WO2008081957A1 - Procédé de fabrication d'oxyde de titane à soufre introduit, à teneur en métal, et oxyde de titane à soufre introduit à teneur en métal - Google Patents

Procédé de fabrication d'oxyde de titane à soufre introduit, à teneur en métal, et oxyde de titane à soufre introduit à teneur en métal Download PDF

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WO2008081957A1
WO2008081957A1 PCT/JP2007/075344 JP2007075344W WO2008081957A1 WO 2008081957 A1 WO2008081957 A1 WO 2008081957A1 JP 2007075344 W JP2007075344 W JP 2007075344W WO 2008081957 A1 WO2008081957 A1 WO 2008081957A1
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metal
sulfur
titanium oxide
titanium salt
compound
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PCT/JP2007/075344
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English (en)
Japanese (ja)
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Daisuke Taki
Taichi Tanaka
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Toho Titanium Co., Ltd
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Publication of WO2008081957A1 publication Critical patent/WO2008081957A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J35/39—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/007—Titanium sulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/12—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to a method for producing a metal-containing sulfur-introduced titanium oxide used for a visible light photocatalyst, a photosensitized solar cell, or the like.
  • Titanium oxide powder has long been used as a white pigment. In recent years, it has been used as an ultraviolet shielding material for cosmetics, photocatalysts, capacitors, thermistors, or sintered materials used in electronic materials such as raw materials for barium titanate. Recently, research and development of application of dye-sensitized titanium oxide to electrodes, etc. has been made. In particular, in recent years, the use as a photocatalyst has been actively attempted, and the use development of the photocatalytic reaction has been actively conducted. This titanium oxide photocatalyst has a wide variety of uses. Generation of hydrogen by water decomposition, synthesis of organic compounds using redox reaction, exhaust gas treatment, air purification, deodorization, sterilization, antibacterial, water treatment, lighting. Numerous applications have been developed, such as preventing contamination of equipment.
  • titanium oxide shows a large refractive index in the wavelength region near visible light, light absorption hardly occurs in the visible light region.
  • most of the spectrum of fluorescent lamps is 400 nm or more, so it is not possible to develop sufficient characteristics as a photocatalyst. In view of this, the development of more highly active photocatalysts that can exhibit catalytic activity in the visible light region is underway.
  • Patent Document 1 JP 2004-1 4 30 3 2 (Claims)
  • Patent Document 2 JP 2006-8 20 7 1 (Claims) According to the production method described in the examples of JP-A-2006-6-2071, there is a problem in that sulfur-containing titanium oxide having sufficient photocatalytic activity cannot be obtained.
  • an object of the present invention is to describe a metal-containing sulfur-introduced titanium oxide (hereinafter referred to as a metal-containing sulfur-introduced titanium oxide) having a high photocatalytic activity under visible light. ) And a metal-containing sulfur-introduced titanium oxide. Disclosure of the invention
  • the present inventors have obtained a metal-containing sulfur-introduced titanium oxide depending on the time when the metal compound used for introducing the metal is contained in the titanium oxide.
  • a difference in the photocatalytic activity of the titanium salt Specifically, before calcining the mixture of the hydrolyzate or alkali neutralized product of the titanium salt and the sulfur compound, the hydrolyzed product or alkali neutralized product of the titanium salt. It has been found that a metal-containing sulfur-introduced titanium oxide having high photocatalytic activity can be obtained by previously containing a metal in the product, and the present invention has been completed.
  • the present invention (1) has a firing step of firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and the metal content in the metal-containing material titanium oxide is , With respect to 10 parts by mass of the metal-containing raw material titanium oxide when converted to ⁇ io 2 , the metal atom is 0.03 to 0.15 parts by mass,
  • the present invention provides a method for producing a metal-containing sulfur-introduced titanium oxide characterized by the following.
  • the present invention (2) includes a baking raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed Z alkali neutralized product and a sulfur compound, the metal-containing titanium salt hydrolyzed Z alkali neutralized product and the sulfur Calcining a mixture with the compound to obtain a metal-containing sulfur-introduced titanium oxide, and
  • the calcining raw material mixture preparation step comprises hydrolyzing Z-al strength re-neutralization treatment to prepare a slurry containing titanium salt hydrolyzed Z-al strength neutralized product by hydrolyzing or neutralizing titanium salt.
  • the amount of the metal compound added in the stirring and mixing treatment of the metal compound is from 0.03 to 0.5 parts by weight as a metal atom with respect to 100 parts by mass of the titanium salt hydrolyzed neutralized product when converted to Ti 0 2 . 0.15 in an amount of 5 parts by mass,
  • the present invention provides a method for producing a metal-containing sulfur-introduced titanium oxide characterized by the following.
  • the present invention (3) includes a baking raw material mixture preparation step for obtaining a mixture of a heat-treated product of a metal-containing titanium salt hydrolyzed Z alkali neutralized product and a sulfur compound, Calcining the mixture of the heat-treated product and the sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and
  • the calcination raw material mixture preparation step comprises hydrolyzing / alkali neutralizing treatment to prepare a slurry containing titanium salt hydrolyzed / al strength neutralized product by hydrolyzing or neutralizing titanium salt.
  • Metal compound is added to slurry containing salt hydrolysis / alkali neutralized product and stirred to obtain metal-containing titanium salt hydrolyzed metal compound stirring and mixing treatment to obtain alkali-neutralized product, and the metal-containing titanium salt in alkali Heat treatment of a Japanese product to obtain a heat-treated product, and
  • the amount of the metal compound added in the stirring and mixing treatment of the metal compound is from 0.03 to 0.5 parts by weight as the metal atom with respect to 100 parts by mass of the hydrolyzed alkali salt of the titanium salt when converted to Ti 2 O 2 . 0.1 5 parts by mass, and mixing the sulfur compound between before the hydrolysis and alkali neutralization treatment and after the heat treatment,
  • the present invention provides a method for producing metal-containing sulfur-introduced titanium oxide.
  • the present invention (4) includes a calcining raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed / alkali neutralized product and a sulfur compound, Calcining the mixture with the sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and
  • hydrolysis and alkali neutralization treatment is performed by hydrolyzing or neutralizing titanium salt in the presence of a metal compound to obtain a metal-containing titanium salt hydrolyzed neutralized product.
  • a sulfur-containing compound is mixed between before the hydrolysis Z-al strength re-neutralization treatment and after the hydrolysis Z-al strength re-neutralization treatment.
  • a method for producing titanium oxide is provided.
  • the present invention (5) includes a baking raw material mixture preparation step for obtaining a mixture of a heat-treated product of metal-containing titanium salt hydrolyzed / alkali neutralized product and a sulfur compound, and a mixture of the heat-treated product and the sulfur compound. Firing step to obtain metal-containing sulfur-introduced titanium oxide, and
  • the firing raw material mixture preparation step comprises hydrolyzing or alkali neutralizing the titanium salt to obtain a titanium salt hydrolyzed Z alkali neutralized product. Heat-treating the metal-containing titanium salt hydrolysis alkali neutralized product to obtain a heat-treated product, and
  • the amount of the metal compound be present in the titanium salt hydrolysis / Al Chikarari neutralization process, with respect to the titanium salt 1 0 0 parts by weight when T i O 2 converted, 0.0 3 metal atom 0.15 in an amount of 5 parts by mass,
  • the present invention provides a method for producing metal-containing sulfur-introduced titanium oxide.
  • the present invention (6) includes a firing raw material mixture preparation step for obtaining a mixture of a metal-containing titanium salt hydrolyzed Z alkali neutralized product and a sulfur compound, Calcining the mixture with the sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and
  • the firing raw material mixture preparation step includes hydrolyzing or neutralizing the titanium salt in the presence of a metal compound to hydrolyze the metal-containing titanium salt. Hydrolysis to prepare re-neutralized product-containing slurry Z metal strength neutralization treatment and metal-containing titanium salt hydrolysis Add alkali metal neutralized product-containing slurry, stir, metal-containing titanium A salt hydrolysis Z-alkali neutralized product to obtain a metal compound stirring and mixing process,
  • the total amount of the metal compound to be present in the hydrolysis and Z-force neutralization treatment and the metal compound to be added in the metal compound stirring and mixing treatment is 100 parts by mass with respect to 100 parts by mass of ⁇ io 2
  • the amount of metal atoms is 0.03 to 0.15 parts by mass
  • the present invention provides a method for producing metal-containing sulfur-introduced titanium oxide.
  • the present invention (7) includes a calcined raw material mixture preparation step for obtaining a mixture of a heat-treated product of metal-containing titanium salt hydrolyzed / alkali neutralized product and a sulfur compound, and a mixture of the heat-treated product and the sulfur compound. Firing step to obtain metal-containing sulfur-introduced titanium oxide, and
  • the baking raw material mixture preparation step hydrolyzes or neutralizes the titanium salt to hydrolyze the metal-containing titanium salt hydrolyzed Z-alloy neutralized product-containing slurry.
  • Metal alkali-containing neutralization treatment, metal-containing titanium salt hydrolysis, alkali-neutralized product-containing slurry, a metal compound is added and stirred to obtain a metal-containing titanium salt hydrolysis alkali-neutralized metal compound stirring and mixing treatment, Hydrolysis of the metal-containing titanium salt, heat treatment of an alkali neutral to obtain a heat-treated product, and the metal compound and the metal to be present in the hydrolysis / al force neutralization treatment.
  • the total amount of the metal compound added in compound stirring and mixing process, with respect to the titanium salt 1 0 0 parts by weight when T i O 2 converted, 0 as the metal atom. 0 3-0. 1 5 parts by mass
  • the present invention provides a method for producing metal-containing sulfur-introduced titanium oxide.
  • the present invention (8) has a metal content of 0.03 to 0.15 mass%, a sulfur content of 0.02 to 0.1 mass%, and a specific surface area of 60 to 1 2 Om 2 Zg, the main component of the crystal structure is anatase-type titanium oxide, sulfur atoms in the titanium oxide are introduced into the titanium oxide titanium site, and the metal is contained on the surface and inside of the titanium oxide, A metal-containing sulfur-introduced titanium oxide is provided.
  • transduction titanium oxide can be provided.
  • the method for producing a metal-containing sulfur-introduced titanium oxide of the present invention includes a firing step of firing a mixture of a metal-containing raw material titanium oxide and a sulfur compound to obtain a metal-containing sulfur-introduced titanium oxide, and the metal-containing raw material oxidation wherein the metal content in the titanium and with respect to the metal-containing raw material titanium oxide 1 00 parts by weight when T i O 2 converted, 0. metal atom 0 3 to 0.1 5 it is parts by weight, the This is a method for producing a metal-containing sulfur-introduced titanium oxide.
  • the mass of the metal atom with respect to 100 parts by mass when converted to Ti 0 2 is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.
  • the mixing amount is 1 part by mass.
  • the method for producing a metal-containing sulfur-introduced titanium oxide according to the first aspect of the present invention comprises a metal-containing titanium salt hydrolyzed alkali neutralized product A and a sulfur compound. Firing raw material mixture preparation step A to obtain a mixture A and the metal-containing titanium salt hydrolysis alkali neutralized product A and the sulfur compound A are calcined to obtain a metal-containing sulfur-introduced titanium oxide.
