CN105451882A - Photocatalyst and photocatalyst dispersion using same, photocatalyst coating, photocatalyst film, and product - Google Patents
Photocatalyst and photocatalyst dispersion using same, photocatalyst coating, photocatalyst film, and product Download PDFInfo
- Publication number
- CN105451882A CN105451882A CN201480013558.1A CN201480013558A CN105451882A CN 105451882 A CN105451882 A CN 105451882A CN 201480013558 A CN201480013558 A CN 201480013558A CN 105451882 A CN105451882 A CN 105451882A
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- tungsten oxide
- photochemical catalyst
- tungsten
- dispersion liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 111
- 239000006185 dispersion Substances 0.000 title claims description 97
- 238000000576 coating method Methods 0.000 title claims description 25
- 239000011248 coating agent Substances 0.000 title claims description 24
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 152
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 152
- 238000001237 Raman spectrum Methods 0.000 claims abstract description 16
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims description 99
- 239000007788 liquid Substances 0.000 claims description 91
- 229910052751 metal Inorganic materials 0.000 claims description 64
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 229910052721 tungsten Inorganic materials 0.000 claims description 24
- 239000010937 tungsten Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000011859 microparticle Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 82
- 239000000843 powder Substances 0.000 description 63
- 238000000034 method Methods 0.000 description 53
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- 239000002585 base Substances 0.000 description 43
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- 150000003658 tungsten compounds Chemical class 0.000 description 29
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- 150000001875 compounds Chemical class 0.000 description 23
- 229910052760 oxygen Inorganic materials 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 239000002994 raw material Substances 0.000 description 20
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
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- 238000004519 manufacturing process Methods 0.000 description 5
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- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
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- TVHALOSDPLTTSR-UHFFFAOYSA-H hexasodium;[oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O TVHALOSDPLTTSR-UHFFFAOYSA-H 0.000 description 1
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
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- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
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Classifications
-
- 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
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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Abstract
The photocatalyst according to an embodiment of the present invention is provided with tungsten oxide base microparticles containing tungsten oxide in a range of 5% by mass to 100% by mass. The ratio (X/Y) of the intensity (X) of a peak observed in a range of 920 cm-1 to 950 cm-1 to the intensity (Y) of a peak observed in a range of 800 cm-1 to 810 cm-1 in a Raman spectrum obtained by Raman spectroscopy of the photocatalyst is from greater than 0 to 0.04.
Description
Technical field
Embodiment of the present invention relates to photochemical catalyst and uses the photocatalyst dispersion liquid of this photochemical catalyst, photocatalyst coating, photocatalyst film and goods.
Background technology
As for antifouling and catalysis material that is deodorizing purposes, there will be a known titanium oxide.Catalysis material is used in the building materials of indoor and outdoor and the various field such as household electrical appliance, closet, hand basin, mirror, bathroom of lighting device, air purifier, air-conditioning and so on.But titanium oxide only just causes in ultraviolet range and excites, and therefore, the indoor few at ultraviolet can not obtain enough photocatalysis performances.Therefore, even if people are carrying out the research and development of the visible-light-responsive photocatalyst that also can demonstrate photocatalysis performance under visible light.In addition, in order to improve the photocatalysis performance of the visible ray of ultraviolet-responsive type titanium oxide, people are studying the situation of to adulterate in titanium oxide nitrogen or sulphur or other metals of load.
As visible-light-responsive photocatalyst, there will be a known tungsten oxide.Use tungsten oxide photocatalyst film such as by the dispersion liquid containing tungsten oxide particulate is applied to need imparting photocatalysis performance goods substrate surface on formed.As photocatalyst dispersion liquid, there will be a known such as by by the tungsten oxide microparticulate of average primary particle diameter (D50) within the scope of 1 ~ 400nm to water etc. to make its pH be in the aqueous dispersion formed in 1.5 ~ 6.5 scopes.Utilize this aqueous dispersion, the dispersiveness of tungsten oxide particulate can be made to improve, and the formative of the film containing tungsten oxide particulate is improved.Therefore, the photocatalyst film of the photocatalysis performance that can play consistently tungsten oxide particulate can be obtained.
Can make the photochemical catalyst that the visible light-responded performance of titanium oxide improves, its photocatalytic activity is directly proportional to light quantity, therefore, only by the light quantity of illumination (number about the lx ~ 3000lx) condition of room lighting, can not get enough photocatalysis performances.Therefore, expecting the living space of application photochemical catalyst, the place only near lighting source or immediately below it just can be effective.In the past containing the photocatalyst film of tungsten oxide particulate, be such as in the environment of about 2000lx in the illumination of visible ray, demonstrate the gas resolution ratio of more than 5%.But, consider the practicality of photocatalyst film, because it may not be abundant to the decomposability of the pernicious gases such as acetaldehyde, therefore, require to improve under low-light (level) the decomposability of gas.In addition, the photocatalyst film containing tungsten oxide particulate in the past, due to weak to the absorption affinity of gas, therefore in the environment that gas concentration is low, slack-off to the decomposition rate of gas, this is the problem existed at present.Therefore, people require that the capacity of decomposition of visible-light-responsive photocatalyst to gas reaches high performance.
Prior art document
Patent document
Patent document 1: No. 2008/117655th, International Publication
Patent document 2: No. 2009/031317th, International Publication
Patent document 3: No. 2009/110234th, International Publication
Summary of the invention
The problem that the present invention will solve is, even if provide in the environment that the illumination of visible ray is low or in the environment that gas concentration is low, the photochemical catalyst also having given play to the photocatalysis performances such as good gas capacity of decomposition and the photocatalyst dispersion liquid using this photochemical catalyst, photocatalyst coating, photocatalyst film and goods.
The photochemical catalyst of embodiment possesses tungsten oxide base particulate, wherein containing the tungsten oxide in the following scope of more than 5 quality % to 100 quality %.Measure in the Raman spectrum of photochemical catalyst, at 920cm adopting Raman spectroscopy
-1above to 950cm
-1the intensity X at the peak observed in following scope with at 800cm
-1above to 810cm
-1the ratio (X/Y) of the intensity Y at the peak observed in following scope, is being greater than the scope below 0 to 0.04.
Accompanying drawing explanation
Fig. 1 is the figure of the Raman spectrum that sample A (comparative example), sample D (embodiment), sample F (comparative example) in the production example of tungsten oxide particulate are shown.
Detailed description of the invention
Below, the scheme for implementing photochemical catalyst of the present invention, photocatalyst dispersion liquid, photocatalyst coating, photocatalyst film, goods is described.
(photochemical catalyst)
The photochemical catalyst of embodiment possesses tungsten oxide base particulate, wherein containing the tungsten oxide within the scope of 5 ~ 100 quality %.As the tungsten oxide base particulate forming photochemical catalyst, the independent particulate of tungsten oxide or the particulate such as the mixture of tungsten oxide and other metallic elements or complex can be enumerated.In the photochemical catalyst of embodiment, the content of tungsten oxide is in the scope of 5 ~ 100 quality %.If the content of tungsten oxide is lower than 5 quality %, then fully can not obtain the visible light responsive photocatalytic performance based on tungsten oxide particulate.The content of tungsten oxide is preferably at more than 45 quality %.
