CN105307770A - Visible light-responsive photocatalyst body and method for producing same - Google Patents
Visible light-responsive photocatalyst body and method for producing same Download PDFInfo
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- CN105307770A CN105307770A CN201480032759.6A CN201480032759A CN105307770A CN 105307770 A CN105307770 A CN 105307770A CN 201480032759 A CN201480032759 A CN 201480032759A CN 105307770 A CN105307770 A CN 105307770A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 152
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000010936 titanium Substances 0.000 claims abstract description 91
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 91
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 89
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 20
- 210000000981 epithelium Anatomy 0.000 claims description 79
- 239000000463 material Substances 0.000 claims description 74
- 239000003054 catalyst Substances 0.000 claims description 48
- 230000001699 photocatalysis Effects 0.000 claims description 43
- 230000000844 anti-bacterial effect Effects 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 37
- 239000005864 Sulphur Substances 0.000 claims description 29
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 25
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 25
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 8
- 238000004080 punching Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000007743 anodising Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 42
- 229910052751 metal Inorganic materials 0.000 description 27
- 239000002184 metal Substances 0.000 description 27
- 239000011148 porous material Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000013527 degreasing agent Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
A visible light-responsive photocatalyst body that is obtained by forming a porous titanium oxide coating film, which contains sulfur and has micropores in the surface, on the surface of a titanium or titanium alloy base by performing anodic oxidation on the surface of the base using an electrolytic bath containing sulfur and then subjecting the base after anodic oxidation to a heat treatment. The base has a thickness of 0.005-0.6 mm. The titanium dioxide contained in the titanium oxide coating film has an anatase crystal structure.
Description
Technical field
The present invention relates to that be made up of titanium or titanium alloy, by obtaining thin base material enforcement anodized and heating photochemical catalyst body, particularly relating to photochemical catalyst body and the manufacture method thereof visible ray to photocatalytic activity.
Background technology
Titanium oxide (TiO
2), particularly possesses the titanium oxide of the crystalline texture of Detitanium-ore-type, if the light of the specific wavelengths such as irradiation ultraviolet radiation (ultraviolet light), then play photocatalytic activity (generation of active oxygen and the photo-catalysis function of Superhydrophilic), therefore by antibacterial (sterilization), deodorization, anti-pollution, antifog etc. for the purpose of, be applied in various component (base material) all the time.
As the method making photocatalytic activity play for various component, what always carry out is following method: make the titanium oxide fine powder with photocatalytic activity be dissolved in solvent, by the surface coating base material containing titanium oxide solution thus, form the method (coating type photochemical catalyst) of the coated film containing titanium oxide; Anodized is implemented for the base material be made up of titanium or titanium alloy, formed after there is the oxide scale film of photocatalytic activity on the substrate, by this base material heating to set point of temperature, thus improve the method (anodic oxidation type photochemical catalyst) of the photocatalytic activity on its surface.
Above-mentioned coating type photochemical catalyst, can for various base material, easily and make photocatalytic activity play at an easy rate, therefore obtains practical widely.But, base material is formed when having the coated film of photocatalytic activity because base material and this coated film adhesion low, so base material can play the lifetime of photocatalytic activity.Therefore there is so large problem, that is, in order to make this base material maintain photocatalytic activity, just produce the needs that will be coated with the coated film with photocatalytic activity to this base material again.In addition because be make to have photocatalytic activity micro mist dispersion in a solvent, so photocatalytic activity is hindered in the solvent solidified, have it active to reduce such problem.
On the other hand, in above-mentioned anodic oxidation type photocatalysis and manufacturing technology thereof, if make base material be titanium or titanium alloys, then base material is high with the adhesion of the titanium oxide epithelium playing photocatalytic activity, in addition the durability of photocatalytic activity and stability high, titanium self is also harmless metal, therefore in recent years, for the base material of various titaniums or titanium alloys, the application of anodic oxidation type photochemical catalyst is gone up.
Always, titanium oxide is the ultraviolet light of below about 380nm for wavelength, has played its photocatalytic activity (ultraviolet light response type).But, because the ratio of the ultraviolet light that sunshine comprises is number %, so by later research and development, the titania photocatalyst that band gap is little is developed, namely, even if for the light (wavelength 380 ~ 800nm) of visible region, the various titanium oxide type photochemical catalyst bodies of the visible-light response type of photocatalytic activity also can be played.The titanium oxide type photochemical catalyst of so-called visible-light response type, represents for the long visible ray of wavelength ratio 380nm, and such as, the light etc. for sunshine, white fluorescent lamp plays the titanium oxide type photochemical catalyst body of photocatalytic activity.
About the method for titanium oxide type photochemical catalyst body obtaining visible-light response type, propose to make containing nitrogen in titanium oxide epithelium, or make in titanium oxide epithelium containing sulphur, carbon, fluorine etc.Such as, the correlation technique of the photochemical catalyst that the titanium oxide of the visible-light response type containing sulphur in titanium oxide epithelium is formed, is proposed by following patent document 1 ~ 2 and non-patent literature 1.
In patent document 1 (Japanese Unexamined Patent Publication 2010-29838 publication), disclose a kind of method, it is the method for the rutile titanium dioxide forming the photocatalytic activity excellence doped with sulphur on the surface of the metal base be made up of titanium or titanium alloy.Rutile titanium dioxide described in patent document 1, manufacture in the following way, the surface of the base material namely titanium or titanium alloy formed, applied voltage and (should be quality % usually 2.6 % by weight ~ 14.1 % by weight, but this is the statement state of patent document 1) concentration aqueous sulfuric acid in, after implementing more than 2 minutes anodized with the voltage of more than 100V, implement heat treatment in more than 1 hour with 400 DEG C ~ 1000 DEG C.Such rutile titanium dioxide, the sulphur containing 200ppm (0.02%) ~ 4000ppm (0.4%) in titanium dioxide, has visible light-responded property.Also describe in patent document 1, metal base is processed in advance the shape of the hope of tabular and paper tinsel etc. or applicable object use form.
