JPH06182205A - Production of photocatalyst and the photocatalyst - Google Patents
Production of photocatalyst and the photocatalystInfo
- Publication number
- JPH06182205A JPH06182205A JP4357123A JP35712392A JPH06182205A JP H06182205 A JPH06182205 A JP H06182205A JP 4357123 A JP4357123 A JP 4357123A JP 35712392 A JP35712392 A JP 35712392A JP H06182205 A JPH06182205 A JP H06182205A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- gold
- titanium oxide
- oxide
- supported
- 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
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052737 gold Inorganic materials 0.000 claims abstract description 31
- 239000010931 gold Substances 0.000 claims abstract description 31
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 30
- 238000010304 firing Methods 0.000 claims description 15
- 239000010419 fine particle Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 32
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 32
- 230000000694 effects Effects 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 6
- -1 titanium oxide Chemical class 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000000746 purification Methods 0.000 description 13
- 229910052878 cordierite Inorganic materials 0.000 description 10
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006552 photochemical reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PGHQEOHSIGPJOC-UHFFFAOYSA-N [Fe].[Ta] Chemical compound [Fe].[Ta] PGHQEOHSIGPJOC-UHFFFAOYSA-N 0.000 description 1
- WZECUPJJEIXUKY-UHFFFAOYSA-N [O-2].[O-2].[O-2].[U+6] Chemical compound [O-2].[O-2].[O-2].[U+6] WZECUPJJEIXUKY-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- PHGMGTWRSNXLDV-UHFFFAOYSA-N diethyl furan-2,5-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)O1 PHGMGTWRSNXLDV-UHFFFAOYSA-N 0.000 description 1
- VIUKNDFMFRTONS-UHFFFAOYSA-N distrontium;niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Sr+2].[Sr+2].[Nb+5].[Nb+5] VIUKNDFMFRTONS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JCDAAXRCMMPNBO-UHFFFAOYSA-N iron(3+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Ti+4].[Fe+3].[Fe+3] JCDAAXRCMMPNBO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229940071182 stannate Drugs 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910000439 uranium oxide Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、光触媒の製造方法、及
びその光触媒に関し、さらに詳しくは、光の照射により
活性が向上して光化学反応を呈し、もって廃棄物の浄化
処理、水の分解による水素の合成、冷蔵庫や車室内等の
各種空間の脱臭等に利用される光触媒の製造方法、及び
その光触媒に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photocatalyst and its photocatalyst. More specifically, the photocatalyst is improved in its activity by irradiation of light and exhibits a photochemical reaction. The present invention relates to a method for producing a photocatalyst used for synthesizing hydrogen, deodorizing various spaces such as a refrigerator and a vehicle compartment, and the photocatalyst.
【０００２】[0002]
【従来の技術】従来の光触媒は酸化チタンを主成分とし
たものが多い。また、この酸化チタンに金を担持させた
ものも提案されている。（化学工業日報 １９９２年１
０月５日号の記事）2. Description of the Related Art Many conventional photocatalysts mainly contain titanium oxide. Further, a titanium oxide on which gold is supported is also proposed. (The Chemical Daily 1992 1
(October 5 issue)
【０００３】[0003]
【発明が解決しようとする課題】しかし、これら従来の
光触媒は、数十Ｗ程度以下の実用的な光強度（例えば、
冷蔵庫等の殺菌灯は１０Ｗ程度である）における光触媒
活性が十分ではない。その理由は、光を吸収して励起し
た酸化チタンにおいて生成する電子と正孔とが容易に再
結合することによるものと思われる。However, these conventional photocatalysts have a practical light intensity of about several tens W or less (for example,
The photocatalytic activity in a germicidal lamp such as a refrigerator is about 10 W) is not sufficient. The reason seems to be that the electrons and holes generated in titanium oxide excited by absorbing light are easily recombined.