  • the calcination raw material mixture preparation step A is hydrolyzed or neutralized with a titanium salt to hydrolyze a titanium salt hydrolyzed Z-alkaline neutralized product A-containing slurry. And a metal compound stirring and mixing treatment A to obtain a metal-containing titanium salt hydrolyzed Z Al power re-neutralized product A by adding a metal compound to the titanium salt hydrolyzed Z alkali neutral A-containing slurry and stirring.
  • hydrolysis or alkali neutralization is also referred to as “hydrolysis alkali neutralization”.
  • the metal-containing titanium salt hydrolyzed Z-al is obtained from the titanium salt by performing the hydrolysis Z-al strength neutralization treatment A and the metal compound stirring and mixing treatment A. Power neutralized product A is obtained.
  • the hydrolysis and alkali neutralization treatment A is performed.
  • the hydrolysis and alkali neutralization treatment A hydrolyzes the titanium salt.
  • the slurry containing the hydrolyzate A of the titanium salt or the neutral force neutralized product A of the titanium salt, ie, the titanium salt hydrolyzed Decomposition Alkali neutralized product A-containing slurry is prepared.
  • titanium salt relating to the hydrolysis / alternative neutralization treatment A examples include, for example, organometallic compounds such as titanium alkoxide, titanium chlorides such as titanium tetrachloride and titanium trichloride, titanyl sulfate, and titanium sulfate. And inorganic salts such as sulfates. Of these, titanium tetrachloride, titanyl sulfate, and titanium sulfate are preferred from the viewpoint of handling and economy.
  • the titanium salt may be hydrolyzed by preparing an aqueous solution in which the titanium salt is dissolved in water and heating the aqueous solution while stirring.
  • the hydrolysis temperature at the time of hydrolysis is preferably 20 ° C. to the boiling point of an aqueous solution, particularly preferably 40 to 80 ° C.
  • the hydrolysis time for the hydrolysis is usually 5 minutes to 10 hours, preferably 10 minutes to 5 hours, and particularly preferably 10 minutes to 1 hour.
  • the titanium salt is dissolved in water.
  • the solvent for dissolving the titanium salt is not particularly limited as long as it dissolves the metal compound.
  • organic solvents such as alcohol.
  • water is preferable from the viewpoint of easy handling and economical efficiency.
  • hydrolysis is preferably performed in a low pH region because a hydrolyzate having a small particle size can be obtained. Therefore, when performing hydrolysis in the hydrolysis Z alkali neutralization treatment A, especially when the hydrolysis temperature is near the boiling point of the aqueous solution. In view of reducing the pH of the reaction system, it is preferable to install a reflux device or the like in the reaction tank to suppress the generated hydrogen chloride from being discharged out of the reaction system as hydrogen chloride gas.
  • the titanium salt hydrolyzate is generated by hydrolyzing the titanium salt, and the titanium salt hydrolyzate is dispersed in an aqueous solvent.
  • the titanium salt hydrolyzate A-containing slurry is obtained.
  • the titanium salt hydrolyzate A is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide.
  • the titanium salt is neutralized by preparing an aqueous solution in which the titanium salt is dissolved in water. And the titanium salt and the alkali are brought into contact with each other. More specifically, for example,
  • the alkali related to the hydrolysis and alkali neutralization treatment A is not particularly limited, and examples thereof include ammonia and aqueous ammonia. Among these, ammonia or aqueous ammonia is contained in the metal-containing sulfur-introduced titanium oxide. Since a metal component derived from Al force is not contained, it is preferable for controlling the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light.
  • the alkali neutralization temperature during the alkali neutralization is preferably 10 to 80 ° C, particularly preferably 30 to 80 ° C, more preferably 4 0 ⁇ 70 ° C.
  • the addition time of the alkali at the time of alkali neutralization is usually 1 minute to 10 hours, preferably 3 minutes to 5 hours, particularly preferably 5 minutes to 1 hour.
  • the titanium salt alkali neutralized product is generated by neutralizing the titanium salt with an alkali force, and the titanium salt alkali force is neutralized in an aqueous medium.
  • the titanium salt aluminum neutralized product A-containing slurry in which the product is dispersed is obtained.
  • the titanium salt alkali neutralized product A is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide.
  • the metal compound stirring and mixing treatment A is performed.
  • the metal compound stirring and mixing treatment A is carried out by adding the metal compound to the titanium salt hydrolyzed Z alkali neutralized product A-containing slurry, and stirring and mixing the metal containing titanium salt hydrolyzed Z alkali neutralized product A. It is a process to obtain.
  • the titanium salt hydrolysis neutralized product A prepared in the hydrolysis Z alkali neutralization treatment A is used in the titanium salt hydrolysis alkali.
  • the metal compound is added to the slurry without separating the solvate A.
  • the metal compound related to the metal compound stirring and mixing treatment A may be any metal compound that dissolves uniformly in the slurry aqueous medium, and includes inorganic metal salts such as chlorides, sulfates and nitrates, or organic metal compounds. .
  • the metal species of the metal compound is preferably iron from the viewpoint that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the metal compound is preferably an inorganic metal salt, and is preferably an iron salt in that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • Examples include iron citrate, fermented ammonium iron, ferric ammonium sulfate, ammonium citrate, iron sulfide, iron phosphate, and ammonium iron oxalate.
  • the mixing amount of the metal compound can be appropriately selected depending on the amount of metal introduced into the metal-containing sulfur-introduced titanium oxide.
  • the mass of metal atoms with respect to 100 parts by mass in terms of T i O 2 is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.1 parts by mass. It is a mixing amount.
  • the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the stirring and mixing temperature at the time of stirring and mixing is preferably 20 to 803 ⁇ 4: particularly preferably 50 to 7, and the stirring and mixing time is preferably 1 to 2 hours.
  • the metal compound stirring and mixing treatment A the metal compound is dissolved in the solvent in the slurry by stirring and mixing in the slurry containing the titanium salt hydrolyzed alkali neutral A, and further stirred.
  • the metal compound is hydrolyzed, neutralized or reduced in the liquid content of the titanium salt hydrolyzed Z alkali neutralized product A-containing slurry, and converted into a hydroxide or an oxide.
  • the produced hydroxide or oxide adheres to the surface of the titan salt hydrolyzed neutralized product A or is taken into the inside. Thereby, the metal-containing titanium salt hydrolyzed Z alkali neutralized product A is formed.
  • the produced metal-containing titanium salt hydrolyzed neutralized neutralized product A is separated from the slurry by a method such as filtration and centrifugation, or the solvent of the slurry is evaporated to remove the solvent, and the solid is removed.
  • Product, and after washing as necessary, drying the metal-containing titanium salt Z alkali neutralized product A is obtained.
  • the drying temperature is usually 90 to 1550 ⁇ : the drying atmosphere is in an oxidizing atmosphere such as air or oxygen gas; inert such as nitrogen gas or argon gas Under gas atmosphere; under vacuum.
  • the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A from the titanium salt in the baking raw material mixture preparing step that is, the titanium salt hydrolyzed Z-alloy.
  • the sulfur compound is mixed, for example,
  • the sulfur compound is mixed with the aqueous solution of the titanium salt, or before dropping the Al force solution to the aqueous solution of the titanium salt.
  • the sulfur compound is mixed with an aqueous solution of the titanium salt.
  • (A 2) for example, when the alkaline aqueous solution is dropped into the titanium salt aqueous solution, the alkaline aqueous solution mixed with the sulfur compound is dropped into the titanium salt aqueous solution.
  • the aqueous solution of alkali By adding dropwise an aqueous solution of the titanium salt mixed with the sulfur compound, the sulfur compound is mixed while performing the hydrolysis and alkali neutralization treatment A.
  • (A 5) for example, after the metal compound stirring and mixing treatment A is performed to obtain the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A, the obtained metal-containing titanium salt hydrolyzed product is obtained. It is mentioned to mix the decomposition / alternative neutralized product A and the sulfur compound.
  • (A 5 _ 1) a solution in which the sulfur compound is dissolved in the metal-containing titanium salt hydrolyzed / al strength neutralized product A (A 5-2) Hydrolysis of the metal-containing titanium salt Z alkali neutral A and the sulfur compound in a dry process, A 5-3) Hydrolysis of the metal-containing titanium salt Z neutralized product A and the sulfur compound are dispersed in a dispersion medium.
  • the method (A 5 -2) is preferable from the viewpoint of operability.
  • the mixing of the sulfur compound may be performed at any time of the above (A 1), (A 2), (A 3), (A 4), or (A 5), or of these It can be divided into two or more periods.
  • the sulfur compound according to the firing raw material mixture preparation step A (the sulfur compound according to the method for producing the metal-containing sulfur-introduced titanium oxide of the present invention, the production of the metal-containing sulfur-introduced titanium oxide according to the first to seventh aspects of the present invention)
  • sulfur-containing organic compounds sulfur-containing inorganic compounds, metal sulfides, sulfur, etc., which are solid or liquid at room temperature, and more specifically, for example, thiourea, thiourea derivatives, Examples include sulfates. Of these, thiourea is particularly preferable because it completely decomposes at 400 to 500 ° C. and does not remain in the metal-containing sulfur-introduced titanium oxide.
  • the amount of the sulfur compound is determined as follows.
  • the mass of sulfur atoms relative to 100 parts by mass when converted to 2 is preferably 5 to 1500 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. Is the amount.
  • the sulfur content is from 0.02 to It becomes easy to obtain 0.1% by mass of metal-containing sulfur-introduced titanium oxide.
  • the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.
  • the metal-containing titanium salt hydrolyzed neutralized product A And a mixture A of the sulfur compound is calcined.
  • the mixture A of the metal-containing titanium salt hydrolyzed neutralized product A and the sulfur compound As a method for firing the mixture A of the metal-containing titanium salt hydrolyzed neutralized product A and the sulfur compound, the mixture A is put into a firing container and the lid is covered. At that time, if the system is completely open, the gas generated from the sulfur compound does not stay in the atmosphere, so a slight gap is left open.
  • the sulfur compound When the mixture is fired, the sulfur compound is decomposed by heat, and SO 2 gas and S 0 3 gas are generated in the decomposition process, and sulfur in these gases is converted into the metal-containing titanium.
  • Salt hydrolysis Z Incorporated into Z-force neutralized product A some of the titanium atoms in the metal-containing titanium salt hydrolyzed neutralized product A are replaced with sulfur atoms.
  • the calcining temperature when calcining the mixture of the metal-containing titanium salt hydrolyzed neutralized product A and the sulfur compound is preferably 3500 to 800, particularly preferably 3500 to 600 ° C.
  • the baking time is preferably 1 to 10 hours, particularly preferably 1 to 5 hours, and further preferably 2 to 5 hours.
  • the atmosphere at the time of firing the mixture of the metal-containing titanium salt hydrolyzed neutral alkali A and the sulfur compound is not particularly limited, and is in an oxidizing atmosphere such as in air or oxygen gas; in nitrogen gas, Under an inert atmosphere such as in argon gas; under vacuum.
  • the metal-containing titanium salt hydrolyzed alkali neutralized product A The sulfur content in the metal-containing sulfur-introduced titanium oxide varies depending on the mixing amount of the sulfur compound in the mixture A and the calcination temperature. Therefore, in the firing step A, the metal-containing titanium salt hydrolyzed Z alkali neutralized product A and the mixture A of the sulfur compound, the amount of the sulfur compound in the mixture A, and the firing temperature are appropriately selected, and the metal The sulfur content in the contained sulfur-introduced titanium oxide can be adjusted, and the sulfur content in the metal-containing sulfur-introduced titanium oxide is preferably set to be from 0.02 to 0.1% by mass. .
