WO2004000459A1 - 高活性光触媒およびその製造方法 - Google Patents
高活性光触媒およびその製造方法 Download PDFInfo
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- WO2004000459A1 WO2004000459A1 PCT/JP2003/007160 JP0307160W WO2004000459A1 WO 2004000459 A1 WO2004000459 A1 WO 2004000459A1 JP 0307160 W JP0307160 W JP 0307160W WO 2004000459 A1 WO2004000459 A1 WO 2004000459A1
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- photocatalyst
- producing
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- photocatalyst according
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 title description 8
- 239000002245 particle Substances 0.000 claims abstract description 87
- 239000000243 solution Substances 0.000 claims abstract description 73
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 150000003388 sodium compounds Chemical class 0.000 claims abstract description 18
- 229940065285 cadmium compound Drugs 0.000 claims abstract description 17
- 150000001662 cadmium compounds Chemical class 0.000 claims abstract description 17
- 239000002775 capsule Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 20
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- -1 dominal compound Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229960000957 prothipendyl Drugs 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 35
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 150000001661 cadmium Chemical class 0.000 abstract 1
- 239000010419 fine particle Substances 0.000 description 26
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000640 hydroxylating effect Effects 0.000 description 8
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 6
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000003574 free electron Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- 238000005215 recombination Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 231100000956 nontoxicity Toxicity 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 3
- 229910052798 chalcogen Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000006193 liquid solution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- MAHNFPMIPQKPPI-UHFFFAOYSA-N disulfur Chemical compound S=S MAHNFPMIPQKPPI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
- B01J27/045—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the present invention relates to a photocatalyst and a method for producing the same, in particular, has a high catalytic activity, has no toxicity, has a long life, and can utilize visible light as it is for a photocatalytic reaction.
- the present invention relates to a photocatalyst useful for hydrogen generation and the like and a method for producing the same. Background art
- photocatalyst technology is applied to tiles and air purifiers that have antibacterial effects because of their ability to promote various chemical reactions such as decomposition of environmental pollutants, odorous components, and various germs. Practical use of antibacterial and deodorizing filters has begun. Furthermore, it is possible to obtain useful chemical substances by reacting harmful substances with photocatalysts. For example, it can be applied to the desulfurization process of crude oil.
- Photocatalyst is added to alkaline water in which hydrogen sulfide is dissolved, ultraviolet light is radiated, and the photoenergy is generated by absorbing the light energy of the ultraviolet light. Free electrons and free holes are used to dissolve the hydrogen sulfide in the alkaline water. If a method of redoxing water to obtain hydrogen and dioxin, that is, a method of decomposing hydrogen sulfide with a photocatalyst to produce hydrogen and dioxin, could be implemented with less energy and harmful substances. It can decompose certain hydrogen sulfide to produce useful substances, hydrogen and ⁇ . In other words, it contributes to the solution of environmental problems and can produce useful substances at low cost.
- photocatalysts have the following problems to be solved.
- catalyst life is short. Irradiation of the photocatalyst with light generates free electrons and free holes, but due to the strong redox reaction, the catalyst itself is redox reduced and dissolved in addition to the target chemical substance. There is a problem of photodissolution such as losing catalysis.
- Japanese Patent Application Laid-Open No. 2001-190964 discloses a photocatalyst having high catalytic activity, non-toxicity and long life, and solved the above three problems.
- JP-A-2001-190964 discloses only a photocatalyst consisting of ZnS. Since the band gap of ZnS is in the ultraviolet region, visible light such as sunlight, which has infinite clean energy, could not be directly used for the photocatalytic reaction. Therefore, an object of the present invention is to overcome the above-mentioned drawbacks of the prior art, to have high catalytic activity, non-toxicity, long life, and to utilize visible light for photocatalysis as it is. An object of the present invention is to provide a photocatalyst particularly useful for generating hydrogen and a method for producing the same. Disclosure of the invention
- the present invention is as follows.
- a photocatalyst containing a force-dominant compound having a capsule structure, and having an average particle diameter of 100 nm or less.
- a method for producing a photocatalyst which comprises dropping a potassium salt solution into a sodium compound solution.
- a method for producing a photocatalyst comprising adding a sodium compound solution to a suspension of force-dominant compound particles and mixing.
