JPH0255373B2 - - Google Patents
Info
- Publication number
- JPH0255373B2 JPH0255373B2 JP60203865A JP20386585A JPH0255373B2 JP H0255373 B2 JPH0255373 B2 JP H0255373B2 JP 60203865 A JP60203865 A JP 60203865A JP 20386585 A JP20386585 A JP 20386585A JP H0255373 B2 JPH0255373 B2 JP H0255373B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- ions
- present
- platinum
- zinc oxide
- 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 - Lifetime
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 150000003752 zinc compounds Chemical class 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 7
- 230000001699 photocatalysis Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-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
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 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
- 239000000843 powder Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 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
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-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
- 230000000694 effects Effects 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
- 150000002431 hydrogen Chemical class 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
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000011734 sodium Substances 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
- -1 sulfide ions Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc 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
- Physical Or Chemical Processes And Apparatus (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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
うな被酸化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)は硫化物イオンや亜硫酸イオン等
の電子供与性物質から電子を奪う性質、即ち光酸
化能であり、その(3)は電子供与性物質から受取つ
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。その(4)は前記の(2)と(3)の過程で生成し
た被酸化物質と被還元物質が結合して酸化や還元
作用を受ける以前の物質に逆戻りする反応、即ち
再結合反応を防止する性能でである。これらの４
つの性能がバランスよく機能を果してはじめて光
触媒活性が発揮される。 When photolyzing an aqueous solution containing oxidizable anions such as alkali metal sulfide or sulfite using visible light using a metal oxide catalyst mainly composed of zinc oxide, the properties required of the catalyst are as follows. There are four main types. (1) is the property of absorbing visible light, (2) is the property of taking electrons from electron-donating substances such as sulfide ions and sulfite ions, that is, photooxidation ability, and (3) is the property of absorbing electrons. This is the property of transferring electrons received from a donating substance to an electron-accepting substance, that is, photoreducibility. Part (4) prevents the reaction in which the oxidized substance and the reduced substance generated in the processes of (2) and (3) above combine and revert to the substance before undergoing oxidation or reduction, that is, the recombination reaction. It has the performance of These 4
Photocatalytic activity is achieved only when the two functions function in a well-balanced manner.
これ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。
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れてい
ない。 These properties are included in the properties of zinc oxide and zinc sulfide as semiconductors.
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. A doping method for formation and dispersion is not known.
本発明者らは、亜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
外部に偏つており、これに対して、一般に硫化物
の光吸収は可視部にわたつているが、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れ、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
するに至つた。
The present inventors discovered that in photoactive catalysts made of zinc oxide and sulfide, the light absorption of oxides is generally concentrated in the ultraviolet region, whereas the light absorption of sulfides is generally concentrated in the visible region. However, sulfides have the disadvantage of being unstable in aqueous solutions, and a composite material that incorporates both the light absorption ability of sulfides and the chemical stability of oxides can be obtained. Focusing on the fact that it can be used as a stable catalytic material in the visible light region, we conducted extensive research and found that particles with highly dispersed Zn + and Cd + formed on the particle surface were suitable for this purpose. This finding led to the completion of 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亜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亜鉛化合物を提供するも
のである。 That is, according to the present invention, on the surface of zinc oxide particles containing platinum or cadmium,
The present invention provides a zinc compound having photocatalytic activity, which is characterized by forming Zn + and Cd + with a high degree of dispersion.