The photochemical catalyst of embodiment can containing the metallic element (being hereafter designated as " interpolation metallic element ") beyond tungsten.As the metallic element contained by photochemical catalyst, the earth metal such as zinc family elements, the aluminium elements such as the transition metal beyond tungsten, zinc can be enumerated.Transition metal refers to the element of atomic number 21 ~ 29,39 ~ 47,57 ~ 79,89 ~ 109, also can containing the metallic element beyond tungsten (atomic number 74) in these transition metal in photochemical catalyst.Zinc family elements are the element of atomic number 30,48,80, and earth metal element is the element of atomic number 13,31,49,81.Also these metallic elements can be contained in photochemical catalyst.By the metallic element making photochemical catalyst contain appropriate scope, the photocatalysis performance of the visible-light response type of photochemical catalyst can be improved.
In photochemical catalyst, add the content of metallic element preferably in the scope of 0.001 ~ 50 quality %.If the content adding metallic element is lower than 0.001 quality %, then can not obtain the effect fully improving photocatalysis performance.If the content adding metallic element is greater than 50 quality %, then the content of tungsten oxide reduces relatively, and the photocatalysis performance based on tungsten oxide particulate may be made to reduce.Add the content of metallic element more preferably in the scope of 0.005 ~ 10 quality %.By making photochemical catalyst contain interpolation metallic element in above-mentioned scope, the photocatalysis performance of the photochemical catalyst of embodiment effectively can be improved.
The metallic element (interpolation metallic element) that can contain in photochemical catalyst is preferably selected from least a kind in titanium (Ti), zirconium (Zr), manganese (Mn), iron (Fe), ruthenium (Ru), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), cerium (Ce) and aluminium (Al).By making photochemical catalyst contain above-mentioned metallic element within the scope of 0.005 ~ 10 quality %, the photocatalysis performance of the photochemical catalyst of embodiment more effectively can be improved.
As the typical example of existing forms adding metallic element in photochemical catalyst, metal oxide can be enumerated.The oxide of photochemical catalyst preferably containing the interpolation metallic element beyond tungsten oxide.In photochemical catalyst, add the content of the oxide of metallic element preferably in the scope of 0.01 ~ 70 quality %.By the oxide making photochemical catalyst contain the interpolation metallic element within the scope of this, the photocatalysis performance of photochemical catalyst can be improved further.The oxide adding metallic element is more preferably at least a kind that is selected from zirconia, titanium oxide and ruthenium-oxide.By making photochemical catalyst contain this metal oxide, more effectively photocatalysis performance can be improved.The content of the metal oxide in photochemical catalyst except tungsten oxide is more preferably in the scope of 0.02 ~ 55 quality %.
In the photochemical catalyst of embodiment, adding metallic element can be contained with various form.Photochemical catalyst can with forms such as the compound such as simple substance, oxide adding metallic element, the complex chemical compounds that formed with tungsten oxide, containing interpolation metallic element.Add metallic element and also can form composite oxides by two or more metallic element.And then the simple substance or the compound that add metallic element also can be carried on tungsten oxide.Or, tungsten oxide also can be carried on add metallic element compound etc. on.
As containing the concrete example of tungsten oxide base particulate adding metallic element, tungsten oxide particulate and the carrier particles etc. of adding the simple substance of complex chemical compound particulate, tungsten oxide and interpolation metallic element that the simple substance of alloy particle, tungsten oxide and interpolation metallic element that the simple substance of mixture particulate, tungsten oxide and interpolation metallic element that the simple substance of mixture, tungsten oxide and interpolation metallic element that the simple substance particulate (metal particle) of metallic element or compound particles etc. are formed or compound etc. are formed or compound etc. are formed or compound etc. are formed or compound etc. and being formed can be enumerated.These particulates are only examples of tungsten oxide base particulate, and the photochemical catalyst of embodiment is not limited to this.
When the photochemical catalyst of embodiment contains interpolation metallic element, tungsten oxide and the complex method adding metallic element are not particularly limited.Tungsten oxide will be made mix or compound tense with interpolation metallic element, can adopt tungsten oxide powder is mixed with the interpolation elemental powders (metal dust) of metallic element or compound powder (such as metal oxide powder) method, at least one party made various mixing method or the composite algorithm such as method, infusion process, load method that solution, dispersion liquid, colloidal sol etc. carry out mixing again.Such as, when the metal oxide added is zirconia, the zirconia of various shape can be adopted, but preferably its primary particle is bar-shaped.Preferably mixed having by the zirconia sol of the particle of bar-shaped primary particle aggegation and tungsten oxide particulate or the dispersion liquid that is scattered in water etc. by it.
The photochemical catalyst of embodiment also can containing the metallic element etc. as trace impurity.Content as the metallic element of impurity element is preferably below 2 quality %.As impurity metallic elements, the element generally contained in tungsten ore or the pollution element etc. be mixed into when manufacturing the tungsten compound used as raw material can be enumerated.As impurity metallic elements, Fe, Mo, Mn, Cu, Ti, Al, Ca, Ni, Cr, Mg etc. can be enumerated.But, when being used as interpolation metallic element by these elements, be just not limited to this.
When adopting Raman spectroscopy to analyze the fine structure such as crystallinity and surface state, the photochemical catalyst of embodiment has following characteristics.As adopt Raman divide≤light method measure photochemical catalyst result Raman spectrum in, at 920 ~ 950cm
-1the intensity X at peak that observes of scope with at 800 ~ 810cm
-1the ratio (X/Y) of the intensity Y at peak observed of scope be in the scope of 0 < X/Y≤0.04.When photochemical catalyst has strength ratio (X/Y) of this Raman peaks, can improve with the tungsten oxide particulate photochemical catalyst that is matrix photocatalysis performances such as the capacities of decomposition of gas.Specifically, even if in the environment that the illumination of visible ray is low or in the environment that gas concentration is low, the photocatalysis performances such as the good capacity of decomposition to gas can also be obtained.
That is, tungsten oxide particulate can play it to photocatalysis performances such as the capacities of decomposition of gas under the irradiation of visible ray.But, in the environment that visible light illumination is low, the photocatalysis performance of tungsten oxide can not be given full play to.And then along with gas concentration reduces gradually from initial stage concentration, the decomposition rate of tungsten oxide to gas is slack-off.Think, this is the decomposability reduction of the intermediate material owing to generating when tungsten oxide decomposes gas, and in gas low concentration environment, tungsten oxide reduces the absorption affinity of gas.The discoveries such as the present inventor, if to improve under the irradiation of low-light (level) visible ray tungsten oxide to the capacity of decomposition of gas and tungsten oxide to the decomposability of intermediate material and at low concentrations tungsten oxide to the absorption affinity of gas, be effective by the scope that the peak intensity of Raman spectrum ratio (X/Y) is set in 0 < X/Y≤0.04.
