CN103079703B - The manufacture method of photochemical catalyst tunicle and photochemical catalyst tunicle - Google Patents

The manufacture method of photochemical catalyst tunicle and photochemical catalyst tunicle Download PDF

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Publication number
CN103079703B
CN103079703B CN201180040228.8A CN201180040228A CN103079703B CN 103079703 B CN103079703 B CN 103079703B CN 201180040228 A CN201180040228 A CN 201180040228A CN 103079703 B CN103079703 B CN 103079703B
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photochemical catalyst
tunicle
slurry
titanium dioxide
water
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CN103079703A (en
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原贺久人
通口友彦
永吉英昭
吉永宏
梅田阳平
山崎健之
横野照尚
森田洋
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Public University University Of Kitakyushu
Kyushu Institute of Technology NUC
Hosokawa Micron Corp
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Kyushu Institute of Technology NUC
Hosokawa Micron Corp
Kitakyushu Foundation for Advancement of Industry Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
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    • 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
    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1258—Spray pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
    • C23C18/127—Preformed particles

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Abstract

The object of the invention is to the high fabrication yield of the titanium dioxide tunicle realizing having supported iron.In order to reach such object, generating the water slurry being mixed with titania powder and ferric chloride in aqueous solution, the water slurry generated is carried out spraying plating by spray technique.FeO (OH) can be made when spraying plating to support in titania powder while by photochemical catalyst tunicle film forming, therefore realize the significantly raising of fabrication yield.

Description

The manufacture method of photochemical catalyst tunicle and photochemical catalyst tunicle
Technical field
The present invention relates to manufacture method and the photochemical catalyst tunicle of photochemical catalyst tunicle.Specifically, manufacture method and the photochemical catalyst tunicle of the photochemical catalyst tunicle such as with the photochemical catalyst function can carrying out the innoxious, antibacterial of polluter and sterilization is related to.
Background technology
Along with the progress of aging society, the ratio shared in total population of the People of immunity degradation is in the tendency of increase, accompany with it, from the view point of the prevention of nosocomial infection, food poisoning etc., the strengthening of the administration of health in medical treatment scene, food production and processing site becomes the problem be critical.Be subject to the background of such society, exploitation has various antibacterial fabricated product, in recent years, receives much concern especially to the utilization of the photochemical catalyst function of antibacterial processing.
At this, so-called " photochemical catalyst function ", when referring to that irradiation is greater than the light energy of band gap energy of its conduction band and valence band, become excited state, generate electron-hole pair and cause the function that the catalyst material (photosemiconductor material) of oxidation and reduction reaction has.
In photochemical catalyst, particularly employ titanium dioxide (TiO 2), especially there is the photochemical catalyst of the TiO 2 particles of the crystalline texture of rutile-type, cheap, the excellent in stability of chemistry, and there is high catalyst activity, active by the organic substance decomposing of its brute force, can merge the harmful substance such as endotoxin and bacteriogenic toxin (dimension sieve toxin that such as pathogenic Escherichia coli produces) of decomposing as the cell membrane outer wall composition of Gram-negative bacteria with the thalline of bacterium, and to have photochemical catalyst self to human body be harmless such advantage simultaneously.
Therefore, carry out the Study and appliance of the photochemical catalyst employing titanium dioxide, in the antibacterial processing of food containers, building materials etc., widely use titanium dioxide optical catalyst (such as with reference to patent document 1 and patent document 2).
It should be noted that, because titanium dioxide only just manifests photocatalyst activity under Ultraviolet radiation, therefore, sufficient catalyst activity can not be manifested under hardly containing the room light of UV-shares.Therefore, there will be a known metal or the FeCl by making iron etc. 3deng metal complex or slaine and the iron compound supported technology manifesting photocatalyst activity in titanium dioxide under visible light illumination.
But, in the past, when manufacture manifest the photochemical catalyst tunicle of photocatalyst activity under visible light illumination, make the Photocatalyst Composite containing the titania powder supporting sensitizer be scattered in such as coating etc., implement application on the surface of the building materials as object etc. to manufacture photochemical catalyst tunicle.
Such as, specifically, first at the iron chloride (FeCl as sensitizer 3) impregnated with titania (TiO in the aqueous solution 2), stir, make and make iron, iron compound supported in titanium dioxide, the Photocatalyst Composite of titanium dioxide having supported iron, iron compound, then, make Photocatalyst Composite be scattered in coating, carry out application (such as with reference to patent document 3) on the surface of building materials etc.
Prior art document
Patent document
Patent document 1: JP 2007-51263 publication
Patent document 2: JP 2006-346651 publication
Patent document 3: JP 2007-090336 publication
Summary of the invention
The problem that invention will solve
But, make iron compound supported in the Photocatalyst Composite of titanium dioxide, in its process, manufacturing process, need the time extremely grown, the raising of quality requiring the shortening realizing manufacturing process to cause, the reduction of cost or their stabilisation.
The present invention invents in view of above aspect, its object is to, the manufacture method of the photochemical catalyst tunicle providing shortening, stay in grade, the cost that can carry out manufacturing process to reduce and photochemical catalyst tunicle.
For solving the means of problem
In order to achieve the above object, the manufacture method of the photochemical catalyst tunicle that the present invention relates to possesses: form the operation containing at least a kind of compound of photocatalyst particles, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water; Described slurry is carried out spraying plating and at least a kind of form of the hydroxide of Fe, Cu, Cr, Ni of making the metal ion of at least a kind of above-claimed cpd and water react and generate, oxyhydroxide or oxide supports the photocatalyst particles in above-mentioned slurry, simultaneously the operation of this photocatalyst particles stacked on object.