- the photocatalyst of the present invention contains a power dominate compound. Therefore, visible light such as sunlight, which is infinitely clean natural energy, can be used as it is for the photocatalytic reaction, and it is nontoxic and has a long life.
- the photocatalyst of the present invention has a capsule structure having an outer shell and a cavity containing a cadmium compound, and contains this force dominate compound.
- An electric field exists between the outer surface and the inner surface of the capsule shell, and the recombination between free electrons and free holes generated by irradiation of visible light such as sunlight is reduced, and the oxidation reaction is generated. It is thought that the recombination between the product and the reduction reaction product also decreases, and high catalytic activity can be obtained.
- the present invention has a high catalytic activity, is non-toxic, has a long life, and can utilize visible light as it is for photocatalytic reactions, particularly for hydrogen generation. It can be useful.
- the photocatalyst of the present invention and the method for producing the same will be described in detail.
- the cadmium compound is not particularly limited as long as it has catalytic activity, and examples thereof include those comprising cadmium and a Group 16 element. Specific examples include cadmium sulfide, serenide cadmium, cadmium telluride and the like, and most preferably cadmium sulfide.
- the average particle size of the photocatalyst having a capsule structure of the present invention is not particularly limited as long as it is 100 nm or less, but the smaller the particle size, the larger the surface area per unit mass. Therefore, the spectral catalytic activity is also increased, and therefore, it is preferable that the thickness be 50 nm or less.
- the average particle diameter of the photocatalyst having the capsule structure was measured as follows. This is done in the following manner.
- the photocatalyst of the present invention preferably supports a Group 8-11 metal for the purpose of further enhancing the photocatalytic activity.
- Group 11 metals include metals selected from the group consisting of Pt, Ru, Ir, Co, Rh, Cu, Pd, and Ni, or oxidations thereof. Materials are used, of which platinum is the most preferred. The amount to be carried is not particularly limited, but is 0.1 to 10% by weight. A range of / 0 is preferred.
- the amount is less than 0.1% by weight, there is a problem that the amount of generated hydrogen decreases and the stability of the catalyst deteriorates. On the other hand, if the amount exceeds 10% by weight, the amount of generated hydrogen decreases only. The problem is that the cost of manufacturing the catalyst increases.
- the photocatalyst according to the present invention has an outer shell containing a force dome compound and a cavity.
- the outer shell of the photocatalyst of the present invention has a stratified structure composed of an ultrafine particle layer of a force-dominant compound having a particle size of 1 nm to 1 O nm. Such a photocatalyst is also called a stratified photocatalyst.
- the outer shell having a stratified structure of the photocatalyst of the present invention has a structure in which the component ratio of cadmium (C d) and the group 16 element and the like changes in the layer thickness direction. May have.
- the photocatalyst of the present invention has an outer shell having a particle size of lnm to 10 nm. Since it has a stratified eye structure consisting of an ultrafine particle layer of force-dominant compound, the gaps between the ultrafine particles have an infinite number of communicating holes. .
- FIG. 1 (A) is a transmission electron micrograph of an aggregate of the layered material of cadmium sulfide fine particles, which is one embodiment of the photocatalyst of the present invention.
- Fig. 1 (B) is an enlarged view of Fig. 1 (A).
- the capsule structure is composed of ultrafine CdS particles of several nanometers.
- the black part outside the one layered material of the cadmium sulfide fine particle layer in Fig. 1 (B) is platinum.
- the method for producing the photocatalyst of the present invention is not particularly limited, but the simplest method is to use a cadmium compound particle having no photocatalytic activity of several tens to several hundreds of nm, Dissolves from the particle surface in an aqueous solution containing ion such as element of group 16 of the formula (1) There is a method of producing by depositing nanoparticles of a dome compound.
- the power dome compound having no photocatalytic activity is not particularly limited, but power dome oxide or power dome hydroxide is preferable.
- the aqueous solution containing a Group 16 element or the like is not particularly limited, but a sodium compound solution is preferred.
- a sodium compound solution is added to a suspension of cadmium oxide or hydroxide hydroxide particles and mixed. Method.
- the sodium compound is not particularly limited, but is preferably sodium sulfide.
- the features of the above-mentioned production method will be described with reference to an example of a sulfuric acid dome, which is a preferred embodiment of a power dome compound having photocatalytic activity.
- the raw material cadmium oxide or hydroxide-doped fine particles are mixed with a sodium sulfide aqueous solution, and the mixed solution is stirred.