In patent document 2 (Japanese Unexamined Patent Publication 2011-120998 publication), disclose a kind of rutile titanium dioxide photochemical catalyst of visible-light response type.Rutile titanium dioxide photochemical catalyst described in patent document 2, obtain in the following way, namely, nitrogen treatment is implemented for the metal base be made up of titanium or titanium alloy, carry out anodized for this base material through nitrogen treatment, the film made for implementing anodic oxidation is implemented heat treatment and obtains.This anodized is in the aqueous sulfuric acid of the sulfuric acid concentration of 0.02 ~ 1.6mol/L, and the current potential of additional 100 ~ 300V, implements between the scope of about 10 ~ about 60 minutes.Such rutile titanium dioxide photochemical catalyst, doped with nitrogen and sulphur, demonstrates highlight catalytic active in visible region.Metal base is same with patent document 1, after being processed into the shape of the hope of tabular and paper tinsel etc. or applicable object use form in advance, then carries out anodized.
At non-patent literature 1 (" formulating titanium dioxide optical catalyst by anodized ", " ま て り あ ", 49th volume, No. 2, 2010) in, describe the correlative study result of anatase titanium dioxide film and the rutile titanium dioxide film generation having visible-light response type, it carries out anodized using aqueous sulfuric acid as electrobath to titanium plate, the titanium plate being formed with oxide scale film (titanium dioxide film) of this anodized will have been carried out, 4 hours burning till is carried out in an atmosphere with 723K, generate the surface with Porous thus, the anatase titanium dioxide film of the visible-light response type containing sulphur and rutile titanium dioxide film.
In this non-patent literature 1, disclose the item described in following (1) ~ (3).
(1) according to the sulfuric acid concentration of electrobath during anodic oxidation, its surface texture of the titanium dioxide film generated, thickness, crystalline texture significantly change.Such as, the surface of the titanium plate made by sulfuric acid concentration 0.02M, observes the pore of about 170nm, the about 330nm of thickness of oxidation film.
(2) along with the increase of the sulfuric acid concentration in electrobath, the shape of pore becomes circle, becomes 950nm during 1.2M.In addition along with the increase of sulfuric acid concentration, the peak strength of anatase reduces, and the peak strength of rutile increases.
(3) visible light-responded property excellence, sulphur concentration in the anode oxide film that makes with the sulfuric acid bath of 1.2M is about 1100ppm, a little order of magnitude compared with the titanium dioxide film made by 0.02M, and this hint band structure changes according to sulfuric acid concentration.
Rutile titanium dioxide described in patent document 1, by the surperficial applied voltage of base material formed for titanium or titanium alloy, in the aqueous sulfuric acid of the concentration of 2.6 % by weight ~ 14.1 % by weight, after implementing more than 2 minutes anodized with the voltage of more than 100V, implement heat treatment in more than 1 hour with 400 DEG C ~ 1000 DEG C again and manufacture, but for the titanium foil that thickness is little, titanium sheet metal etc., if implement anodized in the aqueous sulfuric acid of such high concentration, then due to the aqueous sulfuric acid of high concentration, the stripping on titanium foil surface occurs, carry out, in the case, originally paper tinsel should be born, non-stripping portion (the unoxidized titanium of the shape maintains of thin plate etc., titanium alloy portion) disappear at short notice, generate through hole, the problem likely produced is, easily become broken state etc.
In order to obtain the rutile titanium dioxide lining material described in patent document 2, need the operation heating or undertaken by plasma nitrogen treatment, therefore manufacturing process becomes complicated, causes high cost.The titanium dioxide epithelium of patent document 2 is rutile-types in addition, and anodized and heating are implemented for the little titanium base material of thickness, be difficult to high efficiency and possess the visible-light-responsive photocatalyst body of the titanium oxide epithelium having photocatalytic activity with stable quality responses.When using the vitriolated aqueous solution as electrobath in addition, if suitably do not set the concentration of sulfuric acid, then in anodized, also can produce the possibility of the surperficial stripping of the titanium sheet metal that titanium or titanium alloy are formed, the composition therefore about electrobath also needs to improve.
Describe in non-patent literature 1, the titanium plate that sulfuric acid concentration makes when being 0.02M is Detitanium-ore-type, there is on its surface the pore of about 170nm, thickness of oxidation film is about 330nm, but it is not open about the titanium foil, titanium sheet metal etc. little to thickness, stable and form the titanium dioxide film of the crystalline texture only possessing Detitanium-ore-type accurately.
Summary of the invention
Therefore, the object of the invention is to, a kind of surface of the thin base material at titanium or titanium alloy is provided, be formed titanium oxide epithelium, the visible-light-responsive photocatalyst body of antibiotic property excellence and manufacture method thereof, described titanium oxide epithelium contains sulphur, and the crystalline texture of titanium dioxide is only Detitanium-ore-type.
Therefore, visible-light-responsive photocatalyst body of the present invention, it is characterized in that, after using the electrobath containing sulphur to implement anodized to the surface of the base material of titanium or titanium alloy, the base material complete to described anodized is implemented to heat, the visible-light-responsive photocatalyst body containing sulphur and surface with the titanium oxide epithelium of the Porous of minute aperture is formed on the surface of described base material, the thickness of described base material is 0.005mm ~ 0.6mm, and the crystalline texture of the titanium dioxide contained by described titanium oxide epithelium is Detitanium-ore-type crystalline texture.
Preferred described titanium oxide epithelium contains the sulphur of 0.7 ~ 2.2 atom %.
The thickness of preferred described titanium oxide epithelium is below 200nm.
If during the mean value of the maxima and minima that the hole of described minute aperture the is wide wide W that is hole, the preferred wide W in described hole is 50 ~ 100nm.
Preferred described base material is strip, causes continuous anodic oxidation device and implements anodized continuously.
The size of regulation is preferably cut to according to purposes.
Preferred described base material is foil-like or tabular.
Described base material preferably penetrates into the back side fine through hole from its surface is the punching shape be spaced or mesh-shape that specify.
The wire rod plain weave that titanium or titanium alloy are formed preferably reticulates by described base material.
For the wavelength in the region from visible ray to ultraviolet light, preferably possesses photocatalytic activity.
By the antibacterial activity value (R) obtained according to the photocatalysis antibacterial test of JISR1702, be preferably more than 2.0.
When observing described oxide scale film surperficial with scanning electron microscope, preferably in the square scope being 1000nm × 1000nm in length and breadth, the wide W in described hole is that the minute aperture of 50 ~ 100nm exists more than 30.