  • the amount of the sulfur compound in the mixture A is changed to the amount of the metal-containing titanium salt hydrolyzed alkali hydrate A
  • the amount of sulfur atoms relative to 100 parts by mass in terms of O 2 is preferably 5 to 20 parts by mass, particularly preferably 5 to 10 parts by mass. It is.
  • the amount of the sulfur compound in the mixture A is changed to the metal-containing titanium salt hydrolyzed Z Al force neutralized product A 0
  • 2-converted mass of a sulfur atom for 1 0 0 parts by weight of time is 1 0-5 0 it is preferred to a mass parts become mixed-weight, particularly preferably 2 0-4 0 weight parts to become mixed- It is to be a quantity.
  • the amount of the sulfur compound in the mixture A is changed to the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A It is preferable to set the mixing amount so that the mass of sulfur atoms with respect to 100 parts by mass when converted to O 2 is 40 to 150 parts by mass, and particularly preferably 100 to 150 parts by mass.
  • the mixing amount is a part.
  • a mixture A of the metal-containing titanium salt hydrolyzed neutral alkali A and the sulfur compound is fired, and the total amount of mixing is predetermined for the obtained metal-containing sulfur-introduced titanium oxide.
  • the sulfur compound can be mixed again and fired again within a range not exceeding the mixing amount of.
  • the method for producing the metal-containing sulfur-introduced titanium oxide of the second aspect of the present invention is a metal-containing titanium salt hydrolysis alkali-neutralized product B heat treatment
  • the calcining raw material mixture preparation step B comprises hydrolysis or alkali neutralization treatment B to hydrolyze or neutralize titanium salt to prepare titanium salt hydrolyzed Z aluminum force neutralized product B-containing slurry.
  • a metal compound is added to the slurry containing the alkali salt B of the alkali salt hydrolysis B slurry and stirred to obtain a metal-containing titanium salt hydrolyzed Z-al strength neutralized product B.
  • Heat treatment B to obtain a heat-treated product B by heat-treating the titanium salt hydrolyzed no-alkali neutralized product B, and
  • the amount of the metal compound added in the metal compound stirring and mixing treatment B is 0.003 as a metal atom with respect to 100 parts by mass of the titanium salt hydrolyzed alkali neutralized product B 10 when converted to Ti 0 2 .
  • a sulfur compound is mixed between before the hydrolysis Al force re-neutralization treatment B and after the heat treatment B.
  • the titanium salt hydrolysis Z alkali neutralization treatment B and the metal compound stirring and mixing treatment B are carried out to convert the metal-containing titanium salt hydrolysis Z alcohol from the titanium salt.
  • Power neutralized product B is obtained.
  • the hydrolysis / al strength neutralization treatment B according to the baking raw material mixture preparation step B, the titanium salt, the titanium salt hydrolysis hydroalkali neutralization product B, the titanium salt hydrolysis alkali neutralization product B-containing slurry, Metal compound stirring and mixing treatment B, the metal compound, the metal-containing titanium salt hydrolyzed neutralized product B, Firing raw material mixture preparation step A according to the hydrolysis Z al force neutralization treatment A, the titanium salt, the titanium salt hydrolysis alkali neutralized product A, the titanium salt hydrolysis Z alkali neutralized product A-containing slurry, This is the same as the metal compound stirring and mixing treatment A, the metal compound, and the metal-containing titanium salt hydrolyzed alkali neutralized product A.
  • the heat treatment B is performed after the metal compound stirring and mixing treatment B is performed.
  • the heat treatment temperature when the metal-containing titanium salt hydrolyzed neutralized product B is heat-treated is 200 3550 ⁇ , preferably 250 300 ° C.
  • the specific surface area is 150 500 m 2 Zg
  • the specific surface area of the heat-treated product tends to be larger than 400 m 2 Zg, or the half width of the (1 0 1) peak of anatase is 2 0 1.5 ° Prone to become wider.
  • the heat treatment temperature is If the temperature is lower than 2500 ° C, the specific surface area of the heat-treated product tends to be larger than 3 10 m 2 Zg. If the temperature exceeds 300 ° C, the specific surface area of the heat-treated material is smaller than 200 m 2 / g. easy.
  • the heat treatment time when the metal-containing titanium salt hydrolyzed alkali neutralized product B is heat-treated is preferably 1 to 5 hours, particularly preferably 2 to 3 hours.
  • the atmosphere for heat-treating the metal-containing titanium salt hydrolyzed / al strength neutralized product B is not particularly limited, and is in an oxidizing atmosphere such as in air or oxygen gas; nitrogen In an inert atmosphere such as in a gas or argon gas; in a vacuum, etc. In the air, the air is advantageous.
  • the sulfur compound is mixed to obtain a mixture B of the heat treated product B of the titanium salt hydrolyzed / al strength re-neutralized product B and the sulfur compound. More specifically, in the baking raw material mixture preparation step B, the sulfur compound is mixed, for example, before (B 1) hydrolysis and alkali neutralization treatment B,
  • the (B 1), (B 2), (B 3), (B 4) related to the baking raw material mixture preparation step B are the (A 1), (B 4) related to the baking raw material mixture preparation step A The same as (A2), (A3) and (A4).
  • the metal-containing titanium salt hydrolysis mixture B is obtained to obtain the metal-containing titanium salt hydrolyzed Al force neutralized product B, and then the metal-containing titanium salt hydrolyzed. Examples thereof include mixing the alkali neutralized product B and the sulfur compound.
  • (B 5) more specifically, for example, (B 5-1) a solution in which the sulfur compound is dissolved in the metal-containing titanium salt hydrolyzed neutralized product B is added.
  • (B 5-2) A method of evaporating the solvent containing the metal-containing titanium salt Alkaline hydrate B and the sulfur compound in a dry process, or (B 5-3 )
  • the metal-containing titanium salt hydrolyzed / alkaline neutralized product B and the sulfur compound may be mixed in a dispersion medium.
  • the (B 5-2) The method is preferable from the viewpoint of operability.
  • (B 6) for example, after the heat treatment B is performed to obtain the heat-treated product B, the obtained heat-treated product B and the sulfur compound are mixed.
  • (B 6) more specifically, for example, (B 6-1) A solution in which the sulfur compound is dissolved is added to the heat-treated product B, mixed well, and then the solvent is added.
  • a method of evaporating (B 6-2) a method of mixing the heat-treated product B and the sulfur compound in a dry process
  • (B 6-3) a method of mixing the heat-treated product B and the sulfur compound with a dispersion medium.
  • the method (B6-2) is preferable from the viewpoint of operability.
  • the sulfur compound may be mixed at any time of (B 1), (B 2), (B 3), (B 4), (A 5) or (B 6). Or it can be divided into two or more of these periods.
  • the mixing amount of the sulfur compound In the mixture B of the heat treatment B and the sulfur compound, the mixing amount of the sulfur compound, the mass of the sulfur atom with respect to 1 0 0 parts by weight when the heat treatment was B T i 0 2 converted, preferably 5 to 150 parts by weight, particularly preferably 10 ⁇ 50 parts by mass, more preferably 20 to 40 parts by mass.
  • the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.
  • the mixed amount of the sulfur compound is determined by adding the metal-containing titanium salt hydrolyzed Z alkali neutralized product B to T i O 2
  • the amount of sulfur atoms with respect to 100 parts by mass when converted is preferably 5 to 20 parts by mass, particularly preferably 5 to 10 parts by mass.
  • the amount of the sulfur compound to be mixed before the heat treatment B is within the above range, the catalytic activity of the metal-containing sulfur-introduced titanium oxide is increased.
  • the sulfur compound is further added to the heat-treated product B obtained by performing the heat treatment B within a range not exceeding a predetermined mixing amount. May be mixed.
  • the mixture B of the heat-treated product B and the sulfur compound is fired.
  • the firing step B is mixed with the sulfur compound, and the former is a heat-treated product B of the metal-containing titanium salt hydrolyzed / al strength neutralized product B.
  • the latter is the same as the calcination step A except that the metal-containing titanium salt hydrolyzed alkali neutral A. Therefore, the metal-containing titanium salt hydrolyzed / al strength neutralized product A in the description of the calcination step A may be read as the heat-treated product B and the mixture A as the mixture B.
  • the method for producing a metal-containing sulfur-introduced titanium oxide according to the third aspect of the present invention is a metal-containing titanium salt hydrolyzed / alternative neutralized product C Firing raw material mixture for obtaining a mixture C and sulfur compound C Preparation step C, the metal-containing titanium salt hydrolyzed / al strength re-neutralized product C and the sulfur compound C is calcined, and metal-containing sulfur is introduced.
  • the calcining raw material mixture preparation step C is hydrolyzed or alkalinized in the presence of a metal compound to hydrolyze or neutralize a titanium salt to obtain a metal-containing titanium salt hydrolyzed Z al force reneutralized product C.
  • a step of performing sum process C the amount of the metal compound be present in the hydrolysis Noarukari neutralization C is, with respect to the titanium salt 1 0 0 parts by weight when the T I_ ⁇ 2 terms, as a metal atom 0.03 to 0.15 is an amount of 5 parts by mass,
  • a method for producing a metal-containing sulfur-introduced titanium oxide comprising mixing a sulfur compound before performing the hydrolysis Z-alkali neutralization treatment c and after performing the hydrolysis alkali-neutralization treatment C. It is.
  • the titanium salt according to the hydrolysis Z alkali neutralization treatment C is the same as the titanium salt according to the titanium salt hydrolysis Z alkali neutralization treatment A.
  • the metal compound according to the titanium salt hydrolysis Z-al force neutralization treatment c is the same as the metal compound according to the metal compound stirring and mixing treatment A.
  • the titanium salt is hydrolyzed by preparing an aqueous solution in which the titanium salt and the metal compound are dissolved in water, and stirring the aqueous solution.
  • the method of heating is mentioned.
  • the hydrolysis temperature during the hydrolysis is preferably 20 ° C. to the boiling point of the aqueous solution, particularly preferably 40 to 80 ° C.
  • the hydrolysis time for the hydrolysis is usually 5 minutes to 10 hours, preferably 10 minutes to 5 hours, and particularly preferably 10 minutes to 1 hour.
  • the titanium salt is dissolved in water, but the solvent for dissolving the titanium salt is not particularly limited as long as it dissolves the metal compound.
  • the solvent for dissolving the titanium salt is not particularly limited as long as it dissolves the metal compound. Examples include organic solvents such as alcohol. Among these, water is preferable from the viewpoint of easy handling and economical efficiency.
  • hydrolysis is preferably performed in a low pH region because a hydrolyzate having a small particle size can be obtained. Therefore, when hydrolyzing in the hydrolysis Z alkali neutralization treatment c, particularly when the hydrolysis temperature is near the boiling point of the aqueous solution, a reflux apparatus is installed in the reaction tank, and the generated hydrogen chloride is chlorinated. It is preferable to suppress discharge from the reaction system as hydrogen gas because the pH of the reaction system can be lowered.
  • the titanium salt is hydrolyzed to produce the titanium salt hydrolyzate, and the metal compound is hydrolyzed or reduced.
  • the metal-containing titanium salt hydrolyzate C is obtained by incorporating the hydroxide or the oxide into the surface adhesion or inside of the titanium salt hydrolyzate formed. .