At this, by being formed containing at least a kind of compound of photocatalyst particles, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water, this slurry is carried out spraying plating, the water-soluble metal complexes of Fe, Cu, Cr, Ni or the metal ion of water-soluble metal salt and water react and generate the hydroxide of very fine Fe, Cu, Cr, Ni of nano-scale, oxyhydroxide or oxide, and these hydroxide, oxyhydroxide or oxide uniformly distribute at photocatalyst particles, support.
In addition, the Fe that the metal ion of at least a kind of above-claimed cpd and water react and generates is made by slurry is carried out spraying plating, Cu, Cr, the hydroxide of Ni, at least a kind of form of oxyhydroxide or oxide supports the photocatalyst particles in slurry, this photocatalyst particles stacked on object simultaneously, namely by making Fe in advance before stacked photocatalyst particles on object, Cu, Cr, the hydroxide of Ni, at least a kind of form of oxyhydroxide or oxide does not support in photocatalyst particles ground spraying plating slurry, the very fine Fe of nano-scale, Cu, Cr, the hydroxide of Ni, oxyhydroxide or oxide are scattered in photocatalyst particles surface and are supported, significantly shortening and the performance of photochemical catalyst function tunicle and the stabilisation of quality of manufacturing process can be reached.
It should be noted that, as " water-soluble metal complexes of Fe, Cu, Cr, Ni ", include, for example [Cu (NH 3) 4] 2+, [Fe (CN) 6] 4-, [Fe (CN) 6] 3-, C 10h 12feN 2o 8deng, as " water-soluble metal salt of Fe, Cu, Cr, Ni ", include, for example FeCl 3, Fe 2(SO 4) 3, Fe (NO 3) 3, CuSO 4, Cu (NO 3) 2, CuCl 2, Ni (NO 3) 2, NiCl 2, NiSO 4, Cr (NO 3) 3deng.
In addition, as " hydroxide of Fe, Cu, Cr, Ni that the water-soluble metal complexes of Fe, Cu, Cr, Ni and water react and generates, oxyhydroxide or oxide ", include, for example CuO, Cu (OH) 2, FeO (OH), Fe (OH) 3deng, as " oxide of Fe, Cu, Cr, Ni that the slaine of Fe, Cu, Cr, Ni and water react and generates, oxyhydroxide or oxide ", include, for example FeO (OH), Fe (OH) 3, Cu (OH) 2, CuO, Ni (OH) 2, NiO (OH), Cr (OH) 3, Cr 2o (OH) 4, Cr 2o 3deng.
It should be noted that, think, in metallization process, because spraying plating flame is at a high speed close to vacuum state, so, there is the reaction of the water in the water-soluble metal complexes of Fe, Cu, Cr, Ni or the metal ion of water-soluble metal salt and slurry and the oxygen in air, become hydroxide, oxyhydroxide or oxide, think, the anion of chlorion, nitrate ion etc. etc. are volatilized by the heat of spraying plating, be spread in air.
At this, when the hydroxide of Fe, Cu, Cr, Ni, oxyhydroxide or oxide present visible light-responded function, under visible light illumination, excited by the hydroxide of Fe, Cu, Cr, Ni of having supported, oxyhydroxide or oxide, excitation electron moves to photocatalyst particles side, thus in the hydroxide of Fe, Cu, Cr, Ni, oxyhydroxide or oxide surface generation oxidation reaction, there is reduction reaction on photocatalyst particles surface, manifest visible light-responded property (with reference to Figure 1A).
It should be noted that, what is called presents the hydroxide of Fe, Cu, Cr, Ni of visible light-responded function, oxyhydroxide or oxide, can enumerate FeO (OH), Fe (OH) 3, Cu (OH) 2, CuO, Ni (OH) 2, NiO (OH), Cr (OH) 3, Cr 2o (OH) 4, Cr 2o 3deng.
In addition, when the hydroxide of Fe, Cu, Cr, Ni, oxyhydroxide or oxide present co-catalyst function, under Ultraviolet radiation, photocatalyst particles excites, excitation electron moves to the hydroxide of Fe, Cu, Cr, Ni, oxyhydroxide or oxide side, oxidation reaction is there is thus on photocatalyst particles surface, in the hydroxide of Fe, Cu, Cr, Ni, oxyhydroxide or oxide surface generation reduction reaction, be separated by electrification, properties of catalyst improves (with reference to Figure 1B).
It should be noted that, what is called presents the hydroxide of Fe, Cu, Cr, Ni of co-catalyst function, oxyhydroxide or oxide, can enumerate Fe 2o 3, CuO, NiO etc.
In addition, the manufacture method of the photochemical catalyst tunicle that the present invention relates to possesses: form the operation containing at least a kind of compound of photocatalyst particles, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water; Above-mentioned slurry is carried out spraying plating and the operation of the photocatalyst particles contained in this slurry stacked on object.
At this, form the slurry of at least a kind of compound and the water containing photocatalyst particles, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt, this slurry is carried out spraying plating, the water-soluble metal complexes of Fe, Cu, Cr, Ni or the metal ion of water-soluble metal salt and water react and generate the hydroxide of very fine Fe, Cu, Cr, Ni of nano-scale, oxyhydroxide or oxide thus, and these hydroxide, oxyhydroxide or oxide uniformly distribute at photocatalyst particles, support.