The manufacture method of above-mentioned visible-light-responsive photocatalyst body, use the electrobath containing sodium thiosulfate 0.01mol/L ~ 0.2mol/L to implement after anodized for the surface of described base material, implement the method heated again, wherein, the applied voltage of anodized is preferably made to be+70V ~+140V, anodizing time was 10 seconds ~ 60 seconds, the bath temperature of the electrobath of anodized is 1 DEG C ~ 30 DEG C, heats and carries out with the temperature of 380 DEG C ~ 620 DEG C in oxidizing atmosphere.
Described electrobath is preferably also containing KI 0.005mol/L ~ 0.1mol/L.
The base material of described strip, as described base material, is drawn continuous anodic oxidation device and after implementing anodized continuously by the base material of preferred use strip, and the base material for the complete strip of anodized is implemented to heat continuously.
Visible-light-responsive photocatalyst body of the present invention, can play following effect.
(1) visible-light-responsive photocatalyst body of the present invention, because at the substrate surface of the thickness 0.005mm ~ 0.6mm be made up of titanium or titanium alloys, the crystalline texture be provided with containing titanium dioxide is only Detitanium-ore-type, surface has the titanium oxide epithelium of the Porous of minute aperture, so when the photocatalysis antibacterial test of implementation basis JISR-1752, there is the stable quality that antibacterial activity value (R) is more than 2.0.
(2) visible-light-responsive photocatalyst body of the present invention, to by titanium or titanium alloys structure the base material of thickness 0.005mm ~ 0.6mm use the electrobath containing sodium thiosulfate or sodium thiosulfate and KI to implement anodized after, titanium sheet metal complete to this anodized again heats, therefore, it is possible to the stable and surface being manufactured on titanium sheet metal is accurately formed containing sulphur and has the photochemical catalyst body of visible light-responded titanium oxide epithelium.The titanium sheet metal of strip is particularly used as base material, by the base material of strip being caused continuous anodic oxidation device after implementing anodized continuously, base material again for the complete strip of anodized is implemented to heat continuously, though for strip and the little titanium base material of thickness also can stablize and form titanium oxide epithelium accurately.Thus, the photochemical catalyst body of this strip, according to its purposes, is processed into suitable shape and size by visible-light-responsive photocatalyst body, can as the photocatalytic activity possessing visible light-responded property, the particularly component of antibiotic property excellence, is applicable to various devices and structural elements thereof.
Accompanying drawing explanation
Fig. 1 distinguishes the temperature heated, and shows by X-ray diffraction (XRD) respectively, the result of the crystalline texture of the titanium dioxide comprised in the titanium oxide epithelium that the surface analyzing the visible-light-responsive photocatalyst body of embodiment 1 is formed.
Fig. 2 (A) represents in the visible-light-responsive photocatalyst body of embodiment 1, the figure of the X-ray diffraction value of the titanium oxide epithelium when temperature of heating being set in 450 DEG C.
Fig. 2 (B) represents in the visible-light-responsive photocatalyst body of embodiment 1, the figure of the X-ray diffraction value of the titanium oxide epithelium when temperature of heating being set in 750 DEG C.
Fig. 3 (A) represents in the visible-light-responsive photocatalyst body of embodiment 3, the figure of the concentration of electrobath and the relation of antibacterial activity value (R).
Fig. 3 (B) represents in the visible-light-responsive photocatalyst body of embodiment 4, the figure of the temperature of electrobath and the relation of antibacterial activity value (R).
Fig. 3 (C) represents in the visible-light-responsive photocatalyst body of embodiment 5, the figure of the relation of applied voltage during anodized and antibacterial activity value (R).
Fig. 3 (D) represents in the visible-light-responsive photocatalyst body of embodiment 6, the figure of the relation of anodized time and antibacterial activity value (R).
Fig. 4 represents in the visible-light-responsive photocatalyst body of embodiment 3, the figure of the content of the sulphur that titanium oxide epithelium comprises and the relation of antibacterial activity value (R).
Photo (multiplying power 30,000 times) when Fig. 5 (A) is the titanium oxide epithelium formed with the surface of visible-light-responsive photocatalyst body of scanning electron microscope shooting embodiment 7 surperficial.
Photo (multiplying power 30,000 times) when Fig. 5 (B) is the titanium oxide epithelium formed with the surface of visible-light-responsive photocatalyst body of scanning electron microscope shooting embodiment 8 surperficial.
Photo (multiplying power 30,000 times) when Fig. 6 (A) is the titanium oxide epithelium formed with the surface of visible-light-responsive photocatalyst body of scanning electron microscope shooting conventional example 1 surperficial.
Photo (multiplying power 30,000 times) when Fig. 6 (B) is the titanium oxide epithelium formed with the surface of visible-light-responsive photocatalyst body of scanning electron microscope shooting conventional example 2 surperficial.
Detailed description of the invention
[1] visible-light-responsive photocatalyst body
Visible-light-responsive photocatalyst body of the present invention, has base material and is formed at the titanium oxide epithelium on surface of this base material.Titanium oxide epithelium plays the function as photochemical catalyst, particularly plays excellent photocatalytic activity for visible ray.For the material of base material of the present invention, be the pure titanium (a kind ~ 4 kinds) of JIS specification defined, or the titanium alloy containing Pd, Ni, Cr, Al, V etc.In the following description, having the general designation description of pure titanium or titanium alloy is the situation of " titanium system ".
As for base material of the present invention, the foil-like of titanium or laminal base material can be used, in the foil-like of titanium or the base material of tabular, by punch process etc., perforation has the punching shape of large number of orifices or cancellous base material, or by the netted base material of about the 0.3 ~ 1mm of titanium or its following wire rod plain weave ramify shape.Netted base material preferably uses when the manufacture of the photochemical catalyst body of the filter member for air purifier and wastewater treatment equipment etc.Further, the thickness of the visible-light-responsive photocatalyst body be made up of this netted constructed by lamellae, considers the workability of titanium wire plain weave and is preferably about 0.5mm ~ 2mm.
As the foil-like of titanium or laminal base material (following, describe as " titanium foliation ".), can use after becoming thickness about 0.2mm ~ 1.0mm by the cold rolling plate rolling by titanium, then be that the strip of thickness of 0.005mm ~ 0.6mm (5 μm ~ 600 μm) left and right is (also referred to as " band shape " or " web-like " by cold rolling.) titanium foliation.
