WO1996006675A1 - Photocatalyst, method for preparing the same, and production of hydrogen using the same - Google Patents
Photocatalyst, method for preparing the same, and production of hydrogen using the same Download PDFInfo
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- WO1996006675A1 WO1996006675A1 PCT/KR1995/000110 KR9500110W WO9606675A1 WO 1996006675 A1 WO1996006675 A1 WO 1996006675A1 KR 9500110 W KR9500110 W KR 9500110W WO 9606675 A1 WO9606675 A1 WO 9606675A1
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- Prior art keywords
- hydrogen
- photocatalyst
- support
- oxygen
- accordance
- Prior art date
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 60
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000004480 active ingredient Substances 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 6
- 239000004615 ingredient Substances 0.000 claims abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 4
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract 3
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000011363 dried mixture Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 239000007789 gas Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000006303 photolysis reaction Methods 0.000 description 9
- 230000015843 photosynthesis, light reaction Effects 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 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 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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
Definitions
- the present invention relates to a novel photocatalyst useful for a photoreaction in which hydrogen is produced from water and to a method for the preparation of the same. Also, the present invention is concerned with production of hydrogen with the photocatalyst in combination with promoter.
- Hydrogen is an industrially very useful material over a wide range. For example, synthesis of ammonia and production of hydrogen chloride require hydrogen. It is essential for hydrogenation reactions for the conversion of unsaturated compounds into saturated compounds.
- hydrogen is used in the hydrotreating processes, such as hydrogen addition, desulfurization, denitrogenation and demetallization, with the aim of improving the quality of petroleum products.
- Hydrogen is also ecologically useful. For example, carbon dioxide, a compound which causes the warming of the globe, can be reused by application of the contact hydrogenation of carbon dioxide for which hydrogen is indispensable. Further, hydrogen occupies a powerful position of a pollution-free energy source, substituting the existing fossil fuels.
- Japanese Patent Publication Laid-Open No. Sho. 62-191045 discloses that hydrogen is generated by the photolysis of a NaaS aqueous solution in the presence of a photocatalyst of rare-earth element compound. This photocatalyst is advantageous in its catalytic activity with visible ray.
- Japanese Patent Publication Laid-Open No. Sho. 63-107815 uses a composite oxide of niobium and alkali metal as a photocatalyst. Hydrogen is produced by a photolytic reaction in methanol aqueous solution in the presence of the photocatalyst. There is also an advantage that the catalyst is active to visible ray. However, the above-cited patents are disadvantageous in that the amounts of hydrogen generated are very small.
- Japanese Patent Laid-Open Publication No. Hei. 1-208301 reveals an advantage of high efficiency for hydrogen generation by thermal-reacting water with aluminum. However, a large quantity of thermal energy is consumed as the thermal reaction occurs at high temperatures of more than 600T.
- It is another object of the present invention is to provide a novel photocatalyst capable of producing hydrogen from water without consuming large energy.
- It is a further object of the present invention is to provide a method for preparing the novel photocatalyst.
- It is still another object of the present invention is to provide the production of hydrogen by use of a combination of the photocatalyst and a promoter.
- a photocatalyst for the preparation of hydrogen consisting of a catalytically active ingredient cesium (Cs) impregnated in a support K4Nb ⁇ Oi7, represented by the following Formula I :
- a in parenthesis denotes the amount of the catalytically active ingredient Cs impregnated in the support KaNbsOi? and has a value of 0.05 to 5.0 % by weight based on the total weight of the support.
- a method for preparing the photocatalyst represented by Formula I comprising the steps of : combining R3CO3 with NbaOs in a mole ratio of 2 : 3 of K.CO3 : NbzOs ⁇ sintering the combination at a temperature of about 1,200 to 1.300T, to give K «Nb ⁇ O ⁇ , a support ; and impregnating the support with a catalytically active inorganic ingredient Cs.
- a method for the production of hydrogen comprising illumination of an ultraviolet light on an aqueous solution added with an oxygen-containing organic promoter at a reaction temperature of about 15 to 80TJ under a reaction pressure of about 0.1 to 3 atm, in the presence of the photocatalyst.
- KtNb ⁇ O ⁇ the support for the photocatalyst of the present invention
- K2CO3 potassium carbonate
- NbaOs niobium oxide
- Impregnation of Cs, the catalytically active inorganic ingredient, into the prepared support results in the catalyst of the invention.
