WO2014046305A1 - 複合光触媒および光触媒材 - Google Patents
複合光触媒および光触媒材 Download PDFInfo
- Publication number
- WO2014046305A1 WO2014046305A1 PCT/JP2013/076450 JP2013076450W WO2014046305A1 WO 2014046305 A1 WO2014046305 A1 WO 2014046305A1 JP 2013076450 W JP2013076450 W JP 2013076450W WO 2014046305 A1 WO2014046305 A1 WO 2014046305A1
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- WIPO (PCT)
- Prior art keywords
- photocatalyst
- particles
- visible light
- water
- rhodium
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 550
- 239000002131 composite material Substances 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 96
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000011164 primary particle Substances 0.000 claims abstract description 73
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 179
- 239000001257 hydrogen Substances 0.000 claims description 179
- 229910052739 hydrogen Inorganic materials 0.000 claims description 179
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 143
- 239000001301 oxygen Substances 0.000 claims description 143
- 229910052760 oxygen Inorganic materials 0.000 claims description 143
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 90
- 239000007864 aqueous solution Substances 0.000 claims description 59
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- 239000008139 complexing agent Substances 0.000 claims description 24
- 238000010304 firing Methods 0.000 claims description 20
- 229910052703 rhodium Inorganic materials 0.000 claims description 20
- 150000003609 titanium compounds Chemical class 0.000 claims description 19
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 17
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
Definitions
- the present invention relates to a composite photocatalyst including a photocatalyst particle for hydrogen generation and a photocatalyst particle for oxygen generation capable of photolysis of water by visible light.
- the present invention also relates to a photocatalyst material in which a photocatalyst layer containing hydrogen-producing photocatalyst particles and oxygen-generating photocatalyst particles capable of photolysis of water by visible light is fixed on a substrate.
- the visible light responsive photocatalyst is a photocatalyst that can use visible light contained in a large amount of sunlight. This visible light responsive photocatalyst is expected to be applied to hydrogen production by photolysis of organic substances and water.
- a photocatalyst for water splitting for the purpose of producing hydrogen has attracted attention as a photocatalyst used in a method for producing hydrogen using renewable energy.
- the demand for a photocatalyst for water splitting that provides high activity is increasing year by year.
- Rhodium-doped strontium titanate (Rh-SrTiO3) is known to have a very high ability to generate hydrogen by photolysis of water as a water-decomposing photocatalyst with visible light response.
- the Z scheme type system combining the photocatalyst particles for oxygen generation and the Rh-SrTiO 3 particles irradiates the aqueous suspension in which these two particles are aggregated with each other by pH control, It is known to generate hydrogen and oxygen in a complete water splitting reaction with a high energy conversion efficiency of 0.1% or more (Sasaki et al., J. Phys. Chem. C 17536-17542, 2009 (non- Patent Document 1)).
- the Rh—SrTiO 3 is produced by a solid-phase reaction method or a hydrothermal synthesis method, and in these methods, it is known to perform a high crystallization treatment by baking at about 1000 ° C.
- the Rh—SrTiO 3 particles thus obtained have a primary particle size of about several hundred nm to several ⁇ m, and are known to exhibit high hydrogen generation ability under visible light irradiation.
- Rh-SrTiO 3 particles in order to further highly activate Rh-SrTiO 3 particles, increasing the specific surface area of the Rh-SrTiO 3 particles, that is, Rh-SrTiO 3 particles of fine crystal has been demanded.
- there is a demand for improving the conversion efficiency of the complete water splitting reaction by combining Rh—SrTiO 3 particles having high hydrogen generation ability and photocatalyst particles for oxygen generation and using this composite photocatalyst.
- Patent Document 2 discloses a water splitting photocatalyst immobilization product having a photocatalyst layer on a substrate, wherein the photocatalyst layer includes Ga, Zn, Ti, La, Ta, and Visible light responsive optical semiconductor that is a nitride or oxynitride containing Ba atom, at least one hydrophilicity selected from the group consisting of a cocatalyst supported on the optical semiconductor, silica, alumina, and titanium oxide
- a photocatalyst immobilized product for water splitting containing an inorganic material is described.
- the coexistence of the visible light responsive photocatalyst and the hydrophilic inorganic material in the photocatalyst layer allows water to penetrate not only near the surface of the photocatalyst layer but also into the interior during the water splitting reaction.
- the product surface becoming difficult to adhere to the photocatalyst layer due to the hydrophilic surface, diffusion of the product gas into the gas phase is promoted.
- the present inventors have recently realized the production of visible light responsive photocatalyst particles that achieve both high crystallinity and primary particle miniaturization, and such fine visible light responsive photocatalyst particles for hydrogen generation, oxygen It has been found that a composite photocatalyst with high hydrogen generation ability, preferably a visible light responsive composite photocatalyst for water splitting, can be obtained by combining the visible light responsive photocatalyst particles for generation. Further, the inventors have obtained knowledge that a photocatalyst material having a high hydrogen generation ability can be obtained as a result of fixing such fine photocatalyst particles for hydrogen generation and photocatalyst particles for oxygen generation on a substrate. The present invention is based on such knowledge.
- the present invention provides a hydrogen generating ability obtained by bringing the visible light responsive photocatalyst particles for hydrogen generation and the visible light responsive photocatalyst particles for oxygen generation into contact with each other, which achieves both high crystallinity and miniaturization of primary particles.
- the purpose is to provide a composite photocatalyst with a high level of photosynthesis.
- the present invention provides a hydrogen generating ability in which visible light responsive photocatalyst particles for hydrogen generation and visible light responsive photocatalyst particles for oxygen generation are fixed on a substrate, which achieves both high crystallinity and miniaturization of primary particles.
- the purpose is to provide a highly photocatalytic material.
- the composite photocatalyst according to the present invention includes a visible light responsive photocatalyst particle for hydrogen generation having a primary particle diameter of 100 nm or less and a visible light responsive photocatalyst particle for oxygen generation, and the visible light responsive photocatalyst particle for hydrogen generation. And the visible light responsive photocatalyst particles for oxygen generation are in contact with each other.
- the photocatalyst material according to the present invention includes a base material and a photocatalyst layer fixed to the base material, and the photocatalyst layer has a primary particle diameter of 100 nm or less and a visible light responsive photocatalyst for hydrogen generation. And a visible light responsive photocatalyst particle for oxygen generation, wherein the visible light responsive photocatalyst particle for hydrogen generation and the visible light responsive photocatalyst particle for oxygen generation are in contact with each other. .
- a composite photocatalyst and photocatalyst material of the present invention a composite photocatalyst and a photocatalyst material capable of water splitting exhibiting high photocatalytic activity under visible light irradiation can be obtained.
- 2 is a scanning electron micrograph of rhodium-doped strontium titanate particles contained in a visible light responsive composite photocatalyst for water splitting according to the present invention. It is a scanning electron micrograph of the photocatalyst material which fixed the visible light response type composite photocatalyst for water splitting on the anodized alumina filter by the present invention.
- visible light means electromagnetic waves (light) having a wavelength that can be visually recognized by human eyes. Preferably, it means light containing visible light having a wavelength of 380 nm or longer, more preferably light containing visible light having a wavelength of 420 nm or longer.
- light including visible light sunlight, condensed sunlight with increased energy density by condensing, or an artificial light source such as a xenon lamp, a halogen lamp, a sodium lamp, a fluorescent lamp, or a light emitting diode is used as a light source. It is possible.
- the composite photocatalyst according to the present invention has a primary particle diameter of 100 nm or less, can generate hydrogen by a photolysis reaction of water with visible light, and can generate oxygen by a photolysis reaction of water with visible light.
- the composite photocatalyst includes a photocatalyst particle, and the visible light responsive photocatalyst particle for hydrogen generation and the visible light responsive photocatalyst particle for oxygen generation are in contact with each other.
- composite photocatalyst preferably a visible light responsive composite photocatalyst for water splitting (hereinafter also simply referred to as “composite photocatalyst”), visible light for fine hydrogen generation having a primary particle diameter of 100 nm or less. Since responsive photocatalyst particles (hereinafter, also simply referred to as “photocatalyst particles for hydrogen generation”) are used, it is possible to increase the efficiency of the photolysis reaction for hydrogen generation, which is rate limiting in the complete photolysis reaction of water. Become.
- the composite photocatalyst according to the present invention contacts such a hydrogen generating photocatalyst particle having a high hydrogen generating ability with a visible light responsive photocatalyst particle for oxygen generation (hereinafter also simply referred to as “oxygen generating photocatalyst particle”). Therefore, the ability of each of these two types of photocatalysts can be effectively exhibited. As a result, complete photolysis of water can be achieved with high efficiency.
- the composite photocatalyst according to the present invention exhibits semiconductor physical properties having an optical band gap and absorbs visible light.
- excited electrons are generated in the conduction band (or electron acceptor level existing in the band gap) by electronic transition such as interband transition, and the valence band (or electron donor level existing in the band gap) is generated.
- the reaction object is reduced and oxidized, respectively.
- the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation are in contact. Accordingly, it is possible to perform a hydrogen generation reaction on the hydrogen generation photocatalyst particles and an oxygen generation reaction on the oxygen generation photocatalyst particles.
- the composite photocatalyst according to the present invention can separate the reaction sites, it is possible to prevent the generated hydrogen and oxygen from being regenerated into water by a reverse reaction and reducing the reaction rate of water splitting. is there.
- the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles are in contact with each other, so that the charge carrier (electron) between these two particles And holes) can be transferred.
- the water splitting reaction is considered to occur as follows, but the present invention is not limited to this.
- a photoexcitation reaction occurs in each of the hydrogen-generating photocatalyst particles and the oxygen-generating photocatalyst particles contained in the composite photocatalyst, and excited electrons and excitation are generated inside each of these two particles. Holes are generated.
- the excited holes generated in the hydrogen generating photocatalyst particles and the excited electrons generated in the oxygen generating photocatalyst particles each diffuse to the surface of each particle.
- a charge recombination reaction takes place at the particle interface, and these charge carriers disappear.
- the “charge recombination reaction” is a reaction in which excited electrons and excited holes react and excited carriers disappear.
- the excited electrons remaining in the hydrogen generating photocatalyst particles and the excited holes remaining in the oxygen generating photocatalyst particles diffuse to the surface of each particle, respectively, on the particle surface or the surface of the promoter supported on the particle surface. Hydrogen and oxygen are generated by reducing and oxidizing water, respectively.
- the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation are in contact with each other. Any state may be employed as long as a charge recombination reaction can be caused by excited electrons of the photocatalyst particles for generating holes and oxygen.
- Specific examples of the contact state include a physical contact state, a chemically bonded contact state, and a state in which these two states are formed together.
- the method for producing a composite photocatalyst according to the present invention can realize a state in which a charge recombination reaction between excited holes of hydrogen generating photocatalyst particles and excited electrons of oxygen generating photocatalyst particles can occur at the particle interface. If it includes a process, it will not specifically limit. In order to realize a state in which this charge recombination reaction can occur, the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation are in contact with each other in the composite photocatalyst according to the present invention.
- a physical method and a chemical method can be used.
- a powder composed of each of photocatalyst particles for hydrogen generation and photocatalyst particles for oxygen generation, or a slurry in which this powder is dispersed in a liquid is mixed with a kneading method such as mechanical kneading and manual kneading.
- a method of causing the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles to collide with each other using a mechanical milling method such as a ball mill, a bead mill, and a planetary mill can be preferably used.
- the hydrogen generation photocatalyst particles and the oxygen generation photocatalyst particles in contact with each other. This makes it possible to increase the contact area at the interface between the particles.