The base material of punching shape can manufacture in the following way, namely, above-mentioned titanium foliation is caused hole punched device (punch press), such as, with the interval specified along the small hole of its longitudinally multiple row punching press (circle, four directions, cancellous small gap etc.).Punching shape or the wide of cancellous gap are preferably 0.1 ~ more than 0.2mm.Such punching shape or the visible-light-responsive photocatalyst body of cancellous strip, can cut into suitable size, uses as the filter member for removing harmful substance (sulfide etc.) contained among waste water or waste gas etc.
Titanium oxide epithelium is containing sulphur, and has the Porous epithelium of minute aperture on surface, and the crystalline texture of titanium dioxide is made up of Detitanium-ore-type.Thus, even if when being provided with thin titanium oxide epithelium in foil-like or laminal base material, still there is as visible-light-responsive photocatalyst body the high antibacterial activity value (R) of more than 2.0.The content of sulphur is preferably 0.7 ~ 2.2 atom %, is more preferably 0.7 ~ 1.6 atom %.The thickness of titanium oxide epithelium is preferably below 200nm.
[2] manufacture method of photochemical catalyst
Below, in the manufacturing process of photochemical catalyst of the present invention, an example of the method for the titanium oxide epithelium that the titanium foliation of strip is formed the function had as photochemical catalyst is described.
(1) ungrease treatment and pickling processes
Before anodized is implemented to substrate surface, implement ungrease treatment and pickling processes.Ungrease treatment and pickling processes can be carried out with existing means.
(2) anodized
To the titanium foliation of ungrease treatment and pickling processes be implemented, and cause and be filled with in the anodic oxidation device of electrobath, run with the speed of regulation, while implement anodized to the surface of this titanium foliation.This anodic oxidation device while make the titanium foliation of the strip of web-like run in device successively from top portion to terminal part, can carry out the device (continuous anodic oxidation device) of anodized continuously.By while make titanium foliation run in electrobath in this continuous anodic oxidation device, power to titanium foliation and carry out the anodized of stipulated time, thus forming the titanium oxide epithelium containing sulphur on the surface of titanium foliation.
Electrobath can use the sodium thiosulfate solution of the concentration of 0.01mol/L ~ 0.2mol/L.As the electrobath carrying out anodized, select the reason of above-mentioned sodium thiosulfate as follows.Use the sulfuric acid bath of existing sulfuric acid, because its acidity is very strong, so likely cause adverse effect for the epithelium of titanium oxide on surface of the foil-like titanium sheet metal being formed at strip by anodized.Therefore, as sulfur-bearing there is strong chelation (thiosulfate ion is to the combination of titanium ion), also as the electrobath forming oxidant, selection sodium thiosulfate solution.In addition, the ionic condition in the electrobath of sodium thiosulfate because with sulfuric acid phase ratio, its sulfur content is more, so infer in the titanium oxide epithelium on surface being formed at foil-like titanium sheet metal a large amount of containing sulfur content.The concentration of sodium thiosulfate solution is preferably 0.01mol/L ~ 0.2mol/L, is more preferably 0.05mol/L ~ 0.1mol/L.
Anodizing time was preferably for 10 seconds ~ 60 seconds, was more preferably for 10 seconds ~ 30 seconds, more preferably 20 seconds ~ 25 seconds.The bath temperature of electrobath is preferably 1 DEG C ~ 30 DEG C, is more preferably 5 DEG C ~ 15 DEG C, more preferably 8 DEG C ~ 12 DEG C.If in this scope, then at the substrate surface be made up of titanium foliation, can be formed containing sulphur, surface has the titanium oxide epithelium of the Porous of minute aperture, can stablize the titanium oxide epithelium obtaining and have the antibacterial activity value (R) of more than 2.0.
To the method (method of supplying power to) of titanium foliation applied voltage in anodized, any one of following (means 1) and (means 2) can be adopted.
(means 1)
These means are the methods always extensively adopted, be formed in by electroconductive member the feeding roller used to make titanium foliation move in anodic oxidation device, the anode of anodized with supply unit is connected with this feeding roller, the method for the titanium foliation applied voltage from feeding roller to strip.Further, negative electrode, in electrobath, is arranged on the suitable position vacating the interval of regulation apart from titanium foliation.
(means 2)
Can carry out continuously in the continuous anodic oxidation device of anodized for the base material of strip, titanium foliation is configured on the direction vertical relative to the upper surface of electrobath, the end side of the width of titanium foliation is given prominence to from the upper surface of electrobath.In the end side of the width of the titanium foliation given prominence to from the upper surface of electrobath, arrange with the interval specified and can clamp and multiple conductive clip synchronization-moving with the movement of titanium foliation disassembled and assembled freely.Conductive clip is connected with the anode of anodized with supply unit, and negative electrode is arranged on the suitable position in electrobath.Negative electrode is such as, is provided with the distance of regulation with the surface of the titanium foliation of movement in electrobath, has the minus plate of the width more longer than the width of titanium foliation.If immerse titanium foliation in anodic oxidation device, then clamped the end side of the width of titanium foliation successively by conductive clip, if conductive clip arrives the outlet neighborhood of anodic oxidation device, then remove clamping.Thus, because to the voltage of the additional regulation of titanium foliation be immersed in anodic oxidation device, so anodized can be applied, form on its surface the epithelium be made up of titanium oxide.
Among (means 1) and (means 2) of above-mentioned applied voltage, (means 2) side can additional certain and stable voltage for titanium foliation, therefore in order to manufacture photochemical catalyst body of the present invention, and preferably adopt (means 2).Further, by changing the allocation position being configured in minus plate in the electrobath of anodic oxidation device, can make to carry out anodic oxidation as the two sides of the titanium foliation of base material or one side.
Applied voltage is preferably+70V ~+140V, is more preferably+80V ~+100V.If in this scope, then can obtain the titanium oxide epithelium with stable and good antibacterial activity value.
(3) cleaning-drying process
Cleaning-drying is carried out on the surface of titanium foliation for the strip implementing anodized.Cleaning-drying process can be undertaken by existing means.