- an aqueous cesium carbonate(CSCO3) solution is first prepared, in which the supports are soaked by use of impregnation process. This resultant solution is stirred overnight at room temperature and dried, followed by pulverization into fine powders. Sintering of the fine powders at a temperature of about 100 to about 300TJ for a period of about 1 to about 5 hours gives the photocatalyst of the present invention.
- Cs is impregnated preferably in an amount of about 0.05 to about 5.0 % by weight and more preferably in an amount of about 0.1 to about 3.0 % by weight.
- the oxygen-containing organic promoter used in the present invention is a substance containing aldehyde group, for example, formaldehyde, or alcohol group, for example, ethanol. The more the promoter is used, the more is hydrogen produced.
- the amount of the promoter reaches about 5% by volume of the aqueous solution, the production amount of hydrogen rapidly increases.
- Preferred amount of the promoter is on the order of about 5 to about 30% by volume based on the total volume of the aqueous solution.
- oxygen is generated from the aqueous solution.
- the aldehydes of the promoter are reacted with the oxygen and turned into carboxylic acid. Accordingly, oxygen is not produced in the photoreaction of the present invention.
- the alcohols are changed into aldehydes or lower alcohols as a result of reaction with oxygen.
- a in parenthesis denotes weight percentage of Cs impregnated and had a value of 0.1, 0.3, and 1.0 each.
- Preparation Example 2 was suspended. The suspension was poured in a photoreaction equipment of close gas circulatory system, stirred at 400 rp and illuminated with ultraviolet light from a high pressure mercury lamp.
- the air preexisting in the photoreaction equipment of close gas circulatory system was absolutely removed by a vacuum system and then was nitrogen of 0.2 atm as a circulating gas charged therein.
- nitrogen of 0.2 atm was circulated around the photoreaction equipment, to prevent temperature in the interior of the photoreaction equipment from being increased by the U.V. light.
- Example 1 was repeated using a reac ant which was prepared by suspending 1 g of the photocatalyst prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) in 500m£ of a second distilled water containing 10 vol.% acetaldehyde. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 2.
- Example 1 was repeated using lg of the photocatalyst prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) and 500m£ of 10 vol.% methanol aqueous solution prepared by dissolving methanol in a second distilled water as a suspension. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 3. TABLE 3 Hydrogen and Oxygen production rates in Photolysis of Methanol aqueous Solution in the presence of the Photocatalyst
- Example 1 was repeated using a reactant which was prepared by suspending lg of the photocatalyst prepared in
- Example 1 was repeated using a reactant which was prepared by suspending lg of the photocatalyst prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) in 500m£ of a secondary distilled water containing 10 vol.% propanol. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 5.
- Example 1 was repeated using reactants which were prepared by suspending lg of the respective photocatalysts prepared in Preparation Examples 2, 3 and 4 ( impregnation amount of metal : 0.1 wt.%, 0.3 wt.%, and 1.0 wt.%) in a secondary distilled water. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 6.
- Example 1 was repeated using 500 mi of a secondary distilled water containing 10 vol. % aldehyde as a reactant in the absence of the photocatalyst. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 7. TABLE 7 Hydrogen and Oxygen production rates in Photolysis of Formaldehyde aqueous Solution in the absence of the Photocatalyst
- Example 1 was repeated using a reactant which was prepared by suspending lg of the photocatalysts prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) in 500m£ of a secondary distilled water containing 10 vol.% formic acid. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 8.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
Abstract
There is disclosed a photocatalyst for the preparation of hydrogen consisting of a catalytically active ingredient cesium (Cs) impregnated in a support K4Nb6O17, represented by the formula (I): Cs(a)/K4Nb6O17, wherein a in parenthesis denotes the amout of the catalytically active ingredient Cs impregnated in the support K4Nb6O17 and has a value of 0.05 to 5.0 % by weight based on the total weight of the support. It is prepared by combining K2CO3 with Nb2O5 in a mole ratio of 2:3 of K2CO3:Nb2O5 sintering the combination at a temperature of about 1,200 to 1,300 °C, to give K4Nb6O17, a support; and impregnating the support with a catalytically active inorganic ingredient Cs. Hydrogen is efficiently produced by illuminating an ultraviolet on an aqueous solution added with an oxygen-containing organic promoter at a reaction temperature of about 15 to 80 °C under a reaction pressure of about 0.1 to 3 atm, in the presence of the photocatalyst.