- the firing temperature is preferably 200 ° C. or higher and 700 ° C. or lower, and more preferably 300 ° C. or higher and 600 ° C. or lower. By firing at a temperature in this range, it is possible to suppress the generation of impurities due to the reaction between the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles at a high temperature while improving the contact state.
- a specific functional group is imparted to the surface of either or both of the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles, and the respective particles are contacted and reacted to form an ionic bond or a covalent bond.
- a method of obtaining a chemical bond form such as hydrogen bond can be preferably used.
- the contact state it is preferable to perform firing in a state where the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles are in contact with each other, as described above.
- the firing temperature is the same as above.
- functional groups can be imparted to the surfaces of the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles.
- a means for imparting a functional group a method in which a high molecular compound or a low molecular compound such as a polymer having a functional group is adsorbed on the surfaces of the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles can be preferably used.
- the dispersibility of each particle in the liquid medium can be improved.
- the primary particles of the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles can be brought into contact with each other. As a result, the contact interface between these particles can be increased, and the charge recombination reaction can be promptly promoted, so that the efficiency of the water splitting reaction can be increased.
- the polymer is not particularly limited as long as it can be adsorbed on the surface of the photocatalyst particles and can be removed from the composite photocatalyst by means such as calcination.
- a specific example of such a polymer either a nonionic polymer or an ionic polymer can be used.
- nonionic polymer examples include polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polyvinyl pyrrolidone, carboxymethyl cellulose, carboxypropyl cellulose, and triblock copolymers (for example, polyethylene oxide-polypropylene oxide-polyethylene oxide) in an aqueous solvent system.
- organic solvent system ethyl cellulose, polyvinyl butyral, etc. can be used.
- a carboxylic acid addition polymer such as polyacrylic acid (including ammonium salt, sodium salt and potassium salt) can be used as the anionic polymer, and polyethyleneimine, poly Amine compound addition polymers such as allylamine and polydiallyldimethylammonium can be used.
- the method for producing a composite photocatalyst according to the present invention comprises a solution containing a polymer (anionic polymer and cationic polymer) having different charges for each of the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation. And a step of dispersing the particles in a state close to monodispersion as primary particles. Then, these slurry are mixed, and the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation are spontaneously adsorbed and brought into contact with each other by Coulomb interaction due to different charges of the polymer adsorbed on the surface of each particle. Is possible.
- the primary particles are dispersed by dispersing the photocatalyst particles for hydrogen generation in a solution containing an anionic polymer, dispersing the photocatalyst particles for oxygen generation in an aqueous solution containing a cationic polymer, and then mixing these slurries. It becomes possible to be in a state where contact is possible at high density. Thereafter, firing is performed in a state where the primary particles are in high density contact with each other, and the polymer is removed, thereby realizing a highly active state as a composite photocatalyst.
- the firing temperature is as described above.
- Photocatalyst particles for hydrogen generation contained in the composite photocatalyst according to the present invention have a primary particle diameter of 100 nm or less. Moreover, it can decompose water by irradiation with visible light to generate hydrogen, and is used in contact with photocatalyst particles for oxygen generation.
- the photocatalyst particles for hydrogen generation used in the present invention exhibit semiconductor physical properties having an optical band gap, and absorb visible light, and therefore exist in the conduction band (or within the band gap due to electronic transition such as interband transition).
- the photocatalyst particles for hydrogen generation contained in the composite photocatalyst according to the present invention are photocatalyst particles that can generate hydrogen by reducing water by excited electrons generated by irradiation with visible light.
- the conduction band of the photocatalyst particles for hydrogen generation may be at a position lower than the reduction potential of water (0 V vs. NHE (standard hydrogen electrode potential)).
- the valence band (or the electron donor level present in the band gap) of the hydrogen generating photocatalyst particle may be located at a position higher than the conduction band position of the oxygen generating photocatalyst particle.
- the primary particle size of the hydrogen generating photocatalytic particles contained in the composite photocatalyst according to the primary particle diameter present invention for generating hydrogen photocatalyst particles is at 100nm or less, preferably 70nm or less.
- the advantage that the photocatalyst particles for hydrogen generation contained in the composite photocatalyst according to the present invention have a fine particle size is that excited electrons and excited holes generated in the particles diffuse to the particle surface by visible light irradiation. The distance is short. For this reason, the hydrogen generation reaction due to the reduction of water and the charge recombination reaction with the excited electrons generated in the photocatalyst particles for oxygen generation occur at high efficiency on the surface of the particle where the excited electrons and excited holes are diffused. It is possible.
- the hydrogen generating photocatalyst particles contained in the composite photocatalyst of the present invention have high crystallinity and a fine primary particle diameter. Thereby, it becomes possible to suppress the recombination reaction of excited holes and excited electrons in the photocatalyst particles for hydrogen generation mainly starting from the oxygen defect level. As a result, the reduction of water by the excited electrons of the hydrogen generating photocatalyst particles and the charge recombination reaction at the particle interface between the excited holes of the hydrogen generating photocatalyst particles and the excited electrons of the hydrogen generating photocatalyst particles are promoted. Efficient water splitting reaction is possible.
- Cocatalyst loading on hydrogen generating photocatalyst particles when water is photolyzed using the hydrogen generating photocatalyst particles contained in the composite photocatalyst according to the present invention, the surface of the hydrogen generating photocatalyst particles is assisted. The catalyst is supported. Thereby, generation of hydrogen occurs promptly.
- At least one selected from metal particles such as platinum, ruthenium, iridium and rhodium, or a mixture of these metal particles can be preferably used. More preferably, platinum and ruthenium metal particles can be used.
- Preferred examples of the cocatalyst loading method include an impregnation method and an adsorption method.
- the impregnation method and the adsorption method are methods in which photocatalyst particles are dispersed in a solution in which a cocatalyst precursor is dissolved and adsorbed on the surface of the photocatalyst.
- the cocatalyst precursor include metal chlorides such as platinum, ruthenium, iridium, and rhodium, nitrates, and amine salts.
- the cocatalyst precursor after it is supported on the surface of the photocatalyst particles.
- the activity is increased by reducing the cocatalyst precursor to a metal state.
- a method for reducing the cocatalyst precursor a photoreduction method, a chemical reduction method, or the like is preferably used.
- the photoreduction method is a method in which the promoter precursor adsorbed on the photocatalyst is reduced by the excited electrons generated in the photocatalyst particle when the photocatalyst particle is irradiated with ultraviolet light or visible light.
- the chemical reduction method is a method of reducing the cocatalyst precursor in a hydrogen gas stream at 400 ° C.
- the cocatalyst supported by such a method is in the form of particles, and by supporting the cocatalyst in the form of particles on the surface of the hydrogen generating photocatalyst particles, it becomes possible to reduce the activation energy in the reduction reaction of water. Therefore, prompt generation of hydrogen becomes possible.
- Rhodium-doped strontium titanate particles as photocatalyst particles for hydrogen generation contained in the composite photocatalyst according to the present invention have high crystallinity and a fine primary particle size. .
- Rh—SrTiO 3 it is difficult to achieve both high crystallinity and a large specific surface area, that is, a fine crystal. That is, Rh—SrTiO 3 is a substance that is difficult to grow to be a crystal having high crystallinity while remaining as a fine crystal during crystal growth.
- the generation of oxygen defects can be considered as one of the factors that decrease the crystallinity of the metal oxide. That is, as the number of oxygen site defects in the metal oxide increases, that is, the number of oxygen defects increases, the periodicity of the crystal is disturbed, so that the crystallinity of the metal oxide decreases, that is, the crystallinity decreases.
- the absorption spectrum of titanium oxide having oxygen defects has a broad light absorption band in a wide range from the visible light region to the near infrared region (Cronemeyer et al., Phys. Rev. 113, 1222). ⁇ 1225 pages, 1959).
- the present inventors by measuring the diffuse reflection spectrum of rhodium-doped strontium titanate particles, the present inventors have produced a broad light absorption band from visible light to near-infrared light region, similar to titanium oxide. It was confirmed. Furthermore, it was confirmed that the light absorptance decreased in this near-infrared light region by increasing the firing temperature. From these facts, it was found that the improvement in crystallinity accompanying the increase in the firing temperature can be quantified by measuring the light absorption in the near infrared region from the visible light.
- the present inventors also consider the rhodium state, and light absorption derived from tetravalent rhodium (Rh 4+ ) in the strontium titanate crystal. It was found that the larger the value, the higher the crystallinity. Regarding the influence of the valence of rhodium on the crystallinity, the following mechanism is expected, but the present invention is not limited to this mechanism.
- the valence of rhodium is known as bivalent, trivalent, tetravalent and pentavalent.
- trivalent rhodium (Rh 3+ ) is most stable at room temperature and in the atmosphere.
- strontium titanate (SrTiO 3 ) is fired at high temperature and crystallized, the site of tetravalent titanium (Ti 4+ ) is known to be doped with rhodium. ing.
- Rh 3+ is substituted and dissolved in a crystal site of Ti 4+ , oxygen defects are generated in order to maintain electrical neutrality. Therefore, in order to reduce the oxygen vacancies, the present inventors need to substitute Rh 4+ capable of maintaining the electrical neutrality of the crystal into a solid solution of Ti 4+ , thereby forming particles. It has been found that the crystallinity of is improved.
- the present inventors have found that the optical property parameters of the rhodium-doped strontium titanate particles having high photocatalytic activity of the present invention can be clarified by measuring the particles by the following method.
- an ultraviolet-visible near-infrared spectrophotometer equipped with an integrating sphere unit (manufactured by JASCO Corporation, “V-670”). ”) Can be used. Specifically, an integrating sphere unit (manufactured by JASCO Corporation, “ISV-722”) is attached to the ultraviolet visible near infrared spectrophotometer.
- alumina sintered pellets are used for the baseline measurement.
- the spectral reflectance R can be measured.
- the optical characteristics of the rhodium-doped strontium titanate particles are shown by measuring a diffuse reflection spectrum in the wavelength range of 200 to 2500 nm using this apparatus.
- the light absorption rate A 570 at a wavelength of 570 nm is 0.6 or more and less than 0.8.
- the light absorption ratio A 1800 at a wavelength of 1800nm is 0.3 to 0.7.
- Rhodium-doped strontium titanate particles as a hydrogen generation photocatalytic particles contained in the composite photocatalyst according to the primary particle diameter present invention of a rhodium-doped strontium titanate particles have a fine primary particle size.
- the primary particle diameter is preferably 70 nm or less.
- the rhodium-doped strontium titanate particles can have a high specific surface area.
- the contact area with the substance to be decomposed increases, and the photocatalytic activity of the particles improves.
- a preferable primary particle diameter is 50 nm or less.
- a more preferable primary particle diameter is 30 nm or more and 70 nm or less.
- An even more preferable primary particle size is 30 nm or more and 50 nm or less.
- the primary particle diameter of the rhodium-doped strontium titanate particles can be measured by the evaluation method already described.
- the rhodium-doped strontium titanate particles as the photocatalyst particles for hydrogen generation contained in the composite photocatalyst according to the present invention have a large specific surface area.
- R SP value of rhodium-doped strontium titanate particles as an indicator, rhodium-doped strontium titanate particles having a large surface area or a highly porous powder (secondary particles) in which they are aggregated are shown. Became possible.
- the R SP value is an index that correlates with the amount of water molecules adsorbed on the particle surface, and is an index that depends on the surface area of particles dispersed in water that are in contact with water. Since the rhodium-doped strontium titanate particles contained in the composite photocatalyst according to the present invention are used as a water splitting photocatalyst, the particles are used in contact with water. In this case, water diffuses into the gaps between the primary particles or the pores in the secondary particles, and the water comes into contact with the surface of the particles.
