視光による光分解を行う場合、
触媒に要求される性質は主として４つある。その（１）
は可視光を吸収する性質であり、その（２）は硫化物イ
オンや岨硫酸イオン等の電子供与性物質から電子を奪う
性質、即ち光酸ｒヒ能であり、その（３）は電子供与性
物質から受取った電子を電子受容性物質に渡す性質、即
ち光還元能である。When photolyzing an aqueous solution containing an arsenic anion such as an alkali metal sulfide or sulfite using visible light using a metal oxide catalyst mainly containing zinc oxide,
There are mainly four properties required of a catalyst. Part (1)
(2) is the property of absorbing visible light, (2) is the property of taking electrons from electron-donating substances such as sulfide ions and sulfate ions, that is, photoacid arsenic ability, and (3) is the property of absorbing electron-donating substances. This is the property of transferring electrons received from a reactive substance to an electron-accepting substance, that is, photoreducibility.
その（４）は前記の（２）と１３）の過程で生成した被
酸化物質と被還元物質が納会して酸化や還元作用を受け
る以前の物質に逆戻りする反応、即ち再結合反応を防上
する性能である。これら４つの性能がバランスよく機４
粍を果してはじめて光触媒活性が発揮される。(4) is to prevent the recombination reaction, which is a reaction in which the oxidized substance and the reduced substance generated in the processes of (2) and 13) combine and return to the substance before being oxidized or reduced. It has the ability to These four performances are well-balanced.
Photocatalytic activity is exhibited only after the process is completed.
こｎらの性質は亜鉛の酸化物や亜鉛の硫化物の半導体と
しての性質に含まれているものである。These properties are included in the properties of zinc oxide and zinc sulfide as semiconductors.
これまで多くの半導体物質の光触媒機能が研究され、か
なりの種類の異種物質のドーピングが試みられているが
、本発明において作成したような高度に分散したＺｎ＋
イオンやＣｄイオンを粒子表面に形成分散させるドーピ
ングの方法は知らｎていない。Until now, the photocatalytic function of many semiconductor materials has been studied, and attempts have been made to dope them with a considerable variety of different materials.
There is no known doping method for forming and dispersing ions or Cd ions on the particle surface.
本発明者らは、龍鉛酸化物や硫化物からなる光活性触媒
において、一般に、酸化物の光吸収は紫外部に偏ってお
り、これに対して、一般に硫ｆヒ物の光吸収は可視部に
わたっているが、水溶液中で硫化物は不安定であるとい
う欠点を有している点、そして硫化物の光吸収能力と酸
化物の化学的安定性の両方を取り入れた複合材料が得ら
ｎ、かつそれが可視光領域で安定な触媒材料として使用
できる点に着目し、鋭意研究を重ねた結果、粒子表面に
Ｚｎ やＣｄ−を高分散度で形成させたものがその目
的に適合することを見出し、本発明を完成するに至った
。The present inventors discovered that in photoactive catalysts made of lead oxides and sulfides, the light absorption of oxides is generally biased toward the ultraviolet region, whereas the light absorption of sulfur compounds is generally biased toward the ultraviolet region. However, sulfides have the disadvantage of being unstable in aqueous solutions, and composite materials that incorporate both the light absorption ability of sulfides and the chemical stability of oxides cannot be obtained. , and that it can be used as a stable catalyst material in the visible light region, and as a result of extensive research, we found that particles with highly dispersed Zn and Cd- formed on the particle surface were suitable for this purpose. They discovered this and completed the present invention.
すなわち、本発明によれば、白金あるいはカドミウムを
含有させた即鉛酸化物粒子の表面に、ＺｎやＣｄ を
高分散度で形成させたことを特徴とする光触媒活性を有
する垂鉛化合物を提供するものである。That is, according to the present invention, there is provided a drop lead compound having photocatalytic activity, which is characterized in that Zn or Cd is formed with a high degree of dispersion on the surface of ready-lead oxide particles containing platinum or cadmium. It is something.
本発明の亜鉛化合物は、酸化亜鉛に対して重量で１俤に
相当する白金を化合させてから、短信の間粉砕混合する
っ本発明において、硫化物の形成け、硫化剤として二硫
化炭素、硫化水素、硫化メチル等を含む硫化性ガス雰囲
気中において温度７００°Ｃ８度（酸化カドミウム添加
量の多い場合は６００ ”Ｃ）に加熱することに、ｌ：
って行うことができる。このようにして生成した硫化Ｗ
を酸四または酸素を含む雰囲気中において温度４００
’Ｃ程度に加熱することにより亜鉛化合物粒子の表面に
生成したＳ１イオンを酸化してＯゝイオンに変化させる
ことができる。！た触媒成分として加える白金は塩イヒ
白金酸カリ （Ｋ２ＰｔＣｌ４．に２ＰｔＣ１６）で加
えても、白金黒の形で加えてもよい。白金を加えなくて
も触媒作用は発揮されるが、白金を加えることにより触
媒活性を５０％程度向上させることができる。白金はま
たニッケルにより代用することもできる。The zinc compound of the present invention is produced by combining platinum equivalent to 1 kg by weight with zinc oxide, and then pulverizing and mixing the mixture. In a sulfidic gas atmosphere containing hydrogen sulfide, methyl sulfide, etc., it is heated to a temperature of 700°C and 8°C (600"C if a large amount of cadmium oxide is added).