In addition, the photocatalyst particles contained in this slurry stacked on object by spraying plating slurry, namely by making Fe in advance before stacked photocatalyst particles on object, Cu, Cr, the hydroxide of Ni, at least a kind of form of oxyhydroxide or oxide does not support in photocatalyst particles ground spraying plating slurry, the Fe that nano-scale is very fine, Cu, Cr, the hydroxide of Ni, oxyhydroxide or oxide are scattered in photocatalyst particles surface and are supported, significantly shortening and the performance of photochemical catalyst function tunicle and the stabilisation of quality of manufacturing process can be reached.
And, in the slurry of the photocatalyst particles containing titanium dioxide etc. containing antibacterial metal (containing silver be such as also, copper system, zinc system, aluminium system, nickel system, at least a kind in the metal of cobalt system or chromium system), antibacterial metal salts or antibacterial metal complex, will containing antibacterial metal, the slurry of antibacterial metal salts or antibacterial metal complex carries out spraying plating, thus can be selected from metal together with photocatalyst particles, slaine, metal complex, oxyhydroxide, hydroxide, or the stacked antibacterial metal of at least one form in oxide or antibacterial metal complex, the photochemical catalyst function tunicle with powerful antibacterial action can be manufactured.
In addition, by adding pigment in the slurry of the photocatalyst particles containing titanium dioxide etc., the slurry simultaneously containing photocatalyst particles and pigment being carried out spraying plating, stackedly can contain the photocatalyst particles of pigment, the photochemical catalyst tunicle that coloury design is high can be manufactured.
In addition, by adding sorbing material (such as zeolite etc.) in the slurry of the photocatalyst particles containing titanium dioxide etc., the slurry simultaneously containing photocatalyst particles and sorbing material being carried out spraying plating, can together with photocatalyst particles stacked sorbing material, the photochemical catalyst tunicle with high gas sorption ability can be manufactured.
In addition, in order to achieve the above object, the photochemical catalyst tunicle that the present invention relates to, following manufacture: formed containing at least a kind of compound of photocatalyst particles, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water, described slurry is carried out spraying plating, at least a kind of form of the hydroxide of Fe, Cu, Cr, Ni of making the metal ion of at least a kind of above-claimed cpd and water react and generate, oxyhydroxide or oxide supports the photocatalyst particles in above-mentioned slurry, simultaneously this photocatalyst particles stacked on object.
In addition, the photochemical catalyst tunicle that the present invention relates to, following manufacture: formed containing at least a kind of compound of photocatalyst particles, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water, above-mentioned slurry is carried out spraying plating and the photocatalyst particles that contains in this slurry stacked on object.
It should be noted that, as the object of stacked photocatalyst particles, ceramic tile, sanitary earthenware, glass, mirror, the building materials of concrete, resinous building materials, metal building materials, resin molding, metallic fiber, glass fibre, carbon fiber can be enumerated, employ the filter etc. of these fibers.
The effect of invention
In the manufacture method applying photochemical catalyst tunicle of the present invention, photochemical catalyst tunicle can be manufactured with the manufacturing process shortened significantly, therefore little in the quality of tunicle, the performance upper deviation, high quality and fabrication yield can be realized.In addition, for applying photochemical catalyst tunicle of the present invention, also high quality can be realized.
Accompanying drawing explanation
Figure 1A is the schematic diagram for illustration of visible light-responded function.
Figure 1B is the schematic diagram for illustration of co-catalyst function.
Fig. 2 is the schematic diagram for illustration of coating apparatus.
Fig. 3 is the use of the analysis result of the crystalline texture of the XRD by the manufacture method and the photochemical catalyst tunicle obtained applying photochemical catalyst tunicle of the present invention.
Fig. 4 is the use of the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle obtained by the manufacture method of photochemical catalyst tunicle in the past.
Fig. 5 is the use of and after the film forming of titanium dioxide tunicle, supports iron and the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle obtained.
Fig. 6 is the concept map of the Test model synthetic techniques of the gas decomposability test of photochemical catalyst tunicle.
Fig. 7 is aldehydes gas decomposition run result (1).
Fig. 8 is aldehydes gas decomposition run result (2).
Fig. 9 is the concept map of the evaluation test method of the bactericidal effect of photochemical catalyst tunicle.
Figure 10 is the evaluation test result of the bactericidal effect of photochemical catalyst tunicle.
Figure 11 is the aldehydes gas decomposition run result applying photochemical catalyst tunicle of the present invention.
Figure 12 is the Escherichia coli BA result applying photochemical catalyst tunicle of the present invention.
Figure 13 is the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle having supported pigment.
Figure 14 is the use of the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle obtained with front supporting method.
The analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle that Figure 15 supports method after being the use of and using and obtains.
Detailed description of the invention
Below, for the mode (hereinafter referred to as " embodiment ") for carrying out an invention, with reference to accompanying drawing, while be described.
< 1. supports > for iron
In the example of manufacture method applying photochemical catalyst tunicle of the present invention, set up in 2 techniques of (1) water slurry generating process, (2) sprayed formation process.Below, each technique is described in detail.
[1. water slurry generating process]
In the example of manufacture method applying photochemical catalyst tunicle of the present invention, titania powder (TiO 2) Ti composition and ferric chloride in aqueous solution (FeCl 3) the Fe composition mode of counting Ti:Fe=99:1 by weight generate the water slurry (concentration 30 % by weight) employing titania powder and ferric chloride in aqueous solution.
Specifically, generation employs particle diameter is the titania powder of the rutile-type of about about 30nm and the water slurry of ferric chloride in aqueous solution.It should be noted that, in water slurry, the titania powder of rutile-type condenses and forms the particle diameter of 1 μm ~ about 5 μm.