- the rhodium-doped strontium titanate particles included in the present invention it is possible to accurately measure the surface area of the particles adsorbed with water using the R SP value as an index, thereby obtaining particles having a large specific surface area.
- BET analysis based on nitrogen adsorption / desorption measurement, which is the mainstream in the past, can be mentioned.
- nitrogen is used as a probe, and the molecular diameter of nitrogen is small. Nitrogen is adsorbed on the pore surfaces where water cannot diffuse. Therefore, the specific surface area measurement method based on BET analysis lacks effectiveness when it is intended for particles on which water is adsorbed.
- the R SP value is represented by the following formula.
- the R SP value can be measured by a pulse NMR particle interface evaluation apparatus (for example, “Acorn area”, manufactured by Nippon Lucas).
- R SP (R b ⁇ R av ) / R b (1)
- R av is an average relaxation time constant.
- the relaxation time constant is the reciprocal of the relaxation time of water that is in contact with or adsorbing to the surface when the particles are dispersed in water.
- the average relaxation time constant is a value obtained by averaging the obtained relaxation time constants.
- R b is the relaxation time constant of blank water containing no particles.
- the R SP value of the rhodium-doped strontium titanate particles contained in the composite photocatalyst according to the present invention is preferably 0.86 or more. More preferably, it is 0.88 or more.
- the R SP value is preferably 10 or less.
- composition of rhodium-doped strontium titanate as the photocatalyst particles for hydrogen generation contained in the composite photocatalyst according to the present invention can be represented by SrTi 1-x Rh x O 3 .
- the molar ratio of rhodium-doped strontium titanate particles represented by M (rhodium) / M (titanium + rhodium) is preferably 0.001 to 0.03, and more preferably 0.01 to 0.03. It is. By setting the molar ratio within this range, an increase in the amount of oxygen defects in the crystal can be suppressed and high photocatalytic activity can be realized.
- the rhodium-doped strontium titanate particles contained in the composite photocatalyst according to the present invention achieve high photocatalytic activity by achieving both the above-described light absorption rate and the fine primary particle shape measured by SEM. Is possible.
- a wet reaction method can be used as a method for producing rhodium-doped strontium titanate particles as photocatalyst particles for hydrogen generation used in the composite photocatalyst according to the present invention.
- the wet reaction method include a sol-gel method, a complex polymerization method, and a hydrothermal reaction method.
- the sol-gel method uses a alkoxide of titanium or a chloride of titanium as a raw material.
- a hydroxide containing titanium is generated by a hydrolysis reaction between the raw material and water. The hydroxide is baked at 600 ° C. or higher and crystallized to obtain rhodium-doped strontium titanate particles.
- Aqueous solution pyrolysis method uses a metal-containing precursor as a raw material, and heats an aqueous solution containing this metal-containing precursor, thereby dehydrating polycondensation of metal-containing precursors with the evaporation of water as a solvent. It is a method of causing a reaction.
- a metal compound for example, metal alkoxide or metal chloride
- a metal hydroxide is generated by hydrolysis of metal-containing precursors, Since these dehydration polycondensation occurs rapidly, crystal nuclei are likely to be coarsened.
- aqueous solution thermal decomposition method stable dissolution in water is possible by using a metal-containing precursor, which has a mild hydrolysis reaction, as a raw material.
- a metal-containing precursor which has a mild hydrolysis reaction
- a dehydration polycondensation reaction between the metal-containing precursors can occur gradually with the evaporation of water as a solvent. This slows down the generation rate of crystal nuclei during pyrolysis, and as a result, miniaturization of crystal nuclei becomes possible.
- a rhodium-doped strontium titanate precursor is contained by mixing a titanium compound, a strontium compound, a rhodium compound and a hydrophobic complexing agent and dissolving them in water. It is preferable to prepare an aqueous solution (the aqueous solution thus obtained is hereinafter referred to as an aqueous solution A).
- rhodium-doped strontium titanate precursor means a compound having a six-membered ring structure formed by coordination of a hydrophobic complexing agent to titanium ions generated by dissociation of a titanium compound, and strontium It is a mixture of strontium ions generated by dissociating compounds and rhodium ions generated by dissociating rhodium compounds.
- an aqueous solution containing a water-soluble titanium complex is prepared by mixing a titanium compound and a hydrophobic complexing agent (the aqueous solution thus obtained is hereinafter referred to as an aqueous solution B).
- This aqueous solution B is mixed with a strontium compound and a rhodium compound to prepare an aqueous solution containing the rhodium-doped strontium titanate precursor, that is, an aqueous solution A.
- the water-soluble titanium complex is one in which a hydrophobic complexing agent is coordinated to titanium ions generated by dissociation of a titanium compound.
- a hydrophobic complexing agent in addition to the titanium compound as a raw material as a method for water-solubilizing a titanium compound containing Ti 4+ which is inherently poorly water-soluble.
- a hydrophobic complexing agent By coordinating the hydrophobic complexing agent to titanium ions and complexing the titanium ions, hydrolysis can be suppressed.
- the titanium compound an alkoxide of titanium or a chloride of titanium can be used.
- titanium alkoxide titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-propoxide, titanium tetraisopropoxide, titanium tetra n-butoxide and the like can be used.
- chloride of titanium titanium tetrachloride, titanium tetrafluoride, titanium tetrabromide, or the like can be used.
- the hydrophobic complexing agent used in the method for producing rhodium-doped strontium titanate particles is capable of coordinating to titanium ions, and the hydrophobic part is exposed on the solvent phase side when coordinated to titanium ions.
- a hydrophobic complexing agent for example, diketones and catechols can be preferably used.
- diketones include diketones represented by the general formula: Z 1 —CO—CH 2 —CO—Z 2 (wherein Z 1 and Z 2 are each independently an alkyl group or an alkoxy group). Can be preferably used.
- acetylacetone, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate and the like can be preferably used.
- catechols ascorbic acid, pyrocatechol, tert-butylcatechol and the like can be preferably used.
- acetylacetone or ethyl acetoacetate having a very high complexing ability in an aqueous solution of titanium can be used. Thereby, it is possible to suppress intermolecular polymerization due to intermolecular dehydration polycondensation that occurs when a hydroxyl group that is a hydrophilic portion is exposed on the solvent phase side. Therefore, it is possible to refine crystal nuclei and to refine particles after the pyrolysis reaction during pyrolysis.
- a hydrophilic complexing agent in addition to a hydrophobic complexing agent, can be used.
- a carboxylic acid can be preferably used, and more preferably a carboxylic acid represented by the formula R 1 —COOH (wherein R 1 is a C 1-4 alkyl group), or A hydroxy acid or dicarboxylic acid having 1 to 6 carbon atoms can be used.
- Specific examples of such a hydrophilic complexing agent include water-soluble carboxylic acids such as acetic acid, lactic acid, citric acid, butyric acid and malic acid. Even more preferred water-soluble carboxylic acid is acetic acid or lactic acid. Thereby, it becomes possible to suppress the hydrolysis reaction of the titanium compound and improve the solubility in water.
- the solvent for forming the complex may be water, but according to another preferred embodiment, a water-soluble organic solvent may be used as the solvent.
- a water-soluble organic solvent may be used as the solvent.
- the solubility of a transition metal compound can be improved.
- Specific examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, cellosolve solvent, and carbitol solvent.
- the water-soluble titanium complex described in JP 2012-056947 A can be used.
- a titanium complex having a coordination number of 6 with respect to a titanium ion, which is coordinated with the titanium ion is represented by the general formula: Z 1 —CO—CH 2 —CO—Z 2 (wherein , Z 1 and Z 2 are each independently an alkyl group or an alkoxy group.),
- a third ligand and a fourth ligand each independently selected from the group consisting of an alkoxide and a hydroxide ion, and a fifth ligand that is H 2 O
- a titanium complex consisting of can be used.
- strontium compound containing Sr 2+ a compound that is water-soluble and does not leave an anionic component as a residue upon heat crystallization is preferable.
- strontium nitrate, strontium acetate, strontium chloride, strontium bromide, strontium lactate, strontium citrate and the like are preferably used.
- the rhodium compound containing Rh 3+ is preferably water-soluble and does not leave an anionic component as a residue during heat crystallization.
- the rhodium compound for example, rhodium nitrate, rhodium acetate, rhodium chloride, rhodium bromide, rhodium lactate, rhodium citrate and the like are preferably used. Further, a molecule containing Rh 4+ may be used as the rhodium compound.
- a hydrophilic complexing agent such as lactic acid, butyric acid or citric acid may be used.
- the preferred mixing ratio of various raw materials in the aqueous solution A includes 1 atom of titanium per 100 grams of water.
- the titanium compound is 0.01 to 0.2 mol, more preferably 0.02 to 0.1 mol, and the strontium compound is 1 to 1.1 times the molar amount of the titanium compound containing one titanium atom.
- the rhodium compound is in a desired dope amount
- the hydrophobic complexing agent is 0.005 to 0.4 mol, more preferably 0.015 to 0.15 mol
- the hydrophilic complexing agent is 0.01 to 0.2 mol, more preferably 0.025 to 0.15 mol.
- the molar ratio of the hydrophobic complexing agent to the titanium compound is preferably 0.5 to 2 mol, more preferably 0.8 to 1 with respect to 1 mol of the titanium compound containing 1 atom of titanium. .2 moles.
- the molar ratio of the hydrophilic complexing agent to the titanium compound is preferably 0.2 to 2 mol, more preferably 0.3 to 1 mol with respect to 1 mol of the titanium compound containing 1 atom of titanium. .5 moles.
- the progress of the hydrolysis reaction of the titanium compound can be suppressed, and the solubility of the titanium compound in water can be improved.
- the pH at which the stability of each ion in the aqueous solution can be maintained and the particles after crystallization can be refined is preferably 2 to 6, more preferably 3 to 5.
- rhodium-doped strontium titanate particles as the hydrogen generating photocatalyst particles contained in the composite photocatalyst according to the present invention, it is preferable to add water-dispersed organic polymer particles to the aqueous solution A (obtained thereby).
- a solution obtained by adding water-dispersed organic polymer particles to the aqueous solution A is hereinafter referred to as a dispersion).
- grains can be obtained by heating and crystallizing this dispersion.
- water-dispersed organic polymer particles spherical latex particles or oil-in-water dispersed (O / W type) emulsions can be used.
- fine rhodium-doped strontium titanate particles are obtained, and secondary particles in which such particles are aggregated are porous.
- the mechanism by which fine primary particles are obtained as a result and the porosity of the aggregated secondary particles is considered as follows, but the present invention is not limited to this mechanism. .
- water-soluble titanium complexes, strontium ions and rhodium ions which are also polar molecules, are adsorbed on the surface of the polymer particles having polarity in water.
- the titanium complex on the surface of the polymer particles is hydrolyzed to produce rhodium-doped strontium titanate crystal nuclei.
- the crystal nuclei on the surface of the polymer particles exist with a physical distance from each other, there are few opportunities for bonding between the crystal nuclei, and the crystal growth is considered to proceed slowly. As a result, it is considered that the primary particle diameter of the rhodium-doped strontium titanate particles becomes fine.
- the resulting rhodium-doped strontium titanate particles bind to each other as the polymer particles disappear due to thermal decomposition, but the presence of the polymer particles suppresses aggregation of the rhodium-doped strontium titanate particles, and as a result, It is considered that the porosity of the secondary particles becomes higher, that is, the porosity becomes higher.
- the dispersed particle diameter of the water-dispersed organic polymer particles in water is preferably 10 to 1000 nm, and more preferably 30 to 300 nm. By setting the dispersed particle diameter within this range, the physical distance between the crystal nuclei of rhodium-doped strontium titanate can be increased. Therefore, it becomes possible to refine the rhodium-doped strontium titanate particles after heat crystallization.