You can do this. Sulfide W generated in this way
at a temperature of 400℃ in an atmosphere containing acid or oxygen.
By heating to about 'C', the S1 ions generated on the surface of the zinc compound particles can be oxidized and changed into O' ions. ! Platinum added as a catalyst component may be added in the form of potassium platinum salt (2PtC16 to K2PtCl4) or in the form of platinum black. Although the catalytic effect is exhibited even without the addition of platinum, the catalytic activity can be improved by about 50% by adding platinum. Platinum can also be replaced by nickel.
本発明により触媒中のＺｎ を還元してＺｎ を生
成させる場合、通常の還元方法ではＺｎ＋は局部的に集
中して高濃度に生成してしまい、格子間亜鉛イオンと言
われる、結晶格子外に生長した還元状態にある亜鉛イオ
ンの集合体に変化するのを防止するために、本発明では
硫１°ヒ処理の際には二硫化炭素や硫化メチルのような
弱い硫化剤を用いる。When Zn is produced by reducing Zn in the catalyst according to the present invention, Zn+ is locally concentrated and produced in a high concentration using the usual reduction method, and Zn+ is produced outside the crystal lattice, which is called an interstitial zinc ion. In order to prevent the zinc ions from changing into aggregates of grown reduced zinc ions, a weak sulfiding agent such as carbon disulfide or methyl sulfide is used in the sulfur treatment in the present invention.
その圧力も例えば硫化剤分圧１万分の１〜１万分の２気
圧程度にするのがよく、また酸化処理の際には集団的に
生成したＺｎ＋を酸化してその大部分を元のＺｎ に
戻すため酸素分圧１気圧程度にする。The pressure is preferably set to, for example, 1/10,000 to 2/10,000 atmospheres of the sulfurizing agent partial pressure, and during the oxidation treatment, the collectively generated Zn+ is oxidized and most of it is converted to the original Zn. To restore the oxygen partial pressure to about 1 atm.
よく分散して生成したＺｎ イオンの濃度をより高く
するためには、孤立したＺｎ イオンを安定化するよ
うな亜鉛酸什物の粒子表面の特異点の濃度を高くするこ
とが必要であるうそのためには亜鉛酸什物を電磁弐娠動
乳鉢で粉砕しながらそのような粒子表面の特異点を露出
させ、かつそのような点〕が露出した際にその特異的な
活性状態を保存するために、ハイドロキノンのような還
元剤を加えておく。このようにすることにより、特異点
はハイドロキノンと反応して酸化さ扛にくくなるので、
その後に硫化処理を受ける迄その還元的状態を保つ。ま
た触媒表面はぼ化状態の方が安定であるので、最終処理
は醸化状態でなけ汎ばならない。In order to increase the concentration of well-dispersed and generated Zn ions, it is necessary to increase the concentration of singular points on the surface of zincate particles that stabilize isolated Zn ions. While crushing the zinc acid in an electromagnetic mortar, we exposed the singular points on the surface of the particles, and in order to preserve the specific active state when such points were exposed, we added hydroquinone. Add a reducing agent such as By doing this, the singular point will react with hydroquinone and become difficult to oxidize.
It remains in its reducing state until it is subsequently subjected to sulfurization. Further, since the catalyst surface is more stable in a blurred state, the final treatment must be carried out in a fermented state.
本発明の１重信化合物はバンドギャップの中間にＺｎ＋
の中間電子帯を作って光吸収特性を紫外部より可視部に
拡大改良したものであり、かつ白金の添加により還元能
が向上したため、半導体触媒が本来有している光酸化能
と相まって高い光触媒活性を発揮する。本発明によｎば
、硫化物や亜硫酸塩等の水溶液のほか、電子供与性の強
い液体（例えばメタノール、エチルアミン等）又は電子
供与性の強いＣ固体物質（例えばブドウ糖、グルタミン
酸等）の水溶液に本発明の重信化合物を接触させた状態
で、可視光を照射すると、還元性物質（水素等）と酸ｆ
ヒ性物′α（硫黄、値開イオン、あるいは上記反応基質
が酸化さｎて生ずるアルデヒド、ニトロソ化合！ｌｙ１
等）を製造することができる。The first compound of the present invention has Zn+ in the middle of the band gap.