Description
PHOTOCATALYST, METHOD FOR PREPARING THE SAME, AND PRODUCTION OF HYDROGEN USING THE SAME
BACKGROUND OF THE INVENTION
Field of the invention
The present invention relates to a novel photocatalyst useful for a photoreaction in which hydrogen is produced from water and to a method for the preparation of the same. Also, the present invention is concerned with production of hydrogen with the photocatalyst in combination with promoter.
Description of the Prior Art Hydrogen is an industrially very useful material over a wide range. For example, synthesis of ammonia and production of hydrogen chloride require hydrogen. It is essential for hydrogenation reactions for the conversion of unsaturated compounds into saturated compounds. In addition, hydrogen is used in the hydrotreating processes, such as hydrogen addition, desulfurization, denitrogenation and demetallization, with the aim of improving the quality of petroleum products. Hydrogen is also ecologically useful. For example, carbon dioxide, a compound which causes the warming of the globe, can be
reused by application of the contact hydrogenation of carbon dioxide for which hydrogen is indispensable. Further, hydrogen occupies a powerful position of a pollution-free energy source, substituting the existing fossil fuels.
Many methods have conventionally been undertaken in order to obtain hydrogen, for example, acquirement from fossil fuels, modification of natural gases, reaction of iron with steam, reaction of water with metals, electrolysis of water and etc. Such conventional methods, however, are uneconomical because an enormous quantity of thermal or electric energy is consumed. In addition, oxygen and carbon oxide, the by- products, are produced in large quantities, giving rise to a danger of explosion as well as pollution of environment. Further, the conventional methods are generally poor in production yield and purity of the product. The complexity of process in above-mentioned methods gives another disadvantage. The production of hydrogen by the conventional techniques is carried out at relatively high temperatures, which requires thermal-resistant and thus very expensive gas furnaces and facilities. Accordingly, such high expenditure of facility investment is an obstacle in industrializing the techniques. Most hydrogen is in a form of water or inorganic
substance. Hydrogen gas easily frees itself from the gravity field due to its low mass and thus is present in a very small amount in the air. It is therefore very important to develop a technology for preparing hydrogen from water in high purity and efficiency, in a view of solving the urgent problem of substitute energy source and securing the material of chemical industry.
As efficient techniques for preparing hydrogen from water, there are photoreactions of water using photocatalyβts, which have recently been developed. Not much of prior techniques concerning photocatalyst for preparing hydrogen are known.
Japanese Patent Publication Laid-Open No. Sho. 62-191045 discloses that hydrogen is generated by the photolysis of a NaaS aqueous solution in the presence of a photocatalyst of rare-earth element compound. This photocatalyst is advantageous in its catalytic activity with visible ray.
Japanese Patent Publication Laid-Open No. Sho. 63-107815 uses a composite oxide of niobium and alkali metal as a photocatalyst. Hydrogen is produced by a photolytic reaction in methanol aqueous solution in the presence of the photocatalyst. There is also an advantage that the catalyst is active to visible ray. However, the above-cited patents are disadvantageous in that the amounts of hydrogen generated are very small.
Japanese Patent Laid-Open Publication No. Hei. 1-208301 reveals an advantage of high efficiency for hydrogen generation by thermal-reacting water with aluminum. However, a large quantity of thermal energy is consumed as the thermal reaction occurs at high temperatures of more than 600T.
SUMMARY OF THE INVENTION
it is therefore a principal object of the present invention is to provide a novel photocatalyst capable of producing hydrogen from water in very high efficiency.
It is another object of the present invention is to provide a novel photocatalyst capable of producing hydrogen from water without consuming large energy.
It is a further object of the present invention is to provide a method for preparing the novel photocatalyst.
It is still another object of the present invention is to provide the production of hydrogen by use of a combination of the photocatalyst and a promoter.