- the material of the water-dispersed organic polymer particles is preferably a material that does not leave a residue such as amorphous carbon, which is a heated residue of the organic polymer particles, after heat crystallization at 600 ° C. or higher.
- the amount of the water-dispersed organic polymer particles added is preferably 1 to 20 times, more preferably 3 to 15 times the weight of rhodium-doped strontium after high temperature crystallization.
- the following method is preferably used.
- the dispersion is first dried at a low temperature of 200 ° C. or lower to obtain a dry powder. By firing this dried powder for crystallization, rhodium-doped strontium titanate particles can be produced. Moreover, you may perform the drying and baking process of this dispersion continuously.
- the calcination temperature at the time of crystallization of rhodium-doped strontium titanate is more than 800 ° C. and less than 1100 ° C., more preferably 900 ° C. or more and 1050 ° C. or less. By adjusting to this temperature range, it is possible to highly crystallize high-purity rhodium-doped strontium titanate particles while thermally decomposing the water-dispersed organic polymer particles.
- Photocatalyst particles for oxygen generation contained in the composite photocatalyst according to the present invention can generate oxygen by decomposing water by irradiation with visible light, and are used in contact with the photocatalyst particles for hydrogen generation. is there.
- the photocatalyst particles for oxygen generation used in the present invention exhibit semiconductor physical properties having an optical band gap and absorb visible light, thereby causing excited electrons and valence bands in the conduction band due to electronic transition such as interband transition.
- Photocatalytic materials that can reduce and oxidize the reaction object can be used by generating excited holes in each. That is, the photocatalyst particle for oxygen generation contained in the composite photocatalyst according to the present invention is a photocatalyst material in which excited holes generated by irradiation with visible light can oxidize water to generate oxygen.
- the valence band of the oxygen generating photocatalyst particles only needs to be in a position higher than the oxidation potential of water (+1.23 V vs. NHE (standard hydrogen electrode potential)), and the conduction band of the oxygen generating photocatalyst particles is What is necessary is just to be in a base position rather than the valence band position of the photocatalyst particle for hydrogen generation.
- photocatalyst particles for oxygen generation include BiVO 4 , WO 3 , Bi 2 WO 6 , Fe 2 O 3 , Bi 2 MoO 6 , GaN-ZnO solid solution, LaTiO 2 N, BaTaO 2 N, BaNbO 2.
- photocatalyst particles for oxygen generation include BiVO 4 , WO 3 , Bi 2 WO 6 , Bi 2 MoO 6 , Fe 2 O 3 , GaN-ZnO solid solution, LaTiO 2 N, BaTaO 2 N, BaNbO 2 N, TaON, Ta 3 N 5 , Ge 3 N 4 , CuGaS 2 , CuInS 2 , Cu (Ga, In) S 2 , CuGaSe 2 , CuInSe 2 , Cu (Ga, In) Se 2 , Cu 2 ZnSnS 4 (CZTS), Cu 2 ZnSn (S, Se) 4 .
- the most preferred specific examples of the photocatalyst particles for oxygen generation are BiVO 4 , WO 3 , Bi 2 WO 6 , and Fe 2 O 3 .
- the primary particle size of the oxygen generating photocatalyst particles contained in the composite photocatalyst according to the primary particle diameter present invention of the oxygen generating photocatalyst particles is preferably not 500nm or less, more preferably 200nm or less, even more preferably at 100nm or less Yes, most preferably 70 nm or less.
- the advantage of the photocatalyst particles for oxygen generation contained in the composite photocatalyst according to the present invention having a fine particle size is that excited holes and excited electrons generated in the particles are diffused to the particle surface by visible light irradiation. The distance is short. For this reason, the oxygen generation reaction due to the oxidation of water and the charge recombination reaction with the excitation holes generated by the photocatalyst particles for hydrogen generation are highly efficient on the particle surface where the excited holes and excited electrons are diffused. It is possible to happen.
- the method for evaluating the primary particle size of the photocatalyst particles for oxygen generation is the same as the method for evaluating the primary particle size of the photocatalyst particles for hydrogen generation already described.
- the oxygen generating photocatalyst particles used in the composite photocatalyst according to the present invention have high crystallinity and a fine primary particle diameter. Thereby, it becomes possible to suppress the recombination reaction of excited holes and excited electrons in the photocatalyst particles for oxygen generation mainly starting from the oxygen defect level. As a result, the oxidation of water by the excited holes of the oxygen generating photocatalyst particles and the charge recombination reaction at the particle interface between the excited electrons of the oxygen generating photocatalyst particles and the excited holes of the hydrogen generating photocatalyst particles are promoted. Thus, an efficient water splitting reaction is possible.
- the production method of the oxygen generation photocatalyst particles contained in the composite photocatalyst according to the present invention can employ various wet reaction methods such as a sol-gel method, a complex polymerization method, and a hydrothermal reaction method.
- a sol-gel method which is one of wet reaction methods
- a metal hydroxide is produced by hydrolysis reaction with water using a metal alkoxide or metal chloride as a raw material, and this is produced at 600 ° C. or higher.
- the aforementioned aqueous solution thermal decomposition method can be preferably used.
- the following method can be used.
- BiVO 4 ethylenediaminetetraacetic acid
- EDTA ethylenediaminetetraacetic acid
- tartaric acid or lactic acid is used as V 5+
- the water-soluble complex obtained by complexing is mixed in an aqueous solution, dried, and calcined at a calcining temperature of 400 ° C. or higher, whereby fine BiVO 4 having a primary particle diameter of 100 nm or less can be synthesized.
- Photocatalyst material The photocatalyst material according to the present invention includes a base material and a photocatalyst layer fixed to the base material, and the photocatalyst layer has a primary particle diameter of 100 nm or less for hydrogen generation photocatalyst particles, oxygen
- the photocatalyst particles for generation are included, and the visible light responsive photocatalyst particles for hydrogen generation and the visible light responsive photocatalyst particles for oxygen generation are in contact with each other.
- the photocatalyst layer included in the photocatalyst material according to the present invention includes a photocatalyst particle for generating hydrogen and a photocatalyst particle for generating oxygen having a small primary particle diameter, and exists as an aggregate formed by aggregating these fine particles. To do. For this reason, the porosity of the photocatalyst layer is increased, that is, the porosity is increased, and the specific surface area of the photocatalyst layer is increased. As a result, the photocatalytic activity of the photocatalyst layer formed by combining the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation, which originally have high photocatalytic activity, does not decrease the photocatalytic activity.
- the photocatalyst layer included in the photocatalyst material according to the present invention is formed by agglomerating hydrogen generating photocatalyst particles and oxygen generating photocatalyst particles having a small primary particle diameter, and these particles and The contact area with the substrate is increased. Thereby, it becomes possible to obtain a photocatalyst material having high adhesion between the substrate and the photocatalyst layer.
- the photocatalyst layer contained in the photocatalyst material according to the present invention is an aggregate of fine photocatalyst particles, the binding property between the particles is good. As a result, the particles can form a photocatalytic layer with uniformity. In addition, it is possible to form a photocatalyst layer having a thickness in which photocatalyst particles are deposited on the substrate.
- Such a state of the photocatalyst layer includes, for example, a state in which the photocatalyst particles are present on the surface of the base material, in addition to a complete layer shape or a film shape, for example, a partial film shape.
- the photocatalyst layer may exist discretely in an island shape on the substrate surface.
- the photocatalyst layer may be in a wave shape, a comb shape, a fiber shape, a mesh shape, or the like.
- the “photocatalyst layer” means an aggregate of photocatalyst particles present on the base material in the above-described state.
- the thickness of the photocatalyst layer carried on the photocatalyst material according to the present invention is preferably 0.1 ⁇ m or more and 100 ⁇ m or less.
- a more preferable thickness of the photocatalyst layer is 0.2 ⁇ m or more and 30 ⁇ m or less.
- the thickness of the photocatalyst layer is determined by observation with a scanning electron microscope of the cross section of the photocatalyst material. Specifically, it is the distance from a horizontal tangent at a certain point on the surface of the substrate to the top of the photocatalytic layer at a perpendicular to the tangent. For example, when the substrate is a flat plate as shown in FIG.
- the thickness of the photocatalyst layer is the distance from the substrate surface to the top of the photocatalyst layer in the vertical direction. Further, when the surface of the substrate is like a fiber, the thickness of the photocatalyst layer is a distance from a horizontal tangent at a certain point on the surface of the fiber to the top of the photocatalyst layer at a perpendicular to the tangent.
- the photocatalyst layer contained in the photocatalyst material according to the present invention comprises: a visible light responsive photocatalyst particle for hydrogen generation having a primary particle diameter of 100 nm or less; a visible light responsive photocatalyst particle for oxygen generation; Are formed by aggregating a plurality of composite photocatalyst particles in contact with each other.
- the photocatalyst layer carried on the photocatalyst material according to the present invention has a small primary particle size (100 nm or less, preferably 70 nm or less) and hydrogen generation photocatalyst particles and a small primary particle size ( (Preferably 500 nm or less, more preferably 200 nm or less, even more preferably 100 nm or less, and most preferably 70 nm or less.)
- a plurality of composite photocatalyst particles in contact with oxygen-generating photocatalyst particles are formed.
- the photocatalyst layer contained in the photocatalyst material according to the present invention comprises a visible light responsive photocatalyst particle for hydrogen generation having a primary particle diameter of 100 nm or less, and a visible light response for oxygen generation.
- the photocatalyst particles are mixed with each other, and the particles are in contact with each other.
- the photocatalyst layer carried on the photocatalyst material according to the present invention has a small primary particle size (100 nm or less, preferably 70 nm or less) and hydrogen generation photocatalyst particles and a small primary particle size ( (Preferably 500 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and most preferably 70 nm or less.)
- the photocatalyst particles for oxygen generation are mixed with each other.
- FIG. 1 shows a schematic diagram of a cross section of a photocatalyst material according to the present invention.
- the photocatalyst material is formed by immobilizing a photocatalyst layer having an interparticle void 3 and a thickness 5, which is composed of an aggregate of fine hydrogen-generating photocatalyst particles 1 and oxygen-generating photocatalyst particles 2 on a substrate 4.
- a photocatalyst layer having an interparticle void 3 and a thickness 5 which is composed of an aggregate of fine hydrogen-generating photocatalyst particles 1 and oxygen-generating photocatalyst particles 2 on a substrate 4.
- the photocatalyst layer contained in the photocatalyst material according to the present invention comprises a layer composed of visible light responsive photocatalyst particles for hydrogen generation having a primary particle diameter of 100 nm or less, and oxygen generation.
- the layers of visible light responsive photocatalyst particles for use are alternately laminated, and the visible light responsive photocatalyst particles for hydrogen generation and the visible light responsive photocatalyst particles for oxygen generation are in contact with each other.
- the photocatalyst layer supported on the photocatalyst material according to the present invention has a primary particle size of a layer composed of photocatalyst particles for hydrogen generation having a small primary particle size (100 nm or less, preferably 70 nm or less).
- a small primary particle size 100 nm or less, preferably 70 nm or less.
- layers of photocatalyst particles for oxygen generation preferably 500 nm or less, more preferably 200 nm, even more preferably 100 nm or less, most preferably 70 nm or less).
- the photocatalyst material according to the present invention carries the photocatalyst layer composed of the fine photocatalyst particles as described above, the surface area that can be contacted with water can be increased, and further, the charge recombination reaction at the particle interface is promoted. be able to.