Peak intensity ratio (X/Y) in Raman spectrum represents the crystallinity of tungsten oxide base particulate and the state etc. of surface damage.By being controlled be greater than the scope below 0 to 0.04 by peak intensity ratio (X/Y), the photocatalytic activity of photochemical catalyst (tungsten oxide base particulate) effectively can be improved.If peak intensity ratio (X/Y) is zero, even if then the crystallinity of tungsten oxide particulate improves, the surface of tungsten oxide particulate also almost can not be made to become the state of anoxic etc.High gas capacity of decomposition can not be obtained in this state.The strength ratio (X/Y) at peak is more preferably more than 0.001.If peak intensity ratio (X/Y) is greater than 0.04, then the amount of the surface damage such as anoxic increases too much, and photocatalytic activity reduces on the contrary, therefore can not obtain high gas decomposability.The strength ratio (X/Y) at peak is more preferably less than 0.03.
When the strength ratio (X/Y) of the Raman peaks of photochemical catalyst is when being greater than below 0 to 0.04 in scope, the crystalline state of tungsten oxide base particulate or surface state (there is degree etc. of blemish) can be controlled as being suitable for light-catalysed state.Therefore, can improve under the condition of low-light (level) visible ray, tungsten oxide base particulate is to the decomposability of gas.And then, can improve under the state that gas concentration is low, the decomposability of tungsten oxide base particulate to intermediate material and the absorption affinity to gas.Adopt the photochemical catalyst of embodiment, even if in the environment that the illumination of visible ray is low and in the environment that gas concentration is low, also can give play to the high decomposability to gas.In addition, even if the photochemical catalyst of embodiment also can play its decomposability to gas in ultraviolet irradiation environment.Adopt the photochemical catalyst of embodiment, its decomposability to gas can be played under than photochemical catalyst in the past widely condition.Thus, the photochemical catalyst that can improve practicality can be provided.
The strength ratio (X/Y) of the Raman peaks of above-mentioned photochemical catalyst, can by controlling the heat-treat condition implemented after making tungsten oxide base particulate, and such as heat-treating atmosphere and heat treatment temperature etc. obtain.And then, because the surface state etc. of tungsten oxide base particulate changes along with the environment temperature under keeping state etc., therefore by these conditions of adjustment, the strength ratio of Raman peaks (X/Y) can be maintained suitable scope.As will be described in more detail below, the heat treated temperature implemented after making tungsten oxide base particulate is preferably the scope of 200 ~ 800 DEG C.And then, in order to the crystallinity of tungsten oxide base particulate and surface state are adjusted to suitable state, the programming rate preferably during control heat treatment and cooling rate.
About the crystallinity of tungsten oxide, crystallinity is higher, more can improve photocatalysis performance.But, if implement heat treatment, then the grain growth of tungsten oxide under the crystalline condition excessively improving tungsten oxide, cause the specific area of particulate to reduce.And then if the crystallinity of tungsten oxide is too high, then microparticle surfaces can become the state almost not having the blemish such as anoxic.These are principal elements that the photocatalysis performance of photochemical catalyst is reduced.Consider this point, control be greater than the scope below 0 to 0.04 by the strength ratio (X/Y) of the Raman peaks by photochemical catalyst, the surface state of the crystallinity of tungsten oxide, particulate and particle diameter etc. can be adjusted to the state of appropriateness.Therefore, can provide excellent to photocatalysis performances such as the capacities of decomposition of gas, photochemical catalyst that practicality improves further.
Form in the tungsten oxide base particulate of the photochemical catalyst of embodiment, the peak intensity ratio (X/Y) of Raman spectrum is in the scope be greater than below 0 to 0.04, and in addition, the Raman spectrum of preferred light catalyst has at 268 ~ 274cm
-1the 1st peak (peak intensity is than being maximum peak) existed in scope, at 630 ~ 720cm
-1the 2nd peak (peak intensity is than being the 2nd large peak) existed in scope and at 800 ~ 810cm
-1the 3rd peak (peak intensity is than being the 3rd large peak) existed in scope.
And then the half-peak breadth at the 1st peak is preferably in 8 ~ 25cm
-1scope.The half-peak breadth at the 2nd peak is preferably in 15 ~ 75cm
-1scope, the half-peak breadth at the 3rd peak is preferably in 15 ~ 50cm
-1scope.These Raman peaks illustrate that crystalline texture that the crystallization of tungsten oxide has comprises that to be selected from monoclinic crystal, three tiltedly brilliant and orthorhombic at least a kind, the crystalline texture of the photochemical catalyst for being particularly suitable for visible-light response type shown in it.Adopt the tungsten oxide base particulate with this crystalline texture, excellent photocatalysis performance can be played consistently.
The Raman spectrum of embodiment uses the Ar ion laser that wavelength is 514.5nm, measures under the condition of temperature 20 ~ 30 DEG C, humidity 30 ~ 70%.For the peak intensity of Raman spectrum, peak intensity X take wave number as 900cm
-1spectral value and 1000cm
-1the spectral value straight line of drawing be zero point, and peak intensity Y take wave number as 1000cm
-1spectral value be zero point, be set to the intensity between the summit from this two zero points to peak.Specifically, 920 ~ 950cm is determined at
-1the intensity X to maximum peak summit existed in scope and at 800 ~ 810cm
-1the intensity Y to maximum peak summit existed in scope, is obtained the strength ratio (X/Y) at peak by these intensity X and intensity Y.
Form the tungsten oxide of photochemical catalyst preferably primarily of WO
3(tungstic acid) is formed.Although tungsten oxide is preferably substantially by WO
3form, as long as but meet the peak intensity ratio (X/Y) of Raman spectrum, also can containing other tungsten oxide (WO
2, WO, W
2o
3, W
4o
5, W
4o
11deng).The average grain diameter (D50) of tungsten oxide base particulate is preferably more than 1nm to less than 30 μm.The average grain diameter (D50) of tungsten oxide base particulate is more preferably more than 50nm to less than 1 μm.About the size distribution of tungsten oxide base particulate, D90 footpath is preferably 0.05 ~ 10 μm.The BET specific surface area of tungsten oxide base particulate is preferably 4.1 ~ 820m
2/ g, is more preferably 10 ~ 300m
2/ g.
Photocatalyst dispersion liquid can, by being mixed with water system decentralized medium by tungsten oxide base particulate as described later, be used ultrasonic dispersing machine, wet type airslide disintegrating mill, ball mill etc. to carry out dispersion treatment to make.In the photocatalyst dispersion liquid obtained like this, the photochemical catalyst possessing tungsten oxide base particulate contains by the agglutination particle of primary particle aggegation.Containing agglutination particle and when measuring its size distribution by the laser diffraction formula size distribution meter of wet type etc., if be that D50 footpath in the accumulation particle diameter of benchmark is for more than 1nm is to less than 30 μm with volume, then can obtain good dispersity and even and stable film formative, its result, can obtain high photocatalysis performance.