- the water or hydroxylating dome reacts with water to form a dominoic acid ion and elutes in the aqueous solution. This force-dominate ion reacts with the ion of the aqueous solution of sodium sulfide to form a sulfur-dominate.
- the sulfided dome precipitates on the surface of the oxidized or hydroxylated dominate particles, which are the raw material, to form a cadmium sulfide fine particle layer.
- a cadmium sulfide fine particle layer When the cadmium sulfide fine particle layer is formed, water penetrates the sulfide fine particle layer, and the oxidizing or hydroxylating raw material, which is a raw material, is formed. It reaches the surface of the film and reacts with the oxidizing or hydroxylating dome to produce cadmium ions.
- This cadmium ion diffuses through the cadmium sulfide fine particle layer, reaches the surface, reacts with the zeo ion, and turns into a sulfide dominate to form a sulfide dominate. Dummy Deposits on the fine particle layer. As the sulfur-doped fine particle layer grows, it becomes difficult for the force-dominic acid ion to diffuse through the sulfur-dominated fine particle layer, and the sulfide having a composition deviating from the stoichiometric ratio. A force dam is deposited.
- ultraviolet irradiation may be performed.
- oxidizing or hydroxylating dominate particles are mixed with an aqueous sodium sulfide solution and the mixture is irradiated with ultraviolet light, cadmium oxide or hydroxylating dome becomes light. Since dissolution occurs, the force-dominic acid ion is easily eluted, and the growth of the force-dominium compound fine particle layer is accelerated.
- hydrogen sulfide may be dissolved in order to increase the generation rate of the force-doped compound fine particle layer.
- hydrogen sulfide When hydrogen sulfide is dissolved in a mixed solution of dominate or water particles and water, it becomes a weakly acidic solution containing ions and ions, and has an oxidative or hydration power. Since the dome is well dissolved in the weakly acidic solution, the growth of the fine particle layer of the dominate compound is also accelerated.
- ultraviolet irradiation and dissolution of hydrogen sulfide may be combined.
- a mixture of oxidizing or hydroxide doping microparticles, sodium sulfide aqueous solution and hydrogen sulfide, irradiating with ultraviolet light and stirring further increases the power doming. The growth of the compound fine particle layer is accelerated.
- a layer of the fine particles of the force-dominant compound which is the photocatalyst of the present invention, can be produced.
- cadmium oxide CdO
- Cd (OH) 2 cadmium hydroxide
- This cadmium ion reacts with iowion (S 2 ) in an aqueous solution of sodium sulfide (a 2 S) to form a cadmium compound (CdS).
- the cadmium compound precipitates on the surface of the oxidizing or hydroxylating dome and forms a cadmium compound fine particle layer.
- the force-doped compound fine particle layer which is a photocatalyst according to the present invention, has a structure in which the component ratio of force-doped (C d) to di-doped (S) changes in the layer thickness direction. It is considered to have.
- power dome compound particles having no photocatalytic activity using the above-described production method, commercially available particles may be used, or those prepared as appropriate may be used.
- a method for preparing a force-dominant compound having no photocatalytic activity includes a method of mixing a nitric acid-dominium solution with a solution containing sodium hydroxide. .
- the particle size of the photocatalyst to be produced can be appropriately controlled according to the purpose of the catalytic action.
- the power having no photocatalytic activity is used as a method for controlling the particle size. Controlling the particle size of the dome compound particles can be mentioned.
- the method for controlling the particle diameter of the cadmium compound particles is not particularly limited, but the method for controlling the cadmium compound particles includes the method of preparing the cadmium compound particles, the method containing the sodium hydroxide. It is preferred that the chloride be dissolved in the solution to be dissolved in advance.
- the chloride is not particularly limited, and may be sodium chloride, chloride power. Lithium, etc., but in this case, sodium chloride is preferred.
- a power dome compound having photocatalytic activity is directly used without using the power dome compound particles having no photocatalytic activity.
- Examples of the above production method include a method in which a potassium salt solution is dropped into a sodium compound solution.
- the force dome salt dropped into the sodium compound solution temporarily forms a fine solid phase such as force dominate hydroxide. Then, it instantly becomes a power dome compound having photocatalytic activity, and is considered to constitute the capsule outer shell of the photocatalyst of the present invention.