- the photocatalyst material according to the present invention includes a photocatalyst layer formed from fine photocatalyst particles, the contact points per unit area between the fine photocatalyst particles and the substrate are extremely large. Thereby, the mechanical strength between the substrate and the particles and between the particles and the particles becomes good, and the adhesion between the base material and the photocatalyst particles and the binding property between the photocatalyst particles can be improved.
- the photocatalyst material is installed inside a water-splitting photocatalyst module described later, it is possible to suppress the photocatalyst particles from being detached from the base material or segregating on the base material.
- the photocatalyst material according to the present invention can maintain a stable hydrogen production function for a long period of time.
- the photocatalyst material according to the present invention can decompose and produce water into hydrogen and oxygen stably and with high efficiency over a long period of time under irradiation with visible light.
- the photocatalyst layer formed from the fine photocatalyst particles contained in the photocatalyst material according to the present invention has a highly porous structure in which the interparticle voids form pores, so that water from the outside of the membrane can be efficiently used. It enables diffusion into the film and desorption of hydrogen and oxygen generated in the film to the outside of the film. Thereby, the photocatalyst material according to the present invention can generate hydrogen and oxygen with high efficiency by water splitting reaction with high efficiency.
- the pore diameter of the photocatalyst layer contained in the photocatalyst material according to the present invention is preferably 10 nm or more and 200 nm or less, and more preferably 20 nm or more and 100 nm or less.
- the pore diameter of the photocatalyst layer means the pore diameter of the pores existing between the photocatalyst particles contained in the photocatalyst layer.
- the pore diameter can be measured by pore distribution measurement by nitrogen gas adsorption / desorption, and is determined by analysis by the BJH method. Specifically, for example, the adsorption / desorption isotherm of nitrogen gas is measured using a gas adsorption pore distribution measuring device (“BELSORP-mini”, manufactured by Nippon Bell), and the pore diameter is obtained by analysis by the BJH method. .
- the pore volume distribution is obtained by plotting the Log differential pore volume against the obtained pore diameter. In this pore volume distribution, the pore diameter at the peak position is defined as the pore diameter.
- the base material contained in the photocatalyst material according to the present invention is not particularly limited as long as the photocatalyst layer can be fixed by firing.
- an inorganic material that does not decompose even when heated at 250 ° C. or higher is preferable. More preferably, it is an inorganic substance that does not decompose even when heated at 300 ° C. or higher. More specifically, inorganic oxides or metals can be preferably used. More specifically, inorganic oxides such as glass (soda lime glass, borosilicate glass), quartz, aluminum oxide (alumina), ceramics, and metals such as titanium, aluminum, iron, and stainless steel can be preferably used. More preferably, it is at least one selected from glass, alumina, and quartz.
- the substrate can be used without any particular limitation as long as it has a shape capable of fixing the photocatalyst layer on the surface by firing.
- a base material include a flat plate (eg, a glass substrate or an alumina substrate) having a smooth surface, a surface porous flat plate (eg, anodized alumina), a porous material (eg, porous ceramics), or a fiber.
- a body for example, glass fiber, carbon fiber
- the fibrous body more preferably, a glass fiber having high light transmittance can be used. As a result, light can be transmitted into the film rather than the light irradiation surface of the fibrous body, and an increase in light absorption can be expected.
- the surface shape of the substrate may be a waved shape, a comb shape, a fiber shape, or a mesh shape. Since the photocatalyst material of the present invention is formed by adhering and fixing the above-described photocatalyst layer in a state having a thickness on these base materials, water can be completely photodegraded stably for a long period of time. .
- the base material preferably has pores that are open pores inside the base material.
- the pores preferably have a pore diameter of 0.1 to 30 ⁇ m.
- the method for producing a photocatalyst material according to the present invention is not particularly limited as long as it includes a step capable of immobilizing the photocatalyst particles for hydrogen generation and the photocatalyst particles for oxygen generation on the base material.
- a method for producing a photocatalyst material according to the present invention comprises applying a slurry obtained by wet-dispersing a composite photocatalyst in which photocatalyst particles for hydrogen generation and photocatalyst particles for oxygen generation are in contact with a substrate.
- it is a method of drying and baking.
- a method for producing a photocatalyst material according to the present invention comprises applying a slurry obtained by wet-dispersing photocatalyst particles for generating hydrogen and photocatalyst particles for generating oxygen to a substrate, followed by drying and firing. It is a method to do.
- a method for producing a photocatalyst material comprises preparing a slurry in which hydrogen generating photocatalyst particles are wet dispersed and a slurry in which oxygen generating photocatalyst particles are wet dispersed separately. Then, each of these slurries is alternately applied to the base material (for example, immersed), dried and fired, and a photocatalyst layer in which photocatalyst particles for hydrogen generation and photocatalyst particles for oxygen generation are alternately laminated on the base material is formed.
- This is a production method (so-called “alternate adsorption method”).
- each of the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles is used as a method for dispersing the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles in the liquid medium.
- a method of adsorbing a solvent or dispersant such as water or an organic solvent on the particle surface can be preferably used.
- the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles can exist at a distance close to each other, and the solvent component is volatilized after being applied to the substrate and dried, so that the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles are A photocatalytic material that can be contacted at high density can be obtained.
- a mechanical dispersion method such as ultrasonic irradiation, ball mill, or bead mill can be preferably used.
- the solvent can be used without particular limitation as long as it can disperse the composite photocatalyst according to the present invention or the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles.
- an organic solvent such as water or ethanol, or an organic vehicle solvent such as ⁇ -terpineol can be used as the solvent.
- a dispersant may be added to the solvent.
- a slurry in which a composite photocatalyst in which hydrogen generating photocatalyst particles and oxygen generating photocatalyst particles are in contact with each other, or a slurry in which hydrogen generating photocatalyst particles and oxygen generating photocatalyst particles are wet dispersed is applied to a substrate.
- a spin coating method, a dip coating method, a spray method, a doctor blade method, an electrophoresis method, a screen printing method, or the like can be preferably used.
- coating method can be suitably selected according to the shape and kind of base material.
- the photocatalyst material according to the present invention can have a thickness of the photocatalyst layer contained in the photocatalyst layer of 0.1 to 50 ⁇ m.
- the thickness of the photocatalyst layer can be controlled by the light absorption coefficient of the photocatalyst material used.
- a spin coat method, a dip coat method, a spray method, or the like when obtaining a photocatalyst layer having a thickness of 1 ⁇ m or more, it is preferable to use a screen printing method, a doctor blade method, an electrophoresis method or the like.
- the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles are each made of a polymer having a different charge (anionic property).
- the primary particles are dispersed by dispersing the photocatalyst particles for hydrogen generation in a solution containing an anionic polymer, dispersing the photocatalyst particles for oxygen generation in an aqueous solution containing a cationic polymer, and then mixing these slurries. It becomes possible to be in a state where it can be close to or in contact with high density. Thereafter, the primary particles are baked in a state where they are close to or in close contact with each other at a high density, and the polymer is removed, thereby realizing a highly active state as a composite photocatalyst.
- the firing temperature when the composite photocatalyst according to the present invention, or the hydrogen generating photocatalyst particle and the oxygen generating photocatalyst particle is immobilized on the base material is equal to or higher than the thermal decomposition temperature of a solvent, a dispersant and the like.
- the composite photocatalyst particles, the base material, the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles, or the composite photocatalysts, the hydrogen generating photocatalyst particles and the oxygen generating photocatalyst particles are preferably at a temperature that can promote sintering. Specifically, it is 300 ° C. or higher and 700 ° C.
- an optimum light absorption characteristic can be obtained by increasing the mixing ratio of the photocatalyst having a low light absorption coefficient.
- the water-splitting photocatalyst module according to the present invention includes the photocatalyst material.
- the photocatalyst module for water splitting according to the present invention has a generally transparent light incident surface, has a structure in which light is incident on a photocatalyst material installed inside the module, and the photocatalyst material is It has a sealed panel shape capable of enclosing water so that it can always come into contact with water.
- the photocatalyst module for water splitting according to the present invention further has a mechanism such as a water passage hole that can gradually supply additional water that decreases as the water splitting reaction proceeds. Is preferred.
- the hydrogen production system according to the present invention includes the photocatalyst module for water splitting.
- a hydrogen production system according to the present invention comprises a water supply device, a filtration device for removing impurities in water to some extent, a water splitting photocatalyst module, a hydrogen separation device, and a hydrogen storage device. It is. By setting it as the hydrogen production system of such a structure, it becomes possible to implement
- the solution containing this water-soluble titanium-acetylacetone complex was added to 50 mL of a 0.32 mol / L acetic acid aqueous solution with stirring at room temperature. After the addition, the mixture was stirred at room temperature for about 1 hour, and further stirred at 60 ° C. for about 1 hour to prepare an aqueous solution containing a yellow transparent water-soluble titanium complex.
- an acrylic-styrene O / W emulsion into the aqueous solution, as water-dispersed organic polymer particles, so as to have a solid content of 5 times by weight with respect to rhodium-doped strontium titanate obtained after firing ( “DIC-905EF” (dispersed particle size: 100 to 150 nm, pH: 7 to 9, solid content concentration: 49 to 51%) manufactured by DIC was added to prepare a dispersion.
- the dispersion prepared as described above was dried at 80 ° C. for 1 hour, then calcined at 1000 ° C. for 10 hours, and crystallized at a high temperature to prepare a powder composed of rhodium-doped strontium titanate particles.
- the primary particle size of rhodium-doped strontium titanate was calculated from observation with a scanning electron microscope. Specifically, the primary particle diameter was defined as an average value by circular approximation of 50 crystal particles when observed with a scanning electron microscope (“S-4100” manufactured by Hitachi, Ltd.) at a magnification of 40000 times. As a result, the primary particle diameter was 50 nm or less, and it was confirmed that a fine particle shape was maintained even after the high temperature crystallization treatment.
- a scanning electron micrograph of the rhodium-doped strontium titanate particles 1 is shown in FIG.
- Rhodium-doped strontium titanate particles 2 Rhodium-doped strontium titanate was prepared by a solid phase reaction method. Specifically, each powder of strontium carbonate (manufactured by Kanto Chemical Co., Inc.), titanium oxide (manufactured by Soekawa Richemical Co., Ltd., rutile type), and rhodium oxide (Rh 2 O 3 : manufactured by Wako Pure Chemical Industries, Ltd.) was used. 0.07: 0.98: 0.02 and the mixture was baked at 1000 ° C. for 10 hours.
- rhodium-doped strontium titanate coarse particles had a single-phase perovskite structure.
- the primary particle size of rhodium-doped strontium titanate was calculated from observation with a scanning electron microscope. As a result, the primary particle size was about 500 nm.
- the solution containing this water-soluble titanium-acetylacetone complex was added to 50 mL of a 0.32 mol / L acetic acid aqueous solution with stirring at room temperature. After the addition, the mixture was stirred at room temperature for about 1 hour, and further stirred at 60 ° C. for about 1 hour to prepare an aqueous solution containing a yellow transparent water-soluble titanium complex.
- tantalum aqueous solution and a 5 wt% aqueous solution of chromium nitrate (III) hexahydrate were added so that the molar amounts of tantalum and chromium were 0.096 mmol, respectively, and stirred at room temperature for 3 hours. went.
- an aqueous solution containing orange transparent chromium and tantalum-doped strontium titanate precursor was obtained.
- the pH of this aqueous solution was approximately 4.
- the tantalum aqueous solution used what was produced as follows.
- tantalum-acetylacetone complex solution 0.02 mol (2.003 g) of acetylacetone (manufactured by Wako Pure Chemical Industries) and 0.02 mol (8.125 g) of tantalum pentaethoxide (manufactured by Wako Pure Chemical Industries) were mixed to prepare a tantalum-acetylacetone complex solution.