At this, in the present embodiment, as an example of photocatalyst particles, be described to use the situation of TiO 2 particles to enumerate, but photocatalyst particles need not be TiO 2 particles, such as, can be tungsten oxide, tin oxide etc.But, when being thought of as the excellent in stability of cheap chemistry and having the such aspect of high catalyst activity, preferably adopt titanium dioxide as photochemical catalyst.
In addition, in the present embodiment, as an example of sensitizer, to use iron chloride (FeCl 3), namely the situation of the water-soluble metal salt of iron (Fe) be that example is enumerated and is described, but sensitizer need not be water-soluble metal salt, the water-soluble metal complexes of iron (Fe), can be water-soluble metal salt and the water-soluble metal complexes of copper (Cu), chromium (Cr), nickel (Ni) etc.Wherein, when being thought of as cheap such aspect, as sensitizer, the water-soluble metal salt of iron (Fe), water-soluble metal complexes is preferably adopted.
Shown in table 1 for water slurry concentration be 10 % by weight situation and be 30 % by weight the crystalline titanium dioxide intensity of XRD determining that utilizes of situation count.It should be noted that so-called " crystalline titanium dioxide intensity counting " represents the adhesive rate (there is rate) of material.
[table 1]
Learnt by table 1: by water slurry concentration be 10 % by weight situation and be 30 % by weight situation when comparing, water slurry concentration is higher, and material input amount more increases, and adhesion amount can be made to increase.On the other hand, when water slurry concentration is more than 30 % by weight, the viscosity of water slurry too increases, and gives become difficulty when spraying plating.Therefore in the present embodiment, water slurry concentration is set as 30 % by weight.
[2. sprayed formation process]
In the example of manufacture method applying photochemical catalyst tunicle of the present invention, continue use the water slurry that generates and carry out spraying plating, film forming is carried out to photochemical catalyst tunicle.
At this, in sprayed formation process, such as can use the high speed coating apparatus of the spraying plating variable temperatures type described in JP 2005-68457 publication, specifically, as shown in Figure 2, on the flame (flame) of the high speed sprayed from spray torch by the oxygen of high pressure and the burning of kerosene, the water slurry pumping of generation is given, to collide at a high speed on object base material, thus photochemical catalyst tunicle is carried out film forming.It should be noted that, by using booster compressor mixed high-voltage air in hyperbaric oxygen, realizing the minimizing of oxygen use amount and the further high speed of flame (flame).
With regard to spraying plating temperature conditions now, flame (flame) temperature is 700 ~ 2500 DEG C, and deposition rate is 800 ~ 2000m/sec..
It should be noted that, from the front end of spray torch on flame (flame) center line, measure temperature in each position of 280mm, 300mm, 350mm, 450mm, then using the temperature of mean value as flame (flame) temperature.In addition, with regard to the mensuration of temperature, do not carry out the input of water slurry and the mixing of air, use thermocouple (be SUS material about such as to 1000 DEG C, be the thermocouple of tungsten/rhenium (W-WRe) beyond it), with flame contact and carrying out.In these, too later.
Fig. 3 is the use of the analysis result of the crystalline texture of the x-ray folded back arrangement (XRD) by the manufacture method and the photochemical catalyst tunicle obtained applying above-mentioned photochemical catalyst tunicle of the present invention.
At this, in the photochemical catalyst tunicle that obtains, adopting FeO (OH) and Fe by the manufacture method applying photochemical catalyst tunicle of the present invention 2o 3the first peakedness ratio time, become " FeO (OH): Fe 2o 3=2.25:1 ", the ratio contributing to the FeO (OH) of the Visible-light Irradiation of photochemical catalyst is many.
In addition, oxidized and generate Fe at FeO (OH) 2o 3when, Fe 2o 3although present the function as co-catalyst, be helpless to visible light-responded characteristic, therefore result, visible light-responded deterioration in characteristics.But, as shown in Figure 3, learning: there is Fe hardly in the photochemical catalyst tunicle obtained by the manufacture method applying photochemical catalyst tunicle of the present invention 2o 3peak value, the deterioration of the visible light-responded characteristic that spraying plating causes is subject to low suppression.
At this, by the scanning electron microscope-electron micrograph of energy dispersion type X-Ray Analyzer (SEM-EDS) employed by the manufacture method and the photochemical catalyst tunicle obtained that apply photochemical catalyst tunicle of the present invention and the result of the constituent analysis of element and the distributional analysis of element, learn: by the manufacture method applying photochemical catalyst tunicle of the present invention and in the photochemical catalyst tunicle obtained, the pollutant etc. of aftermentioned such Cl does not exist.This situation think because: the Cl be added under ionic condition in water slurry is volatilized by the heat of spraying plating, spread in an atmosphere before arrival object (base material), can realize the photochemical catalyst tunicle that purity is high.It should be noted that, with the EDS analysis result of the manufacture method and the photochemical catalyst tunicle obtained that apply photochemical catalyst tunicle of the present invention shown in the b of table 2.
[table 2]
Fig. 4 is the use of the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle obtained by the manufacture method of photochemical catalyst tunicle in the past.
Specifically, with rutile titania powder (TiO 2) Ti composition and ferric chloride in aqueous solution (FeCl 3) Fe composition count the mode of Ti:Fe=99:1 by weight by TiO 2powder is at FeCl 3stir 2 hours in solution, Fe is supported in TiO 2powder.Then, after this solution be dry, pulverize, carry out the classification of particle diameter, make granularity consistent with about 100 μm.Then, the water slurry (concentration 30 % by weight) of the powder of use carries out spraying plating, and carry out film forming to photochemical catalyst tunicle, the photochemical catalyst tunicle XRD obtained like this is carried out the analysis of crystalline texture, Fig. 4 is its result.It should be noted that, the manufacture method of such photochemical catalyst tunicle is conveniently called " front support method ".