- the sodium compound solution contains sodium sulfite or sodium sulfide. Further, it is preferable that the power dominate is a nitrate power dome.
- the photocatalyst of the present invention preferably supports a metal of Group 8 to 11 such as platinum, but the method of supporting the metal is not particularly limited.
- the photocatalyst particles obtained by the above production method and the like are further suspended in a solution containing sodium sulfite and irradiated with light in order to enhance the photocatalytic activity. Is preferred.
- visible light such as sunlight or simulated sunlight is preferable.
- the sodium chloride is dissolved in the sodium hydroxide solution, and the nitric acid solution is added dropwise to the solution, and the mixture is stirred at room temperature. A water-soluble suspension of white particles having a water-soluble property is obtained.
- the sodium sulfide solution is mixed with this suspension and stirred. This results in a cd S particle suspension. Further, after adding a hexachloroplatinic acid solution and stirring, the mixture is irradiated with ultraviolet light using a mercury lamp type ultraviolet irradiation apparatus.
- the solution is subjected to suction filtration and washing with distilled water using a Nitrocellulose membrane filter (pore diameter: 0.2 m), and then dried in a thermostat at 60 ° C.
- FIG. 1 (A) is an electron micrograph showing the process of producing a photocatalyst according to the present invention, and (B) is an enlarged view thereof.
- FIG. 2 is a configuration diagram of an apparatus used for measuring the amount of generated hydrogen.
- FIG. 3 is a comparison diagram of the hydrogen generation performance between the photocatalyst of the present invention and the conventional photocatalyst.
- the filtrate was suction-filtered using a filter filter with a filter diameter of 47 mm and a pore diameter of 0.22 / m (6).
- the solid content obtained in 6 was put into a desiccator together with the filter, and dried at room temperature to 60 ° C.
- particles having a reddish brown color were obtained on the filter ( ⁇ ⁇ ).
- the particles obtained in step ⁇ ⁇ are suspended in a mixture of 5 O ml of a 0.1 M sodium sulfide solution and 1 O m 1 of a 1 M sodium sulfite solution. Simulated sunlight was irradiated using a 0 W—Xe lamp. As a result, the particle color changed from reddish brown to greenish brown, and hydrogen was generated.
- the suspension is subjected to suction filtration, and the photocatalyst powder is dried together with the filter.
- photocatalyst particles having a greenish brown color were obtained on the filter, the amount of the catalyst particles was about 110 mg, and the particle diameter was 46 nm.
- Example 3 instead of 100 ml of the 0.1 M sodium hydroxide solution of the aqueous solution of Photocatalyst Production Method 1 (Example 1), 100 ml of 0.1 M sodium sulfite solution was added. The same operation as in Example 1 was performed except for using the same. Green-brown photocatalyst particles were obtained on the filter. The amount of the catalyst particles was about 11 Omg, and the particle size was 62 nm. (Example 3)
- the solution was irradiated with ultraviolet light for 2 minutes using a mercury lamp type ultraviolet irradiation device. As a result, a particle suspension having an intermediate color from orange to brown was obtained (Liquid solution).
- the filtrate was suction-filtered using a filter with a filter diameter of 47 mm and a pore size of 0.2 jam (6).
- the solid content obtained in 6 was put into a desiccator together with a filter, and dried at room temperature to 60 ° C. As a result, particles having a reddish brown color were obtained on the filter ( ⁇ ⁇ ).
- step ⁇ ⁇ The particles obtained in step ⁇ ⁇ are suspended in a mixture of 5 O ml of 0.1 M sodium sulfide solution and 1 O ml of 1 M sodium sulphite solution. Simulated sunlight was irradiated using a 0 W—Xe lamp. As a result, the particle color changed from reddish brown to greenish brown, and hydrogen was generated.
- the suspension is filtered by suction, and the photocatalyst powder is dried together with the filter.
- photocatalyst particles having a greenish brown color were obtained on the filter, the amount of the catalyst particles was about 40 mg, and the particle diameter was 70 nm.
- Example 1 a commercially available reagent C d O (manufactured by Kojundo Chemical Co., Ltd., particle size: 300 to 400 nm) lOO mg
- reagent C d O manufactured by Kojundo Chemical Co., Ltd., particle size: 300 to 400 nm
- lOO mg The same operation as in Example 1 (including the sulfidation treatment and the treatment for supporting platinum) was performed, except that the above suspension was used.