  • the metal-containing titanium salt hydrolyzate is titanium oxide or an intermediate in the process of changing from the titanium salt to titanium oxide.
  • hydrolysis Z-al strength neutralization treatment c as a method for neutralizing the titanium salt, an aqueous solution in which the titanium salt and the metal compound are dissolved in water is prepared. While stirring, mix the alkali, A method of bringing the titanium salt into contact with the alkali, and more specifically, for example,
  • the metal compound can be added to the reaction vessel regardless of whether it is present in the aqueous solution of the titanium salt or in the aqueous solution of the alkali.
  • the metal compound may be present in the added water, that is, the metal compound may be present in the dropped aqueous solution, or the metal compound may be present in the dropped aqueous solution.
  • the alkali related to the hydrolysis-no-alkali neutralization treatment C is not particularly limited, and examples thereof include ammonia and aqueous ammonia. Among these, ammonia or aqueous ammonia is contained in the metal-containing sulfur-introduced titanium oxide. Since a metal component derived from Al force is not contained, it is preferable for controlling the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light.
  • the alkali neutralization temperature during the alkali neutralization is preferably 10 to 80 ° C, particularly preferably 30 to 80, more preferably 40. ⁇ 70. When the alkali neutralization temperature is less than 10 ° C, the neutralization reaction hardly occurs.
  • the addition time of the alkali at the time of alkali neutralization is usually 1 minute to 10 hours, preferably 3 minutes to 5 hours, particularly preferably 5 minutes to 1 hour. Then, in the hydrolysis Z alkali neutralization treatment c, the titanium salt Al force re-neutralized product is formed by performing the Al force re-neutralization of the titanium salt, and the metal compound is hydrolyzed or reduced.
  • the hydroxide or the oxide is taken into the surface of the alkali neutralized product of the produced titanium salt or is taken into the inside thereof, in the metal-containing titanium salt alkali.
  • Japanese product C is obtained.
  • the metal-containing titanium salt alkali neutralized product C is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide.
  • the mixing amount of the metal compound, 1 00 mass when can be appropriately selected by the introduction of the metal of the metal-containing sulfur introduced titanium oxide, which the titanium salt T io 2 converted
  • the mixing amount is such that the mass of the metal atom with respect to parts is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.1 parts by mass. When the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the metal-containing titanium salt hydrolyzed alkali-neutralized product C after drying is mainly composed of anatase type crystal structure, and has a specific surface area of 150 to 400 m 2 Zg, preferably 200 to 30 m 2 / g.
  • the metal-containing titanium salt hydrolyzed alkali neutralized product C from the titanium salt in the step of preparing the firing raw material mixture that is, the hydrolysis / al force re-neutralization treatment.
  • the sulfur compound between before the C and after the hydrolytic neutralization treatment C the titanium salt hydrolyzed Z alkali neutralized product C and the sulfur compound are mixed.
  • the sulfur Mixing compounds for example
  • the sulfur compound is mixed with the aqueous solution of the titanium salt, or before the alkali is added dropwise to the aqueous solution of the titanium salt. And mixing the sulfur compound with an aqueous solution of the titanium salt.
  • (C 2) for example, when the alkaline aqueous solution is dropped into the titanium salt aqueous solution, the alkaline aqueous solution mixed with the sulfur compound is dropped into the titanium salt aqueous solution.
  • the sulfur aqueous solution is added to the alkali aqueous solution.
  • the sulfur compound is mixed while performing the hydrolysis-no-alkali neutralization treatment C.
  • the metal-containing titanium obtained is obtained by performing the hydrolysis Z-al strength neutralization treatment C to obtain the metal-containing titanium salt hydrolyzed al- strength neutralized product C.
  • the salt hydrolyzed neutralized product C and the sulfur compound may be mixed.
  • (C 3-1) A solution containing the sulfur compound dissolved in the metal-containing titanium salt hydrolyzed Z alkali neutralized product C is added.
  • the mixing of the sulfur compound can be performed at any one of the above (CI), (C2) or (C3), or can be performed at two or more of these times. .
  • the amount of the sulfur compound in the mixture C is determined as follows.
  • the mass of sulfur atoms relative to 100 parts by mass when converted to 2 is preferably 5 to 1500 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. Is the amount.
  • Hydrolysis of the metal-containing titanium salt Z Al force neutralized product c and the mixture c of the sulfur compound
  • the sulfur content is from 0.02 to It becomes easy to obtain 0.1% by mass of metal-containing sulfur-introduced titanium oxide.
  • the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.
  • the calcination step C is mixed with the sulfur compound.
  • the former is the metal-containing titanium salt hydrolyzed / al strength neutralized product C
  • the latter is the metal-containing Titanium salt hydrolysis Z Similar to the calcination step A except that it is a neutralized alkali A. Therefore, the metal-containing titanium salt hydrolyzed / al strength neutralized product A in the description of the calcination step A, the metal-containing titan salt hydrolyzed / al strength neutralized product C, and the mixture A It should be read as Mixture C.
  • the method for producing the metal-containing sulfur-introduced titanium oxide of the fourth aspect of the present invention is a method for hydrolyzing metal-containing titanium salt Solution Z-strength neutralized product D Heat-treated product D and sulfur compound D are obtained D Preparation process D for calcining raw material and hydrolysis of the metal-containing titanium salt Z-strength neutralized product D A mixture D of D and the sulfur compound is calcined to obtain a metal-containing sulfur-introduced titanium oxide; and
  • the firing raw material mixture preparation step D hydrolyzes or neutralizes the titanium salt to obtain a titanium salt hydrolyzed neutralized neutralized product D.
  • Heat-treating D and the metal-containing titanium salt hydrolyzed Al force neutralized product D to obtain a heat-treated product D.
  • the amount of the metal compound be present in the hydrolysis Z Al Chikarari neutralization D is, with respect to the titanium salt 1 0 0 parts by weight when T i O 2 converted, by a metal atom 0.0 3-0 1
  • the amount is 5 parts by mass
  • a sulfur compound is mixed between before the hydrolysis Z al force re-neutralization treatment D and after the heat treatment D.
  • the titanium; ⁇ hydrolysis Z neutralization treatment D and the heat treatment D are carried out, whereby the metal-containing titanium salt hydrolysis in alkali Heat D of Japanese product D is obtained.
  • the calcination raw material mixture preparation step D The hydrolysis Z al force neutralization treatment D, the titanium salt, the metal compound, the metal-containing titanium salt hydrolysis Z alkali neutralization product D is the calcination raw material mixture preparation step C. This is the same as the hydrolysis / alkaline neutralization treatment C, the titanium salt, the metal compound, and the metal-containing titanium salt hydrolyzed Z alkali neutralized product C.
  • the heat treatment D is performed after the hydrolysis / al strength neutralization treatment D is performed.
  • the heat treatment D is heat-treated compared to the heat treatment B.
  • the former is the metal-containing titanium salt hydrolyzed / alkaline neutralized product D
  • the latter is the metal-containing titanium. Salt hydrolysis
  • the metal-containing titanium salt hydrolyzed Z-alkaline neutralized product B in the explanation of the heat-treated B is converted into the metal-containing titanium salt hydrolyzed Z alkali-neutralized product D and the heat-treated product B.
  • the heat-treated product D may be replaced with this.
  • the sulfur compound is mixed to obtain a mixture D of the heat-treated product D of the titanium salt hydrolysis neutralized product D and the sulfur compound. More specifically, in the baking raw material mixture preparation step D, the sulfur compound is mixed, for example, before (D 1) hydrolysis Z alkali neutralization treatment D,
  • the (D 1) and (D 2) relating to the baking raw material mixture preparation step D This is the same as (C 1) and (C 2) in the raw material mixture preparation step C.
  • the hydrolysis-alkali neutralization treatment D is performed to obtain the metal-containing titanium salt hydrolyzed Z-al strength neutralized product D, and then the obtained metal-containing titanium salt hydrolyzed.
  • An example of this is to mix the decomposed Z-al strength neutralized product D with the sulfur compound.
  • (D3) more specifically, for example, (D3-1) hydrolysis of the metal-containing titanium salt alkali neutralized product D is added with a solution in which the sulfur compound is dissolved, (D 3-2) Hydrolysis of the metal-containing titanium salt Z Al force re-neutralized product D and the sulfur compound, or (D 3 — 3) Hydrolysis of metal-containing titanium salt Z Alkali neutralized product D and sulfur compound are mixed in a dispersion medium.
  • (D 3 -2) The method is preferable from the viewpoint of operability.
  • (D4) for example, after the heat treatment D is performed to obtain the heat-treated product D, the obtained heat-treated product D and the sulfur compound are mixed.
  • (D 4) more specifically, for example, (D 4-1) A solution in which the sulfur compound is dissolved is added to the heat-treated product D, and after sufficiently mixing, the solvent is added.
  • the method (D4-2) is preferred from the viewpoint of operability.
  • the mixing of the sulfur compound may be performed at any one of the times (D 1), (D 2), (D 3) or (D 4), or two or more of these times. It can also be divided into two.
  • the amount of the sulfur atom is preferably 5 to 1550 parts by mass, particularly preferably 10 to 50 parts by mass, and still more preferably 20 to 40 parts by mass.
  • the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.
  • the amount of the sulfur compound is determined by converting the metal-containing titanium salt hydrolyzed alkali neutralized product D to Ti 0 2
  • the mass of sulfur atoms with respect to 100 parts by mass is preferably 5 to 20 parts by mass, particularly preferably 5 to 10 parts by mass.
  • the mixture D of the heat-treated product D and the sulfur compound is fired.
  • the firing step D is mixed with the sulfur compound, and the former is a heat-treated product D of the metal-containing titanium salt hydrolyzed / al strength neutralized product D.
  • the latter is the same as the calcination step A except that the metal-containing titanium salt hydrolyzed Z-alkaline intermediate A. Therefore, the metal-containing titanium salt hydrolyzed Z al force neutralized product A in the description of the firing step A may be read as the heat-treated product D, and the mixture A as the mixture D.
  • the photocatalytic activity of the resulting metal-containing sulfur-introduced titanium oxide can be further increased.
  • the fifth metal-containing sulfur-introduced titanium oxide production method of the present invention (hereinafter referred to as the present invention) Also described as Ming's manufacturing method (5). ) Is a calcined raw material mixture preparation step E to obtain a mixture E of a metal-containing titanium salt hydrolyzed / alkali neutralized product E (2) and a sulfur compound, and the metal-containing titanium salt hydrolyzed / alkaline neutralized product A mixture E of E (2) and the sulfur compound is calcined to obtain a metal-containing sulfur-introduced titanium oxide, and
  • the titanium salt is hydrolyzed or alkali neutralized to obtain a metal-containing titanium salt hydrolyzed / alkali neutralized product E (1) -containing slurry.
  • Hydrolysis to be prepared Z alkali neutralization treatment E and the metal-containing titanium salt hydrolyzed Z alkali-neutralized product E (1) Add the metal compound to the slurry and stir to obtain the metal-containing titanium salt hydrolyzed Z
  • the metal compound stirring and mixing treatment E to obtain the alkali neutralized product E (2), and
  • the hydrolysis / alkali neutralization treatment E and the metal compound stirring and mixing treatment E are performed.
  • hydrolysis / alkali neutralization treatment E by hydrolyzing the titanium salt in the presence of the metal compound, or by neutralizing the titanium salt in the presence of the metal compound.