- This tantalum-acetylacetone complex solution was added to 50 mL of a 0.32 mol / L acetic acid aqueous solution to which 0.1 mol citric acid (manufactured by Wako Pure Chemical Industries) was added with stirring at room temperature. Then, the tantalum aqueous solution was produced by stirring for about 1 hour at room temperature.
- acrylic-styrene-based O / W type so that the solid content is 5 times by weight with respect to chromium and tantalum-doped strontium titanate obtained as the water-dispersible organic polymer particles in the aqueous solution.
- An emulsion (manufactured by DIC, “EC-905EF”, dispersed particle size: 100 to 150 nm, pH: 7 to 9, solid concentration: 49 to 51%) was added to prepare a dispersion.
- the dispersion prepared as described above was dried at 80 ° C. for 1 hour, then calcined at 1000 ° C. for 10 hours, and crystallized at a high temperature to prepare a powder composed of chromium and tantalum-doped strontium titanate particles.
- the primary particle diameter of chromium and tantalum doped strontium titanate was calculated from observation with a scanning electron microscope. As a result, the primary particle size was about 50 nm.
- the BiVO 4 precursor aqueous solution prepared as described above was dried at 80 ° C. for 1 hour and then calcined at 500 ° C. for 2 hours to prepare a powder composed of BiVO 4 particles.
- the primary particle size of BiVO 4 particles was about 70 nm.
- the primary particle size of BiVO 4 particles was about 200 nm.
- the primary particle size of BiVO 4 particles was about 2000 nm.
- Tungsten Oxide Tungsten oxide
- WO 3 Tungsten oxide
- Each photocatalyst for hydrogen generation (rhodium-doped strontium titanate, or chromium and tantalum) prepared as described above in a glass flask with a supported Pyrex (registered trademark) window by the photoreduction method of ruthenium promoter to doped strontium titanate 0.1 g of doped strontium titanate particles, 0.2 g of an aqueous solution containing 1 wt% of ruthenium chloride n-hydrate (manufactured by Wako Pure Chemical Industries) as a promoter material, and 10 vol% of methanol as an oxidative sacrificial reagent 200 mL of ultrapure water was added.
- rhodium-doped strontium titanate particles (1) supporting 1 wt% of ruthenium, which is a photocatalyst for hydrogen generation, with respect to 0.4 g of this organic vehicle solution and 0.2 g of ⁇ -terpineol, and for oxygen generation For screen printing containing a composite photocatalyst by manually mixing 0.1 g of bismuth vanadate particles (1-3) or tungsten oxide particles (4) as photocatalyst particles in the combination shown in Table 2 in a mortar for 3 hours. A paste was prepared.
- Example 6 A composite of 0.1 g of the screen printing paste prepared in Example 3 and 0.9 g of ethanol was dropped on a circular quartz glass fiber filter (Whatman) having a diameter of 47 mm while being filtered. The photocatalyst was adsorbed. Then, the photocatalyst material which carried the said composite photocatalyst on the glass fiber filter was baked at 350 degreeC for 30 minutes, and was produced.
- Example 7 A composite photocatalyst is obtained by performing suction filtration while dropping 0.1 g of the screen printing paste prepared in Example 3 and 0.9 g of ethanol onto an anodized alumina filter (manufactured by Whatman) having a diameter of 47 mm. Was adsorbed. Then, the photocatalyst material which carried the said composite photocatalyst on the anodic oxidation alumina filter by baking at 350 degreeC for 30 minutes was produced.
- the photograph by the scanning electron microscope observation of the obtained photocatalyst material is shown in FIG. (A) is the photograph which observed the surface of the photocatalyst material, (B) is the photograph which observed the cross section of the photocatalyst material.
- the thickness of the photocatalyst layer was measured from a photograph of the cross section of each photocatalyst material obtained by observation with a scanning electron microscope.
- the thicknesses of the photocatalyst layers of Examples 1 to 5 were measured at a magnification of 2000 times.
- the thickness of the photocatalyst layer of Examples 6 and 7 was measured at a magnification of 10,000 times.
- the thickness of the photocatalyst layer was measured as the height from the substrate surface to the top of the photocatalyst layer. The results were as shown in Table 2.
- the average pore diameter in the photocatalyst layer of each photocatalyst material was measured by the following procedure using a nitrogen adsorption / desorption measurement method.
- the screen printing paste prepared above was formed on a borosilicate glass substrate by screen printing with a coating thickness of 120 ⁇ m and an area of 8 cm ⁇ 8 cm.
- the photocatalyst material for visible light response type water splitting for an average pore diameter measurement was produced by baking at 450 degreeC for 30 minutes.
- the photocatalyst material obtained after firing was separated from the borosilicate glass substrate using a resin squeegee, and the photocatalyst layer was recovered as a powder.
- This powder 0.1 g was analyzed by BJH method using a nitrogen adsorption / desorption measuring device (“BELSORP-mini” manufactured by Nippon Bell) to obtain a nitrogen adsorption / desorption isotherm by nitrogen gas.
- the hole diameter was obtained.
- Plot volume distribution was obtained by plotting the Log differential pore volume against the obtained pore diameter. In this pore volume distribution, the pore diameter at the peak position was determined as the average pore diameter in each photocatalyst layer. The results were as shown in Table 2.
- Adhesion test Mending tape (manufactured by Sumitomo 3M, thickness 63 ⁇ m) was stuck on the photocatalyst layer provided on the substrate, and the adhesion between the substrate and the photocatalyst layer was evaluated by a tape peeling test in which the tape was peeled off.
- the evaluation method was as follows. That is, the mending tape was stuck on the photocatalyst layer, and the finger was slid 5 times while pressing the tape with the belly of the finger. After 10 seconds, the tape was peeled off at once.
- the criteria for determination were as follows. The results were as shown in Table 2.
- ⁇ The photocatalyst layer remained on the substrate after the tape was peeled