- Fi Green-brown photocatalyst particles were obtained on the filter, the amount of the catalyst particles was about 11 Omg, and the particle size was 365 nm.
- Example 1 0.5 ml of 0.1 M sodium sulfide solution was diluted with deionized water to make 5 O ml (l solution). 2 Add 5 O ml of 0.01 M cadmium nitrate solution to the solution and mix. As a result, a CdS particle suspension (primary particle size: 5 nm) having a neutral color from orange to brown was obtained (liquid (3)). Except for the use of this liquid (3), the same operations (1) and (2) (platinum-supporting treatment) as in Example 1 were carried out, and the photocatalyst particles having a brownish brown capsular structure on the filter were obtained. The catalyst particles were obtained in an amount of about 50 mg and the particle size was 7 nm.
- Example 4 The same operation as in Comparative Example 2 was performed. However, the operations of (1) and (2) (platinum loading treatment) were deleted as in Example 1. Photocatalyst particles without a capsule structure having orange to brown colors were obtained on the filter. The catalyst particle amount was about 50 mg and the particle size was 6 nm. (Comparative Example 4)
- a suspension of 100 mg of commercially available reagent CdS (manufactured by Kojundo Chemical Co., Ltd., particle size: 30 to 40 nm) was used instead of the CdS particles prepared in Comparative Example 3.
- the operation of removing the platinum-supporting treatment was performed to obtain brown-colored photocatalyst particles having a non-capsule structure on the filter.
- the amount of the catalyst particles was about 100 mg, and the particle size was 42 nm.
- the hydrogen generation amount of the photocatalyst particles obtained from the above Examples and Comparative Examples was measured by the following test method.
- 50 OW— Xe lamp is used to simulate pseudo-sunlight with an intensity of 5 O mWZ cm 2 under the instrument.
- Figure 2 shows the equipment used to measure the amount of hydrogen production.
- this device consists of a photoreactive part 1 made of quartz glass, a hydrogen quantitative part 2 for determining the amount of generated hydrogen, and a sulfurizing part for the volume of generated hydrogen gas.
- a solution reservoir 4 for preventing an increase in hydrogen pressure
- a 50 OW—Xe lamp 5 for simulated sunlight irradiation
- a simulated sunlight 6 And a reflector 8 for reflecting the simulated sunlight 6 and irradiating the photocatalyst 7 with the lens L.
- the entire system is filled with aqueous sodium sulfide solution 3, a certain amount of photocatalyst 7 is precipitated at the bottom of the photoreaction part 1, the generated gas recovery port 9 is closed, and 50 OW _ X Turn on the e lamp.
- the amount of hydrogen generated is measured at regular irradiation times.
- Figure 3 shows the dependence of hydrogen production on visible light irradiation time.
- the photocatalysts of the examples according to the present invention each obtained satisfactory results as described above.
- the results of the hydrogen generation measurement test were unsatisfactory.
- the photocatalyst particles according to Example 1 exhibited a maximum hydrogen generation rate of 74.SmlZhr one hour after the start of irradiation, and a total hydrogen generation of 210.000 hours after the start of irradiation. 3 m 1, and the photocatalyst particles according to Example 3 showed a maximum hydrogen generation rate of 70.8 m 1 / hr 1 hour after the start of irradiation, and the total amount of hydrogen generated 4 hours after the start of irradiation. Is 1 8 9. It was 2 m 1. Industrial applicability
- the photocatalyst of the present invention has high catalytic activity, has no toxicity, has a long life, and can use visible light as it is for the photocatalytic reaction. And it is useful for generating hydrogen.
- the photocatalyst of the present invention is used in a method for decomposing hydrogen sulfide to produce hydrogen and zeolite, it contributes to solving environmental problems and can produce useful substances at low cost. To play.