【０００４】そこで本発明者は、上記のような不具合の
ない新規な光触媒を提供すべく、酸化チタンその他の金
属酸化物への一種又は二種以上の各種の触媒金属の担持
や、その触媒金属への各種の処理等を行ってその光触媒
活性の向上を試験・研究した結果、本発明に到達した。Therefore, in order to provide a novel photocatalyst free from the above-mentioned problems, the present inventor carried one or more kinds of various catalytic metals on titanium oxide and other metal oxides, and the catalytic metals thereof. The present invention has been achieved as a result of conducting various treatments and the like to test and study the improvement of its photocatalytic activity.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
の本願第一発明（請求項１に記載した光触媒の製造方法
の発明）の構成は、金属酸化物に金及び／又は遷移金属
及び／又は希土類元素の微粒子を担持させ、これをアン
モニア処理した後、焼成する光触媒の製造方法である。The structure of the first invention of the present application (the invention of the method for producing a photocatalyst according to claim 1) for solving the above-mentioned problems is that the metal oxide is gold and / or the transition metal and / or Alternatively, it is a method for producing a photocatalyst in which fine particles of a rare earth element are supported, and the fine particles are treated with ammonia and then calcined.
【０００６】上記課題を解決するための本願第二発明
（請求項２に記載した光触媒の発明）の構成は、金属酸
化物と、これに担持されてアンモニア処理された金及び
／又は遷移金属及び／又は希土類元素の微粒子との焼成
体からなる光触媒である。The second invention of the present application (the invention of the photocatalyst described in claim 2) for solving the above-mentioned problems is composed of a metal oxide and a gold and / or transition metal supported on the metal oxide and treated with ammonia. And / or a photocatalyst composed of a fired body with fine particles of a rare earth element.
【０００７】[0007]
【作用】本願第一発明の還元処理ないし焼成のプロセス
において金属酸化物や金等の微粒子に起こる変化は必ず
しも解明されていないが、推定として、アンモニア処理
によって金属酸化物に担持した金及び／又は遷移金属及
び／又は希土類元素の塩がアンモニウム塩（又は水酸化
物）に変化し、これが金属酸化物と特殊な錯塩を形成し
ているのではないか、と考えている。The change occurring in the fine particles such as metal oxides and gold in the reduction or calcination process of the first invention of the present application has not always been clarified, but it is presumed that gold and / or metal supported on the metal oxides by the ammonia treatment is estimated. It is considered that the salt of the transition metal and / or the rare earth element is changed to an ammonium salt (or hydroxide), which may form a special complex salt with the metal oxide.
【０００８】本願第二発明の光触媒の作用についても必
ずしも解明されていないが、推定として、光を吸収して
励起した金属酸化物が生成する電子と、その正孔との再
結合を、金属酸化物と錯塩を形成した金及び／又は遷移
金属及び／又は希土類元素が阻止し、従って電子の活性
状態が維持されて、光エネルギーを有効に酸化還元反応
に関与させているのではないか、と考えている。Although the action of the photocatalyst of the second invention of the present application has not always been elucidated, it is presumed that the recombination between the electron and the hole produced by the metal oxide excited by absorbing light and the hole thereof is prevented by the metal oxidation. The gold and / or transition metal and / or the rare earth element forming a complex salt with the substance may be blocked, and thus the active state of the electron may be maintained, and the light energy may be effectively involved in the redox reaction. thinking.
【０００９】[0009]
【効果】本願第一発明の光触媒の製造方法により本願発
明の光触媒が有効に製造され、また、こうして製造され
た本願第二発明の光触媒は、数十Ｗ以下の実用的な光強
度においても十分な光触媒活性を示す。[Effect] The photocatalyst of the present invention is effectively produced by the method for producing a photocatalyst of the first invention of the present application, and the photocatalyst of the second invention of the present application produced in this manner is sufficient even at a practical light intensity of several tens of W or less. It exhibits excellent photocatalytic activity.
【００１０】[0010]
【実施態様】次に本願第一、第二発明の実施態様につい
て説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the first and second inventions of the present application will be described.