Based on the intensive and through research and study by the present invention, the above objects could be accomplished by providing a photocatalyst for the preparation of hydrogen consisting of a catalytically active ingredient cesium (Cs) impregnated in a support
K4NbβOi7, represented by the following Formula I :
In another aspect of the present invention, there is provided a method for preparing the photocatalyst represented by Formula I , comprising the steps of : combining R3CO3 with NbaOs in a mole ratio of 2 : 3 of K.CO3 : NbzOs \ sintering the combination at a temperature of about 1,200 to 1.300T, to give K«NbβOπ, a support ; and impregnating the support with a catalytically active inorganic ingredient Cs.
In accordance with a further aspect of the present invention, there is provided a method for the production of hydrogen, comprising illumination of an ultraviolet light on an aqueous solution added with an oxygen-containing organic promoter at a reaction temperature of about 15 to 80TJ under a reaction pressure of about 0.1 to 3 atm, in the presence of the photocatalyst.
These and other objects and advantages of the present invention will be more apparent as following description proceeds.
DETAILED DESCRIPTION OF THE INVENTION
KtNbβOπ, the support for the photocatalyst of the present invention, is prepared by combining potassium carbonate (K2CO3), an alkali metal compound, with niobium oxide (NbaOs), a metal oxide, in a mole ratio of 2:3, pulverizing, pelletizing and then sintering the combination at a temperature of about 1,200 to about 1,300 TJ for about 20 minutes. Impregnation of Cs, the catalytically active inorganic ingredient, into the prepared support results in the catalyst of the invention.
For impregnation of the catalytically active ingredient, an aqueous cesium carbonate(CSCO3) solution is first prepared, in which the supports are soaked by use of impregnation process. This resultant solution is stirred overnight at room temperature and dried, followed by pulverization into fine powders. Sintering of the fine powders at a temperature of about 100 to about 300TJ for a period of about 1 to about 5 hours gives the photocatalyst of the present invention. For the moment Cs is impregnated preferably in an amount of about 0.05 to about 5.0 % by weight and more preferably in an amount of about 0.1 to about 3.0 % by weight.
With regard to production of hydrogen with such obtained photocatalyst, it is suspended in an aqueous
solution mixed with an oxygen-containing organic promoter and the resulting reaction suspension is exposed to ultraviolet light with stirring in a photoreaction equipment, such as close gas circulatory system. This hydrogen production reaction is carried out at a temperature of about 15 to about 80TJ and more preferably at a temperature of about 15 to about 20TJ. For pressure condition, about 0.1 to about 3 atm is adapted and more preferably, the atmospheric pressure. The oxygen-containing organic promoter used in the present invention is a substance containing aldehyde group, for example, formaldehyde, or alcohol group, for example, ethanol. The more the promoter is used, the more is hydrogen produced. From where the amount of the promoter reaches about 5% by volume of the aqueous solution, the production amount of hydrogen rapidly increases. Preferred amount of the promoter is on the order of about 5 to about 30% by volume based on the total volume of the aqueous solution. in the course of photoreacting in the presence of the photocatalyst, oxygen is generated from the aqueous solution. However, the aldehydes of the promoter are reacted with the oxygen and turned into carboxylic acid. Accordingly, oxygen is not produced in the photoreaction of the present invention.
In the case of the alcohol-containing organic promoter, the alcohols are changed into aldehydes or lower alcohols as a result of reaction with oxygen.
The preferred embodiment of the present invention will now be further described with reference to the following specific examples. In the following Examples, hydrogen
production rate is defined as follows '
Hvdrotren number of moles of hydrogen produced production rate " reaction time
PREPARATION EXAMPLE 1 Preparation of the Support
0.06 mole of potassium carbonate (8.30 g) and 0.09 mole of niobium oxide (23.92 g) were mixed. Following pulverization in agate mortar, the mixture in a platinum crucible was sintered at a temperature of about 1,200 to about 1,300 TJ for about 20 minutes, to obtain a KaNbβOπ support with a lamellar structure.
PREPARATION EXAMPLES 2 THROUGH 4 Preparation of the Photocatalyst
Predetermined amounts of cesium carbonate were each dissolved in 10 m£ of secondary distilled water. The
resulting solutions were mixed with 5.0 g of the support prepared in Preparation Example 1, stirred overnight at room temperature, distilled in vacuo, and subjected to sinter at about 200TJ for about 3 hours, to yield Cs(a)/K4NbEOi7 photocatalysts.
In the photocatalystβ, a in parenthesis denotes weight percentage of Cs impregnated and had a value of 0.1, 0.3, and 1.0 each.