(4) heat
The titanium foliation implementing the strip of cleaning-drying process is guided in continuous heating, makes it to run in device with the speed of regulation, while implement to heat with the temperature and time of regulation.By this heating, the crystalline texture being formed at the titanium dioxide contained by titanium oxide epithelium containing sulphur on the surface of the titanium foil of strip becomes Detitanium-ore-type.Thereby, it is possible to obtain for the high photochemical catalyst body of the response (photocatalytic activity) of visible ray.Implement the titanium foliation (photochemical catalyst body) of the strip of heating, as required, its purposes corresponding and cut into the size of regulation.
The temperature heated is preferably 400 DEG C ~ 600 DEG C, is more preferably 430 DEG C ~ 500 DEG C, most preferably is 440 DEG C ~ 460 DEG C.If heating-up temperature is lower than 400 DEG C, then titanium oxide epithelium cannot contain the crystalline texture of uniform Detitanium-ore-type on the whole, and titanium oxide epithelium is insufficient for the response (photocatalytic activity) of visible ray.If heating-up temperature is higher than 600 DEG C, then as shown in Figure 1, comprise the crystalline texture of rutile-type in the crystalline texture of titanium oxide epithelium after, the phenomenon that titanium oxide epithelium self is peeled off occurs, and is not therefore preferred.Heat in the oxidizing atmosphere preferably existed at oxygen and carry out, carry out particularly preferably in easy air atmosphere.The time of heating is preferably 40 seconds ~ 80 seconds, is more preferably 50 seconds ~ 70 seconds.
In the manufacture of the photochemical catalyst body being base material with the titanium foliation of above-mentioned strip, the ungrease treatment of the titanium foliation of strip, pickling processes, anodized, cleaning-drying process and heating, the manufacture line be connected by each treating apparatus carrying out these process can be used, also can carry out each process continuously.The manufacture efficiency of the photochemical catalyst body of strip can be made thus to improve, significantly reduce manufacturing cost.Implement, among these manufacturing processes processed, the device pipelining from ungrease treatment to cleaning-drying process of the titanium foliation of strip can be made, the heat treatment apparatus of the titanium foliation of strip also can be made to be various flows waterline.
As the titanium foliation (coiled material) of the strip of one of the base material of photochemical catalyst body, preferably its length is number m ~ hundreds of m, more preferably 50m ~ 1000m.The width (with the width of longitudinally orthogonal direction) of this titanium foliation, although different based on the specification of each device, is preferably about 80mm ~ 400mm.
The photochemical catalyst body of the strip of the present invention manufactured by said method, also can cut off in the mode with suitable length and width according to its use.Therefore, photochemical catalyst body of the present invention comprises the photochemical catalyst body of strip or cuts into both photochemical catalyst bodies of suitable size.
Illustrate in greater detail the present invention by following embodiment, but the present invention is not limited by it.
Embodiment 1
As base material, use the foil-like titanium sheet metal of the strip of the 8 kinds of web-likes be made up of the pure titanium (a kind) of long 100m, thickness 80 μm (0.08mm), wide 125mm.This base material is passed through in the alkali system degreaser of temperature 60 C, carries out ungrease treatment thus, make it containing HF (hydrogen fluoride) 1 quality %, H
2o
2be 5 quality %, HNO
3be pass through in the pickle of 15 quality %, carry out pickling processes thus.
Use continuous anodic oxidation device and the continuous heating of above-mentioned (means 2), with following condition, continuously anodized and heating are carried out successively from top to terminal for base material.(condition of anodized)
The condition of anodized is as follows.Also having the time of anodized, deciding by setting the speed making the foil-like titanium sheet metal of strip run in the electrobath of continuous anodic oxidation device.
Electrobath: the aqueous solution of the sodium thiosulfate containing 0.1mol/L
The temperature of electrobath: 10 DEG C
Applied voltage: direct current 100V
Current density: 1.4A/dm
2
The time of anodized: 22.5 seconds
(condition of heating)
The condition heated is implemented at following 8 kinds of temperature.Also have the heat time, decided by the speed of service be set in the continuous heating of the foil-like titanium sheet metal of strip.
Heat time: 60 seconds
Heating-up temperature: 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C
The crystalline texture of the titanium dioxide that the titanium oxide epithelium formed by the surface of the foil-like titanium sheet metal of X-ray diffraction [XRD (X-RayDiffraction)] analysis after implementing heating by each heating-up temperature is comprised.
X-ray diffraction result L1 during 7 kinds of heating-up temperatures of 400 DEG C ~ 700 DEG C ~ L7 display in FIG.As shown in Figure 1, represent that the value of the angle of diffraction (2 θ/θ) of transverse axis manifests the peak value of anatase titanium dioxide near 25 °.The peak value in (101) face of known anatase titanium dioxide manifests (2 θ/θ)=25.28 °, therefore, it is possible to judge above-mentioned 7 kinds of heating-up temperatures any one under, all can there is the peak value of anatase titanium dioxide.When heating-up temperature is 400 DEG C of (L1) ~ 600 DEG C (L5), the crystalline texture being formed at the titanium dioxide contained by titanium oxide epithelium of foil-like titanium sheet metal is only made up of Detitanium-ore-type.On the other hand, when heating-up temperature is 650 DEG C (L6), 700 DEG C (L7), distinguish that the peak value of the titanium dioxide of rutile-type manifests.The peak value of the titanium dioxide of known rutile-type is in (2 θ/θ)=27.45 ° of appearance.
X-ray diffraction result when Fig. 2 (A) represents that heating-up temperature is 450 DEG C, X-ray diffraction result when Fig. 2 (B) represents that heating-up temperature is 750 DEG C.As shown in Fig. 2 (A) and Fig. 2 (B), as the peak value of the titanium of the foil-like titanium sheet metal of substrate in (2 θ/θ)=40.17 ° of appearance.As shown in Fig. 2 (A), the crystalline texture of the titanium dioxide that heating-up temperature is comprised for titanium oxide epithelium when 450 DEG C is all Detitanium-ore-type.In contrast, as shown in Fig. 2 (B), when heating-up temperature is 750 DEG C, the crystalline texture comprising Detitanium-ore-type and rutile-type in titanium oxide epithelium can be confirmed.