- x The photocatalyst layer was completely peeled from the substrate after the tape was peeled off
- a photocatalyst material is introduced into a separable glass flask with a window made of Pyrex (registered trademark), and 200 ml of ultrapure water is added to the reaction solution. It was. The glass flask containing the reaction solution was attached to a closed circulation device, and the atmosphere in the reaction system was replaced with argon. Then, visible light was irradiated from the Pyrex (registered trademark) window side by a 300 W xenon lamp (manufactured by Cermax, PE-300BF) equipped with a UV cut filter (L-42, manufactured by HOYA).
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Abstract
Description
本明細書において、「可視光」とは、人間の目で視認可能な波長の電磁波(光)を意味する。好ましくは、波長380nm以上の可視光線を含む光、より好ましくは、波長420nm以上の可視光線を含む光を意味する。また、可視光線を含む光としては、太陽光、集光してエネルギー密度を高めた集光太陽光、あるいはキセノンランプ、ハロゲンランプ、ナトリウムランプ、蛍光灯、発光ダイオード等の人工光源を光源として用いることが可能である。好ましくは、地球上に無尽蔵に降り注いでいる太陽光を光源として用いることが可能である。これにより、太陽光線の60%以上を占める可視光線を利用可能であるので、水から水素及び酸素を取り出せる指標となるエネルギー変換効率を高めることが可能となる。
本発明による複合光触媒は、一次粒子径が100nm以下である、可視光による水の光分解反応により水素を発生可能な光触媒粒子と、可視光による水の光分解反応により酸素を発生可能な光触媒粒子とを含み、水素発生用可視光応答型光触媒粒子と酸素発生用可視光応答型光触媒粒子とが互いに接触している複合光触媒である。本発明による複合光触媒、好ましくは水分解用可視光応答型複合光触媒(以下、これらを単に「複合光触媒」ともいう。)によれば、一次粒子径が100nm以下である微細な水素発生用可視光応答型光触媒粒子(以下、単に「水素発生用光触媒粒子」ともいう。)を用いているため、水の完全光分解反応において律速となる水素発生用の光分解反応の効率を高めることが可能となる。また、本発明による複合光触媒は、このような水素発生能の高い水素発生用光触媒粒子と酸素発生用可視光応答型光触媒粒子(以下、単に「酸素発生用光触媒粒子」ともいう。)とを接触させて用いているため、これら2種の光触媒各々の能力を有効に発揮させることが可能となる。その結果、水の完全光分解を高い効率で実現することができる。
本発明による複合光触媒にあっては、これに含まれる水素発生用光触媒粒子と酸素発生用光触媒粒子同士が接触していることで、これら2つの粒子間の荷電キャリア(電子および正孔)の移動が可能となる。水分解反応は、具体的には以下のように起こると考えられるが、本発明はこれに限定されるものではない。
本発明による複合光触媒にあっては、水素発生用光触媒粒子と酸素発生用光触媒粒子とが互いに接触しているが、この接触の状態として、水素発生用光触媒粒子の励起正孔と酸素発生用光触媒粒子の励起電子による電荷再結合反応が起こり得る状態であればよい。接触状態の具体例としては、物理的に接触している状態、化学的に結合して接触している状態、これら2つの状態が共に形成されている状態が挙げられる。
本発明による複合光触媒の製造方法は、水素発生用光触媒粒子の励起正孔と酸素発生用光触媒粒子の励起電子との電荷再結合反応が粒子界面において起こり得る状態を実現し得る工程を含むものであれば特に限定されない。この電荷再結合反応が起こり得る状態を実現するため、本発明による複合光触媒は水素発生用光触媒粒子と酸素発生用光触媒粒子とが互いに接触している。
本発明による複合光触媒に含まれる水素発生用光触媒粒子は、一次粒子径が100nm以下である。また、可視光照射により水を分解して水素を生成可能なものであり、酸素発生用光触媒粒子と接触させて用いるものである。
本発明による複合光触媒に含まれる水素発生用光触媒粒子の一次粒子径は100nm以下であり、好ましくは70nm以下である。このような微細な粒径を有することで、水素発生用光触媒粒子の単位重量当たりの水と接触可能な表面積が大きくなる。これにより、水の還元反応サイトが増加し、その結果、高効率な水素発生が可能となる。
本発明による複合光触媒に含まれる水素発生用光触媒粒子は、高い結晶性、かつ微細な一次粒子径を有する。これにより、主に酸素欠陥準位が起点となる水素発生用光触媒粒子内での励起正孔と励起電子の再結合反応を抑制することが可能となる。その結果、水素発生用光触媒粒子の励起電子による水の還元、および水素発生用光触媒粒子の励起正孔と水素発生用光触媒粒子の励起電子の粒子界面での電荷再結合反応が促進されることで、効率的な水分解反応が可能となる。
本発明の好ましい態様によれば、本発明による複合光触媒に含まれる水素発生用光触媒粒子を用いて水を光分解する場合、水素発生用光触媒粒子表面に助触媒を担持させる。これにより、水素の発生が速やかに起こる。
本発明による複合光触媒に含まれる水素発生用光触媒粒子としてのロジウムドープチタン酸ストロンチウム(Rh−SrTiO3)粒子は、高い結晶性、かつ微細な一次粒子径を有する。
本発明による複合光触媒に含まれる水素発生用光触媒粒子としてのロジウムドープチタン酸ストロンチウム粒子は、微細な一次粒子径を有している。一次粒子径は、70nm以下であることが好ましい。これにより、ロジウムドープチタン酸ストロンチウム粒子は高い比表面積を有することができる。また、分解対象物質との接触面積が増加し、粒子の光触媒活性が向上する。好ましい一次粒子径は50nm以下である。より好ましい一次粒子径は30nm以上70nm以下である。さらにより好ましい一次粒子径は30nm以上50nm以下である。ロジウムドープチタン酸ストロンチウム粒子の一次粒子径は、既に述べた評価方法により測定することができる。
本発明による複合光触媒に含まれる水素発生用光触媒粒子としてのロジウムドープチタン酸ストロンチウム粒子は、比表面積が大きいものである。本発明においては、ロジウムドープチタン酸ストロンチウム粒子のRSP値を指標として用いることで、表面積の大きいロジウムドープチタン酸ストロンチウム粒子又はこれが集合した多孔質度の高い粉体(二次粒子)を示すことが可能となった。
RSP=(Rb−Rav)/Rb (1)
ここで、Ravは、平均緩和時定数である。緩和時定数は、粒子が水に分散している際に表面に接触あるいは吸着している水の緩和時間の逆数である。平均緩和時定数は得られた緩和時定数を平均した値である。
Rbは、粒子が含まれていないブランクの水の緩和時定数である。
本発明による複合光触媒に含まれる水素発生用光触媒粒子としてのロジウムドープチタン酸ストロンチウムの組成は、SrTi1−xRhxO3で表わすことができる。ロジウムドープチタン酸ストロンチウム粒子の、M(ロジウム)/M(チタン+ロジウム)で表わされるモル比率は、0.001~0.03であることが好ましく、より好ましくは、0.01~0.03である。モル比率をこの範囲とすることで、結晶中の酸素欠陥量の増加を抑制し、高い光触媒活性を実現することが可能である。
本発明による複合光触媒に用いられる水素発生用光触媒粒子としてのロジウムドープチタン酸ストロンチウム粒子の製造方法として、湿式反応法を利用することが可能である。湿式反応法としては、ゾル−ゲル法、錯体重合法、水熱反応法等が挙げられる。例えば、ゾル−ゲル法による製造方法は、チタンのアルコキシドやチタンの塩化物を原料として用いる。この原料と水との加水分解反応によりチタンを含む水酸化物を生成させる。この水酸化物を600℃以上で焼成し、結晶化させることでロジウムドープチタン酸ストロンチウム粒子を得ることができる。
本発明による複合光触媒に含まれる水素発生用光触媒粒子としてのロジウムドープチタン酸ストロンチウム粒子の製造方法として、ストロンチウムイオン、チタンイオン、ロジウムイオンを含む水溶液を用いた熱分解法(水溶液熱分解法)を好ましく用いることが可能である。「水溶液熱分解法」とは、金属含有前駆体を原料として用い、この金属含有前駆体を含む水溶液を加熱することで、溶媒である水の蒸発に伴い、金属含有前駆体同士の脱水重縮合反応を起こす方法である。水との加水分解反応が速やかに起こる金属化合物(例えば、金属のアルコキシドや金属の塩化物等)を用いるゾル−ゲル法では、金属含有前駆体同士の加水分解により金属水酸化物が生成し、これらの脱水重縮合が速やかに起こることで、結晶核が粗大化しやすい。これに対して、水溶液熱分解法では、加水分解反応が緩やかな金属含有前駆体を原料として用いることで、水への安定な溶解が可能となる。また、このような金属含有前駆体を含む水溶液を加熱することで、溶媒である水の蒸発に伴い、金属含有前駆体同士の脱水重縮合反応が緩やかに起こり得る。これにより、熱分解時の結晶核の生成速度が遅くなり、結果的に結晶核の微細化が可能となる。
本発明による複合光触媒に含まれる酸素発生用光触媒粒子は、可視光照射により水を分解して酸素を生成可能なものであり、水素発生用光触媒粒子と接触させて用いるものである。
本発明による複合光触媒に含まれる酸素発生用光触媒粒子の一次粒子径は、好ましくは500nm以下であり、より好ましくは200nm以下であり、さらにより好ましくは100nm以下であり、最も好ましくは70nm以下である。このような微細な粒径を有することで、酸素発生用光触媒粒子の単位重量当たりの水と接触可能な表面積が大きくなる。これにより、水の酸化反応サイトが増加し、その結果、高効率な酸素発生が可能となる。
本発明による複合光触媒に用いられる酸素発生用光触媒粒子は、高い結晶性、かつ微細な一次粒子径を有する。これにより、主に酸素欠陥準位が起点となる酸素発生用光触媒粒子内での励起正孔と励起電子の再結合反応を抑制することが可能となる。その結果、酸素発生用光触媒粒子の励起正孔による水の酸化、および酸素発生用光触媒粒子の励起電子と水素発生用光触媒粒子の励起正孔の粒子界面での電荷再結合反応が促進されることで、効率的な水分解反応が可能となる。
本発明による複合光触媒に含まれる酸素発生用光触媒粒子の製造方法は、ゾル−ゲル法、錯体重合法、水熱反応法等、各種湿式反応法を用いることができる。例えば、湿式反応法の1つであるゾル−ゲル法による製造方法としては、金属アルコキシドや金属塩化物を原料として、水との加水分解反応により金属水酸化物を生成し、これを600℃以上で焼成することにより、結晶化させる方法がある。
本発明による光触媒材は、基材と、当該基材に固定化されてなる光触媒層とを含んでおり、光触媒層が、一次粒子径が100nm以下である水素発生用光触媒粒子と、酸素発生用光触媒粒子を含み、前記水素発生用可視光応答型光触媒粒子と前記酸素発生用可視光応答型光触媒粒子とが互いに接触しているものである。本発明による光触媒材に含まれる光触媒層は、一次粒子径の小さい微細な構造の水素発生用光触媒粒子と酸素発生用光触媒粒子とを含み、これら微細粒子が集合して形成された集合体として存在する。このため、光触媒層の空隙率は高くなり、すなわち多孔質度は高くなり、光触媒層の比表面積は大きくなる。その結果、元々高い光触媒活性を有する水素発生用光触媒粒子と酸素発生用光触媒粒子とが集合して形成された光触媒層の光触媒活性は低くならない活性が発揮される。
本発明による光触媒材に含まれる基材は、焼成により光触媒層を固定化し得るものであれば特に限定されず用いることができる。基材の具体例としては、250℃以上の加熱によっても分解しない無機物が好ましい。さらに好ましくは、300℃以上の加熱によっても分解しない無機物である。さらに具体的には、無機酸化物あるいは金属を好ましく用いることができる。より具体的には、ガラス(ソーダライムガラス、ホウケイ酸ガラス)、石英、酸化アルミニウム(アルミナ)、セラミックス等の無機酸化物や、チタン、アルミニウム、鉄、ステンレス等の金属を好ましく用いることができる。より好ましくは、ガラス、アルミナ、石英から選ばれる少なくとも1種である。
本発明による光触媒材の製造方法は、基材に水素発生用光触媒粒子と酸素発生用光触媒粒子を固定化し得る工程を含むものであれば特に限定されない。本発明の好ましい態様によれば、本発明による光触媒材の製造方法は、水素発生用光触媒粒子と酸素発生用光触媒粒子とが接触している複合光触媒を湿式分散させたスラリーを、基材に塗布して、乾燥および焼成する方法である。
本発明による水分解用光触媒モジュールは、前記光触媒材を含む。本発明の好ましい態様によれば、本発明による水分解用光触媒モジュールは、概ね透明な光入射面を有し、モジュール内部に設置した光触媒材に光が入射する構造を有し、かつ光触媒材が常に水と接触可能なように、水を封入可能な密閉パネル形状を有するものである。また、本発明のより好ましい態様によれば、本発明による水分解用光触媒モジュールは、水分解反応の進行により減少する水を遂次的に追加供給可能な通水孔等の機構をさらに有することが好ましい。このような構成の水分解光触媒モジュールとすることで、実用的に利用可能な水素を製造することが可能となる。
本発明による水素製造システムは、前記水分解用光触媒モジュールを含む。本発明の好ましい態様によれば、本発明による水素製造システムは、水の供給装置、水中の不純物をある程度除去するためのろ過装置、水分解光触媒モジュール、水素分離装置、および水素貯蔵装置からなるものである。このような構成の水素製造システムとすることで、再生可能エネルギーである太陽光と水から水素を実用的に製造可能なシステムを実現することが可能となる。