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Abstract
Description
Claims
Priority Applications (5)
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US10/518,934 US7608557B2 (en) | 2002-06-25 | 2003-06-05 | Highly active photocatalyst and process for producing the same |
EP03733300.2A EP1516668B1 (en) | 2002-06-25 | 2003-06-05 | Highly active photocatalyst and process for producing the same |
EA200401573A EA009448B1 (ru) | 2002-06-25 | 2003-06-05 | Фотокатализатор с высокой активностью и способ его получения |
CA002499579A CA2499579A1 (en) | 2002-06-25 | 2003-06-05 | Highly active photocatalyst and process for producing the same |
AU2003242189A AU2003242189B2 (en) | 2002-06-25 | 2003-06-05 | Highly active photocatalyst and process for producing the same |
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JP2002184748A JP4357801B2 (ja) | 2002-06-25 | 2002-06-25 | 高活性光触媒およびその製造方法 |
JP2002-184748 | 2002-06-25 |
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US (1) | US7608557B2 (ja) |
EP (1) | EP1516668B1 (ja) |
JP (1) | JP4357801B2 (ja) |
KR (1) | KR20050077259A (ja) |
CN (1) | CN100357028C (ja) |
AU (1) | AU2003242189B2 (ja) |
CA (1) | CA2499579A1 (ja) |
EA (1) | EA009448B1 (ja) |
WO (1) | WO2004000459A1 (ja) |
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KR100853737B1 (ko) | 2005-06-10 | 2008-08-25 | 지엠 글로벌 테크놀러지 오퍼레이션스, 인코포레이티드 | 광촉매와 그 사용방법 |
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JP2003265962A (ja) * | 2002-03-18 | 2003-09-24 | Nittetsu Mining Co Ltd | 光触媒およびその製造方法 |
EP1867390A4 (en) * | 2005-03-31 | 2010-11-24 | Univ Tohoku | PROCESS FOR TREATING HYDROGEN SULFIDE, METHOD FOR PRODUCING HYDROGEN, AND PHOTOCATALYST REACTOR |
US9824107B2 (en) | 2006-10-25 | 2017-11-21 | Entit Software Llc | Tracking changing state data to assist in computer network security |
US9593053B1 (en) | 2011-11-14 | 2017-03-14 | Hypersolar, Inc. | Photoelectrosynthetically active heterostructures |
US10100415B2 (en) | 2014-03-21 | 2018-10-16 | Hypersolar, Inc. | Multi-junction artificial photosynthetic cell with enhanced photovoltages |
CN107051548B (zh) * | 2017-04-18 | 2019-11-05 | 曲阜师范大学 | 一种简易制备六边形CdO/CdS异质结纳米复合材料的方法 |
EP3612495B1 (en) | 2017-04-18 | 2022-07-13 | Breakthrough Technologies, LLC | Sulfur production |
RU2752496C1 (ru) * | 2020-12-15 | 2021-07-28 | федеральное государственное автономное образовательное учреждение высшего образования "Российский государственный университет нефти и газа (национальный исследовательский университет) имени И.М. Губкина" | Композитный мезопористый фотокатализатор |
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See also references of EP1516668A4 |
TAKEO ARAI ET AL., HYDROGEN GENERATION BY VISIBLE LIGHT USING STRATIFIED CDS PHOTOCATALYST, no. 2, 28 March 2002 (2002-03-28), pages 126 - 127 |
TAKEO ARAI ET AL.: "Stratified CdS hikari shokubai o mochiita kashiko ni yoru suiso seiiku", SHIGEN SOZAI GAKKAI SHUNKI TAIKAI KOENSHU, no. 2, 28 March 2002 (2002-03-28), pages 126 - 127, XP002972259 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100853737B1 (ko) | 2005-06-10 | 2008-08-25 | 지엠 글로벌 테크놀러지 오퍼레이션스, 인코포레이티드 | 광촉매와 그 사용방법 |
Also Published As
Publication number | Publication date |
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CA2499579A1 (en) | 2003-12-31 |
AU2003242189B2 (en) | 2009-05-21 |
AU2003242189A1 (en) | 2004-01-06 |
EP1516668A1 (en) | 2005-03-23 |
EA200401573A1 (ru) | 2005-06-30 |
US7608557B2 (en) | 2009-10-27 |
KR20050077259A (ko) | 2005-08-01 |
EP1516668B1 (en) | 2016-10-12 |
CN100357028C (zh) | 2007-12-26 |
CN1671476A (zh) | 2005-09-21 |
JP4357801B2 (ja) | 2009-11-04 |
US20050215421A1 (en) | 2005-09-29 |
EP1516668A4 (en) | 2010-08-25 |
EA009448B1 (ru) | 2007-12-28 |
JP2004025032A (ja) | 2004-01-29 |
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