Shown in Fig. 2 (A) make the temperature of heating be 450 DEG C time the thickness of titanium oxide epithelium be shown in 100nm ~ 200nm, Fig. 2 (B) make the temperature of heating be 750 DEG C time the thickness of titanium oxide epithelium be 250nm ~ 300nm.The reason that when enabling the temperature of heating be 750 DEG C, Film Thickness Ratio 450 DEG C is thick is speculated as, because heating-up temperature sets high, so the generation of titanium oxide epithelium is promoted.
Embodiment 2
Embodiment 1 make the temperature of heating reach 450 DEG C time foil-like titanium sheet metal in, measure the content of the sulphur comprised in the titanium oxide epithelium formed at top portion neighborhood (being about the position of 2m from top portion towards terminal part side) and terminal part neighborhood (being about the position of 2m from terminal part towards beginning end side), and for the sample measurement antibacterial activity value (R) from these local extractions.The content of the sulphur comprised in titanium oxide epithelium, measures the content of the dark 20nm in surface apart from titanium oxide epithelium.Antibacterial activity value (R) is tried to achieve by the photocatalysis antibacterial test according to JISR-1752 (the antibiotic property test method of visible-light-responsive photocatalyst body fabricated product).The display of these measurement results in Table 1.
[table 1]
| Measuring position | Sulfur content (atom %) | Antibacterial activity value (R) |
| Top portion neighborhood | 1.6 | 2.38 |
| Terminal part neighborhood | 1.4 | 2.31 |
As shown in table 1, carry out with the temperature of 450 DEG C in the titanium oxide epithelium heated, the sulphur containing 1.6 atom % at its top portion neighborhood can be confirmed, contain the sulphur of 1.4 atom % at terminal part neighborhood.The titanium foil of titanium oxide epithelium is formed for this, the photocatalysis antibacterial based on visible ray of implementation basis JISR-1752 is tested, and its result can confirm, as shown in table 1, at top portion neighborhood and terminal part neighborhood, antibacterial activity value (R) is the value of more than 2.0.Generally speaking, if the value of antibacterial activity value (R) is higher than 2.0, then can say that antibiotic property is excellent.Can confirm thus, carry out heating with the temperature of 450 DEG C low like this and the titanium oxide epithelium forming the surface of foil-like titanium sheet metal only comprises containing sulphur and the titanium dioxide be made up of the crystalline texture of Detitanium-ore-type, even if the thickness of titanium oxide epithelium is at below 200nm, still possesses the photocatalytic activity having visible light-responded property.
There is the photocatalysis paper tinsel (photochemical catalyst body) of the strip of visible light-responded property in addition, as shown in table 1, can confirm at its top portion neighborhood and terminal part neighborhood, the content of sulphur and the value of antibacterial activity value (R) do not produce huge difference, and the total length running through the foil-like titanium sheet metal (photochemical catalyst) of strip all possesses the photocatalytic activity with stable visible light-responded property.
Embodiment 3
For carrying out the condition display of anodized in table 2.As base material, use length 50m, thickness 0.08mm (80 μm), the foil-like titanium sheet metal that the pure titanium foil (a kind) of width 125mm is formed.The temperature of electrobath is made to be 10 DEG C, applied voltage is 100V, processing time is 20 seconds, the concentration of the electrobath of the sodium thiosulfate solution shown in table 2 is set as respectively 7 kinds of concentration (0.01,0.02,0.05,0.06,0.1,0.15,0.2mol/L), manufacture photochemical catalyst body.Manufacturing condition beyond it is identical with embodiment 2.
[table 2]
| Electrobath | Sodium thiosulfate solution |
| The concentration (mol/L) of electrobath | 0.01、0.02、0.05、0.06、0.1、0.15、0.2 |
| The temperature of electrobath | 10℃ |
| Applied voltage (direct current) | 100V |
| Processing time | 20 seconds |
(note) mol/L represents the concentration (mol/L) of electrobath.
The result obtained is presented in Fig. 3 (A).As shown in Fig. 3 (A), if the concentration of the sodium thiosulfate contained by electrobath is set as 0.01mol/L ~ 0.2mol/L, the antibacterial activity value (R) of more than 2.0 can be obtained.Further, when the concentration of sodium thiosulfate is set as 0.01mol/L ~ 0.2mol/L, the thickness of the titanium oxide epithelium that the surface of photochemical catalyst is formed is 150nm ~ 210nm.
Embodiment 4
For carrying out the condition display of anodized in table 3.Make the concentration of electrobath be 0.1mol/L, applied voltage is 100V, and the processing time is 20 seconds, the temperature of the electrobath shown in table 3 is set as respectively 5 kinds of temperature (1 DEG C, 5 DEG C, 10 DEG C, 20 DEG C, 30 DEG C), manufactures photochemical catalyst body.Manufacturing condition beyond it is identical with embodiment 2.
[table 3]
| Electrobath | Sodium thiosulfate solution |
| The concentration (mol/L) of electrobath | 0.1 |
| The temperature of electrobath | 1℃、5℃、10℃、20℃、30℃ |
| Applied voltage (direct current) | 100V |
| Processing time | 20 seconds |
The result obtained is presented in Fig. 3 (B).As shown in Fig. 3 (B), if the temperature of electrobath is set in 1 DEG C ~ 30 DEG C, the antibacterial activity value (R) of more than 2.0 can be obtained, if but be set as 5 DEG C, then can obtain the highest antibacterial activity value (R).Although not shown, but when the temperature of electrobath being set as 1 DEG C ~ 30 DEG C, the thickness being formed at the titanium oxide epithelium on the surface of photochemical catalyst body is 130nm ~ 190nm.If the temperature of electrobath is low, then the thickness of titanium oxide epithelium has the tendency of increase.
Embodiment 5
For carrying out the condition display of anodized in table 4.Make the concentration of electrobath be 0.1mol/L, the temperature of electrobath is 10 DEG C, and the processing time is 20 seconds, the applied voltage shown in table 4 is set as respectively the applied voltage (50V, 60V, 70V, 80V, 100V, 120V) of 5 kinds, manufactures photochemical catalyst body.Manufacturing condition beyond it is identical with embodiment 2.