本発明の亜鉛化合物は、酸化亜鉛に対して重量
で１％に相当する白金を化合させてから、亜鉛の
一部を還元してZn+を形成分散させたものであ
る。酸化カドミウムを加する場合には、酸化亜鉛
と酸化カドミウム粉末を電磁式振動乳鉢に入れて
１時間粉砕混合する。本発明において、硫化物の
形成は、硫化剤として２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℃程度（酸化カドミウム添加量の多い場合
は600℃）に加熱することによつて行うことがで
きる。このようにして生成した硫化物を酸素また
は酸素を含む雰囲気中において温度400℃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S2-イオンを酸化してO2-イオンに変化させ
ることができる。また触媒成分として加える白金
は塩化白金酸カリ（K2PtCl4、K2PtCl6）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。白金はまたニツケルにより代用することも
できる。 The zinc compound of the present invention is obtained by combining platinum equivalent to 1% by weight with respect to zinc oxide, and then reducing a portion of the zinc to form and disperse Zn + . When adding cadmium oxide, zinc oxide and cadmium oxide powder are placed in an electromagnetic vibrating mortar and ground and mixed for one hour. In the present invention, sulfides are formed by heating to a temperature of approximately 700°C (600°C if a large amount of cadmium oxide is added) in a sulfurizing gas atmosphere containing carbon disulfide, hydrogen sulfide, methyl sulfide, etc. as a sulfurizing agent. This can be done by By heating the sulfide thus generated to a temperature of approximately 400°C in oxygen or an atmosphere containing oxygen, the S 2- ions generated on the surface of the zinc compound particles are oxidized and converted into O 2- ions. Can be done. Further, platinum added as a catalyst component may be added in the form of potassium chloroplatinate (K 2 PtCl 4 , K 2 PtCl 6 ) or in the form of platinum black. Catalytic activity can be achieved without adding platinum, but adding platinum can improve catalytic activity by about 50%. Platinum can also be substituted by nickel.
本発明により触媒中のZn2+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、本発明では硫化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。
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Zn2+に戻すため酸素分圧１気圧程度にす
る。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、弧立したZn+イオンを安定
化するような亜鉛酸化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。そのためには亜
鉛酸化物を電磁式振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れにくくなるの
で、その後の硫化処理を受ける迄その還元的状態
を保つ。また触媒表面は酸化状態の方が安定であ
るので、最終処理は酸化状態でなければならな
い。 When Zn + is produced by reducing Zn 2+ in the catalyst according to the present invention, with the usual reduction method, Zn + is locally concentrated and produced at a high concentration, which is called an interstitial zinc ion. In order to prevent zinc ions from changing into aggregates of reduced zinc ions grown outside the crystal lattice, a weak sulfiding agent such as carbon disulfide or methyl sulfide is used in the sulfiding process in the present invention.
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 back to the original Zn. To return to 2+ , reduce the oxygen partial pressure to about 1 atm. In order to increase the concentration of well-dispersed Zn + ions, it is necessary to increase the concentration of singular points on the surface of zinc oxide particles that stabilize the erect Zn + ions. . For this purpose, zinc oxide is crushed in an electromagnetic vibrating mortar to expose the singular points on the particle surface, and when such points are exposed, hydroquinone is added to preserve the specific active state. Add a reducing agent such as By doing so, the singular point becomes less likely to react with hydroquinone and be oxidized, so that it maintains its reducing state until it is subjected to the subsequent sulfurization treatment. Further, since the catalyst surface is more stable in an oxidized state, the final treatment must be in an oxidized state.
本発明の亜鉛化合物はバンドギヤツプの中間に
Zn+の中間電子帯を作つ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つて高い光触媒活
性を発揮する。本発明によれば、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亜鉛化合物を接触させ
た状態で、可視光を照射すると、還元性物質（水
素等）と酸化性物質（硫黄、硫酸イオン、あるい
は上記反応基質が酸化されて生ずるアルデヒド、
ニトロソ化合物等）を製造することができる。
The zinc compound of the present invention is placed in the middle of the band gap.
By creating an intermediate electron band in Zn + , the light absorption properties have been expanded from the ultraviolet region to the visible region, and the reduction ability has been improved by adding platinum, which is compatible with the photooxidation ability that semiconductor catalysts inherently have. It exhibits high photocatalytic activity. According to the present invention, in addition to aqueous solutions of sulfides, sulfites, etc., the present invention can be applied to aqueous solutions of strongly electron-donating liquids (e.g., methanol, ethylamine, etc.) or aqueous solutions of strongly electron-donating solid substances (e.g., glucose, glutamic acid, etc.). When exposed to visible light while in contact with a zinc compound, reducing substances (hydrogen, etc.) and oxidizing substances (sulfur, sulfate ions, or aldehydes produced by oxidation of the above reaction substrates,
nitroso compounds, etc.) can be produced.