  • a slurry containing the metal-containing titanium salt hydrolyzed alkali neutralized product E (1), that is, a metal-containing titanium salt hydrolyzed / alkali neutralized product E (1) -containing slurry is obtained.
  • the hydrolysis Z-al strength re-neutralization treatment E is the same as the hydrolysis Z-al strength re-neutralization treatment C.
  • the titanium salt according to the hydrolysis Z-al strength re-neutralization treatment E, the metal compound, The titanium salt hydrolyzed Z alkali neutralized product E (1) is the same as the titanium salt, the metal compound, and the titanium salt hydrolyzed neutralized product C of the hydrolyzed alkali neutralized treatment C. .
  • the metal-containing titanium salt hydrolyzed neutralized product E (1) is It is an intermediate in the process of changing from titanium oxide or the titanium salt to titanium oxide.
  • the metal compound stirring / mixing treatment E the metal compound is added to the slurry containing the metal-containing titanium salt hydrolyzed / alkali neutralized product E (1), stirred and mixed, and the metal-containing titanium salt hydrolyzed /
  • This is a treatment for obtaining the metal-containing titanium salt hydrolyzed Z-alkaline intermediate E (2) in which the metal is further introduced into the alkali neutralized product E (1).
  • the thing before processing by this metal compound stirring mixing process E is described as this metal containing titanium salt hydrolysis alkali neutralized product E (1), The treated product was described as the metal-containing titanium salt hydrolyzed neutralized product E (2).
  • the metal compound stirring and mixing treatment E is contained in a slurry. / Alkali neutralized product E (1), while the latter is the same as the metal compound stirring and mixing treatment A except that the latter is the titanium salt hydrolyzed neutral force neutralized product A. Accordingly, the titanium salt hydrolysis Z alkali power neutralized product A in the description of the metal compound stirring and mixing treatment A is used as the metal-containing titanium salt hydrolyzed / alkali neutralized product E (1) and the metal-containing product.
  • the titanium salt hydrolyzed neutralized product A may be read as the metal-containing titanium salt hydrolyzed Z alkali neutralized product E (2).
  • the total amount of the metal compound to be present in the hydrolysis / al neutralization treatment E and the metal compound stirring and mixing treatment E depends on the amount of metal introduced into the metal-containing sulfur-introduced titanium oxide.
  • the mass of the metal atom with respect to 100 parts by mass when the titanium salt is converted to TiO 2 is preferably 0.03 to 0.15 parts by mass, particularly preferably 0.05 to 0.1 Mixing amount to be 1 part by mass.
  • the mixing amount of the metal compound is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the metal-containing titanium salt hydrolyzed Z Al force re-neutralized product E (2) from the titanium salt in the firing raw material mixture preparation step E that is, the titanium salt hydrolyzed
  • the sulfur compound is mixed, for example,
  • the (E 1) and (E 2) related to the baking raw material mixture preparation step E are the same as the (C 1) and (C 2) related to the baking raw material mixture preparation step C, and
  • the (E 3), (E 4), and (E 5) related to the baking raw material mixture preparation step E are the (A 3), (A4), and (( Same as A5).
  • the mixing of the sulfur compound may be performed at any time of the above (E 1), (E 2), (E 3), (E 4) or (E 5), or these It can be divided into two or more of them.
  • the amount of the sulfur compound in the mixture E of the metal-containing titanium salt hydrolyzed Z alkali neutralized product E (2) and the sulfur compound is determined by the metal-containing titanium salt hydrolyzed Z alkali neutralized product E
  • the mass of sulfur atoms with respect to 100 parts by mass when (2) is converted to Ti 0 2 is preferably 5 to 150 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass. It is an amount that becomes a part.
  • the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods. In the firing step E, a mixture E of the metal-containing titanium salt hydrolyzed Z-al strength neutralized product E (2) and the sulfur compound is fired.
  • the calcination step E is mixed with the sulfur compound.
  • the former is the metal-containing titanium salt hydrolyzed alkali neutralized product E (2)
  • the latter is the metal It is the same as the calcination step A except that the titanium salt is hydrolyzed with an alkali neutralized product A. Therefore, in the firing step A
  • the metal-containing titanium salt hydrolyzed Z-alkaline neutralized product A can be read as the metal-containing titanium salt hydrolyzed Z-alkali neutralized product E (2), and the mixture A can be read as the mixture E. That's fine.
  • the sixth metal-containing sulfur-introduced titanium oxide production method of the present invention (hereinafter also referred to as the production method (6) of the present invention) is a metal-containing titanium salt hydrolyzed Z alkali neutralized product F (2).
  • Heat-processed product F and sulfur compound mixture F Preparation step F for obtaining a raw material mixture F, Metal-containing titanium salt hydrolysis Z Al force re-neutralized product F (2) Heat-processed product F and the sulfur compound And firing step F to obtain a metal-containing sulfur-introduced titanium oxide, and a mixture F of
  • the titanium salt is hydrolyzed or alkali-neutralized to obtain a metal-containing titanium salt hydrolyzed alkali neutralized product F (1) -containing slurry.
  • Hydrolysis-no alkali neutralization treatment F to be prepared and the metal-containing titanium salt hydrolysis Z alkali-neutralized product F (1) Add the metal compound to the slurry and stir to hydrolyze the metal-containing titanium salt in alkali.
  • the metal compound stirring and mixing treatment F to obtain a hydrate F (2), the metal-containing titanium salt hydrolysis / alkali neutralized product F (2), and the heat treatment F to obtain the heat treatment product F, Is a process to perform,
  • the total amount of the metal compound to be present in the hydrolysis and the neutralization treatment F and the metal compound to be mixed in the metal compound stirring and mixing treatment F is the titanium salt when converted to Ti 0 2 1 0 0 It is an amount of 0.03 to 0.15 parts by mass with respect to parts by mass as metal atoms,
  • a sulfur compound is mixed between before the hydrolysis-no-alkali neutralization treatment F and after the heat treatment F.
  • the hydrolysis Z al force neutralization treatment F, the metal compound stirring and mixing treatment F, and the heating treatment F are performed.
  • the metal-containing titanium salt hydrolysis / alkali neutralized product F (2) is the hydrolysis / alkali neutralization treatment E, the metal compound stirring / mixing treatment E, the titanium salt according to the baking raw material mixture preparation step E.
  • the hydrolysis Z alkali neutralization treatment F is performed to obtain the metal-containing titanium salt hydrolysis neutral alkali treatment product F (1) -containing slurry, and then the metal By carrying out compound stirring treatment F, the metal-containing titanium salt hydrolyzed neutralized neutralized product F (2) is obtained.
  • the heat treatment F is performed after the metal compound stirring and mixing treatment F is performed.
  • the heat treatment F is heat-treated compared to the heat treatment B.
  • the former is the metal-containing titanium salt hydrolyzed Z-alkaline neutralized product F (2)
  • the latter is the metal Containing titanium salt hydrolysis It is the same as the heat treatment B except that it is an alkali neutralized product B. Therefore, the gold in the description of the heat treatment B
  • Metal-containing titanium salt hydrolysis Z Al force neutralized product B can be read as the metal-containing titanium salt hydrolyzed Z alkali neutralized product F (2), and the heat-treated product B can be read as the heat-treated product F. That's fine.
  • the heat-treated product F is obtained from the titanium salt in the baking raw material mixture preparation step F, that is, before the titanium salt hydrolyzing neutralization treatment F is performed, the heat treatment is performed.
  • the sulfur compound is mixed, for example,
  • (F 1) and (F 2) relating to the firing raw material mixture preparation step F are the same as the (C 1) and (C 2) relating to the firing raw material mixture preparation step C, and
  • the (F 3) and (F 4) relating to the firing raw material mixture preparation step F are the same as the (A 3) and (A4) relating to the firing raw material mixture preparation step A, and the firing raw material mixture
  • the preparation steps (F 5) and (F 6) are the same as the (B 5) and (B 6) according to the baking raw material mixture preparation step B.
  • the sulfur compound may be mixed at any time of the above (F 1), (F 2), (F 3), (F 4), (F 5) or (F 6). Or it can be divided into two or more of these periods.
  • the mass of the sulfur atom with respect to 1 0 0 parts by weight when the heat treatment was F T i O 2 converted preferably Is in an amount of 5 to 1500 parts by mass, particularly preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass.
  • the mixing amount of the sulfur compound is the total amount when mixing the sulfur compound in two or more periods.
  • the mixing amount of the sulfur compound 1 0 0 mass when the heat treatment was F T i 0 2 converted
  • the amount of sulfur atoms with respect to parts is preferably 5 to 20 parts by weight, particularly preferably 5 to 10 parts by weight.
  • the mixture F of the heat-treated product F and the sulfur compound is fired.
  • the firing step F is mixed with the sulfur compound, whereas the former is a heat-treated product F of the metal-containing titanium salt hydrolyzed Z alkali neutralized product F (2).
  • the latter is the same as the calcination step A except that the metal-containing titanium salt hydrolyzed / alkali neutralized product A. Therefore, the metal-containing titanium salt hydrolyzed Z-al strength neutralized product A in the description of the firing step A may be read as the heat-treated product F, and the mixture A as the mixture F.
  • the photocatalytic activity of the obtained metal-containing sulfur-introduced titanium oxide can be further increased.
  • the heat-treated product F of the titanium salt hydrolyzed neutralized product F (2) containing the main component of the crystal structure is anatase type and has the following physical properties (i), (ii), and (iii) It is preferable in that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the metal content is 0.03 to 0.15 mass%.
  • the main component of the crystal structure is anatase type
  • the metal-containing titanium salt hydrolyzed neutralized product A having the physical properties (i) to (iii), the metal-containing titanium salt hydrolyzed Z-al strength neutralized product B heat-treated product B, metal-containing titanium salt hydrolyzed alkali neutralized product C, metal-containing titanium salt hydrolyzed neutral force neutralized product D heat-treated product D, metal-containing titanium salt hydrolyzed / alloy Potassium neutralized product E (2) and the heat-treated product F of the metal-containing titanium salt hydrolyzed / alkali neutralized product F (2) are mixed amount of metal compound, hydrolysis condition, alkaline neutralized condition, slurry Separation of solids from the liquid or by appropriately selecting conditions such as washing and drying as necessary to obtain the solids, or by performing heat treatment and appropriately selecting the heat treatment conditions Can be obtained.
  • a method for producing a metal-containing sulfur-introduced titanium oxide according to the seventh aspect of the present invention (hereinafter, This is also referred to as the production method (7) of the present invention. )
  • the metal content in the metal-containing raw material titanium oxide is 0.03 to 0.15 parts by mass as metal atoms with respect to 100 parts by mass of the metal-containing raw material titanium oxide when converted to Tio 2 .
  • the metal-containing raw material titanium oxide according to the production method (7) of the present invention metal-containing organic weight, relative to the metal-containing raw material titanium oxide 1 00 parts by weight when T i 0 2 terms, 0 as a metal atom 03 to 0.1 1 Titanium oxide in 5 parts by mass.
  • the metal-containing raw material titanium oxide according to the production method (7) of the present invention is mainly composed of anatase type crystal structure, and has the following physical properties (i),
  • Titanium oxide having (ii) and (iiii) is preferred in that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the specific surface area is 150 to 400 m 2 / g, preferably 2000 to 3 10 m 2 Z g.