EXAMPLES 1 THROUGH 3
Predetermined amounts of formaldehydes were dissolved in secondary distilled water, to prepare 5 vol. %, 10 vol. % and 20 vol.% formaldehyde aqueous solutions. In each 500 ml of these solutions 1 g of the photocatalyst
(impregnation amount of metal : 0.1 wt.S>) prepared in
Preparation Example 2 was suspended. The suspension was poured in a photoreaction equipment of close gas circulatory system, stirred at 400 rp and illuminated with ultraviolet light from a high pressure mercury lamp.
The amounts of hydrogen and oxygen generated were analyzed by gas chromatography and the results are given in the following Table 1.
Before the photoreaction, the air preexisting in the photoreaction equipment of close gas circulatory system
was absolutely removed by a vacuum system and then was nitrogen of 0.2 atm as a circulating gas charged therein. For the moment cooling water was circulated around the photoreaction equipment, to prevent temperature in the interior of the photoreaction equipment from being increased by the U.V. light.
In this Example, the temperature was maintained at 15 to 20TJ
TABLE 1
Hydrogen and Oxygen production rates in Photolysis of Formaldehyde aqueous Solution in the presence of the Photocatalyst
Gas Production Rate (μmol/hr)
Concentration —
Exam. No. of Promoter Sol'n Hydrogen Oxygen
1 5* 19141.7 None
2 10* 33278.9 None
3 20% 37445.0 None
EXAMPLE 4
Example 1 was repeated using a reac ant which was prepared by suspending 1 g of the photocatalyst prepared in Preparation Example 2 ( impregnation amount of metal :
0.1 wt.%) in 500m£ of a second distilled water containing 10 vol.% acetaldehyde. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 2.
TABLE 2 Hydrogen and Oxygen production rates in Photolysis of Acetaldehyde aqueous Solution in the presence of the Photocatalyst
Gas Production Rate ( μ mol/hr) troncencrauion
Exam. No. of Promoter Sol'n Hydrogen Oxygen
4 10% 7532.7 None
EXAMPLE 5
Example 1 was repeated using lg of the photocatalyst prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) and 500m£ of 10 vol.% methanol aqueous solution prepared by dissolving methanol in a second distilled water as a suspension. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 3.
TABLE 3 Hydrogen and Oxygen production rates in Photolysis of Methanol aqueous Solution in the presence of the Photocatalyst
Gas Production Rate (μmol/hr) isOncenuracion
Exam. No. of Promoter Sol'n Hydrogen Oxygen
5 10% 6868.9 None
EXAMPLE 6
Example 1 was repeated using a reactant which was prepared by suspending lg of the photocatalyst prepared in
Preparation Example 2 ( impregnation amount of metal : 0.1
wt.%) in 500m£ of a secondary distilled water containing 10 vol.% ethanol. Gas chromatography analysis for oxygen
and hydrogen was performed and its results are given as
shown in Table 4.
TABLE 4 Hydrogen and Oxygen production rates in Photolysis of Ethanol aqueous Solution in the presence of the Photocatalyst
Gas Production Rate (μmol/hr)
Concentration -
Exam. No. of Promoter Sol'n Hydrogen Oxygen
6 10% 10642.7 None
EXAMPLE 7
Example 1 was repeated using a reactant which was prepared by suspending lg of the photocatalyst prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) in 500m£ of a secondary distilled water containing 10 vol.% propanol. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 5.
TABLE 5 Hydrogen and Oxygen production rates in Photolysis of Propanol aqueous Solution in the presence of the Photocatalyst
Gas Production Rate ( mol/hr) concentration
Exam. No. of Promoter Sol'n Hydrogen Oxygen
7 10% 33278.9 None
COMPARATIVE EXAMPLES 1 THROUGH 3
Example 1 was repeated using reactants which were prepared by suspending lg of the respective photocatalysts prepared in Preparation Examples 2, 3 and 4 ( impregnation amount of metal : 0.1 wt.%, 0.3 wt.%, and 1.0
wt.%) in a secondary distilled water. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 6.