【００１１】金属酸化物とは、その代表的なものが酸化
チタンＴｉＯ2 であるが、これに限定されるものではな
い。その他の金属酸化物として、例えば、酸化タングス
テンＷＯ3 、酸化鉄Ｆｅ2 Ｏ3 、酸化ビスマスＢｉ2 Ｏ
3 、酸化スズＳｎＯ2 、酸化ウランＵ3 Ｏ8 、酸化カド
ミウムＣｄＯ、酸化インジウムＩｎＯ3 、酸化ニオブＮ
ｂ2 Ｏ3 ，ＮｂＯ、酸化亜鉛ＺｎＯ、酸化ニッケルＮｉ
Ｏ、酸化銅Ｃｕ2 Ｏ、チタン酸ストロンチウムＳｒＴｉ
Ｏ3 、チタン酸バリウムＢａＴｉＯ3 、チタン酸マンガ
ンＭｎＴｉＯ3 、チタン酸鉄ＦｅＴｉＯ3 、チタン酸カ
ルシウムＣａＴｉＯ3 、ニオブ酸ストロンチウムＳｒＮ
ｂ2 Ｏ6 、スズ酸カドミウムＣｄＳｎＯ4 、タンタル酸
鉄ＦｅＴａ2 Ｏ6 ，ＦｅＴａＯ4 、タンタル酸カリウム
ＫＴａＯ3 等を用いることができる。A typical example of the metal oxide is titanium oxide TiO 2 , but the metal oxide is not limited to this. Other metal oxides include, for example, tungsten oxide WO 3 , iron oxide Fe 2 O 3 , bismuth oxide Bi 2 O.
3 , tin oxide SnO 2 , uranium oxide U 3 O 8 , cadmium oxide CdO, indium oxide InO 3 , niobium oxide N
b 2 O 3 , NbO, zinc oxide ZnO, nickel oxide Ni
O, copper oxide Cu 2 O, strontium titanate SrTi
O 3 , barium titanate BaTiO 3 , manganese titanate MnTiO 3 , iron titanate FeTiO 3 , calcium titanate CaTiO 3 , strontium niobate SrN
b 2 O 6, cadmium stannate CdSnO 4, tantalum iron FeTa 2 O 6, FeTaO 4, it is possible to use potassium tantalate KTaO 3 or the like.
【００１２】金属酸化物に担持させる金、遷移金属、希
土類元素については、それらのうちの一種類のみを担持
させても良く、二種類以上を適宜組み合わせて担持させ
ても良い。上記のうち一種類のみを担持させる場合は金
が最も良い。上記のうち二種類を組み合わせて担持させ
る場合は、特段の制約はないが、一般的には、金と、遷
移金属あるいは希土類元素のうちの一種類との組み合わ
せが良く、特に金とニッケルとの組み合わせが望まし
い。With respect to gold, transition metals, and rare earth elements to be carried on the metal oxide, only one kind of them may be carried, or two or more kinds may be appropriately combined and carried. Gold is best when only one of the above is supported. In the case of supporting two kinds of the above in combination, there is no particular limitation, but in general, a combination of gold and one kind of a transition metal or a rare earth element is good, and particularly gold and nickel. A combination is desirable.
【００１３】金属酸化物に対する金の担持量については
特段の制約はないが、好適な担持量としては０．００５
〜０．５重量％程度、最適の担持量としては０．１重量
％前後の担持量である。The amount of gold supported on the metal oxide is not particularly limited, but a preferable amount is 0.005.
Approximately 0.5% by weight, and the optimum supported amount is about 0.1% by weight.
【００１４】遷移金属としては、例えばニッケル、クロ
ム、銅、コバルトを用いることができ、特にニッケルが
望ましい。As the transition metal, for example, nickel, chromium, copper or cobalt can be used, and nickel is particularly desirable.
【００１５】希土類元素としては、例えば、ランタン、
セリウム、プラセオジウム、ネオジウム、ジスプロシウ
ム、ホルミウム、エルビウム、ルテチウム等を用いるこ
とができる。Examples of rare earth elements include lanthanum and
Cerium, praseodymium, neodymium, dysprosium, holmium, erbium, lutetium and the like can be used.
【００１６】金属酸化物に対する遷移金属又は希土類元
素の担持量について特段の制約はないが、例えば０．１
重量％程度を担持させることができる。There is no particular limitation on the amount of the transition metal or rare earth element supported on the metal oxide, but, for example, 0.1.
It is possible to support about wt%.
【００１７】本発明の光触媒は、例えば粉状、粒状で用
いても良く、また、コージェライト、活性炭、シリカ等
の所定形状（例えば、ハニカム形状）の担体に担持させ
て用いても良い。The photocatalyst of the present invention may be used, for example, in the form of powder or particles, or may be used by being supported on a carrier having a predetermined shape (for example, honeycomb shape) such as cordierite, activated carbon or silica.