If the D50 footpath of tungsten oxide base particulate is greater than 30 μm, then can not obtain the sufficient characteristic as photocatalyst dispersion liquid.When the D50 footpath of tungsten oxide base particulate is less than 1nm, particle is too small, and the operability of photochemical catalyst is poor, and the practicality of the dispersion liquid of photochemical catalyst and this photochemical catalyst of use reduces.And then when the D90 footpath of tungsten oxide base particulate is less than 0.05 μm, the dispersiveness of tungsten oxide base particulate reduces.Therefore, be difficult to obtain uniform dispersion liquid and coating.If D90 footpath is greater than 10 μm, then uses dispersion liquid or coating to form even and stable film and become difficulty, can not photocatalysis performance be given full play to.And then, in order to improve photocatalysis performance during photochemical catalyst membranization, in the dispersion treatment preferably when making dispersion liquid, do not make particulate too be out of shape.
About the photochemical catalyst of embodiment, when representing its color with L*a*b* color specification system, preferably having that a* is less than 10, b* is more than-5, L* is the catalyst color of more than 50.L*a*b* color specification system is the method for representing object color, and within 1976, carry out standardization by International Commission on Illumination (CIE), Japan is then according to the regulation of JISZ-8729.By there is the photochemical catalyst of this color and using the dispersion liquid be scattered in water system decentralized medium by it to form photocatalyst film, so not only can obtain good photocatalysis performance, nor the tone of base material can be damaged.Therefore, except the characteristic original except the goods with photocatalyst film and quality, the photocatalysis performance based on photocatalyst film can also be played consistently.
The tungsten oxide particulate of the photochemical catalyst of main composition embodiment, preferably makes according to method shown below.But, the preparation method of tungsten oxide base particulate is not particularly limited.Tungsten oxide base particulate preferably adopts sublimation process to make.And then, preferably in sublimation process, combine heat treatment step.Adopt the tungsten oxide base particulate made in this way, stably can realize the strength ratio (X/Y) of above-mentioned Raman peaks and the crystalline state, crystalline texture, average grain diameter etc. based on this strength ratio.
First, sublimation process is described.Sublimation process obtains the operation of tungsten oxide particulate by making tungsten powder, tungsten compound powder or tungsten compound solution distil in oxygen atmosphere.Distillation is that the state becoming gas phase from solid phase or become solid phase from gas phase changes the phenomenon caused without liquid phase.By making to distil while be oxidized as the tungsten powder of raw material, tungsten compound powder or tungsten compound solution, the tungsten oxide of graininess can be obtained.
As the raw material (tungsten raw material) of sublimation process, any one in tungsten powder, tungsten compound powder or tungsten compound solution can be used.As the tungsten compound being used as raw material, such as tungstic acid (WO can be enumerated
3), tungsten dioxide (WO
2), tungsten oxide, tungsten carbide tool, ammonium tungstate, artificial schellite, the wolframic acid etc. such as lower oxyde.
By carrying out the sublimation process of tungsten raw material as described above in oxygen atmosphere, make tungsten powder and/or tungsten compound powder is instantaneous becomes gas phase from solid phase, then will the tungsten vapor-phase oxidation of gas phase be become, obtain tungsten oxide particulate.Even if when using solution, be also through tungsten oxide or compound becomes gas phase.So, by utilizing the oxidation reaction in gas phase, tungsten oxide particulate can be obtained.And then, can the crystalline texture etc. of controlled oxidization tungsten particulate.
As the raw material of sublimation process, not easily containing impurity in the tungsten oxide particulate obtained to make to distil in oxygen atmosphere, preferably use at least a kind that is selected from tungsten powder, tungsten oxide powder, tungsten-carbide powder and ammonium tungstate powder.Because tungsten powder and tungsten oxide powder are not contained in the harmful substance as accessory substance (material beyond tungsten oxide) formed in sublimation process, therefore, particularly preferably as the raw material of sublimation process.
As the tungsten compound for raw material, preferably contain as the tungsten (W) of its constitution element and the compound of oxygen (O).If containing as W and O of constituent, then adopt in sublimation process during inductively coupled plasma process described later etc. and easily distil instantaneously.As this tungsten compound, WO can be enumerated
3, W
20o
58, W
18o
49, WO
2deng.In addition, wolframic acid, be also effective to the solution or salt etc. of ammonium tungstate, ammonium metatungstate.
When making by tungsten oxide with when adding complex particulate that the simple substance of metallic element or compound etc. formed, except tungsten raw material, also can with forms such as metal, oxidiferous compound, complex chemical compounds by metallic element mixing such as transition metal or earth metal elements.By tungsten oxide and other metallic elements being processed simultaneously, the complex chemical compound particulates such as the composite oxides formed by tungsten oxide and other metallic elements can be obtained.Complex particulate also can by mixing the simple substance particle of tungsten oxide particulate and other metallic elements or compound particles, make its load to obtain.The complex method of tungsten oxide and other metallic elements is not particularly limited, and can adopt various known method.
The scope of 0.1 ~ 100 μm is preferably in as the tungsten powder of tungsten raw material and/or the average grain diameter of tungsten compound powder.The average grain diameter of tungsten raw material is more preferably in the scope of 0.3 μm ~ 10 μm, is preferably in the scope of 0.3 μm ~ 3 μm further, wishes the scope being in 0.3 μm ~ 1.5 μm.If use average grain diameter to be in tungsten powder in above-mentioned scope and/or tungsten compound powder, easily distil.When the average grain diameter of tungsten raw material is lower than 0.1 μm, because material powder is too fine, therefore, must arrange in advance material powder, otherwise operability can be made to reduce, and price is raised, this is industrially disadvantageous.If the average grain diameter of tungsten raw material is greater than 100 μm, be then difficult to cause the reaction that distils uniformly.Even if although average grain diameter is large, as long as use large energy to process, also can make it that reaction that distils uniformly occurs, be industrially not preferred.
As the method making tungsten raw material distil in oxygen atmosphere in sublimation process, at least a kind of process be selected from inductive type plasma treatment, arc discharge process, laser treatment, electron ray process and gas burner process can be enumerated.Laser treatment wherein or electron ray process are the operations of being undertaken distilling by irradiating laser or electron ray.Because the irradiation spot diameter of laser or electron ray is little, need the time that cost is longer when the large content of starting materials of disposable process, but strictly need not control the particle diameter of material powder and the stability of quantity delivered, this is the advantage of the method.