But, front supporting method, namely at the iron chloride (FeCl as sensitizer 3) pre-soaked in the aqueous solution, stir titanium dioxide (TiO 2), make iron, iron compound supported in titanium dioxide, make supported iron, iron compound titanium dioxide Photocatalyst Composite method in, sometimes process need long-time, add drying process, think: support in the iron of titanium dioxide surface, possibility that the cohesion, growth, segregation etc. of iron compound cause high during this period.
On the other hand, in the present invention, the water slurry that sensitizer, antisepsis metallic compound are dissolved with the size of molecular level by spraying plating at titanium dioxide surface instantaneous set, therefore, think: sensitizer, antisepsis metallic compound carry out disperseing with nano-scale and support in titanium dioxide surface.
Therefore, think, sensitizer of the present invention, antisepsis metallic compound are compared with conventional art, and dispersiveness is very excellent, therefore can obtain high effect of enhanced sensitivity, the antibacterial effect that exceed anticipation.
At this, in the result shown in Fig. 4, learn: FeO (OH) and Fe can be observed 2o 3both peak values, the FeO (OH) contributing to the Visible-light Irradiation of photochemical catalyst utilizes heat during spraying plating oxidized, is formed and is helpless to the Fe of Visible-light Irradiation 2o 3.
It should be noted that, learn: take FeO (OH) and Fe 2o 3the first peakedness ratio time, become " FeO (OH): Fe 2o 3=1.78:1 ", with apply the manufacture method of photochemical catalyst tunicle of the present invention and the photochemical catalyst tunicle obtained compares time, Fe 2o 3ratio many.It should be noted that, due to Fe 2o 3ratio many, therefore, visible light-responded property is insufficient.
At this, by the result of the distributional analysis of the electron micrograph of SEM-EDS and the constituent analysis of element and element that employ the photochemical catalyst tunicle obtained by the method that front supports, Cl composition can be confirmed.It thinks the FeCl employed when Fe supports 3impact to cause.That is, think because: when supporting, Cl forms certain compound, utilizes the heat of spraying plating and becomes nonvolatile state, worries that the pollution of such impurity causes the photochemical catalyst characteristic of photochemical catalyst tunicle to decline.It should be noted that, the EDS analysis result of the photochemical catalyst tunicle obtained by the method that front supports shown in a of table 2.
Fig. 5 is the use of and after the film forming of titanium dioxide tunicle, supports iron and the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle obtained.
Specifically, rutile titania powder (TiO is used 2) water slurry (concentration 30 % by weight) carry out spraying plating, by TiO 2tunicle carries out film forming, and the tunicle by film forming is counting the mode of Ti:Fe=99:1 by weight at FeCl 3flood 2 hours in solution, Fe is supported in TiO 2tunicle, the photochemical catalyst tunicle XRD obtained like this is carried out the analysis of crystalline texture, Fig. 5 is its result.It should be noted that, the manufacture method of such photochemical catalyst tunicle is conveniently called " supporting method afterwards ".
It should be noted that, in the result shown in Fig. 5, do not see Fe 2o 3peak value.It is thought because FeO (OH) is not by the heat affecting that spraying plating causes.
At this, by employ with after support the result of the electron micrograph of SEM-EDS of the photochemical catalyst tunicle that method obtains and the distributional analysis of the constituent analysis of element and element, learn: with the present invention and frontly support compared with photochemical catalyst tunicle that method obtains, the ratio of Ti and Fe is high.Its think because: after supporting Fe on tunicle surface, support the characteristic of method, Fe segregation is in analysis surface.Under these circumstances, when tunicle forms the such situation of wearing and tearing, there is not Fe in tunicle inside, therefore produce the life-span of visible light-responded characteristic short like this worry.It should be noted that, after using shown in the c of table 2, support the EDS analysis result of the photochemical catalyst tunicle that method obtains.
Being learnt by above-mentioned, when front supporting method, worrying following bad: (1) to iron support need long-time; (2) ratio due to FeO (OH) is few, and therefore, visible light-responded property is poor; (3) solution when Fe supports produces baneful influence.In addition, when after support method, worry that Fe segregation is in life-span of surface, visible light-responded property short like this bad.
On the other hand, in the photochemical catalyst tunicle that obtains, do not producing so bad by the manufacture method applying photochemical catalyst tunicle of the present invention, visible light-responded property is excellent, realizes the long lifetime of visible light-responded property simultaneously.
In addition, in the manufacture method applying photochemical catalyst tunicle of the present invention, use the titania powder being in a ratio of cheap rutile-type crystalline texture with Detitanium-ore-type crystalline texture, realize cost and reduce.
At this, carry out the gas decomposability test of photochemical catalyst tunicle.
The concept map of the method for evaluation test shown in Fig. 6.Sprayed test film for evaluating is the dimetric size of about 50mm, uses chinaware ceramic tile in the substrate.Alcohol clean surface used in advance by test film, implements irradiation 12 hours ultraviolet (uitraviolet intensities: 1mW/cm 2) pre-treatment and for gas decompose evaluation test.
Decompose object gas and use acetaldehyde, adjust in the mode becoming about 450ppm in Tedlar sampler bag (125cc).Light source uses LED light (wavelength 415nm), with luminous intensity 6mW/cm 2irradiate the tunicle surface of sample.