【００１８】担体に金属酸化物を担持させ、また金属酸
化物に金、遷移金属、希土類元素を担持させる手段は特
に限定しない。通常は、担持させたい金属酸化物の水溶
液や担持させたい金属の硝酸塩水溶液等を用いたいわゆ
るウオッシュ・コート法により、まず担体に金属酸化物
を担持させ、ついで、この金属酸化物に金、遷移金属、
希土類元素を担持させる。The means for supporting the metal oxide on the carrier and for supporting the metal oxide on gold, transition metal or rare earth element is not particularly limited. Usually, by a so-called wash-coat method using an aqueous solution of a metal oxide to be supported or an aqueous solution of a nitrate of a metal to be supported, the metal oxide is first supported on the carrier, and then gold, transition metal,
Support rare earth elements.
【００１９】アンモニア処理は、上記の担持処理を終え
た担体をアンモニア水（ＮＨ4 ＯＨ）に浸漬して行う。
この際のアンモニア水の濃度や浸漬時間等の処理条件は
特に制約がない。The ammonia treatment is carried out by immersing the carrier, which has been subjected to the above supporting treatment, in ammonia water (NH 4 OH).
At this time, the treatment conditions such as the concentration of the ammonia water and the immersion time are not particularly limited.
【００２０】焼成温度は、コージェライト等のセラミッ
ク質の担体を用いる場合、４００〜６００°Ｃ程度が良
い。４００°Ｃを下回る温度で焼成しても前記した錯塩
の形成が不十分に終わる可能性があり、また、６００°
Ｃを上回る温度で焼成すると、金属酸化物の結晶形が崩
れたり、変化したりする可能性がある。特に望ましい焼
成温度は４００〜５００°Ｃ前後である。一方、活性炭
を担体に用いる場合の焼成温度は１５０〜２００°Ｃ程
度が良い。１５０°Ｃを下回る温度で焼成しても金が分
解し難く、２００°Ｃを上回る温度で焼成すると活性炭
が燃えてしまうからである。焼成時間は、数時間程度、
例えば２時間程度で足りるが、本発明の光触媒は耐熱性
が優れているため、５００°Ｃ前後の温度で８時間にも
及ぶ焼成を行っても、その活性はあまり低下しない。The firing temperature is preferably about 400 to 600 ° C. when a ceramic carrier such as cordierite is used. The formation of the above-mentioned complex salt may be insufficiently completed even if the temperature is lower than 400 ° C.
If the temperature is higher than C, the crystal form of the metal oxide may be broken or changed. A particularly desirable firing temperature is around 400 to 500 ° C. On the other hand, when activated carbon is used as the carrier, the firing temperature is preferably about 150 to 200 ° C. This is because gold is difficult to decompose even if fired at a temperature lower than 150 ° C, and activated carbon burns when fired at a temperature higher than 200 ° C. The firing time is about several hours,
For example, about 2 hours is sufficient, but since the photocatalyst of the present invention has excellent heat resistance, its activity does not decrease so much even if it is fired at a temperature of about 500 ° C. for 8 hours.
【００２１】担体に担持させた本発明の光触媒を得る場
合、まず担体に金属酸化物を担持させた後に一度焼成
し、さらに金属酸化物に金、遷移金属、希土類元素を担
持させた後に再度焼成しても良い。In order to obtain the photocatalyst of the present invention supported on a carrier, first, a metal oxide is supported on a carrier and then calcined once, and then gold, a transition metal and a rare earth element are further supported on the metal oxide and then calcined again. You may.
【００２２】本発明の光触媒は他種多様な対象物質を光
化学反応により分解するが、特に極性物質に対する活性
が高い。非極性物質、例えばトルエン等に対しても有効
な活性を示す。The photocatalyst of the present invention decomposes various kinds of target substances by photochemical reaction, and has particularly high activity for polar substances. It also shows effective activity against non-polar substances such as toluene.
【００２３】[0023]
【実施例】次に本発明の実施例について述べる。なお、
以下の各実施例において担持のプロセスは全てウオッシ
ュ・コート法によった。EXAMPLES Next, examples of the present invention will be described. In addition,
In each of the following examples, the loading process was all performed by the wash coat method.