In inductive type plasma treatment and arc discharge process, the generation area of plasma and arc discharge must be adjusted, but a large amount of material powder generation oxidation reaction can be made once in oxygen atmosphere.In addition, can also control can the amount of raw material of disposable process.The power cost of gas burner process is relatively more cheap, but is difficult to process material powder and material solution in a large number.Therefore, the production rate variance of gas burner process.Be explained, as long as gas burner process has enough energy that raw material can be made to distil, be not particularly limited.Propane gas burner or acetylene gas burner etc. can be used.
When inductive type plasma treatment is applied to sublimation process, usually adopts and use argon gas or oxygen to produce plasma, in this plasma, supply the method for tungsten powder and/or tungsten compound powder.As the method supplying tungsten raw material in plasma, can enumerate such as tungsten powder and/or tungsten compound powder are blown into together with carrier gas method, tungsten powder and/or tungsten compound powder dispersion are blown into the method etc. of dispersion liquid in the liquid dispersion medium of regulation.
When tungsten powder and/or tungsten compound powder being blown in plasma, as carrier gas used, such as air, oxygen, oxygen containing inert gas etc. can be enumerated.Wherein, because the cost of air is low, therefore preferably use.When being also blown into oxygen containing reacting gas except carrier gas or tungsten compound powder is that the situation of tungsten oxide is inferior, when in conversion zone containing enough oxygen time, the inert gas such as argon gas or helium also can be used as carrier gas.Reacting gas preferably uses oxygen or oxygen containing inert gas etc.When using oxygen containing inert gas, preferably set the amount of oxygen, can fully supply necessary oxygen amount to oxidation reaction.
By adopting the method that tungsten powder and/or tungsten compound powder is blown into together with carrier gas, adjust the pressure etc. in gas flow or reaction vessel simultaneously, can the crystalline texture of easily controlled oxidization tungsten particulate.Specifically, easily can obtain to have and be selected from monoclinic crystal and triclinic at least a kind (monoclinic crystal, three is brilliant or monoclinic crystal and triclinic mixed crystal tiltedly) or wherein also mix the tungsten oxide particulate having orthorhombic crystalline texture.The crystalline texture of tungsten oxide particulate is preferably crystalline texture, three that crystalline texture that monoclinic crystal and three oblique crystalline substances mix, monoclinic crystal and iris mix tiltedly brilliant crystalline texture, any one tiltedly in the brilliant crystalline texture mixed with iris of monoclinic crystal, three mixed with iris.
As the decentralized medium of the dispersion liquid for making tungsten powder and/or tungsten compound powder, the liquid dispersion medium in the molecule with oxygen atom can be enumerated.When using dispersion liquid, the operation of material powder becomes easy.As the liquid dispersion medium in the molecule with oxygen atom, the liquid dispersion medium of at least a kind be such as selected from containing 20 more than volume % in water and alcohol can be used.As the alcohol being used as liquid dispersion medium, preference is as being selected from least a kind in methyl alcohol, ethanol, 1-propyl alcohol and 2-propyl alcohol.Volatilize due to the heat of water or the easy subject plasma of alcohol, therefore, distillation reaction and the oxidation reaction of material powder can not be hindered, due in the molecule containing aerobic, therefore easily accelerating oxidation reaction.
When by tungsten powder and/or tungsten compound powder dispersion are made dispersion liquid in decentralized medium, the tungsten powder preferably containing 10 ~ 95 quality % scopes, more preferably 40 ~ 80 quality % scopes in dispersion liquid and/or tungsten compound powder.By making the dispersion ratio in dispersion liquid be within the scope of this, tungsten powder and/or tungsten compound powder can be made to be scattered in equably in dispersion liquid.Time dispersed, the distillation reaction of material powder is easily carried out equably.If the content in dispersion liquid is lower than 10 quality %, then the amount of material powder is very few, can not manufacture efficiently.If be greater than 95 quality %, then because dispersion liquid is few, the viscosity of material powder increases, and be easily cemented on container, therefore operability is poor.
By adopting, tungsten powder and/or tungsten compound powder are made dispersion liquid and be blown into the method in plasma, can the crystalline texture of easily controlled oxidization tungsten particulate.Particularly, easily can to obtain its crystalline texture be at least a kind of being selected from monoclinic crystal and three oblique crystalline substances or wherein also mix and have orthorhombic tungsten oxide particulate.And then, by tungsten compound solution is used as raw material, distillation also can be made to react and to carry out equably, the controlling of the crystalline texture of tungsten oxide particulate can be improved further.Use the method for dispersion liquid as described above, also go for arc discharge process.
When irradiating laser or electron ray implements sublimation process, preferably tungsten or tungsten compound being made after graininess and using as raw material.Because the irradiation spot diameter of laser or electron ray is little, therefore, if use tungsten powder, tungsten compound powder, then supply becomes difficult, making granular tungsten or tungsten compound, can it be made efficiently to distil by using.As laser, as long as have the laser being enough to the energy making tungsten or tungsten compound distillation, be just not particularly limited, CO
2laser, owing to being high-octane, is therefore preferred.
When by laser or electronbeam irradiation to particle time, if make at least one party of the light of laser or the irradiation source of electron ray or particle move, then the whole surface of the particle with to a certain degree size can be made effectively to distil.Thus, can obtain to have and mix the tungsten trioxide powder having orthorhombic crystalline texture being selected from monoclinic crystal and triclinic at least a kind.Particle as described above also goes for inductive type plasma treatment or arc discharge process.
The photochemical catalyst of embodiment can obtain well by heat-treating repeatability to the tungsten oxide base particulate obtained in above-mentioned sublimation process.In heat treatment step, the tungsten oxide base particulate obtained in sublimation process is heat-treated with the temperature and time of regulation in oxidizing atmosphere.Heat treatment step is preferably implemented in atmosphere or in oxygen-containing gas.Oxygen-containing gas refers to the inert gas containing aerobic.Heat treatment temperature preferably the scope of 200 ~ 800 DEG C, more preferably the scope of 340 ~ 650 DEG C.Heat treatment time preferably the scope of 10 minutes ~ 5 hours, more preferably the scope of 30 minutes ~ 2 hours.By making the temperature and time of heat treatment step in above-mentioned scope, the crystallinity of tungsten oxide base particulate and the amount etc. of blemish can be made to become the state being suitable for photochemical catalyst.
When heat treatment temperature is lower than 200 DEG C, likely can not fully obtain the oxidation effectiveness making the powder not yet becoming tungstic acid become tungstic acid in sublimation process.And then, fully can not improve the crystallinity of the tungstic acid obtained in sublimation process.If heat treatment temperature is higher than 800 DEG C, then the crystallinity of tungsten oxide is too high, easily becomes the state that microparticle surfaces does not almost have the blemish such as oxygen debt.In any one situation, all fully can not improve the photocatalytic activity of tungsten oxide base particulate.And then, by programming rate during heat treatment and cooling rate are adjusted in proper range, can repeatability well the crystallinity of tungsten oxide base particulate and surface state be controlled in applicable light-catalysed state.In heat treatment step, preferably tungsten oxide powder is joined and be warming up in the stove of design temperature, after the stipulated time, tungsten oxide powder is taken out from stove, make it be cooled to room temperature.Programming rate during heat treatment is preferably the scope of 80 ~ 800 DEG C/min, and cooling rate is preferably the scope of-800 ~-13 DEG C/min.