  • the metal content is 0.03 to 0.15 mass%.
  • the mixture G of the metal-containing raw material titanium oxide and the sulfur compound is fired.
  • the firing step G according to the production method (7) of the present invention is mixed with the sulfur compound.
  • the latter is the same as calcination step A except that the metal-containing titanium salt hydrolyzed Z alkali neutralized product A. Therefore, the metal-containing titanium salt hydrolyzed Z
  • the neutralized product A may be read as the metal-containing raw material titanium oxide, and the mixture A as the mixture G.
  • the obtained metal-containing sulfur-introduced titanium oxide is further metal-introduced to obtain metal-containing sulfur-introduced titanium oxide in which the metal is reintroduced.
  • An introduction process may be performed.
  • the metal-containing sulfur-introduced titanium oxide obtained by the firing step is immersed in a solution of the metal compound, hydrolyzed, alkali neutralized, irradiated with light, or the solvent is evaporated, and then heated as necessary. Processing may be performed.
  • the metal-containing sulfur-introduced titanium oxide obtained by performing the firing step and the metal compound can be obtained by CVD, PVD (sputtering method, vacuum deposition method, ion plating method, etc.), plating method, etc.
  • a metal may be contained on the surface of the sulfur-introduced titanium oxide.
  • a sulfur re-introduction step may be performed in which the metal-containing sulfur-introduced titanium oxide further contains sulfur. Further, the metal reintroduction step and the sulfur reintroduction step may be repeated.
  • the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention is a compound in which a sulfur atom is introduced into the skeleton structure of titanium oxide, and is one of anatase-type titanium oxide titanium sites (cation sites). Part has a structure substituted with a sulfur atom. That is, the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention is a sulfur cation-substituted titanium oxide.
  • the confirmation that the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention has a structure in which a part of the titanium site is substituted with a sulfur atom is confirmed by X-ray photoelectron spectroscopy (XPS). Done by analysis.
  • XPS X-ray photoelectron spectroscopy
  • Sulfur-containing acid When titanium fluoride is sulfur-containing titanium oxide in which part of the titanium site is replaced with sulfur atoms, a characteristic peak around 1 69 eV derived from S 4 + is observed. In other words, if a characteristic peak around 1 69 eV is seen, it is assumed that a part of the titanium site (force thione site) is replaced with sulfur atoms.
  • the sulfur-containing titanium oxide is not sulfur-containing titanium oxide in which part of the titanium site is substituted with sulfur atoms, but sulfur-containing titanium oxide in which some oxygen atoms are substituted with sulfur atoms, S 2 _ characteristic peak around 1 6 0 e V derived is observed, the characteristic peaks in the vicinity of 1 6 9 e V derived from the S 4 + is not observed.
  • the sulfur-containing titanium oxide is not a compound in which some of the atoms in the titanium oxide are substituted with sulfur atoms, but a simple mixture of titanium oxide and sulfur, There is no characteristic peak in any of the vicinity of eV.
  • the metal compound is present in the form of metal ions or oxides on the surface and inside of the metal-containing sulfur-introduced titanium oxide particles. Ratio of the amount of metal present in titanium oxide to the total amount of metal contained (%) ((Amount of metal present in titanium oxide Z Total amount of metal contained in titanium oxide) X
  • the metal compound is 15% or more and 90% or less, preferably 20% or more and 85% or less, and particularly preferably 50% or more and 75% or less. Since the metal compound is present not only on the sulfur-containing titanium oxide surface but also inside thereof, the decomposition performance into carbon dioxide is particularly good.
  • the amount of metal present on the surface is a value obtained by boiling the metal-containing sulfur-introduced titanium oxide in a 9% hydrochloric acid aqueous solution and analyzing the weight composition.
  • the amount of metal present inside is the total amount of metal minus the amount of metal present on the surface.
  • the total amount of metal is a value obtained by analyzing the amount of metal from a product obtained by boiling and melting the metal-containing sulfur-introduced titanium oxide with hydrofluoric acid.
  • the metal species photocatalyst with visible light From the viewpoint of high activity, iron is preferable.
  • the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention has a metal content of 0.03 to 0.15% by mass, a sulfur content of 0.02 to 0.1% by mass,
  • the surface area is 60 to 120 m 2 Z g, and the main crystal structure is the anatase type.
  • the metal-containing sulfur-introduced titanium oxide of the present invention has a metal content of 0.03 to 0.15 mass%, a sulfur content of 0.02 to 0.1 mass%, and a specific surface area of 60 to 1. 20m 2 Zg,
  • the main part of the crystal structure is the anatase type
  • Sulfur atoms in titanium oxide are introduced into the titanium oxide titanium site.
  • the metal content of the metal-containing sulfur-introduced titanium oxide of the present invention is 0.03 to 0.15% by mass, preferably 0.05 to 0.1% by mass. When the metal content is within the above range, the photocatalytic activity of visible light of the metal-containing sulfur-introduced titanium oxide is increased.
  • the sulfur content of the metal-containing sulfur-introduced titanium oxide of the present invention is 0.02 to 0.1% by mass, preferably 0.03 to 0.1% by mass. When the sulfur content is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the specific surface area of the metal-containing sulfur introduced titanium oxide of the present invention 6 0 ⁇ 1 20 m 2 / g, preferably 6 5 ⁇ 1 0 5m 2 / g , particularly preferably 80: is I 00 m 2 / g .
  • the specific surface area is within the above range, the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide with visible light is increased.
  • the crystal structure of the metal-containing sulfur-introduced titanium oxide of the present invention is suitable for X-ray diffraction analysis. According to this, it is a phase mainly composed of anatase.
  • the fact that the crystal structure is mainly anatase type means that the rutile ratio defined by the following formula is 1% or less (AS TM D 3 7 2 0-8 4 ).
  • the metal-containing sulfur-introduced titanium oxide of the present invention may contain wurtzite.
  • Rutile ratio (mass%) 1 0 0-1 0 0 / (1 + 1. 2 X 1 ⁇ / I d) I r: strongest interference line of rutile crystalline titanium oxide in the X-ray diffraction pattern (face index 1 1 0) peak area,
  • I d Peak area of the strongest interference line (surface index 1 0 1) of anatase-type titanium oxide powder in the X-ray diffraction pattern
  • the metal is present in the form of metal ions or oxides on the particle surface and inside of the metal-containing sulfur-introduced titanium oxide, and the titanium oxide with respect to the total amount of metal contained in the titanium oxide.
  • the ratio of the amount of metal present in the interior (%) ((the amount of metal present in the titanium oxide and the total amount of metal contained in the titanium oxide) XI 0 0) is 15% or more and 90% or less.
  • the ratio (%) of the amount of metal present in the titanium oxide to the total amount of metal contained in the titanium oxide is within the above range, so that the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide in visible light, particularly to carbon dioxide gas
  • the ratio (%) of the amount of metal present in the titanium oxide to the total amount of metal contained in the titanium oxide is the photocatalytic activity of the metal-containing sulfur-introduced titanium oxide under visible light, decomposition characteristics of organic matter, and carbon dioxide.
  • the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention and the metal-containing sulfur-introduced titanium oxide of the present invention have excellent visible light absorption characteristics and photocatalytic activity in visible light. Compared with the metal-containing sulfur-introduced titanium oxide obtained by the production method, the photocatalytic activity under visible light is high. In addition, since the metal compound is present not only on the surface of the sulfur-containing titanium oxide but also inside thereof, the decomposition performance into carbon dioxide gas is particularly good.
  • the metal-containing sulfur-introduced titanium oxide obtained by the production method of the present invention and the metal-containing sulfur-introduced titanium oxide of the present invention are useful as photocatalysts that exhibit catalytic activity by irradiation with visible light.
  • the production method of the present invention is simpler than the conventional method for producing metal-containing sulfur-introduced titanium oxide because the introduction of metal is performed before obtaining sulfur-containing titanium oxide, that is, before introducing sulfur. It is.
  • the width (angle) at which the height of the anatase (1 0 1) peak is 1 to 2 was measured.
  • the rutile ratio depends on the peak area (I r) of the strongest interference line (plane index 1 1 0) of rutile crystalline titanium oxide in the X-ray diffraction pattern according to AS TM D 3 7 2 0— 8 4 and the anatase
  • the peak area (Id) of the strongest interference line (surface index 10 1) of the type titanium oxide powder was obtained, and obtained from the following calculation formula.
  • Rutile ratio (mass%) 1 0 0-1 0 0 / (1 + 1.2 X 1 ⁇ / I d)
  • IPA isopropyl alcohol
  • I P A decomposition performance was determined by the following equation.
  • Degradation performance A (%) (I PA concentration of Y 1 after 2 hours-X 1 after 2 hours IPA concentration) X 1 00 Z (IPA concentration of Y 1 after 2 hours)
  • the concentration of carbon dioxide produced as a result of the decomposition of acetonitrile and the decomposition of acetonitrile was measured.
  • Decomposition performance B (ppm) 1 8 h CO 2 concentration after the irradiation - CO 2 concentration after 5 hours left without irradiating
  • Decomposition performance C (%) (Acetaldehyde concentration after standing for 5 hours without irradiation) 1 1 0 (Acetaldehyde concentration after 5 hours without irradiation) X 1 00 (Acetaldehyde concentration after 5 hours without irradiation)
  • the measurement was performed under the following measurement conditions. No pretreatment of the sample such as etching was performed.
  • XPS system XP S-5 700 manufactured by PH I
  • X-ray source Monochrome A l Kct (1 4 8 6. 6 e V) 200 W Measurement area: 800 ⁇ m diameter
  • Neutralizing electron gun used (7) Measurement of iron content in titanium oxide (total iron content in titanium oxide) 2 g of titanium oxide, 15 m 1 hydrofluoric acid with a concentration of 50%, nitric acid with a concentration of 60%
  • this slurry one iron chloride (F e C 1 3 ⁇ H 2 O ( KK Wako Pure Chemical)) aqueous solution, when the titanium salt alkali neutralized product in slurries and T io 2 conversion calculation It added so that it might become 0.05 mass part as an iron atom with respect to 100 mass parts, and it stirred and mixed at 60 degreeC for 1 hour, and obtained the liquid mixture.
  • this mixed solution was heated at 110 ° C. for 24 hours to evaporate and remove water to obtain a solid.
  • the obtained solid was washed twice with pure water and filtered twice, and the filtered solid was It was dried at 110 ° C. for 24 hours to obtain an iron-containing titanium salt alkali neutralized product a1.
  • the iron-containing titanium salt alkali neutralized product a 1 was heat-treated at 25 ° C. for 3 hours under atmospheric pressure to obtain a heat-treated product b 1.
  • iron chloride Fe C 1 3 ⁇ H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.)
  • aqueous solution titanium oxide in the slurry converted to Ti O 2 100 mass
  • iron chloride Fe C 1 3 ⁇ H 2 O (Wako Pure Example 1)
  • the aqueous solution is added so that the titanium oxide in the slurry is 0.03 parts by mass as iron atoms with respect to 100 parts by mass when converted to Ti 0 2.
  • the same procedure was followed to obtain an iron-containing titanium salt aluminum neutralized product a2.
  • a heat treatment is performed in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a 1 is used instead of the iron-containing titanium salt alkaline neutralized product a 2.
  • Object b 2 was obtained.