20mLサンプル瓶に、疎水性錯化剤としてアセチルアセトン(和光純薬製)0.02mol(2.003g)を添加し、室温で撹拌しながら、チタンテトライソプロポキシド(和光純薬製)0.02mol(5.684g)を添加して、黄色の水溶性チタン−アセチルアセトン錯体を含む溶液を調製した。この水溶性チタン−アセチルアセトン錯体を含む溶液を、0.32mol/Lの酢酸水溶液50mLに、室温で攪拌しながら添加した。添加後、室温で約1時間攪拌を行い、更に60℃で約1時間撹拌を行うことで、黄色透明な水溶性チタン錯体を含む水溶液を調製した。
固相反応法によりロジウムドープチタン酸ストロンチウムを作製した。具体的には、炭酸ストロンチウム(関東化学製)、酸化チタン(添川理化学製、ルチル型)、および酸化ロジウム(Rh2O3:和光純薬製)の各粉末を、Sr:Ti:Rh=1.07:0.98:0.02のモル比率となるように混合し、1000℃で10時間焼成した。
20mLサンプル瓶に、疎水性錯化剤としてアセチルアセトン(和光純薬製)0.02mol(2.003g)を添加し、室温で撹拌しながら、チタンテトライソプロポキシド(和光純薬製)0.02mol(5.684g)を添加して、黄色の水溶性チタン−アセチルアセトン錯体を含む溶液を調製した。この水溶性チタン−アセチルアセトン錯体を含む溶液を、0.32mol/Lの酢酸水溶液50mLに、室温で攪拌しながら添加した。添加後、室温で約1時間攪拌を行い、更に60℃で約1時間撹拌を行うことで、黄色透明な水溶性チタン錯体を含む水溶液を調製した。
20mLサンプル瓶に、水10gと錯化剤であるL−(+)酒石酸(和光純薬製)0.0017mol(0.2536g)を添加し、室温で撹拌しながら、メタバナジン酸アンモニウム(アルドリッチ製)0.0017mol(0.20g)を添加し、50℃で1時間撹拌して、赤茶色透明な水溶性バナジウム錯体を含む水溶液を調製した。また、20mLサンプル瓶に、水10gと、錯化剤であるエチレンジアミン四酢酸(和光純薬製)0.017mol(0.494g)を添加し、25%アンモニア水を1g滴下して水に溶解させた後、室温で撹拌しながら、硝酸ビスマス五水和物(和光純薬製)0.0017mol(0.82g)を添加し、室温で1時間撹拌して、無色透明な水溶性ビスマス錯体を含む水溶液を作製した。
100mLサンプル瓶に、0.5M硝酸水溶液50gを添加して、硝酸ビスマス五水和物(和光純薬製)0.0016mol(0.75g)と、メタバナジン酸アンモニウム(アルドリッチ製)0.0016mol(0.14g)を添加し、25℃において2日間マグネティックスターラーで撹拌を行い、黄色懸濁液を作製した。この黄色懸濁液を、遠心分離により、固形分を回収し、45℃で3時間乾燥させることで、BiVO4粒子からなる粉末を作製した。
固相反応法によりBiVO4粒子からなる粉末を作製した。具体的には、酸化ビスマス(和光純薬製)、五酸化バナジウム(和光純薬製)の各粉末を、Bi:V=1:1のモル比率となるように混合し、700℃で8時間焼成し、BiVO4粒子からなる粉末を作製した。
酸化タングステン(WO3)(和光純薬製)を準備した。この酸化タングステンは、X線回折測定を行った結果、単相の単斜晶構造を有することが確認された。また、走査型電子顕微鏡観察からWO3粒子の一次粒子径を算出した。その結果、一次粒子径は約200nmであった。
パイレックス(登録商標)製窓付きのガラスフラスコに、上記のとおり作製した各水素発生用光触媒(ロジウムドープチタン酸ストロンチウム、あるいは、クロム及びタンタルドープチタン酸ストロンチウム)粒子0.1gと、助触媒原料となる塩化ルテニウム・n水和物(和光純薬製)を1wt%含む水溶液0.2gと、酸化的犠牲試薬となるメタノールを10vol%含む超純水200mLを入れた。この溶液をスターラーで撹拌しながら、アルゴン雰囲気下で、UVカットフィルター(L−42、HOYA製)を装着した300Wキセノンランプ(Cermax製、PE−300BF)により、可視光をパイレックス(登録商標)製窓側から、3時間照射することで、水素発生用光触媒粒子表面で塩化ルテニウムを還元して、ルテニウム微粒子を1wt%表面に担持させた水素発生用光触媒粒子をそれぞれ作製した。さらに、このルテニウム担持水素発生用光触媒粒子を、200℃で2時間、水素気流中で焼成することで、ルテニウムの完全還元を実施した。
実施例1~7、および比較例1
ルテニウムを1wt%担持させたロジウムドープチタン酸ストロンチウム粒子(1および2)あるいはルテニウムを1wt%担持させたクロム及びタンタルドープチタン酸ストロンチウム粒子(3)と、バナジン酸ビスマス粒子(1~3)あるいは酸化タングステン粒子(4)を、表1に示す組合せで、かつ同表に示す重量ずつ、蒸留水0.5gに懸濁させて、超音波照射処理を5分行うことで、各粒子がほぼ一次粒子の状態で湿式分散したスラリーを作製した。その後、乳鉢で手動混練しながら、溶媒となる水を徐々に蒸発させて、水素発生用光触媒粒子と酸素発生用光触媒粒子が接触した複合光触媒粒子を作製した。その後、表1に示す温度で焼成することで、実施例1~7、および比較例1各々の複合光触媒を作製した。
パイレックス(登録商標)製窓付きのガラスフラスコに、複合光触媒0.05gと超純水200mlを入れて、反応溶液とした。そして、この反応溶液を入れたガラスフラスコを閉鎖循環装置に装着し、反応系内の雰囲気をアルゴン置換した。そして、UVカットフィルター(L−42、HOYA製)を装着した300Wキセノンランプ(Cermax製、PE−300BF)により、可視光をパイレックス(登録商標)製窓側から照射した。そして、光触媒反応により、水が還元されて生成した水素の発生量を、ガスクロマトグラフ(島津製作所製、GC−8A、TCD検出器、MS−5Aカラム)により経時的に調べ、照射開始後、3時間評価を行った。結果は表1に示されるとおりであった。
実施例1~5、および比較例1、2
α−テルピネオール(関東化学製):2−(2−ブトキシエトキシ)エタノール(和光純薬製):ポリビニルブチラール(東京化成製、分子量600)=65:15:20(重量比)となるように混合し、ガラス製密閉容器中で、60℃で15時間加熱することで、有機ビヒクル溶液を作製した。この有機ビヒクル溶液0.4gと、α−テルピネオール0.2gに対して、水素発生用光触媒粒子であるルテニウムを1wt%担持させたロジウムドープチタン酸ストロンチウム粒子(1)0.1gと、酸素発生用光触媒粒子であるバナジン酸ビスマス粒子(1~3)あるいは酸化タングステン粒子(4)0.1gを、表2に示す組合せで、3時間乳鉢にて手動混合することで、複合光触媒を含むスクリーン印刷用ペーストを作製した。このスクリーン印刷用ペーストを用いて、ホウケイ酸ガラス基板(5cm×5cm×1mm厚)に設けられた4cm×4cmの開口部に、表2に示す塗布厚となるように、スクリーン印刷法で塗布した。その後、60℃で1時間乾燥させた後、450℃で30分焼成することで、実施例1~5、および比較例1、2各々の可視光応答型水分解用光触媒材を作製した。
上記実施例3で作製したスクリーン印刷用ペースト0.1gとエタノール0.9gを混合したものを、直径47mmの円形石英ガラス繊維フィルター(Whatman製)に滴下しながら、吸引ろ過を行うことで、複合光触媒を吸着させた。その後、350℃で30分焼成することで、上記複合光触媒をガラス繊維フィルターに担持させた光触媒材を作製した。
上記実施例3で作製したスクリーン印刷用ペースト0.1gとエタノール0.9gを混合したものを、直径47mmの陽極酸化アルミナフィルター(Whatman製)に滴下しながら、吸引ろ過を行うことで、複合光触媒を吸着させた。その後、350℃で30分焼成することで、上記複合光触媒を陽極酸化アルミナフィルターに担持させた光触媒材を作製した。得られた光触媒材の走査型電子顕微鏡観察による写真を図3に示す。(A)は光触媒材の表面を観察した写真であり、(B)は光触媒材の断面を観察した写真である。
得られた各光触媒材断面の走査型電子顕微鏡観察による写真から、光触媒層の厚みを測定した。実施例1~5の光触媒層の厚みは倍率2000倍で測定した。また、実施例6及び7の光触媒層の厚みは、倍率10000倍により測定した。ここで、光触媒層の厚みは基材表面から光触媒層の最上部までの高さとして測定した。結果は表2に示されるとおりであった。
各光触媒材の光触媒層における平均細孔径の測定は、窒素吸脱着測定法を用いて以下の手順で行った。まず、上記で作製したスクリーン印刷用ペーストをホウケイ酸ガラス基板上に、塗布厚120μmで、8cm×8cmの面積で、スクリーン印刷により製膜した。そして、60℃で1時間乾燥させた後、450℃で30分焼成することで、平均細孔径測定のための可視光応答型水分解用光触媒材を作製した。焼成後に得られた光触媒材を、樹脂製スキージを用いて、光触媒層のみホウケイ酸ガラス基板から剥離させ、光触媒層を粉体として回収した。この粉体0.1gを、窒素吸脱着測定装置(日本ベル製、“BELSORP−mini”)を用いて、窒素ガスによる窒素吸脱着等温線を求めて、BJH法による解析を行うことで、細孔直径を得た。この得られた細孔直径に対するLog微分細孔容積をプロットすることにより、細孔容積分布を得た。この細孔容積分布において、ピーク位置の細孔直径を、各光触媒層における平均細孔径として求めた。結果は表2に示されるとおりであった。
メンディングテープ(住友3M製、厚み63μm)を基板上に設けられた光触媒層上に張り付けて、テープを剥離するテープ剥離試験により、基板と光触媒層との密着性を評価した。評価方法は以下のとおりとした。すなわち、メンディングテープを光触媒層上に張り付け、指の腹でテープを押しつけながら指を5往復摺動させた。10秒後に、テープを一気に剥離させた。なお、判定基準は以下のとおりとした。結果は表2に示されるとおりであった。
○:テープ剥離後、基材に光触媒層が残存していた
×:テープ剥離後、基材から完全に光触媒層が剥離された
パイレックス(登録商標)製窓付きのセパラブルガラスフラスコに、光触媒材を導入し、超純水200mlを入れて、反応溶液とした。そして、この反応溶液を入れたガラスフラスコを閉鎖循環装置に装着し、反応系内の雰囲気をアルゴン置換した。そして、UVカットフィルター(L−42、HOYA製)を装着した300Wキセノンランプ(Cermax製、PE−300BF)により、可視光をパイレックス(登録商標)製窓側から照射した。そして、光触媒反応により、水が還元されて生成する水素の発生量を、ガスクロマトグラフ(島津製作所製、GC−8A、TCD検出器、MS−5Aカラム)により経時的に調べ、照射開始後、3時間評価を行った。結果は表2に示されるとおりであった。
2 酸素発生用光触媒粒子
3 粒子間空隙
4 基材
5 厚み
Claims (17)
- 一次粒子径が100nm以下である水素発生用可視光応答型光触媒粒子と、酸素発生用可視光応答型光触媒粒子とを含み、前記水素発生用可視光応答型光触媒粒子と前記酸素発生用可視光応答型光触媒粒子とが互いに接触している、複合光触媒。
- 前記水素発生用可視光応答型光触媒粒子が、その表面に水素発生用助触媒が担持されてなるものである、請求項1に記載の複合光触媒。
- 前記酸素発生用可視光応答型光触媒粒子の一次粒子径が500nm以下である、請求項1または2に記載の複合光触媒。
- 前記水素発生用可視光応答型光触媒粒子の一次粒子径が70nm以下である、請求項1~3のいずれか一項に記載の複合光触媒。
- 前記水素発生用可視光応答型光触媒粒子が、ロジウムドープチタン酸ストロンチウム粒子である、請求項1~4のいずれか一項に記載の複合光触媒。
- 前記ロジウムドープチタン酸ストロンチウム粒子が、拡散反射スぺクトルにより測定される、波長570nmにおける光吸収率が0.6以上であり、かつ、波長1800nmにおける光吸収率が0.7以下である、請求項5に記載の複合光触媒。
- 前記ロジウムドープチタン酸ストロンチウム粒子の、M(ロジウム)/M(チタン+ロジウム)で表わされるモル比率が0.001~0.03である、請求項5または6に記載の複合光触媒。
- 前期ロジウムドープチタン酸ストロンチウムが、チタン化合物と、ストロンチウム化合物と、疎水性錯化剤とを水に溶解させた水溶液を用意し、これを乾燥および焼成することにより製造されるものである、請求項5~7のいずれか一項に記載の複合光触媒。
- 前記酸素発生用可視光応答型光触媒粒子が、WO3、BiVO4、Fe2O3、Bi2WO6、TaON、Ta3N5、BaTaO2NおよびLaTiO2Nから選ばれる少なくとも1種である、請求項1~8のいずれか一項に記載の複合光触媒。
- 前記酸素発生用可視光応答型光触媒粒子が、WO3、BiVO4およびFe2O3から選ばれる少なくとも1種である、請求項1~8のいずれか一項に記載の複合光触媒。
- 可視光による水の光分解反応に用いられる、請求項1~10のいずれか一項に記載の複合光触媒。
- 基材と、当該基材に固定化されてなる光触媒層とを含んでなる光触媒材であって、
前記光触媒層が、一次粒子径が100nm以下である水素発生用可視光応答型光触媒粒子と、酸素発生用可視光応答型光触媒粒子とを含み、前記水素発生用可視光応答型光触媒粒子と前記酸素発生用可視光応答型光触媒粒子とが互いに接触している、光触媒材。 - 前記光触媒層の細孔径が、20nm以上100nm以下である、請求項12に記載の光触媒材。
- 前記基材が、250℃以上の加熱によって分解されない無機物からなるものである、請求項12又は13に記載の光触媒材。
- 可視光による水の光分解反応に用いられる、請求項12~14のいずれか一項に記載の光触媒材。
- 請求項15に記載の光触媒材を含んでなる、水分解用光触媒モジュール。
- 請求項16に記載の水分解用光触媒モジュールを含んでなる、水素製造システム。
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JP2015112501A (ja) * | 2013-12-06 | 2015-06-22 | 株式会社 グリーンケミー | 可視光領域応答触媒体とこれを利用した水の分解方法 |
JP2015217373A (ja) * | 2014-05-21 | 2015-12-07 | 国立大学法人山梨大学 | 光触媒組成物及びその製造方法 |
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JPWO2014046305A1 (ja) | 2016-08-18 |
US20150251172A1 (en) | 2015-09-10 |
CN104755166A (zh) | 2015-07-01 |
EP2898951A4 (en) | 2016-05-25 |
JP5920478B2 (ja) | 2016-05-18 |
EP2898951A1 (en) | 2015-07-29 |
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