【００２４】（実施例１）No. １〜No. ４のコージェラ
イト製のハニカム担体にそれぞれ同量の酸化チタンを担
持させた後、No. １とNo. ２の試料体には希土類元素で
あるジスプロシウムを、No. ３とNo. ４の試料体にはや
はり希土類元素であるエルビウムを、それぞれ酸化チタ
ンに対して０．１重量％になるように担持させ、さらに
No. ２とNo. ４の試料体は１％のアンモニア水に３０分
間浸漬した。そして各試料体を空気気流中、５００°Ｃ
で２時間焼成した。Example 1 No. 1 to No. 4 cordierite honeycomb carriers were loaded with the same amount of titanium oxide, and the No. 1 and No. 2 sample bodies were treated with rare earth elements. A certain amount of dysprosium was loaded on the sample bodies of No. 3 and No. 4 such that erbium, which is also a rare earth element, was loaded to the titanium oxide in an amount of 0.1% by weight.
The sample bodies of No. 2 and No. 4 were immersed in 1% ammonia water for 30 minutes. Then, each sample body is placed in an air stream at 500 ° C.
It was baked for 2 hours.
【００２５】こうして得たNo. １〜No. ４の試料体を用
い、５Ｗの集光した光照射のもとに２４０分間、アセト
アルデヒドの浄化試験（図８に示す閉鎖循環系評価装置
１を用い、５０〜２００ｐｐｍのアルデヒドを含む空気
を５ｌ／ｍｉｎ．で光触媒層２に通じて一定時間毎にサ
ンプリングし、ガスクロマトグラフ３でアセトアルデヒ
ドの残存率を求めた。）を行ったところ、２４０分後の
浄化率はNo. １が６３．５％、No. ２が８１．４％、N
o. ３が６２．３％、No. ４が７４．３％であった。な
お、ハニカム担体に酸化チタンのみを担持させ、アンモ
ニア処理した標準試料体についても同様の浄化試験を行
ったところ、浄化率は７３．5 ％であった。Using the No. 1 to No. 4 sample bodies thus obtained, an acetaldehyde purification test (using the closed circulation system evaluation apparatus 1 shown in FIG. 8) for 240 minutes under the irradiation of 5 W of condensed light. , Air containing 50 to 200 ppm of aldehyde was passed through the photocatalyst layer 2 at a rate of 5 l / min and sampled at regular intervals, and the residual rate of acetaldehyde was determined by the gas chromatograph 3.) After 240 minutes The purification rate is 63.5% for No. 1, 81.4% for No. 2, N
o.3 was 62.3% and No. 4 was 74.3%. When a similar purification test was performed on a standard sample body obtained by supporting only titanium oxide on a honeycomb carrier and treating with ammonia, the purification rate was 73.5%.
【００２６】（実施例１の評価）以上の結果より、酸化
チタンへの希土類元素の担持は、アンモニア処理を伴な
った場合には、光触媒活性の向上が見られる。(Evaluation of Example 1) From the above results, it can be seen that the loading of the rare earth element on the titanium oxide improves the photocatalytic activity when accompanied by the ammonia treatment.
【００２７】（実施例２）No. ５〜No. ８のコージェラ
イト製のハニカム担体にそれぞれ同量の酸化チタンを担
持させ、ついでこれらに、それぞれ酸化チタンに対して
０．１重量％になるように金を担持させた。そして、N
o. ５は１％のアンモニア水に、No. ６は１％のカ性ソ
ーダ水溶液に、No. ７は１％のカ性カリ水溶液に、No.
８は１％の炭酸ソーダ水溶液に、それぞれ３０分間浸漬
した後、いずれも５００°Ｃで２時間焼成した。Example 2 No. 5 to No. 8 cordierite honeycomb carriers were each loaded with the same amount of titanium oxide, and then 0.1% by weight of titanium oxide was added to each of them. Thus, gold was supported. And N
o.5 to 1% aqueous ammonia, No. 6 to 1% caustic soda solution, No. 7 to 1% caustic potash solution, No.
Sample No. 8 was immersed in a 1% sodium carbonate aqueous solution for 30 minutes, and then baked at 500 ° C. for 2 hours.
【００２８】こうして得たNo. ４〜No. ８の試料体を用
い、実施例１と同様の浄化試験を行ったところ、図１の
結果を得た。Using the No. 4 to No. 8 sample bodies thus obtained, the same purification test as in Example 1 was carried out, and the results shown in FIG. 1 were obtained.
【００２９】（実施例２の評価）図１の結果より、酸化
チタンへの金の担持は、アンモニア処理を伴なった場合
には、光触媒活性の著しい向上が見られる。(Evaluation of Example 2) From the results shown in FIG. 1, when gold is supported on titanium oxide, the photocatalytic activity is remarkably improved when the treatment with ammonia is accompanied.