The sample tested, for apply the manufacture method of photochemical catalyst tunicle of the present invention and the photochemical catalyst tunicle obtained and with after support the photochemical catalyst tunicle that method obtains.And in order to compare, commercially available photochemical catalyst ceramic tile and sprayed as the doping sulphur titanium oxide (Sulfur ド ー プ acidifying チ タ Application) of visible light type photochemical catalyst in also test.
The aldehydes gas decomposition run result of tunicle respective shown in Fig. 7 and Fig. 8.Learnt by Fig. 7 and Fig. 8, by the manufacture method applying photochemical catalyst tunicle of the present invention and the photochemical catalyst tunicle obtained shows high aldehydes gas degrading activity.In addition, for carbon dioxide, also see the generation of about 2 times amount of acetaldehyde, think and decompose completely.
On the other hand, even if the photochemical catalyst tunicle that the method that supports after using obtains is compared with doping sulphur titanium oxide, equal gas removing performance is also shown.But and with applying compared with the manufacture method of photochemical catalyst tunicle of the present invention and the photochemical catalyst tunicle that obtains, carbon dioxide generation is few, produces after experiment and thinks that the tart flavour of intermediate product is smelly.Therefore, infer that gas decomposition reaction is now incomplete.
To the gas decomposition run result that commercially available photochemical catalyst ceramic tile carries out, with apply the manufacture method of photochemical catalyst tunicle of the present invention and the photochemical catalyst tunicle obtained compares time, become quite low degrading activity.
In addition, the bactericidal effect of photochemical catalyst tunicle is also evaluated.
Fig. 9 represents the concept map of evaluation test method.For the sprayed test film evaluated, be the dimetric size of about 50mm, use chinaware ceramic tile in the substrate.With regard to test film, acetone clean surface, implements irradiation ultraviolet radiation (uitraviolet intensity: 1mW/cm 2) pre-treatment of 6 hours, for the evaluation test of antibacterial activity.
With regard to evaluation test method, in culture dish (diameter 90mm), respective sample is set, add colibacillary suspension 30ml, by its utilizing under the illuminate condition of fluorescent lamp (illumination 1700lux), under the state being held in 30 DEG C place after, through time measure remaining bacterial population.It should be noted that, the measurement colony counting method of bacterial population is carried out.
The sample evaluated, for applying the manufacture method of photochemical catalyst tunicle of the present invention and the photochemical catalyst tunicle, the doping sulphur titanium oxide coating film and commercially available photochemical catalyst ceramic tile that obtain.The result of evaluation test shown in Figure 10.
Learnt by Figure 10: relative to the colibacillary sterilizing power display minimizing 4 grades (order) in 30 minutes by the manufacture method and the photochemical catalyst tunicle that obtains that apply photochemical catalyst tunicle of the present invention, high sterilization idiocratic with all bacterium of 180 points of sterilization 6 grades.This respect, does not reach the sterilizing power of use 30 minutes 6 grades seen in doping sulphur titanium oxide, but in practical, has sufficient performance.It should be noted that, even if the minimizing of aerobic plate count almost do not seen by commercially available photochemical catalyst ceramic tile compared with blank yet, be low performance.
< 2. variation 1 >
In the manufacture method applying above-mentioned photochemical catalyst tunicle of the present invention, generate and employ the titania powder of rutile-type and the water slurry of ferric chloride in aqueous solution, also can generate and employ the titania powder of Detitanium-ore-type and the water slurry of ferric chloride in aqueous solution.Specifically, such as can generate that to employ particle diameter be the titania powder of the Detitanium-ore-type of about 10nm and the water slurry of ferric chloride in aqueous solution.It should be noted that, now, in water slurry, the titania powder of Detitanium-ore-type condenses and forms the particle diameter of 1 μm ~ about 5 μm.
But, in the titania powder of Detitanium-ore-type, it is difficult for being exceeded band gap by the excitation electron of excited by visible light, is difficult to produce visible light-responded property, therefore needs making spraying plating temperature be high temperature, thermal change when utilizing spraying plating is coated on object after turning to the crystalline texture of rutile-type.Specifically, to need be the high temperature of more than 2000 DEG C by flame (flame) temperature, by the heat during spraying plating crystalline texture of titania powder to be become rutile-type, photochemical catalyst tunicle is carried out film forming.Therefore, when making FeO (OH) support, preferably dare for not using the anatase-type titanium oxide of high price, from using Titanium Dioxide Rutile Top grade at first.
< 3. variation 2 >
In the manufacture method applying above-mentioned photochemical catalyst tunicle of the present invention, support to make the FeO (OH) presenting visible light-responded function and enumerate be described in the titania powder of rutile-type, the situation that realizes visible-light-responsive photocatalyst tunicle.
But, support and do not need to be defined in the material presenting visible light-responded function in photocatalyst particles, also can for presenting the Fe of co-catalyst function 2o 3deng.
Specifically, such as can generate employ titania powder that particle diameter is the Detitanium-ore-type of about 10nm and ferric chloride in aqueous solution water slurry (now, in water slurry Detitanium-ore-type titania powder cohesion and form the particle diameter of 1 μm ~ about 5 μm), carry out spraying plating by having supported the water slurry employing generation and present the Fe of co-catalyst function 2o 3the titanium dioxide of Detitanium-ore-type carry out stacked, film forming is carried out to photochemical catalyst tunicle.
With regard to spraying plating temperature conditions now, flame (flame) temperature is 300 ~ 2000 DEG C, and deposition rate is 800 ~ 2000m/sec..
It should be noted that, a side of the titanium dioxide of Detitanium-ore-type, compared with the titanium dioxide of rutile-type, can present high catalyst activity.