[table 4]
| Electrobath | Sodium thiosulfate solution |
| The concentration (mol/L) of electrobath | 0.1 |
| The temperature of electrobath | 10℃ |
| Applied voltage (direct current) | 50V、60V、70V、80V、100V、120V |
| Processing time | 20 seconds |
The result obtained is presented in Fig. 3 (C).As shown in Fig. 3 (C), if applied voltage is set as 100V ~ 120V, then can obtain the stable antibacterial activity value (R) of more than 2.0.Further, although not shown, but when applied voltage is set as 100V ~ 120V, the thickness being formed at the titanium oxide epithelium on the surface of photochemical catalyst is 180nm ~ 210nm.
Embodiment 6
Condition for carrying out anodized is presented at table 5.Make the concentration of electrobath be 0.1mol/L, applied voltage is 100V, and the temperature of electrobath is 10 DEG C, is set as 5 kinds of processing times (10 seconds, 15 seconds, 20 seconds, 30 seconds, 60 seconds) processing time shown in table 4 respectively, manufactures photochemical catalyst body.Manufacturing condition beyond it is identical with embodiment 2.
[table 5]
| Electrobath | Sodium thiosulfate solution |
| The concentration (mol/L) of electrobath | 0.1 |
| The temperature of electrobath | 10℃ |
| Applied voltage (direct current) | 100V |
| Processing time | 10 seconds, 15 seconds, 20 seconds, 30 seconds, 60 seconds |
The result that obtains is presented in Fig. 3 (D).As shown in Fig. 3 (D), carry out the time of anodized, if implement 10 seconds ~ 60 seconds, then can obtain the antibacterial activity value (R) of more than 2.0.Particularly with the processing time of 15 seconds ~ 30 seconds can obtain antibacterial activity value (R) close to 2.5 value.Distinguish thus, carry out the time of anodized, even the time that 15 seconds ~ 30 seconds short like this, also can be obtained the photochemical catalyst body of high antibacterial activity value (R) by the foil-like titanium sheet metal manufacture of strip.Also have although not shown, but when being set as 10 seconds ~ 60 seconds the time of carrying out anodized, the thickness being formed at the titanium oxide epithelium on the surface of photochemical catalyst is 170nm ~ 180nm.
The sulfur content comprised in the titanium oxide epithelium of the photochemical catalyst of embodiment 3 and antibacterial activity value (R), tried to achieve by method similarly to Example 2.The sulfur content of titanium oxide epithelium and the relation of antibacterial activity value (R) show in the diagram.
Distinguish as shown in Figure 4, the content of the sulphur contained by titanium oxide epithelium, at least in the scope of 0.7 ~ 2.2 atom %, can obtain the antibacterial activity value (R) of more than 2.0.In addition as previously mentioned, even if titanium oxide epithelium has the thickness of very thin below the 200nm of thickness, the antibacterial activity value (R) of more than 2.0 also can be obtained.
Embodiment 7 and 8, conventional example 1 and 2
Adopt the condition of the anodized shown in table 6 and heating, manufacturing condition is in addition all identical with embodiment 2, manufactures the photochemical catalyst body of strip.
[table 6]
Embodiment 7 makes electrobath be that the sodium thiosulfate solution of concentration 0.06mol/L carries out anodized, and embodiment 8 makes electrobath be that the aqueous solution of the sodium thiosulfate of concentration 0.02mol/L and the KI of concentration 0.01mol/L carries out anodized.In embodiment 8, make the reason containing KI in electrobath, be for above-mentioned using sodium thiosulfate as the identical thought of electrobath, the ionic condition produced by sodium thiosulfate and KI, sulfur content is more compared with sodium thiosulfate, therefore can infer the effect that the visible light-responded property that can produce the titanium oxide epithelium being formed at foil-like titanium sheet metal and antibacterial activity value (R) improve.
Conventional example 1 makes electrobath be that the aqueous sulfuric acid of concentration 0.02mol/L carries out anodized, and conventional example 2 makes electrobath be that the aqueous sulfuric acid of concentration 0.05mol/L carries out anodized.
By the photo (multiplying power 30 when titanium oxide epithelium surperficial that foil-like titanium sheet metal (visible-light-responsive photocatalyst body) surface is formed of scanning electron microscope shooting embodiment 7 and 8 and conventional example 1 and 2,000 times), be presented at respectively in Fig. 5 (A), Fig. 5 (B), Fig. 6 (A) and Fig. 6 (B).
Observe in the photo shown in Fig. 5 (A), the surface of titanium oxide epithelium is made up of the Porous that there is rounded fine hole (pore) 1a of countless cardinal principle.The diameter of pore 1a, by after the photographic print of Fig. 5 (A) is to photographic paper, is surveyed by engineer's scale, and according to the result of doubly rate conversion, the diameter of pore is evaluated as 50 ~ 100nm.
In the photo shown in Fig. 5 (B), similarly to Example 7, the surface observing titanium oxide epithelium is made up of the Porous that there is the rounded fine pore 1b of countless cardinal principle.By the photo of Fig. 5 (B), when measuring the diameter of pore 1b by method similarly to Example 7, be 50 ~ 100nm similarly to Example 7.
As shown in Fig. 6 (A) and Fig. 6 (B), confirm the surface of the titanium oxide epithelium in conventional example 1 and 2, be made up of the Porous that there is countless pore 1c and 1d respectively, but its shape is in rotund pore and the pore of ovalize mixes.In addition, for about 170nm when measuring the diameter of these pores 1c, 1d with the method that embodiment 7 is identical, larger than embodiment 7 and 8 about 2 times.
Based on the photo figure (SEM camera data) shown in Fig. 5 (A), Fig. 5 (B), Fig. 6 (A) and Fig. 6 (B), measure the distribution density being created on the pore (1a, 1b, 1c, 1d) on the surface of titanium oxide epithelium.The measurement of this distribution density, from the central portion (region 1 shown in table 7) and 4 jiaos (2 ~ region, region 5 shown in table 7) of each photo figure, the 5 kinds of square area selecting 1000nm × 1000nm in length and breadth to form, measurement is present in the number of the pore in this region, using the mean value of the mean value of these values as pore distribution density.The measurement result display of the distribution density of this pore (1a, 1b, 1c, 1d) in table 7.
[table 7]
The distribution density of (note) pore, represents the number in the region of 1000nm × 1000nm in length and breadth.