(photocatalyst dispersion liquid, photocatalyst coating, photocatalyst film and goods)
Below, the photocatalyst dispersion liquid of embodiment and photocatalyst coating and the photocatalyst film using them to make are described and possess the goods of photocatalyst film.The photocatalyst dispersion liquid of embodiment is by making the photochemical catalyst of embodiment be dispersed in water system decentralized medium according to the scope that particle concentration is 0.001 ~ 50 quality %.If particle concentration is lower than 0.001 quality %, then photochemical catalyst containing quantity not sufficient, the performance of wishing can not be obtained.If particle concentration is greater than 50 quality %, then during membranization, the particulate of photochemical catalyst exists with too close state, and can not obtain can in order to give full play to the surface area of photocatalysis performance.Therefore, not only can not give full play to performance, and in order to containing being necessary above photochemical catalyst, cost can be caused to increase.The concentration of photochemical catalyst is more preferably in the scope of 0.01 ~ 20 quality %.
In the photocatalyst dispersion liquid of embodiment, the pH of dispersion liquid is preferably the scope of 1 ~ 9.By making the pH of photocatalyst dispersion liquid be the scope of 1 ~ 9, because Zeta potential becomes negative value, the dispersity of photochemical catalyst therefore can be improved.As long as the coating adopting this dispersion liquid or be made up of it, can be coated on base material thinly and equably.If the pH of photocatalyst dispersion liquid is less than 1, then because Zeta potential is close to zero, therefore dispersed variation.If the pH of photocatalyst dispersion liquid is greater than 9, then tungsten oxide becomes easy dissolving.In order to adjust the pH of photocatalyst dispersion liquid, also as required, the aqueous solution of the acid such as hydrochloric acid, sulfuric acid, TMAH (TMAH), ammonia, NaOH or alkali can be added.
The pH of photocatalyst dispersion liquid more preferably 2.5 ~ 7.5 scope.Thus, the photocatalysis performance (gas decomposability) of the film using dispersion liquid or coating to be formed can be improved further.Be the photocatalyst dispersion liquid of 2.5 ~ 7.5 scopes in coating pH value and after making its drying, when observing the surface state of particle with FT-IR (Fourier transform infrared spectroscopy), observe at 3700cm
-1near there is the absorption of hydroxyl.By this film is used as photocatalyst film, excellent organic gas decomposability can be obtained.When being coated with pH value and being adjusted to the photocatalyst dispersion liquid of 8 and making it dry, the absorption of hydroxyl reduces, and gas decomposability is also easily deteriorated.When the pH value of photocatalyst dispersion liquid is adjusted to 1.5, although there is hydroxyl, Zeta potential is close to 0, and therefore, dispersiveness has some reductions, and gas decomposability also has some reductions.
The photocatalyst dispersion liquid of embodiment can obtain by making the photochemical catalyst of embodiment be scattered in water system decentralized medium.The photochemical catalyst disperseed in water system decentralized medium, is not limited to the independent particulate of tungsten oxide as described above, also can be the particulate of the mixture or complex etc. of tungsten oxide and other metallic elements.Tungsten oxide and other metallic elements can be pre-mixed or the state of compound is dispersed in water system decentralized medium, also can as the mixture in water system decentralized medium or complex.The kind of the metallic element beyond tungsten and form etc. are described above.
For tungsten oxide being mixed in decentralized medium with other metallic elements or the method for compound, be not particularly limited.Below record representational complex method.As the method with ruthenium compound, the method for adding the aqueous solution of ruthenic chloride in the aqueous dispersion being dispersed with tungsten oxide particulate can be enumerated.As the method with platinum compound, the method mixing platinum powder end in the aqueous dispersion containing tungsten oxide particulate can be enumerated.And then, that use the aqueous solution of copper nitrate or copper sulphate or ethanolic solution with complex method that is copper, use ferric chloride in aqueous solution with the complex method of iron, use the silver chlorate aqueous solution with the complex method of silver, use chloroplatinic acid aqueous solution with the complex method of platinum, what use palladium chloride aqueous solution is also effective with the complex method etc. of palladium.In addition, also the oxide sol such as titanium oxide sol or alumina sol be can use, tungsten oxide and metallic element (oxide) compound made.Also various complex method other than the above can be adopted.
As the photocatalyst dispersion liquid of embodiment, water system decentralized medium can be used.As the typical example of water system decentralized medium, water can be enumerated.In water system decentralized medium, in addition to water, also can containing the alcohol lower than 50 quality %.As alcohol, such as methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol etc. can be used.If the content of alcohol is greater than 20 quality %, then likely can there is aggegation in photochemical catalyst, and therefore, the content of alcohol is more preferably at below 20 quality %.Content more preferably below the 10 quality % of alcohol.The photochemical catalyst of embodiment also can to mix with the material that active carbon or zeolite etc. have an absorption property, load, dipping state, be dispersed in the water system such as water or alcohol decentralized medium.Photocatalyst dispersion liquid can contain the photochemical catalyst of such state.
The photocatalyst dispersion liquid of embodiment can be used as film formation material with original state.Also photocatalyst dispersion liquid can be mixed with adhesive ingredients and make coating, this coating is used as film formation material.At least a kind of adhesive ingredients containing aqueous dispersion in coating and be selected from inorganic bond and organic bond.The content of adhesive ingredients is preferably in the scope of 5 ~ 95 quality %.If the content of adhesive ingredients is greater than 95 quality %, then likely can not get the photocatalysis performance of wishing.When the content of adhesive ingredients is lower than 5 quality %, can not get sufficient bonding force, membrane property likely reduces.By being coated with this coating, can by film strength, hardness, the closing force etc. of base material is adjusted to the state of expectation.
As inorganic bond, such as alkyl silicate (ester), silicon halide and their partial hydrolystate etc. can be used to be decomposed by water-disintegrable silicon compound and metal oxide, Quadrafos, cement, gypsum, lime, the enamel frit etc. such as the phosphate such as product, organopolysiloxane compound and condensation polymer thereof, silica, cataloid, waterglass, silicon compound, trbasic zinc phosphate, zinc oxide, zirconia that obtain.As organic bond, such as fluororesin, organic siliconresin, acrylic resin, epoxy resin, mylar, melmac, polyurethane resin, alkyd resins etc. can be used.