< 4. supports > for silver
In an example of the manufacture method of the above-mentioned photochemical catalyst tunicle of the present invention applied, enumerate for the situation of by using the water slurry that have employed titania powder and ferric chloride in aqueous solution to carry out spraying plating, the titanium dioxide tunicle of at least a kind of form of the oxide supporting iron, hydroxide, oxyhydroxide being carried out film forming and be described, also can carry out film forming to the titanium dioxide tunicle also supporting not only at least a kind of form of the oxide of iron but also silver, hydroxide, oxyhydroxide.
Specifically, such as, can with titania powder (TiO 2) Ti composition and ferric chloride in aqueous solution (FeCl 3) Fe composition count mode, the in addition titania powder (TiO of Ti:Fe=99.7:0.3 by weight 2) Ti composition and silver nitrate aqueous solution (AgNO 3) the Ag composition mode of counting Ti:Ag=99:1 by weight generate the water slurry (concentration 30 % by weight) using the titania powder, ferric chloride in aqueous solution and the silver nitrate aqueous solution that there are rutile-type, use the water slurry generated to carry out spraying plating, film forming is carried out to photochemical catalyst tunicle.
By carrying out film forming like this, make the oxide (AgO of a kind of silver as antibacterial metal 2) support the titanium dioxide tunicle of rutile-type in having visible light-responded function, co-catalyst function, photochemical catalyst tunicle can be made thus also to undertake extremely high antibacterial functions, if be applied to the flooring material, wall material, ceiling tile materials, attendant equipment etc. in the facility of the attention health aspect of hospital, People nursing facility, food processing factory etc., then prevent from being also effective to nosocomial infection, food poisoning etc.
At this, by the surface observation result (not diagram) of SEM-EDS employing the photochemical catalyst tunicle obtained by the manufacture method of above-mentioned photochemical catalyst tunicle, learn: the oxide not segregation of the silver of nano-scale, probably disperse equably.It should be noted that, probably disperseed equably by the oxide of silver, stable antibacterial effect can be produced.
But, carried out the surface observation of the SEM-EDS employing the photochemical catalyst tunicle obtained by the method that front supports.
Specifically, with titania powder (TiO 2) Ti composition and ferric chloride in aqueous solution (FeCl 3) Fe composition count the mode of Ti:Fe=99.7:0.3 by weight by TiO 2powder is at FeCl 3stir 2 hours in solution, Fe is supported in TiO 2powder.Then, with titania powder (TiO 2) Ti composition and silver nitrate aqueous solution (AgNO 3) the Ag composition mode of counting Ti:Ag=99:1 by weight add silver nitrate aqueous solution in the solution, irradiation ultraviolet radiation, while stir, at TiO 2ag is supported further in powder.Then, after this solution be dry, pulverize, carry out the classification of particle diameter, make granularity consistent.Then, use the water slurry (concentration 30 % by weight) of the powder be made carry out spraying plating and photochemical catalyst tunicle carried out film forming, carried out the surface observation of the SEM-EDS employing the photochemical catalyst tunicle obtained like this.
Its result, learns the segregation of the silver of existence more than 3 μm.It should be noted that, during silver-colored segregation, photochemical catalyst function, antibacterial effect are different according to place, the unstable properties of photochemical catalyst tunicle.
In addition, the surface observation of the SEM-EDS of the photochemical catalyst tunicle that method obtains is supported after having carried out employing use.
Specifically, titania powder (TiO is used 2) water slurry (concentration 30 % by weight) and carry out spraying plating, by TiO 2tunicle carries out film forming, and the tunicle by film forming impregnated in FeCl in the mode counting Ti:Fe=99.7:0.3 by weight 3in solution 2 hours, Fe is supported in TiO 2tunicle.Then, impregnated in silver nitrate aqueous solution in the mode counting Ti:Ag=99:1 by weight, irradiation ultraviolet radiation, Ag is supported in TiO 2tunicle, carries out the surface observation of the SEM-EDS employing the photochemical catalyst tunicle obtained like this.And, use the gas decomposition run result and the BA result that there are this tunicle shown in Figure 11, Figure 12.
Its result, learns the segregation of the silver of existence more than 3 μm.It should be noted that, during silver-colored segregation, photochemical catalyst function, antibacterial effect are different according to place, the unstable properties of photochemical catalyst tunicle.
In addition, can confirm the existence of the segregation of thick silver on tunicle top layer, the segregation of the silver on such top layer causes the luminous intensity arriving titanium dioxide to decline, and worries the decline of properties of catalyst.
It should be noted that, learnt by Figure 11, decompose the acetaldehyde of 300ppm with 120min.In addition, carbon dioxide also times amount produces, and can confirm to decompose completely.And, learnt by Figure 12, make 10 with 180min 6the Escherichia coli of cfu/mL are 0, show high bactericidal property.
< 5. supports > for pigment
Apply in an example of the manufacture method of photochemical catalyst tunicle of the present invention above-mentioned, carrying out spraying plating by adopting the water slurry that employs titania powder and ferric chloride in aqueous solution, the titanium dioxide tunicle having supported iron being carried out the situation of film forming and enumerate and be described, also the titanium dioxide tunicle not only supporting iron but also supported pigment can be carried out film forming.It should be noted that, by making pigment support, can photochemical catalyst tunicle be carried out painted, according to the degree of the adhesion amount of pigment, color change.
At this, (the TiO of titania powder shown in Figure 13 2) Ti composition and pigment (composition is mica (muscovite), TiO 2, Fe 2o 3) count Ti by weight: the mode of pigment=7:3 generates water slurry (concentration 30 % by weight), use the water slurry that generates and carry out the analysis result that spraying plating carrys out the crystalline texture of the XRD of the photochemical catalyst tunicle of film forming.