It has improved light absorption properties by expanding it from the ultraviolet region to the visible region by creating an intermediate electron band of Demonstrate activity. According to the present invention, in addition to aqueous solutions of sulfides and sulfites, liquids with strong electron donating properties (e.g., methanol, ethylamine, etc.) or aqueous solutions of C solid substances with strong electron donating properties (e.g., glucose, glutamic acid, etc.) can be used. When visible light is irradiated with the compound of the present invention in contact with it, reducing substances (hydrogen etc.) and acid f
Arsenic compound 'α (sulfur, value ion, or aldehyde produced by oxidation of the above reaction substrate, nitroso compound!ly1
etc.) can be manufactured.
実施例 次に本発明を実施例により更に詳細に説明する。Example Next, the present invention will be explained in more detail with reference to Examples.
実施例１゜
１０重量係のハイドロキノンと１時間電磁式振動乳鉢で
粉砕（見合した酸化頃鉛を０．１’ｒｏｒｒのＣ８２中
で７００°Ｃ１３０分間処理し、次いで１気圧の酸素中
で４００ ’Ｃ１３０分間処理する。さらに３０分間Ｃ
８２中で７００ ’Ｃに加熱処理する。得られた粉末に
対して１．０重量係に相当する白金を含有する塩化白金
酸カリウムを水溶液から吸着させ、インプロパツールと
水とピロガロールの混合溶液中で紫外線照射により白金
を還元する。この粉末をさらに７００℃のＣ，９□中で
３０分間加熱し、さらに４００°Ｃの酸素中で３０分間
加熱して本発明の亜鉛化合物を得た。Example 1: Grinding with 10 parts by weight of hydroquinone in an electromagnetic vibrating mortar for 1 hour (comparable oxidized lead was treated in C82 at 0.1'rorr for 130 minutes at 700°C, then in 1 atm of oxygen for 400' Process for 130 minutes.C for an additional 30 minutes.
82 to 700'C. Potassium chloroplatinate containing 1.0 weight percent of platinum is adsorbed from an aqueous solution to the obtained powder, and the platinum is reduced by ultraviolet irradiation in a mixed solution of Impropatol, water, and pyrogallol. This powder was further heated in C, 9□ at 700°C for 30 minutes, and further heated in oxygen at 400°C for 30 minutes to obtain the zinc compound of the present invention.
次に前記手鎖化合物０３ｇを、１０ ｍｌノ０．３５
Ｍ＃度のＮａ ２ＳＯ３溶液に入れ、光波長領域４８０
ｎｍ〜７５０ ｎｍの光を３００μアイ／シユタイ〉
照射した。Next, add 0.35 g of the hand chain compound to 10 ml.
M# degree of Na2SO3 solution, light wavelength range 480
nm ~ 750 nm light at 300μ eye/shaft>
Irradiated.
その結果光エネルギーの変換効率２３チで水素０．８３
ｍ１を発生させることができた。またこの際水相には０
８３μモルの硫酸イオンを生成させることができた。As a result, the conversion efficiency of light energy is 23 cm and hydrogen is 0.83 cm.
It was possible to generate m1. Also, at this time, the water phase has 0
It was possible to generate 83 μmol of sulfate ions.
実施例２゜
酸化カドミウムと酸化亜鉛をモル比で１：１の割に混合
したものを電磁式撮動乳鉢で１時間粉砕混合したものを
実施例１と同じ方法で硫化・酸化処理および白金添加を
行って本発明の亜鉛化合物を得た。Example 2 A mixture of cadmium oxide and zinc oxide at a molar ratio of 1:1 was pulverized and mixed in an electromagnetic mortar for 1 hour, and then sulfurized and oxidized and platinum was added in the same manner as in Example 1. The zinc compound of the present invention was obtained.
次にここに得た鰍鉛化合物０．３．９を実施例１と同じ
方法で０．３５Ｍ岨硫酸ソーダ水溶液中で可視光照射を
行ったところ、光エネルギーの変換効率２２係で水素０
．７９ ｍｌを発生させることができた。Next, when 0.3.9 of the lead compound obtained here was irradiated with visible light in a 0.35M sodium sulfate aqueous solution in the same manner as in Example 1, the conversion efficiency of light energy was 22, and hydrogen was 0.
．． It was possible to generate 79 ml.
また水溶液中に３３μモルの硫酸イオンが生成した。Additionally, 33 μmol of sulfate ions were generated in the aqueous solution.