Shown by table 7, the mean value of the distribution density in the hole (pore) in the square area that the 1000nm × 1000nm on the surface of titanium oxide epithelium is formed, embodiment 7 and 8 is respectively 38.8 and 34.2, conventional example 1 and 2 is respectively 20.6 and 22.6, compare with 8 with embodiment 7, distribution density is low by about 50% nearly.This represents, if make containing sodium thiosulfate or sodium thiosulfate and KI in electrobath, then compare and make electrobath contain sulfuric acid, the diameter of pore diminishes, and the surface area of titanium oxide epithelium increases thus, and photocatalytic activity improves.
Embodiment 9
Be in the visible-light-responsive photocatalyst body of 0.02mol/L in the concentration of the sodium thiosulfate of embodiment 3, with method similarly to Example 2, try to achieve the content of sulphur, implement the photocatalysis antibacterial of visible ray test, and for ultraviolet light photocatalysis antibacterial test and try to achieve antibacterial activity value (R).For visible ray photocatalysis antibacterial test in antibacterial activity value (R) be 2.04, for ultraviolet light photocatalysis antibacterial test in antibacterial activity value (R) be 2.68.Can distinguish that photochemical catalyst of the present invention all has photocatalytic activity for visible ray and ultraviolet light thus.Be formed at the sulfur content of the titanium oxide epithelium on the surface of photochemical catalyst, be 1.1 atom % under the degree of depth of the surperficial 20nm apart from titanium oxide epithelium.
Using the foil-like titanium sheet metal of above-described embodiment as the visible-light-responsive photocatalyst body of base material, as the various component (photocatalytic elements) for playing visible light-responded property, such as, can as the various equipment of medicine equipment etc. and part thereof, using these equipment and part as packaging or collecting plate members or packaging element, particularly can utilize as the effective component for playing antibiotic property.
Claims (15)
1. a visible-light-responsive photocatalyst body, it is characterized in that, it is after using the electrobath containing sulphur to implement anodized to the surface of the base material of titanium or titanium alloy, the base material complete to described anodized is implemented to heat, and be formed containing sulphur on the surface of described base material and there is on surface the visible-light-responsive photocatalyst body of the titanium oxide epithelium of the Porous of minute aperture
The thickness of described base material is 0.005mm ~ 0.6mm,
The crystalline texture of the titanium dioxide comprised in described titanium oxide epithelium is Detitanium-ore-type crystalline texture.
2. visible-light-responsive photocatalyst body according to claim 1, is characterized in that, described titanium oxide epithelium contains the sulphur of 0.7 ~ 2.2 atom %.
3. visible-light-responsive photocatalyst body according to claim 1 and 2, is characterized in that, the thickness of described titanium oxide epithelium is below 200nm.
4. visible-light-responsive photocatalyst body according to any one of claim 1 to 3, is characterized in that, if during the mean value of the wide maxima and minima in the hole of the described minute aperture wide W that is hole, the wide W in described hole is 50 ~ 100nm.
5. visible-light-responsive photocatalyst body according to any one of claim 1 to 4, is characterized in that, described base material is strip, causes continuous anodic oxidation device and implements anodized continuously.
6. visible-light-responsive photocatalyst body according to claim 5, is characterized in that, cuts off in the mode of the size reaching regulation according to purposes.
7. visible-light-responsive photocatalyst body according to any one of claim 1 to 6, is characterized in that, described base material is foil-like or tabular.
8. visible-light-responsive photocatalyst body according to any one of claim 1 to 6, is characterized in that, described base material is with the punching shape be spaced of regulation or mesh-shape from its surperficial through fine through hole to the back side.
9. visible-light-responsive photocatalyst body according to any one of claim 1 to 6, is characterized in that, described base material is reticulated by the wire rod plain weave be made up of titanium or titanium alloy.
10. visible-light-responsive photocatalyst body according to any one of claim 1 to 9, is characterized in that, possesses photocatalytic activity for visible ray to the wavelength in the region of ultraviolet light.
11. visible-light-responsive photocatalyst bodies according to any one of claim 1 to 10, is characterized in that, are more than 2.0 by testing according to the photocatalysis antibacterial of JISR1702 the antibacterial activity value R obtained.
12. visible-light-responsive photocatalyst bodies according to any one of claim 1 to 11, it is characterized in that, when observing described oxide scale film surperficial with scanning electron microscope, in the square scope being 1000nm × 1000nm in length and breadth, the wide W in described hole is that the minute aperture of 50 ~ 100nm exists more than 30.
13. 1 kinds of photochemical catalyst manufacturing method, it is characterized in that, it is after the electrobath enforcement anodized by using the surface of described base material containing sodium thiosulfate 0.01mol/L ~ 0.2mol/L, implement again to heat and the manufacture method of visible-light-responsive photocatalyst body according to any one of manufacturing claims 1 to claim 12
Make the applied voltage of anodized be+70V ~+140V, anodizing time is 10 seconds ~ 60 seconds, and the bath temperature of the electrobath of anodized is 1 DEG C ~ 30 DEG C, heats and carries out with the temperature of 380 DEG C ~ 620 DEG C in oxidizing atmosphere.
The manufacture method of 14. visible-light-responsive photocatalyst bodies according to claim 13, is characterized in that, described electrobath is also containing KI 0.005mol/L ~ 0.1mol/L.
The manufacture method of 15. visible-light-responsive photocatalyst bodies according to claim 13 and 14, it is characterized in that, use the base material of strip as described base material, the base material of described strip is caused continuous anodic oxidation device and after implementing anodized continuously, the base material of the strip that antianode oxidation processes is complete is implemented to heat continuously.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-176038 | 2013-08-12 | ||
| JP2013176038 | 2013-08-12 | ||
| PCT/JP2014/071288 WO2015022960A1 (en) | 2013-08-12 | 2014-08-12 | Visible light-responsive photocatalyst body and method for producing same |
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| FR3059342B1 (en) * | 2016-11-28 | 2022-06-17 | Institut De Recherche Tech Materiaux Metallurgie Procedes | PARTS WITH CERAMIC COATING ON TITANIUM OR TITANIUM ALLOY SURFACES, OBTAINED BY MICRO-ARC ANODIZATION AND ELECTROLYTE SUITABLE FOR OBTAINING THEM |
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| MY163255A (en) * | 2010-02-02 | 2017-08-30 | Nat Univ Singapore | A buoyant multifunctional composite material for effective removal of organic compounds in water and wastewater |
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