【００３０】（実施例３）No. ９〜No. １３のコージェ
ライト製のハニカム担体にそれぞれ同量の酸化チタンを
担持させ、ついでこれらに、それぞれ酸化チタンに対し
て０．１重量％（No. ９）、０．０１重量％（No. １
０）、０．００１重量％（No. １１）、０．００５重量
％（No. １２）、０．２重量％（No. １３）になるよう
に金を担持させた。ついで、いずれの試料体についても
前記No. ５と同じアンモニア処理及び焼成を行った。Example 3 No. 9 to No. 13 cordierite honeycomb carriers were loaded with the same amount of titanium oxide, and then 0.1 wt% (No. .9), 0.01% by weight (No. 1
0), 0.001 wt% (No. 11), 0.005 wt% (No. 12) and 0.2 wt% (No. 13) were loaded with gold. Then, the same ammonia treatment and firing as those in No. 5 were performed on all the sample bodies.
【００３１】こうして得たNo. ９〜No. １３の試料体を
用い、実施例１と同様の浄化試験を行ったところ、図２
の結果を得た。Using the No. 9 to No. 13 sample bodies thus obtained, the same purification test as in Example 1 was conducted.
Got the result.
【００３２】（実施例３の評価）図２の結果より、酸化
チタンに金を担持させ、かつアンモニア処理を行った光
触媒においては、金の担持量は酸化チタンに対して０．
００５〜０．２重量％程度が望ましく、最適の担持量と
しては０．１重量％前後の担持量であることが分かっ
た。(Evaluation of Example 3) From the results shown in FIG. 2, in the photocatalyst in which titanium oxide was supported with gold and the ammonia treatment was performed, the supported amount of gold was 0.
It was found that about 005 to 0.2% by weight is desirable, and the optimum supported amount is about 0.1% by weight.
【００３３】（実施例４）No. １４〜No. １８のコージ
ェライト製のハニカム担体にそれぞれ同量の酸化チタン
を担持させ、ついでこれらに、それぞれ酸化チタンに対
して０．１重量％になるように金を担持させて前記No.
５と同じアンモニア処理を行い、No. １４は１５０°
Ｃ、No. １５は３００°Ｃ、No. １６は４００°Ｃ、N
o. １７は６００°Ｃ、No. １８は５００°Ｃでそれぞ
れ２時間、前記No. ５と同じ焼成を行った。(Example 4) No. 14 to No. 18 cordierite honeycomb carriers were loaded with the same amount of titanium oxide, respectively, and then 0.1% by weight relative to titanium oxide. No.
Same ammonia treatment as No.5, No.14 is 150 °
C, No. 15 is 300 ° C, No. 16 is 400 ° C, N
The same firing as No. 5 was performed for 2 hours at 600 ° C. for o. 17 and 500 ° C. for No. 18.
【００３４】こうして得たNo. １４〜No. １８の試料体
を用い、実施例１と同様の浄化試験を行ったところ、図
３の結果を得た。Using the samples No. 14 to No. 18 thus obtained, the same purification test as in Example 1 was carried out, and the results shown in FIG. 3 were obtained.
【００３５】（実施例４の評価）図３の結果より、酸化
チタンに金を担持させ、かつアンモニア処理を行って焼
成した光触媒においては、その焼成温度は４００，５０
０，６００°Ｃのものが良く、特に良い焼成温度は５０
０°Ｃであった。(Evaluation of Example 4) From the results of FIG. 3, in the photocatalyst in which titanium oxide was supported with gold and which was subjected to ammonia treatment and fired, the firing temperature was 400, 50.
0,600 ° C is preferable, and particularly good firing temperature is 50
It was 0 ° C.
【００３６】（実施例５）No. １９，２０のコージェラ
イト製のハニカム担体にそれぞれ同量の酸化チタンを担
持させ、ついでこれらに、それぞれ酸化チタンに対して
０．１重量％になるように金を担持させて前記No. ５と
同じアンモニア処理を行い、いずれも５００°Ｃで、N
o. １９は２時間、No. ２０は８時間にわたり、前記No.
５と同じ焼成を行った。(Embodiment 5) The same amount of titanium oxide was carried on each of the honeycomb carriers made of cordierite of Nos. 19 and 20, and then 0.1% by weight of titanium oxide was added to each of them. The same ammonia treatment as No. 5 above was carried with gold supported, and at 500 ° C, N
o. 19 was for 2 hours and No. 20 was for 8 hours.