In result shown in Figure 13, learn Fe 2o 3peak value attachment ratio that is little, pigment few.
At this, by the result (not diagram) of the distributional analysis of the electron micrograph of SEM-EDS and the constituent analysis of element and element that employ the photochemical catalyst tunicle obtained by above-mentioned method, learn, compared with situation about supporting before described later, the yield rate of pigment is low.
Figure 14 is the analysis result of the crystalline texture of the XRD employing the photochemical catalyst tunicle obtained by the method that front supports.
Specifically, with titania powder (TiO 2) Ti composition and pigment count Ti by weight: two powder mix by the mode of pigment=7:3, burn till 30 minutes at 1200 DEG C, are pulverized by the pellet obtained, and carry out the classification of particle diameter and make granularity consistent with about 100 μm.Then, use the water slurry (concentration 30 % by weight) of the powder be made and carry out spraying plating, photochemical catalyst is carried out film forming, the photochemical catalyst tunicle XRD obtained like this is carried out the analysis of crystalline texture, Figure 14 is its result.
In the result shown in Figure 14, learn the Fe of the composition as pigment 2o 3peak value adhere to pigment greatly, how.
At this, by employing with the result supporting the electron micrograph of SEM-EDS of the photochemical catalyst tunicle that method obtains and the distributional analysis of the constituent analysis of element and element before above-mentioned (not diagram), learn: the Fe of pigment composition is about 16% of Ti, and the yield rate of pigment is high.Its think because: by pigment and TiO 2composite, the quality of particle adds.
Figure 15 supports the analysis result of the crystalline texture of the XRD of the photochemical catalyst tunicle that method obtains after being the use of and using.
Specifically, titania powder (TiO is used 2) water slurry (concentration 30 % by weight) carry out spraying plating, by TiO 2tunicle carries out film forming.Then, pigment is formed water slurry (concentration 30 % by weight), at TiO 2on tunicle after coating, at 1250 DEG C, burn till 1 hour, by the TiO obtained thus 2carry out the analysis of crystalline texture with the compound tunicle XRD of pigment, Figure 15 is its result.
In result shown in Figure 15, think: there is no TiO 2peak value, at the penetration depth of X-ray with paint covering surfaces.
At this, by employing with the result supporting the electron micrograph of SEM-EDS of the photochemical catalyst tunicle that method obtains and the distributional analysis of the constituent analysis of element and element after above-mentioned (not diagram), learn: the ratio of Ti is very low, the complete clad surface of pigment.Such pigment causes the luminous intensity arriving titanium dioxide to decline, and worries the decline of photochemical catalyst function.

Claims (6)

1. a manufacture method for photochemical catalyst tunicle, it possesses:
Form the operation containing at least a kind of compound of rutile titanium dioxide particle, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water;
Described slurry is carried out spraying plating at flame temperature 700 ~ 2500 DEG C, the anion of at least a kind of described compound is volatilized by the heat of spraying plating, oxygen in the water of the metal ion of described compound and described slurry and air is reacted generate, present visible light-responded function and co-catalyst function, Fe, Cu, Cr, the hydroxide of Ni or at least a kind of form of oxyhydroxide, and generate together with described hydroxide or described oxyhydroxide, present visible light-responded function and co-catalyst function, Fe, Cu, Cr, at least a kind of form of the oxide of Ni supports the rutile titanium dioxide particle in described slurry, the simultaneously operation of this rutile titanium dioxide particle stacked on object.
2. the manufacture method of photochemical catalyst tunicle as claimed in claim 1, wherein, with regard to the operation of described stacked rutile titanium dioxide particle on object, slurry described in spraying plating at flame temperature 2000 ~ 2500 DEG C.
3. the manufacture method of photochemical catalyst tunicle as claimed in claim 1 or 2, wherein,
Described slurry is formed containing at least one being selected from antibacterial metal, antibacterial metal salts or antibacterial metal complex,
Described slurry is carried out spraying plating and to be selected from form stacked described antibacterial metal, antibacterial metal salts or antibacterial metal complex on object of at least one in metal, slaine, metal complex, oxyhydroxide, hydroxide or oxide together with described rutile titanium dioxide particle.
4., as the manufacture method of photochemical catalyst tunicle according to claim 1 or claim 2, wherein, form described slurry containing pigment, described slurry is carried out spraying plating and together with described rutile titanium dioxide particle on object stacked pigment.
5., as the manufacture method of photochemical catalyst tunicle according to claim 1 or claim 2, wherein, form described slurry containing sorbing material, described slurry is carried out spraying plating and together with described rutile titanium dioxide particle on object stacked sorbing material.
6. a photochemical catalyst tunicle, it manufactures as follows:
Formed containing at least a kind of compound of rutile titanium dioxide particle, the water-soluble metal complexes being selected from Fe, Cu, Cr, Ni or water-soluble metal salt and the slurry of water;
Described slurry is carried out spraying plating at flame temperature 700 ~ 2500 DEG C, the anion of at least a kind of described compound is volatilized by the heat of spraying plating, oxygen in the water of the metal ion of described compound and described slurry and air is reacted generate, present visible light-responded function and co-catalyst function, Fe, Cu, Cr, the hydroxide of Ni or at least a kind of form of oxyhydroxide, and generate together with described hydroxide or described oxyhydroxide, present visible light-responded function and co-catalyst function, Fe, Cu, Cr, at least a kind of form of the oxide of Ni supports the rutile titanium dioxide particle in described slurry, this rutile titanium dioxide particle stacked on object simultaneously.
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