By above-mentioned photocatalyst dispersion liquid or photocatalyst coating are coated on base material, can stablize and be formed uniformly the film containing photochemical catalyst.As the base material forming photocatalyst film, the resins such as glass, pottery, plastics, acrylic resin, paper, fiber, metal, timber etc. can be used.Thickness is preferably in the scope of 2 ~ 1000nm.If thickness is lower than 2nm, then may can not get the state that tungsten oxide base particulate homogenous exists.If thickness is more than 1000nm, then photocatalyst film reduces the closing force of base material.Thickness is more preferably in the scope of 2 ~ 400nm.
The photocatalyst film of embodiment not only also can play photocatalysis performance under visible light but also under Ultraviolet radiation.In general, visible ray refers to the light of wavelength in 380 ~ 830nm region, is using the general illuminations such as sunshine or white fluorescent lamp, White LED, bulb, Halogen lamp LED, xenon lamp or blue LED, blue laser etc. as the light of light source irradiation.Ultraviolet refers to the light of wavelength in 10 ~ 400nm region, comprises the light irradiated by the sun and mercury vapor lamp etc.The photocatalyst film of embodiment not only can play photocatalysis performance in common indoor environment, and also can play photocatalysis performance under ultraviolet irradiation.Photocatalysis performance refers to: absorb light and the pair of electrons that inspires relative to 1 photon and hole, the electronics be excited and hole will be in hydroxyl and oxygen (acid) activation on surface by redox, utilize the active oxygen that this activation produces, the effect of oxidation Decomposition organic gas etc., and the effect playing hydrophily and antibacterial/degerming performance etc.
The goods of embodiment possess the film by using above-mentioned photocatalyst dispersion liquid or photocatalyst coating to be formed.Specifically, be coating photocatalyst dispersion liquid or photocatalyst coating and form the goods of film on the substrate surface forming goods.The film that substrate surface is formed also can contain zeolite, active carbon, porous ceramic etc.Under the irradiation of visible ray, photocatalyst film is excellent with the decomposability of goods to the organic gas such as acetaldehyde and formaldehyde possessing photocatalyst film, particularly under low-light (level), also demonstrates high activity.In addition, compared with visible-light-responsive photocatalyst in the past, even if the goods of embodiment also have high photocatalysis performance under Ultraviolet radiation, environment for use can be expanded.The photocatalyst film of embodiment demonstrates hydrophily in the contact angle determination of water.And then, in staphylococcus aureus and colibacillary antibiotic property being evaluated under the irradiation of visible ray, give play to high antibacterial action.
As the concrete example of goods of photocatalyst film possessing embodiment, air-conditioning can be enumerated, air purifier, fan, refrigerator, micro-wave oven, wash the dishes drying machine, electric cooker, kettle, pot cover, IH heater, washing machine, dust catcher, lighting apparatus (bulb, lamp main body, lampshade etc.), amenities, closet, hand basin, mirror, bathroom (wall, ceiling, floor etc.), building materials (indoor wall, ceiling tile materials, floor, exterior wall etc.), indoor article (curtain, carpet, desk, chair, sofa, shelf class, bed, bedding etc.), glass, window frame, railing, door, handle, clothes, for the filter in family's electrical article etc., stationery, kitchen articles, for the parts etc. in car room space.By possessing the photocatalyst film of embodiment, photocatalysis effect can be given to goods.As the base material be suitable for, glass, pottery, plastics, acrylic resin, paper, fiber, metal, timber etc. can be enumerated.
When using fiber as base material, as fibrous material, the natural fibers such as the regenerated fiber such as synthetic fibers, artificial silk, cotton, wool, silk such as polyester, nylon, acrylic compounds, their mixed fibre, intertexture, blending product etc. can be used.Fibrous material can be scattered hair shape.Fiber can have fabric, compile any form such as thing, non-woven fabrics, also can apply common Colour Difference or printing.When photocatalyst dispersion liquid is applied to fibrous material, by the photochemical catalyst of embodiment and resin binder and use, the method be fixed on fibrous material is easily.
As resin binder, the resin of water soluble type, water-dispersion type, solvent-soluble type can be used.Specifically, melmac, epoxy resin, polyurethane resin, acrylic resin, fluororesin etc. can be used, but be not limited to this.When using the photocatalyst dispersion liquid of embodiment that photochemical catalyst is fixed on fibrous material, such as the resin binder of photocatalyst dispersion liquid with water dispersible or water-soluble is mixed, make resin liquid, impregnated fiber material in this resin liquid, then roll with mangle roller etc., make it dry.By by resin liquid thickening, the side of fibrous material can be coated on the surface with well known devices such as doctor knife coaters.On one side surface that gravure roll (Gravureroll) also can be used to make photochemical catalyst be attached to fibrous material or two sides.
When using photocatalyst dispersion liquid to make photochemical catalyst be attached to fiber surface, if adhesion amount is very few, then can not give full play to the photocatalysis performances such as gas decomposability that tungsten oxide has and anti-microbial property.If adhesion amount is too much, although the performance that tungsten oxide has can play, the feel as fibrous material is often deteriorated.Therefore, preferably suitable adhesion amount is selected according to material and purposes.The clothes class of the fiber using surface attachment to have photochemical catalyst contained in photocatalyst dispersion liquid attached and indoor article, can play excellent deodorizing effect and antibacterial effect under visible light illumination in indoor environment.In addition, even if when irradiation ultraviolet radiation, also photocatalysis performance can be played.
Embodiment
Below, specific embodiments of the invention and evaluation result thereof are described.Be explained, as the manufacture method of the powder in following embodiment, use the method applying inductive type plasma treatment in sublimation process, but the present invention be not limited thereto.
(embodiment 1, comparative example 1)
As material powder end, prepare the tungsten trioxide powder that average grain diameter is 0.5 μm.This material powder end is sprayed in RF plasma together with carrier gas (Ar), and then, as reacting gas, pass into argon gas with the flow of 40L/min, pass into oxygen with the flow of 40L/min.Like this, carry out the sublimation process of oxidation reaction through the material powder that distils, make tungsten oxide powder.Will without heat treated tungsten oxide powder as sample A (comparative example).By above-mentioned tungsten oxide powder in an atmosphere, 300 DEG C, 500 DEG C, 575 DEG C, 600 DEG C heat-treat at each temperature, prepare sample B ~ E (embodiment) thus.In addition, by identical tungsten oxide powder in an atmosphere, heat-treat at the temperature of 1000 DEG C, sample F (comparative example) is prepared thus.Heat treatment time is 1 hour.In addition, in the process making sample B ~ E, during heat treatment, Fast Heating is warming up to set point of temperature, after 1 hour, takes out from stove, at room temperature lowers the temperature.
The average primary particle diameter (D50) of working sample A ~ F (tungsten oxide powder) and BET specific surface area.Average primary particle diameter is measured by the graphical analysis of TEM photo.In tem observation, use Hitachi, Ltd H-7100FA, enlarged photograph is carried out graphical analysis, extracts more than 50 particles, obtain the accumulation particle diameter of volume reference, calculate D50 footpath.The mensuration of BET specific surface area uses the specific area measuring device Macsorb1201 (trade name) of マ ウ ンテック society to carry out.Pretreatment is implemented in nitrogen, under the condition of 200 DEG C × 20 minutes.The average primary particle diameter (D50 footpath) of sample A ~ F and the measurement result of BET specific surface area are shown in table 1.