The same firing as 5 was performed.
【００３７】こうして得たNo. １９，No. ２０の試料体
を用い、実施例１と同様の浄化試験を行ったところ、図
４の結果を得た。Using the samples No. 19 and No. 20 thus obtained, the same purification test as in Example 1 was carried out, and the results shown in FIG. 4 were obtained.
【００３８】（実施例５の評価）図４の結果より、酸化
チタンに金を担持させ、かつアンモニア処理を行って焼
成した光触媒においては、その焼成温度が５００°Ｃで
ある場合、焼成時間は２時間もあれば十分であり、一
方、８時間も焼成しても光触媒活性が余り落ちていない
ことから、本実施例の光触媒の耐熱性が優れていること
が分かった。(Evaluation of Example 5) From the results shown in FIG. 4, in the case of a photocatalyst in which titanium oxide was supported with gold and subjected to ammonia treatment and fired, when the firing temperature was 500 ° C., the firing time was It was found that 2 hours is enough, while the photocatalyst activity did not deteriorate much even after firing for 8 hours. Therefore, it was found that the photocatalyst of this example has excellent heat resistance.
【００３９】（実施例６）No. ２１のコージェライト製
のハニカム担体に酸化チタンを担持させ、ついでこれ
に、酸化チタンに対して金とニッケルとを、それぞれ
０．１重量％、０．１重量％になるように担持させて前
記No. ５と同じアンモニア処理を行い、かつ前記No. ５
と同じ焼成を行った。Example 6 Titanium oxide was supported on a No. 21 cordierite honeycomb carrier, and then 0.1 wt% and 0.1% by weight of gold and nickel were added to the titanium oxide, respectively. The same ammonia treatment as that of No. 5 was carried out by supporting so as to become the weight%, and No. 5
The same firing was performed.
【００４０】このNo. ２１の試料体を用い、前記したア
ルデヒド浄化試験と同じ要領で、トルエン濃度２０ｐｐ
ｍでトルエン浄化試験を行ったところ、図５の結果を得
た。Using this No. 21 sample body, the toluene concentration was 20 pp in the same manner as in the aldehyde purification test described above.
When a toluene purification test was conducted at m, the results shown in FIG. 5 were obtained.
【００４１】（実施例６の評価）図５の結果より、酸化
チタンに金とニッケルとを担持させ、かつアンモニア処
理を行って焼成した光触媒は、アルデヒドの場合程では
ないが、浄化活性を示すことが分かった。(Evaluation of Example 6) From the results shown in FIG. 5, the photocatalyst obtained by supporting titanium and titanium oxide with gold and nickel, and treating with ammonia and calcining shows a purifying activity, though not so much as in the case of aldehyde. I found out.
【００４２】（実施例７）No. ２２〜No. ２４のコージ
ェライト製のハニカム担体にそれぞれ同量の酸化チタン
を担持させ、ついでこれらに、それぞれ酸化チタンに対
して０．１重量％になるように、No. ２２には銅、No.
２３にはコバルト、No. ２４にはニッケルをそれぞれ担
持させて前記No. ５と同じアンモニア処理と焼成とを行
った。(Example 7) No. 22 to No. 24 cordierite honeycomb carriers were loaded with the same amount of titanium oxide, and then these were each added to 0.1 wt% with respect to titanium oxide. So, No. 22 is copper, No.
Cobalt was carried on No. 23 and nickel on No. 24, respectively, and the same ammonia treatment and baking as those in No. 5 were carried out.
【００４３】これらのNo. ２２〜No. ２４の試料体を用
い、実施例１と同様の浄化試験を行ったところ、図６の
結果を得た。Using these No. 22 to No. 24 sample bodies, the same purification test as in Example 1 was conducted, and the results shown in FIG. 6 were obtained.
【００４４】（実施例７の評価）図６の結果より、酸化
チタンに遷移金属を担持させ、かつアンモニア処理を行
って焼成した光触媒は、金を担持させた場合程ではない
が、一定の浄化活性を示すことが分かった。(Evaluation of Example 7) From the results shown in FIG. 6, the photocatalyst obtained by supporting transition metal on titanium oxide and treating with ammonia and calcining was not purified to a certain degree, but was purified to a certain degree. It was found to show activity.