TABLE 6
Hydrogen and Oxygen production rates in Photolysis of Water in the presence of the Photocatalyst
(wt.%) Gas Production Rate (μmol/hr) Amount of
Exam. No. Metal impregnated Hydrogen Oxygen c. 1 0.1% 1474.0 6.2 c. 2 0.3% 1180.9 2.1 c. 3 1.0% 370.6 0.4
COMPARATIVE EXAMPLE 4
Example 1 was repeated using 500 mi of a secondary distilled water containing 10 vol. % aldehyde as a reactant in the absence of the photocatalyst. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 7.
TABLE 7 Hydrogen and Oxygen production rates in Photolysis of Formaldehyde aqueous Solution in the absence of the Photocatalyst
Gas Production Rate (μmol/hr) concentration
Exam. No. of Promoter Sol'n Hydrogen Oxygen
C.4 10% 4818.6 None
COMPARATIVE EXAMPLE 5
Example 1 was repeated using a reactant which was prepared by suspending lg of the photocatalysts prepared in Preparation Example 2 ( impregnation amount of metal : 0.1 wt.%) in 500m£ of a secondary distilled water containing 10 vol.% formic acid. Gas chromatography analysis for hydrogen and oxygen was performed and its results are given as shown in Table 8.
TABLE 8 Hydrogen and Oxygen production rates in Photolysis of Formic acid aqueous Solution in the presence of the Photocatalyst
Gas Production Rate (μmol/hr) concen ru ion ■—
Exam. No. of Promoter Sol'n Hydrogen Oxygen
C.5 10% 3987.7 852.5
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as described and claimed.
Claims
1. A photocatalyst for the preparation of hydrogen consisting of a catalytically active ingredient cesium (Cs) impregnated in a support KiNbβOπ, represented by the following Formula I :
Cs(a) / KiNbβOiv ( I ) wherein a in parenthesis denotes the amount of the catalytically active ingredient Cs impregnated in the support l NbeOi? and has a value of 0.05 to 5.0 % by weight based on the total weight of the support.
2. A photocatalyst in accordance with Claim 1, wherein the catalytic active ingredient Cs is impregnated in an amount of 0.1 to 3.0% by weight.
3. A method for preparing the photocatalyst of Claim 1, comprising the steps of : combining K2CO3 with Nb20s in a mole ratio of 2 : 3 of 
sintering the combination at a temperature of about 1,200 to 1,300 TJ, to give 
a support ; and impregnating the support with a catalytically active inorganic ingredient Cs.
4. A method in accordance with Claim 3, wherein the impregnation step is accomplished by mixing the support in a C82CO3 aqueous solution, stirring the mixture overnight at room temperature, distilling the mixture in vacuo, and sintering the dried mixture at a temperature of about 100 to 300 J for a period of about 1 to 5 hours.
5. A method for the production of hydrogen, comprising illumination of an ultraviolet light on an aqueous solution added with an oxygen-containing organic promoter at a reaction temperature of about 15 to 80TJ under a reaction pressure of about 0.1 to 3 atm, in the presence of the photocatalyst of Claim 1.
6. A method in accordance with Claim 5, wherein the reaction pressure is the atmospheric pressure.
7. A method in accordance with Claim 5, wherein the oxygen-containing organic promoter is a compound containing aldehyde group.
8. A method in accordance with Claim 5, wherein the oxygen-containing organic promoter is a compound containing alcohol group.