実施例
次に本発明を実施例により更に詳細に説明す
る。EXAMPLES Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
1.0重量％のハイドロキノンと１時間電磁式振
動乳鉢で粉砕混合した酸化亜鉛を0.1TorrのCS2
中で700℃、30分間処理し、次いで１気圧の酸素
中で400℃、30分間処理する。さらに30分間CS2
中で700℃に加熱処理する。得られた粉末に対し
て1.0重量％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、イソプロパノ
ールと水とピロガロールの混合液中で紫外線照射
により白金を還元する。この粉末をさらに700℃
のCS2中で30分間加熱し、さらに400℃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 1.0% by weight of hydroquinone and zinc oxide ground and mixed in an electromagnetic vibrating mortar for 1 hour were mixed with 0.1 Torr of CS 2
700° C. for 30 minutes in an atmosphere of 1 atmosphere of oxygen, and then 400° C. for 30 minutes in 1 atmosphere of oxygen. Another 30 minutes CS 2
Heat-treated at 700℃ in a vacuum chamber. Potassium chloroplatinate containing platinum corresponding to 1.0% by weight of the obtained powder is adsorbed from an aqueous solution, and the platinum is reduced by ultraviolet irradiation in a mixed solution of isopropanol, water, and pyrogallol. This powder is further heated to 700℃.
The zinc compound of the present invention was obtained by heating in CS 2 at 400° C. for 30 minutes and further heating in oxygen at 400° C. for 30 minutes.
次に前記亜鉛化合物0.3ｇを、10mlの0.35M濃
度のNa2SO3溶液に入れ、光波長領域480nm〜
750nmの光を300μアインシユタイン照射した。そ
の結果光エネルギーの変換効率23％で水素0.83ml
を発生させることができた。またこの際水相には
0.83モルの硫酸イオンを生成させることができ
た。 Next, 0.3 g of the zinc compound was added to 10 ml of Na 2 SO 3 solution with a concentration of 0.35 M, and a light wavelength range of 480 nm ~
750nm light was irradiated with a 300μ einstein beam. As a result, 0.83ml of hydrogen with a light energy conversion efficiency of 23%
was able to occur. Also, at this time, in the aqueous phase
It was possible to generate 0.83 moles of sulfate ion.
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振動乳鉢で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つ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 vibrating mortar for 1 hour, and then sulfurized and oxidized and platinum was added in the same manner as in Example 1. Thus, the zinc compound of the present invention was obtained.
次にここに得た亜鉛化合物0.3ｇを実施例１と
同じ方法で0.35M亜硫酸ソーダ水溶液中で可視光
照射を行つたところ、光エネルギーの変換効率22
％で水素0.79mlを発生させることができた。また
水溶液中に33μモルの硫酸イオンが生成した。 Next, when 0.3 g of the zinc compound obtained here was irradiated with visible light in a 0.35M sodium sulfite aqueous solution in the same manner as in Example 1, the conversion efficiency of light energy was 22.
%, it was possible to generate 0.79ml of hydrogen. Additionally, 33 μmol of sulfate ions were generated in the aqueous solution.
Claims (1)
物を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 sulfidation 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 JPS6265743A (en) | 1987-03-25 |
| JPH0255373B2 true 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002306966A (en) * | 2001-04-11 | 2002-10-22 | Japan Science & Technology Corp | Method for manufacturing highly activated photocatalyst and method for treating hydrogen sulfide using highly activated photocatalyst |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0180606B1 (en) * | 1995-09-18 | 1999-03-20 | 강박광 | Novel photocatalyst, its preparation process and hydrotreating process using it |
| KR100202238B1 (en) * | 1996-10-07 | 1999-06-15 | 이서봉 | Novel zns photocatalyst, method thereof and production of hydrogen gas |
| JP4191373B2 (en) | 2000-09-01 | 2008-12-03 | 独立行政法人科学技術振興機構 | Method for producing highly active photocatalyst and method for treating hydrogen sulfide for recovering hydrogen gas with low energy using highly active photocatalyst |
| JP2003181297A (en) * | 2001-12-19 | 2003-07-02 | Japan Science & Technology Corp | Thin film-like photocatalyst, forming method thereof, method of treating hydrogen sulfide using the thin film- like photocatalyst, and method of manufacturing hydrogen |
| 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 |
| JP4997454B2 (en) * | 2005-09-06 | 2012-08-08 | 独立行政法人産業技術総合研究所 | Semiconductor electrode and energy conversion system using the same |
-
1985
- 1985-09-14 JP JP60203865A patent/JPS6265743A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002306966A (en) * | 2001-04-11 | 2002-10-22 | Japan Science & Technology Corp | Method for manufacturing highly activated photocatalyst and method for treating hydrogen sulfide using highly activated photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6265743A (en) | 1987-03-25 |
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