Claims (1)
硫化酸化処理することによりＺｎイオンあるいはＣｄイ
オンを粒子表面に高分散度に形成させることを特徴とす
る光触媒活性を有する亜鉛化合物。(1) A zinc compound having photocatalytic activity, which is characterized by forming Zn ions or Cd ions with a high degree of dispersion on the particle surface by subjecting a zinc oxide containing platinum or cadmium to a sulfiding oxidation treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203865A JPS6265743A (en) | 1985-09-14 | 1985-09-14 | Zinc compound having photocatalytic activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60203865A JPS6265743A (en) | 1985-09-14 | 1985-09-14 | Zinc compound having photocatalytic activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6265743A true JPS6265743A (en) | 1987-03-25 |
| JPH0255373B2 JPH0255373B2 (en) | 1990-11-27 |
Family
ID=16480981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60203865A Granted JPS6265743A (en) | 1985-09-14 | 1985-09-14 | Zinc compound having photocatalytic activity |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6265743A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997012668A3 (en) * | 1995-09-18 | 1997-06-19 | Korea Res Inst Chem Tech | Novel photocatalyst, preparation therefor and method for producing hydrogen using the same |
| 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 |
| WO2002018049A1 (en) | 2000-09-01 | 2002-03-07 | Japanese Science And Technology Corporation | Method for preparing highly active photocatalyst and method for treating hydrogen sulfide allowing recovery of hydrogen gas with low energy consumption by use of highly active photocatalyst |
| WO2002083308A1 (en) * | 2001-04-11 | 2002-10-24 | Japan Science And Technology Corporation | Method for preparing high active photocatalyst and method for treating hydrogen sulfide using the high active photocatalyst |
| WO2003051512A1 (en) * | 2001-12-19 | 2003-06-26 | Japan Science And Technology Corporation | Thin-film photocatalyst, its production method, hydrogen sulfide processing method using the thin-film optical catalyst, and hydrogen producing method |
| JP2006082071A (en) * | 2004-02-20 | 2006-03-30 | Sekisui Jushi Co Ltd | Photocatalytic composition, building material for interior finish, coating material, synthetic resin molded body, method for utilizing photocatalyst and method for decomposing harmful substance |
| JP2007070675A (en) * | 2005-09-06 | 2007-03-22 | Nissan Motor Co Ltd | Semiconductor electrode and energy conversion system using the same |
-
1985
- 1985-09-14 JP JP60203865A patent/JPS6265743A/en active Granted
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997012668A3 (en) * | 1995-09-18 | 1997-06-19 | Korea Res Inst Chem Tech | Novel photocatalyst, preparation therefor and method for producing hydrogen using the same |
| 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 |
| 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 |
| WO2002018049A1 (en) | 2000-09-01 | 2002-03-07 | Japanese Science And Technology Corporation | Method for preparing highly active photocatalyst and method for treating hydrogen sulfide allowing recovery of hydrogen gas with low energy consumption by use of highly active photocatalyst |
| EP1314478A1 (en) * | 2000-09-01 | 2003-05-28 | Japanese Science and Technology Corporation | Method for preparing highly active photocatalyst and method for treating hydrogen sulfide allowing recovery of hydrogen gas with low energy consumption by use of highly active photocatalyst |
| EP1314478A4 (en) * | 2000-09-01 | 2004-10-20 | Japan Science & Tech Agency | Method for preparing highly active photocatalyst and method for treating hydrogen sulfide allowing recovery of hydrogen gas with low energy consumption by use of highly active photocatalyst |
| US6964755B2 (en) * | 2000-09-01 | 2005-11-15 | Japan Science And Technology Agency | Method for producing high activity photocatalyst, photoactivity catalyst, and method for treating hydrogen sulfide for recovering hydrogen gas under low energy by using high activity photocatalyst |
| WO2002083308A1 (en) * | 2001-04-11 | 2002-10-24 | Japan Science And Technology Corporation | Method for preparing high active photocatalyst and method for treating hydrogen sulfide using the high active photocatalyst |
| WO2003051512A1 (en) * | 2001-12-19 | 2003-06-26 | Japan Science And Technology Corporation | Thin-film photocatalyst, its production method, hydrogen sulfide processing method using the thin-film optical catalyst, and hydrogen producing method |
| JP2006082071A (en) * | 2004-02-20 | 2006-03-30 | Sekisui Jushi Co Ltd | Photocatalytic composition, building material for interior finish, coating material, synthetic resin molded body, method for utilizing photocatalyst and method for decomposing harmful substance |
| JP2007070675A (en) * | 2005-09-06 | 2007-03-22 | Nissan Motor Co Ltd | Semiconductor electrode and energy conversion system using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0255373B2 (en) | 1990-11-27 |
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