【００４５】（実施例８）No. ２５〜No. ２７のコージ
ェライト製のハニカム担体にそれぞれ同量の酸化チタン
を担持させ、ついでこれらに、それぞれ酸化チタンに対
して０．１重量％になるように金を担持させ、かつNo.
２５については更に酸化チタンに対して０．１重量％に
なるように銅を担持させ、No. ２６については更に酸化
チタンに対して０．１重量％になるようにニッケルを担
持させた後、前記No. ５と同じアンモニア処理と焼成と
を行った。(Embodiment 8) No. 25 to No. 27 cordierite honeycomb carriers were loaded with the same amount of titanium oxide, and then these were each added to 0.1% by weight with respect to titanium oxide. No.
For No. 25, copper was further loaded to 0.1% by weight of titanium oxide, and for No. 26, nickel was further loaded to 0.1% by weight of titanium oxide. The same ammonia treatment and firing as in No. 5 were performed.
【００４６】これらのNo. ２５〜No. ２７の試料体を用
い、実施例１と同様の浄化試験を行ったところ、図７の
結果を得た。Using these No. 25 to No. 27 sample bodies, the same purification test as in Example 1 was conducted, and the results shown in FIG. 7 were obtained.
【００４７】（実施例８の評価）図７の結果より、酸化
チタンに金又は金と遷移金属とを担持させ、かつアンモ
ニア処理を行って焼成した光触媒においては、金とニッ
ケルとを担持させた場合に特に優れた浄化活性を示すこ
とが分かった。(Evaluation of Example 8) From the results shown in FIG. 7, in the photocatalyst in which titanium oxide was supported with gold or gold and a transition metal, and ammonia treatment was performed, gold and nickel were supported. It has been found that in this case it exhibits a particularly good cleaning activity.
【図１】実施例２の試験結果を示すグラフである。FIG. 1 is a graph showing the test results of Example 2.
【図２】実施例３の試験結果を示すグラフである。FIG. 2 is a graph showing the test results of Example 3.
【図３】実施例４の試験結果を示すグラフである。FIG. 3 is a graph showing the test results of Example 4.
【図４】実施例５の試験結果を示すグラフである。FIG. 4 is a graph showing the test results of Example 5.
【図５】実施例６の試験結果を示すグラフである。FIG. 5 is a graph showing the test results of Example 6.
【図６】実施例７の試験結果を示すグラフである。FIG. 6 is a graph showing the test results of Example 7.
【図７】実施例８の試験結果を示すグラフである。FIG. 7 is a graph showing the test results of Example 8.
【図８】本発明の浄化試験に用いた装置の概略図であ
る。FIG. 8 is a schematic view of an apparatus used for the purification test of the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ０１Ｊ 23/89 ＺＡＢ Ａ 8017−4Ｇ 35/02 Ｊ 7821−4Ｇ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location B01J 23/89 ZAB A 8017-4G 35/02 J 7821-4G
Claims (2)
／又は希土類元素の微粒子を担持させ、これをアンモニ
ア処理した後、焼成することを特徴とする光触媒の製造
方法。1. A method for producing a photocatalyst, which comprises supporting fine particles of gold and / or a transition metal and / or a rare earth element on a metal oxide, subjecting the fine particles to an ammonia treatment, and then firing.
ニア処理された金及び／又は遷移金属及び／又は希土類
元素の微粒子との焼成体からなることを特徴とする光触
媒。2. A photocatalyst comprising a calcined body of metal oxide and fine particles of gold and / or transition metal and / or rare earth element supported on the metal oxide and treated with ammonia.
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|---|---|---|---|
| JP35712392A JP3360333B2 (en) | 1992-12-22 | 1992-12-22 | Method for producing photocatalyst and photocatalyst thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35712392A JP3360333B2 (en) | 1992-12-22 | 1992-12-22 | Method for producing photocatalyst and photocatalyst thereof |
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| Publication Number | Publication Date |
|---|---|
| JPH06182205A true JPH06182205A (en) | 1994-07-05 |
| JP3360333B2 JP3360333B2 (en) | 2002-12-24 |
Family
ID=18452502
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35712392A Expired - Fee Related JP3360333B2 (en) | 1992-12-22 | 1992-12-22 | Method for producing photocatalyst and photocatalyst thereof |
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| Country | Link |
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