9. A method in accordance with Claim 5, wherein the oxygen-containing organic promoter is added in an amount of about 5 to 30% by volume based on the total volume of the aqueous solution.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8508627A JP3005647B2 (en) | 1994-08-30 | 1995-08-29 | Photocatalyst, method for producing the same, and method for producing hydrogen using the same |
| EP95930047A EP0778793B1 (en) | 1994-08-30 | 1995-08-29 | Photocatalyst, method for preparing the same, and production of hydrogen using the same |
| CA002198777A CA2198777C (en) | 1994-08-30 | 1995-08-29 | Photocatalyst, method for preparing the same, and production of hydrogen using the same |
| US08/793,354 US5865960A (en) | 1994-08-30 | 1995-08-29 | Photocatalyst, method for preparing the same, and production of hydrogen using the same |
| AU33555/95A AU679868B2 (en) | 1994-08-30 | 1995-08-29 | Photocatalyst, method for preparing the same, and production of hydrogen using the same |
| DE69513186T DE69513186T2 (en) | 1994-08-30 | 1995-08-29 | PHOTOCATALYST, METHOD FOR THE PRODUCTION AND PRODUCTION OF HYDROGEN USING THE PHOTOCALYST |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR19940021541 | 1994-08-30 | ||
| KR1994/21541 | 1994-08-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1996006675A1 true WO1996006675A1 (en) | 1996-03-07 |
Family
ID=19391463
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR1995/000110 WO1996006675A1 (en) | 1994-08-30 | 1995-08-29 | Photocatalyst, method for preparing the same, and production of hydrogen using the same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5865960A (en) |
| EP (1) | EP0778793B1 (en) |
| JP (1) | JP3005647B2 (en) |
| KR (1) | KR0130515B1 (en) |
| CN (1) | CN1080585C (en) |
| AU (1) | AU679868B2 (en) |
| CA (1) | CA2198777C (en) |
| DE (1) | DE69513186T2 (en) |
| ES (1) | ES2141376T3 (en) |
| WO (1) | WO1996006675A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997012668A2 (en) * | 1995-09-18 | 1997-04-10 | Korea Research Institute Of Chemical Technology | Novel photocatalyst, preparation therefor and method for producing hydrogen using the same |
| DE10000716A1 (en) * | 2000-01-11 | 2001-07-12 | Stefan Haegel | Hydrogen and oxygen production from water using solar energy is effected in membrane-separated compartments with only one compartment containing a photosensitizer |
| US11654412B2 (en) | 2020-10-11 | 2023-05-23 | Toyota Jidosha Kabushiki Kaisha | Hydrogen gas producing apparatus using photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6866755B2 (en) * | 2001-08-01 | 2005-03-15 | Battelle Memorial Institute | Photolytic artificial lung |
| KR100400630B1 (en) * | 2000-04-03 | 2003-10-04 | (주)아이블포토닉스 | Surface acoustic wave filter using new piezoelectric single crystal wafer |
| KR100352662B1 (en) * | 2000-08-12 | 2002-09-12 | 송삼원 | the method of poly urethaneform having resistance for fire |
| US7399717B2 (en) | 2004-05-14 | 2008-07-15 | Battelle Memorial Institute | Oxygen generation in whole blood by photolytic activation |
| US7909788B2 (en) * | 2001-08-01 | 2011-03-22 | Battelle Memorial Institute | Carbon dioxide removal from whole blood by photolytic activation |
| US20040210289A1 (en) * | 2002-03-04 | 2004-10-21 | Xingwu Wang | Novel nanomagnetic particles |
| US20050226808A1 (en) * | 2004-04-12 | 2005-10-13 | King Fahd University Of Petroleum And Minerals | Laser photo-catalytic process for the production of hydrogen |
| CN1307416C (en) * | 2004-05-10 | 2007-03-28 | 西安交通大学 | Multichannel rapid evaluating device for photolysis hydrogen making catalyst performance |
| CN100358626C (en) * | 2004-08-30 | 2008-01-02 | 南京大学 | Preparation method of high specific surface tantalate and niobate photo catalyst |
| US9593053B1 (en) | 2011-11-14 | 2017-03-14 | Hypersolar, Inc. | Photoelectrosynthetically active heterostructures |
| CN103752312B (en) * | 2013-12-26 | 2016-01-20 | 深圳大学 | A kind of photochemical catalyst and preparation method thereof |
| US10100415B2 (en) | 2014-03-21 | 2018-10-16 | Hypersolar, Inc. | Multi-junction artificial photosynthetic cell with enhanced photovoltages |
| US9902614B2 (en) * | 2015-05-21 | 2018-02-27 | Sabic Global Technologies B.V. | Light-switchable catalyst for the hydrogen production from para-formaldehyde |