  • Example 2 An iron-containing sulfur-introduced titanium oxide c 2 was obtained in the same manner as in Example 1 except that the heat-treated product b 2 was used instead of the heat-treated product b 1.
  • Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 2 and the measurement results of its photocatalytic performance.
  • a heat-treated product b3 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a3 was used instead of the iron-containing titanium salt alkaline neutralized product a1.
  • a heat-treated product b4 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a4 was used instead of the iron-containing titanium salt alkaline neutralized product a1.
  • Example 5 An iron-containing sulfur-introduced titanium oxide c 4 was obtained in the same manner as in Example 1 except that the heat-treated product b 4 was used instead of the heat-treated product b 1. Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c4 and the photocatalytic performance measurement results. [Example 5]
  • the neutralized slurry is mixed with iron chloride (F e C 1 3 ⁇ H 2 0 (stock the company manufactured by Wako pure Chemical Industries, Ltd.)) aqueous solution, and 0.1 parts by iron atoms relative to 1 0 0 parts by weight when the titanium emission salt Al Chikarari neutralized product of the slurry in one T i O 2 converted
  • iron chloride Fe C 1 3 ⁇ H 2 0 (stock the company manufactured by Wako pure Chemical Industries, Ltd.)
  • the iron-containing titanium salt alkali neutralized product a5 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a5 was obtained.
  • a heat-treated product b5 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkali neutralized product a1 was used instead of the iron-containing titanium salt alkaline neutralized product a1.
  • the iron content was 0.10% by mass.
  • An iron-containing sulfur-introduced titanium oxide c5 was obtained in the same manner as in Example 1 except that the heat-treated product b5 was used instead of the heat-treated product b1.
  • Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c5 and the photocatalytic performance measurement results.
  • a heat-treated product e1 was obtained in the same manner as in Example 1 except that the titanium salt alkali neutralized product dl was used instead of the iron-containing titanium salt alkali neutralized product a1.
  • a sulfur-containing titanium oxide f 1 was obtained in the same manner as in Example 1 except that the heat-treated product b 1 was used instead of the heat-treated product b 1.
  • Table 1 shows the characteristics of this sulfur-containing titanium oxide f1 and the photocatalytic performance measurement results.
  • an aqueous solution of iron chloride (F e C 1 3 ⁇ H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.)) and neutralized titanium salt alkali in the slurry when converted to T io 2
  • iron chloride Fe C 1 3 'H 2 0 (stock) (Wako Pure Chemicals Co., Ltd.)
  • An aqueous solution is made of iron with respect to 100 parts by mass when converted to Ti 0 2 of the neutralized titanate in the slurry. Except for adding 0.1 part by mass as an atom, the same procedure as in Example 1 was performed to obtain an iron-containing titanium salt aluminum force neutralized product d2.
  • a heat-treated product e2 was obtained in the same manner as in Example 1 except that the iron-containing titanium salt alkaline neutralized product a1 was used instead of the iron-containing titanium salt alkaline neutralized product d2.
  • An iron-containing sulfur-introduced titanium oxide f 2 was obtained in the same manner as in Example 1 except that the heat-treated product b 2 was used instead of the heat-treated product b 1.
  • Table 1 shows the characteristics of this iron-containing sulfur-introduced titanium oxide f 2 and the photocatalytic performance measurement results.
  • titanium tetrachloride aqueous solution titanium concentration: 4% by mass
  • iron chloride FeC 1 3 ⁇ H 2 o (Made by Mitsuru Pure Chemical Co., Ltd.)
  • the aqueous solution was added so that the amount of iron atom was 0.05 parts by mass with respect to 100 parts by mass of titanium tetrachloride when converted to Tio 2 , and then heated to 60 ° C.
  • aqueous ammonia was added all at once, and neutralized at 60 ° C. for 1 hour so that the pH of the reaction system was maintained at 7.4 to obtain a slurry.
  • This slurry was heated at 110 for 24 hours to evaporate and remove water to obtain a solid.
  • the obtained solid was washed with pure water twice and filtered twice. It was dried at 10 hours for 24 hours to obtain an iron-containing titanium salt aluminum neutralized product a6.
  • a heat-treated product b 6 was prepared in the same manner as in Example 1, except that the iron-containing titanium salt alkaline neutralized product a 1 was used instead of the iron-containing titanium salt alkaline neutralized product a 6.
  • Example 7 Example except that the heat-treated product b 6 is used instead of the heat-treated product b 1 In the same manner as in Example 1, iron-containing sulfur-introduced titanium oxide c6 was obtained. Table 2 shows the measurement results of the characteristics and photocatalytic performance of the iron-containing sulfur-introduced titanium oxide c6. [Example 7]
  • Iron chloride (Fe C 1 3 ⁇ H 2 0 (Wako Pure Chemical Industries, Ltd.)) Aqueous solution of iron tetrachloride relative to 100 parts by mass of titanium tetrachloride when converted to TiO 2 Instead of putting it in mass parts, the iron chloride (Fe C 1 3 ⁇ H 2 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) aqueous solution was used to convert titanium tetrachloride into Ti O 2 at 1 00
  • An iron-containing titanium salt alkali neutralized product a7 was obtained in the same manner as in Example 6 except that the iron atom was added in an amount of 0.1 part by mass with respect to part by mass.
  • a heat-treated product b7 was obtained in the same manner as in Example 1, except that the iron-containing titanium salt alkali neutralized product a1 was used instead of the iron-containing titanium salt alkaline neutralized product a7. It was.
  • An iron-containing sulfur-introduced titanium oxide c7 was obtained in the same manner as in Example 1 except that the heat-treated product b1 was used instead of the heat-treated product b1.
  • Table 2 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c7.
  • Comparative Example 3 Put the sulfur-containing titanium oxide f 1 obtained in Comparative Example 1 in pure water, stir it, and then add an aqueous solution of iron chloride (Fe C 1 3 ⁇ H 2 0 (manufactured by Wako Pure Chemical Industries, Ltd.)) The titanium oxide fl contained was added so as to be 0.05 parts by mass of iron atoms with respect to 100 parts by mass when converted to Ti 0 2 and stirred for 30 minutes to obtain a suspension. After stirring, the obtained suspension was filtered, and the filtered powder was dried at 110 ° C. for 12 hours to obtain a copper-colored sulfur-containing titanium oxide g 3. Table 2 shows the measurement results of the characteristics and photocatalytic performance of this sulfur-containing titanium oxide powder g3.
  • Iron chloride Fe C 1 3 ⁇ H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.) Sulfur-containing ⁇ "Titanium oxide f 1 when converted to TiO 2 , iron atoms with respect to 100 parts by mass Instead of adding 0.05 parts by mass, iron chloride (Fe C 1 3 'H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.)) aqueous solution, sulfur-containing titanium oxide f 1 T i O 2 A bronze sulfur-containing titanium oxide g 4 was obtained in the same manner as in Comparative Example 3 except that the iron atom was added in an amount of 0.1 part by mass with respect to 100 parts by mass when converted. Table 2 shows the measurement results of characteristics and photocatalytic performance of this sulfur-containing titanium oxide g4.
  • the iron-containing titanium salt Al force neutralization obtained by adding an iron compound to the slurry containing the neutralized titanium salt alkali obtained by neutralizing the titanium salt with Al force
  • the iron-containing sulfur-introduced titanium oxide obtained by reacting the product with the sulfur compound has the best decomposition performance into carbon dioxide gas, and then the titanium salt in the titanium salt solution containing the iron compound.
  • the iron-containing titanium salt alkali neutralized product obtained by neutralization with Al is reacted with the sulfur compound.
  • the iron-containing sulfur-introduced titanium oxide obtained in this way had good decomposition performance into carbon dioxide.
  • a heat-treated product b8 was obtained in the same manner as in Example 4 except that the heat treatment temperature in the heat treatment was changed to 350 ° C instead of 250 ° C.
  • Example 9 An iron-containing sulfur-introduced titanium oxide c8 was obtained in the same manner as in Example 4 except that the heat-treated product b4 was used instead of the heat-treated product b4. Table 3 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c8.
  • a heat-treated product b9 was obtained in the same manner as in Example 4 except that the heat treatment temperature in the heat treatment was changed to 300 ° C instead of 250 ° C.
  • An iron-containing sulfur-introduced titanium oxide c9 was obtained in the same manner as in Example 4 except that the heat-treated product b9 was used instead of the heat-treated product b4.
  • Table 3 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c9.
  • a heat-treated product b 10 was obtained in the same manner as in Example 4 except that the heat treatment temperature in the heat treatment was changed to 200 ° C. instead of 250 ° C.
  • Example 1 An iron-containing sulfur-introduced titanium oxide c 10 was obtained in the same manner as in Example 4 except that the heat-treated product b 4 was used instead of the heat-treated product b 4.
  • Table 3 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c10.
  • Example 4 Manufacture of iron-containing titanium salt aluminum neutralized product, heat treatment and calcination
  • Example 4 except that the calcination temperature in the calcination was set to 4-50 ° C instead of 400 ° C.
  • iron-containing sulfur-introduced titanium oxide c 1 1 was obtained.
  • Table 3 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c 11.
  • Example 4 The same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 2.
  • the iron-containing titanium salt aluminum strength neutralized product a 1 2 and thiourea pulverized in a mortar are converted to Ti 0 2 of the iron-containing titanium salt aluminum strength neutralized product a 12 It mixed so that the mass of a sulfur atom might be 5 mass parts with respect to a mass part, and the mixture was obtained.
  • the mixture was heat-treated at 300 ° C. for 3 hours under atmospheric pressure, and the fired product obtained was pulverized with a ball mill to obtain the heat-treated product b 12.
  • the iron content was 36 ° C. and 36 ° C.
  • the mass of sulfur atoms is 40 parts by mass with respect to 100 parts by mass of the heat-treated product b 1 2 and thiourea pulverized in a mortar when the heat-treated product b 1 2 is converted to Ti 0 2 So that a mixture was obtained.
  • the mixture was baked at 400 ° C. for 2.5 hours in a baking furnace.
  • the obtained fired product was pulverized with a ball mill, washed with pure water, and dried at 110 ° C. to obtain yellow to yellow-orange iron-containing sulfur-introduced titanium oxide c 12.
  • Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c12.
  • the heating was carried out in the same manner as in Example 12 except that the iron-containing titanium salt aluminum strength neutralized product a 1 2 was used instead of the iron-containing titanium salt aluminum strength neutralized product a 1 3.
  • the treated product b 1 3 was obtained.
  • the mass of sulfur atoms is 40 parts by mass with respect to 100 parts by mass of the heat-treated product b 1 2 and thiourea pulverized in a mortar when the heat-treated product b 1 2 is converted to Ti 0 2
  • the heat-treated product b 1 3 is converted to TiO 2
  • the mass of sulfur atoms is 20 parts by mass with respect to 100 parts by mass of the obtained iron
  • the iron-containing sulfur-introduced titanium oxide c 1 3 is obtained. It was.
  • Table 4 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c13.
  • Example 4 The same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 4.
  • the heating was carried out in the same manner as in Example 12 except that the iron-containing titanium salt aluminum strength neutralized product a 1 2 was used instead of the iron-containing titanium salt aluminum strength neutralized product a 1 4.
  • the treated product b 1 4 was obtained.
  • the iron-containing sulfur-introduced titanium oxide c 14 was obtained in the same manner as in Example 13 except that the firing temperature in the firing was changed to 400 ° C. instead of 450 ° C.
  • Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c14.
  • the iron-containing titanium salt alkaline product a 15 is used, and thiourea is added to the iron-containing titanium salt alkaline product a 1 2.
  • the so mass of sulfur atom relative to 1 00 parts by weight when T i O 2 converted is 5 parts by weight, instead of mixing, the Chio urea, iron-containing titanium salts Al Chikarari neutralization Except for mixing so that the mass of sulfur atoms is 10 parts by mass with respect to 100 parts by mass of product a 15 converted to Ti O 2 , the same procedure as in Example 12 was performed. And the heat-treated product b 15 was obtained.
  • An iron-containing sulfur-introduced titanium oxide c 15 was obtained in the same manner as in Example 14 except that the heat-treated product b 15 was used instead of the heat-treated product b 14.
  • Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide c 15.
  • Example 12 heat treatment was carried out in the same manner as in Example 12 except that the iron-containing titanium salt Al neutralized product d 5 was used. 5 was obtained.
  • Example 14 A treatment was performed in the same manner as in Example 14 except that the heating compound e 5 was used instead of the heating compound b 14 to obtain iron-containing sulfur-introduced titanium oxide f 5.
  • Table 4 shows the measurement results of the characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide f5.
  • the iron-containing titanium salt A heat-treated product e6 was obtained in the same manner as in Example 12 except that the neutralized product d6 was used.
  • An iron-containing sulfur-introduced titanium oxide f6 was obtained in the same manner as in Example 14 except that the heat-treated product e6 was used instead of the heat-treated product b14.
  • Table 4 shows the measurement results of characteristics and photocatalytic performance of this iron-containing sulfur-introduced titanium oxide f6.
  • the heat-treated product b 1 was prepared in the same manner as in Example 12 except that the iron-containing titanium salt alkaline neutralized product a 1 6 was used instead of the iron-containing titanium salt alkaline neutralized product a 1 2. 6 was obtained.
  • An iron-containing sulfur-introduced titanium oxide h 16 was obtained in the same manner as in Example 12 except that the heat-treated product b 1 6 was used instead of the heat-treated product b 1 2.
  • the obtained iron-containing sulfur-introduced titanium oxide h 1 6 was put into pure water, stirred, and an aqueous solution of iron chloride (Fe C 1 3 ⁇ H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.))
  • the sulfur-introduced titanium oxide h 16 is added to 100 parts by mass when converted to Ti 0 2 so that it becomes 0.05 parts by mass as iron atoms, and stirred for 30 minutes to obtain a suspension. It was.
  • Table 5 shows the measurement results of characteristics and photocatalytic performance of the iron-containing sulfur-introduced titanium oxide c 16.
  • An iron-containing sulfur-introduced titanium oxide h 1 7 was obtained in the same manner as in Example 13 except that the heat-treated product b 1 7 was used instead of the heat-treated product b 1 3.
  • the iron-containing sulfur-introduced titanium oxide h 1 7 is put into pure water, stirred, and an aqueous solution of iron chloride (FeC 1 3 ⁇ H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.)) Sulfur-introduced titanium oxide h 17 was added to 100 parts by mass when converted to Ti O 2 so that the amount was 0.1 parts by mass as iron atoms, and stirred for 30 minutes to obtain a suspension. .
  • Example 4 The same procedure as in Example 4 was performed to obtain an iron-containing titanium salt aluminum neutralized product a 1 8.
  • the heat-treated product b 1 was prepared in the same manner as in Example 12 except that the iron-containing titanium salt alkaline neutralized product a 1 8 was used instead of the iron-containing titanium salt alkaline neutralized product a 1 2. 8 got.
  • An iron-containing sulfur-introduced titanium oxide h 1 8 was obtained in the same manner as in Example 13 except that the heat-treated product b 1 8 was used instead of the heat-treated product b 1 3.
  • the iron-containing sulfur-introduced titanium oxide h 1 8 is put into pure water, stirred, and an aqueous solution of iron chloride (Fe C 1 3 ⁇ H 2 O (manufactured by Wako Pure Chemical Industries, Ltd.)) and 0.0 3 parts by weight of iron atoms of sulfur introduced titanium oxide h 1 8 and against the 1 0 0 parts by weight when T i O 2 converted - so as to put, stirred for 30 minutes, A suspension was obtained.
  • Table 5 shows the measurement results of the properties and photocatalytic performance of this iron-introduced sulfur-containing titanium oxide c 18.
  • titanium tetrachloride aqueous solution titanium concentration: 4% by mass
  • iron chloride Fe C 1 3 ⁇ H 2 O (Made by Mitsuru Pure Chemical Co., Ltd.)
  • Aqueous solution was put in an amount of 0.05 parts by mass as iron atoms with respect to 100 parts by mass of titanium tetrachloride when converted to Ti O 2 , and then heated to 60 ° C. Heated. Next, ammonia water was added all at once, and the mixture was neutralized at 60 for 1 hour so that the pH of the reaction system was maintained at 7.4 to obtain a slurry.
  • This slurry was heated at 110 ° C. for 24 hours to evaporate and remove water to obtain a solid, and the obtained solid was washed twice with pure water and filtered twice. It was dried at 110 ° C for 24 hours to obtain a neutralized iron-containing titanium salt.
  • the heat-treated product was obtained in the same manner as in Example 13 except that the iron-containing titanium salt aluminum strength neutralized product a 1 3 was used instead of the iron-containing titanium salt aluminum strength neutralized product a 19. b 1 9 was obtained.
  • An iron-containing sulfur-introduced titanium oxide c 19 was obtained in the same manner as in Example 13 except that the heat-treated product b 19 was used instead of the heat-treated product b 13.
  • Table 5 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 19 and the measurement results of its photocatalytic performance.
  • a round bottom flask equipped with a stirrer was charged with 1 000 g of pure water and then heated to 60 ° C. Titanium tetrachloride aqueous solution (titanium concentration: 6% by mass) 2 00 g and ammonia water (28%) diluted 5 times with pure water 2 05 7 g Over time, dripping and neutralization were performed.
  • An iron-containing sulfur-introduced titanium oxide c20 was obtained in the same manner as in Example 1 except that the heat-treated product b1 was used instead of the heat-treated product b1.
  • Table 6 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 20 and the measurement results of its photocatalytic performance.
  • Example 2 1 A round bottom flask equipped with a stirrer was charged with 1 000 g of pure water and then heated to 60 ° C. Titanium tetrachloride aqueous solution (titanium concentration: 6% by mass) 20 00 g and ammonia water (28%) diluted 5 times with pure water 2057 g, both of which take 3 hours to neutralize Then, dripping and neutralization were performed. This liquid was heated at 110 ° C. for 24 hours to evaporate and remove water, and then the obtained solid was washed with pure water and filtered twice. The filtered powder was dried at 110 ° C. for 24 hours.
  • Example 2 The same procedure as in Example 1 was conducted except that the iron-containing titanium salt alkali neutralized product a 2 1 was used instead of the iron-containing titanium salt alkali neutralized product a 1, and the heat-treated product b 2 1 was used. Obtained.
  • the iron content was 0.07% by mass.
  • An iron-containing sulfur-introduced titanium oxide c 2 1 was obtained in the same manner as in Example 1 except that the heat-treated product b 2 1 was used instead of the heat-treated product b 1.
  • Table 6 shows the characteristics of this iron-containing sulfur-introduced titanium oxide c 21 and the photocatalytic performance measurement results.
  • titanium oxide having high photocatalytic activity with visible light can be produced.

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Abstract

L'invention concerne un procédé de fabrication d'un oxyde de titane à soufre introduit, à teneur en métal, qui est caractérisé par le fait qu'il comprend une étape de cuisson pour obtenir un oxyde de titane à soufre introduit, à teneur en métal, par cuisson d'un mélange d'une matière première oxyde de titane à teneur en métal et d'un composé du soufre. Ce procédé de fabrication d'un oxyde de titane à soufre introduit, à teneur en métal, est encore caractérisé par le fait que la teneur en métal dans la matière première à oxyde de titane à teneur en métal est de 0,03-0,15 partie en masse en tant qu'atomes métalliques, par rapport à 100 parties en masse de la matière première à oxyde de titane à teneur en métal en termes de TiO2. Ce procédé permet de fabriquer un oxyde de titane à teneur en soufre à métal introduit qui présente une activité photocatalytique élevée sous la lumière visible. L'invention concerne également un oxyde de titane à soufre introduit à teneur en métal.
PCT/JP2007/075344 2006-12-26 2007-12-21 Procédé de fabrication d'oxyde de titane à soufre introduit, à teneur en métal, et oxyde de titane à soufre introduit à teneur en métal WO2008081957A1 (fr)

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JP2006-349264 2006-12-26
JP2006-349265 2006-12-26
JP2006349264 2006-12-26
JP2006349265 2006-12-26

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WO2008081957A1 true WO2008081957A1 (fr) 2008-07-10

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Cited By (2)

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JP2010104963A (ja) * 2008-10-31 2010-05-13 Toho Titanium Co Ltd 硫黄含有酸化チタン化合物、硫黄含有酸化チタン化合物の製造方法および硫黄含有酸化チタン化合物分散液
CN113972381A (zh) * 2021-10-22 2022-01-25 广东技术师范大学 硫电极电化学反应双功能催化剂及其制备方法

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WO2019142695A1 (fr) * 2018-01-16 2019-07-25 昭和電工株式会社 Catalyseur de réduction d'oxygène

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JP2003190811A (ja) * 2001-12-27 2003-07-08 Sumitomo Chem Co Ltd 光触媒体、その製造方法およびそれを用いてなる光触媒体コーティング剤
WO2005014170A1 (fr) * 2003-08-08 2005-02-17 Kabushiki Kaisha Toyota Chuo Kenkyusho Materiau photocatalyseur activable par lumiere visible, materiau brut correspondant, et procede de production dudit materiau photocatalyseur
WO2005087372A1 (fr) * 2004-03-12 2005-09-22 Toho Titanium Co., Ltd. Oxide de titane photo-catalysateur et methode de préparation

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JP2003190811A (ja) * 2001-12-27 2003-07-08 Sumitomo Chem Co Ltd 光触媒体、その製造方法およびそれを用いてなる光触媒体コーティング剤
WO2005014170A1 (fr) * 2003-08-08 2005-02-17 Kabushiki Kaisha Toyota Chuo Kenkyusho Materiau photocatalyseur activable par lumiere visible, materiau brut correspondant, et procede de production dudit materiau photocatalyseur
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OHNO T. ET AL.: "Sensitization of photocatalytic activity of S- or N-doped TiO2 particles by adsorbing Fe3+ cations", APPLIED CATALYSIS A: GENERAL, ELSEVIER B.V., vol. 302, no. 1, 21 March 2006 (2006-03-21), pages 62 - 68 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010104963A (ja) * 2008-10-31 2010-05-13 Toho Titanium Co Ltd 硫黄含有酸化チタン化合物、硫黄含有酸化チタン化合物の製造方法および硫黄含有酸化チタン化合物分散液
CN113972381A (zh) * 2021-10-22 2022-01-25 广东技术师范大学 硫电极电化学反应双功能催化剂及其制备方法
CN113972381B (zh) * 2021-10-22 2023-03-31 广东技术师范大学 硫电极电化学反应双功能催化剂及其制备方法

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