| JP2023094488A (en) | 2021-12-23 | 2023-07-05 | トヨタ自動車株式会社 | Hydrogen gas production apparatus using photocatalyst |
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| JPS61197033A (en) * | 1985-02-28 | 1986-09-01 | Nippon Kogaku Kk <Nikon> | Catalyst for photolyzing water |
| JPS6274452A (en) * | 1985-09-27 | 1987-04-06 | Nippon Kogaku Kk <Nikon> | Photolytic catalyst of water |
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| US3615216A (en) * | 1968-03-26 | 1971-10-26 | Exxon Research Engineering Co | Water gas shift process for producing hydrogen using a cesium compound catalyst |
| JPS62191045A (en) * | 1986-02-17 | 1987-08-21 | Agency Of Ind Science & Technol | Rare earth element compound having photocatalytic activity |
| JPS63107815A (en) * | 1986-10-25 | 1988-05-12 | Agency Of Ind Science & Technol | Niobium compound with photocatalytic activity |
| JPH01208301A (en) * | 1988-02-15 | 1989-08-22 | Mitsubishi Heavy Ind Ltd | Generating method of hydrogen |
| JPH075281B2 (en) * | 1991-08-20 | 1995-01-25 | 工業技術院長 | Method for producing hydrogen and oxygen from water by metal-supported semiconductor photocatalyst using highly concentrated carbonate aqueous solution |
-
1995
- 1995-04-03 KR KR1019950007721A patent/KR0130515B1/en not_active IP Right Cessation
- 1995-08-29 US US08/793,354 patent/US5865960A/en not_active Expired - Fee Related
- 1995-08-29 ES ES95930047T patent/ES2141376T3/en not_active Expired - Lifetime
- 1995-08-29 AU AU33555/95A patent/AU679868B2/en not_active Ceased
- 1995-08-29 EP EP95930047A patent/EP0778793B1/en not_active Expired - Lifetime
- 1995-08-29 CA CA002198777A patent/CA2198777C/en not_active Expired - Fee Related
- 1995-08-29 JP JP8508627A patent/JP3005647B2/en not_active Expired - Lifetime
- 1995-08-29 CN CN95194841A patent/CN1080585C/en not_active Expired - Fee Related
- 1995-08-29 WO PCT/KR1995/000110 patent/WO1996006675A1/en active IP Right Grant
- 1995-08-29 DE DE69513186T patent/DE69513186T2/en not_active Expired - Fee Related
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| JPS61197033A (en) * | 1985-02-28 | 1986-09-01 | Nippon Kogaku Kk <Nikon> | Catalyst for photolyzing water |
| JPS6274452A (en) * | 1985-09-27 | 1987-04-06 | Nippon Kogaku Kk <Nikon> | Photolytic catalyst of water |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997012668A2 (en) * | 1995-09-18 | 1997-04-10 | Korea Research Institute Of Chemical Technology | Novel photocatalyst, preparation therefor and method for producing hydrogen using the same |
| WO1997012668A3 (en) * | 1995-09-18 | 1997-06-19 | Korea Res Inst Chem Tech | Novel photocatalyst, preparation therefor and method for producing hydrogen using the same |
| AU692406B2 (en) * | 1995-09-18 | 1998-06-04 | Korea Research Institute Of Chemical Technology | Novel photocatalyst, preparation therefor and method for producing hydrogen using the same |
| US6017425A (en) * | 1995-09-18 | 2000-01-25 | Korea Research Institute Of Technology | Photocatalyst, preparation therefor and method for producing hydrogen using the same |
| DE10000716A1 (en) * | 2000-01-11 | 2001-07-12 | Stefan Haegel | Hydrogen and oxygen production from water using solar energy is effected in membrane-separated compartments with only one compartment containing a photosensitizer |
| US11654412B2 (en) | 2020-10-11 | 2023-05-23 | Toyota Jidosha Kabushiki Kaisha | Hydrogen gas producing apparatus using photocatalyst |
| US11931715B2 (en) | 2020-10-11 | 2024-03-19 | Toyota Jidosha Kabushiki Kaisha | Hydrogen gas producing apparatus using photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960007001A (en) | 1996-03-22 |
| AU679868B2 (en) | 1997-07-10 |
| ES2141376T3 (en) | 2000-03-16 |
| JPH09510657A (en) | 1997-10-28 |
| AU3355595A (en) | 1996-03-22 |
| CA2198777C (en) | 2000-01-18 |
| CN1080585C (en) | 2002-03-13 |
| CN1156416A (en) | 1997-08-06 |
| DE69513186D1 (en) | 1999-12-09 |
| EP0778793A1 (en) | 1997-06-18 |
| KR0130515B1 (en) | 1998-04-03 |
| US5865960A (en) | 1999-02-02 |
| EP0778793B1 (en) | 1999-11-03 |
| CA2198777A1 (en) | 1996-03-07 |
| JP3005647B2 (en) | 2000-01-31 |
| DE69513186T2 (en) | 2000-02-24 |
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