Then, the Raman spectrum analysis of sample A ~ F (tungsten oxide powder) is carried out.To the Raman spectrum analysis of each sample, use the spectrograph PDP-320 (trade name) of Off ォ ト Application デ ザ イ Application society, measure in the environment of temperature 25 DEG C, humidity 50%.Condition determination is: mode determination is microscopic Raman, and measuring multiplying power is 100 times, and beam diameter is less than 1 μm, and light source is the Ar of wavelength 514.5nm
+laser, the laser power in pipe is 0.5mW, and diffraction grating is single 600gr/mm, and cross slit (crossslit) is 100 μm, and slit is 100 μm, and detector is the CCD of 1340 passages of Japanese ロ ー パ ー society.The measurement range of Raman shift is 100 ~ 1500cm
-1.Raman spectrum as the measurement result of sample A, sample D and sample F is shown in Fig. 1.In the Raman spectrum of each sample, investigate at 268 ~ 274cm
-1the 1st peak existed in scope, at 630 ~ 720cm
-1the 2nd peak existed in scope, at 800 ~ 810cm
-1each wave number at the 3rd peak existed in scope.And then, calculate respectively at 920cm
-1above to 950cm
-1the following peak intensity X of scope existence and the ratio (X/Y) of peak intensity Y.These results are shown in table 1.
[table 1]
Then, being dispersed in water to particle concentration by the tungsten oxide powder of sample A ~ F is 10 quality %, makes photocatalyst dispersion liquid respectively thus.The photocatalyst dispersion liquid obtained is used for evaluating characteristics described later.
(embodiment 2, comparative example 2)
Use the tungsten oxide powder of the sample A ~ F same with embodiment 1 and comparative example 1, make photocatalyst dispersion liquid as follows.First, tungsten oxide powder is dispersed in water to its concentration be 10 quality %.The aqueous dispersion that the dispersion liquid obtained being dispersed in water by tungsten oxide powder is dispersed in water with the Zirconium oxide powder being 70nm by average primary particle diameter (D50) and obtains mixes, and makes zirconia be 33 quality % relative to the ratio of tungsten oxide and zirconic total amount.Be the scope of 6.5 ~ 5.5 by hydrochloric acid and ammonia adjustment mixed dispersion liquid to the pH of mixed dispersion liquid.Dispersion treatment uses ball mill to implement.The particle concentration of the photocatalyst dispersion liquid obtained like this is 10 quality %.
(embodiment 3, comparative example 3)
Use the tungsten oxide powder of the sample A ~ F same with embodiment 1 and comparative example 1, make photocatalyst dispersion liquid as follows.Tungsten oxide powder is dispersed in water to its concentration be 10 quality %.The dispersion liquid obtained being dispersed in water by tungsten oxide powder mixes with ruthenic chloride solution, makes ruthenium-oxide be 0.02 quality % relative to the ratio of the total amount of tungsten oxide and ruthenium-oxide.In mixed liquor, instill ammonia, pH is adjusted to 7.And then the Zirconium oxide powder that to instill by average grain diameter (D50) in mixed liquor be 70nm is scattered in the aqueous dispersion obtained in water, pH is adjusted to the scope of 6.5 ~ 5.5.About the tungsten oxide in dispersion liquid, ruthenium-oxide and zirconic mixing ratio, relative to their total amount, the ratio of ruthenium-oxide is about 0.017 quality %, and zirconic ratio is about 33 quality %.The particle concentration of the photocatalyst dispersion liquid obtained is 13 quality %.
(embodiment 4, comparative example 4)
Use the tungsten oxide powder of the sample A ~ F same with embodiment 1 and comparative example 1, make photocatalyst dispersion liquid as follows.Tungsten oxide powder is dispersed in water to its concentration be 10 quality %.Being mixed into being scattered in by tungsten oxide powder in the dispersion liquid that obtains in water the platinum particles that average grain diameter is 2nm, being 0.02 quality % to platinum relative to the ratio of the total amount of tungsten oxide and platinum, making photocatalyst dispersion liquid.
Then, use the photocatalyst dispersion liquid made in embodiment 1 ~ 4 and comparative example 1 ~ 4, form photocatalyst film on the glass surface.Evaluate photocatalyst film photocatalysis performance under visible light illumination.Photocatalytic is evaluated by the resolution ratio measuring aldehydes gas.Specifically, use evaluates identical flow-through devices, mensurated gas composition resolution ratio under condition shown below with the removing performance (capacity of decomposition) of JIS-R-1701-1 (2004) to nitrogen oxide.
The decomposition run of aldehydes gas is implemented as follows.The initial stage concentration of acetaldehyde is 10ppm, and gas flow is 140mL/min, and sample size is 0.2g.The adjustment of sample is by coated sample on the glass plate of 5 × 10cm and makes it dry.Pretreatment is irradiated 12 hours under black light lamp.Light source uses white fluorescent lamp (Toshiba ラ イ テ ッ Network society FL20SSW/18), use edge filter (Cutfilter) (Dong Resin Industry society Network ラ レ ッ Network ス N-169), filter the wavelength turned down in 380nm.Illumination is adjusted to 1000lx.Do not irradiate light at the beginning, wait until no longer adsorbed gas always and just start to irradiate light after settling out.
Irradiate light under these conditions, measure the gas concentration after 15 minutes, obtain gas resolution ratio.But, when gas concentration after 15 minutes is still unstable, then continue to measure concentration, until concentration stabilize.The gas concentration of light pre-irradiation is set to A, gas concentration penetrating from illumination through more than 15 minutes and when reaching stable is set to B, and the value that will be calculated according to [formula: (A-B)/A × 100] by gas concentration A and gas concentration B is as gas resolution ratio (%).As gas analyzing apparatus, use many gas monitors 1412 of INOVA Inc..The measurement result of gas resolution ratio is shown in table 2.
[table 2]
As shown in table 2, during the photocatalyst film using the photocatalyst dispersion liquid of embodiment 1 ~ 4 to be formed, confirm that the decomposition rate of acetaldehyde is fast, and decompose completely.This is presumably because that the strength ratio (X/Y) of Raman peaks is being greater than the scope below 0 to 0.04, the crystalline state of tungsten oxide particulate and surface state etc. become the cause being suitable for light-catalysed state.Therefore, even if in the environment that the illumination of visible ray is low and gas concentration is low, the decomposability of photocatalyst film to gas can also be improved.And then, utilize zirconia adsorbed gas, can further improve the gas decomposability of photocatalyst film.
Then, be mixed in the resin liquid of acrylic resin by the photocatalyst dispersion liquid of embodiment 1 ~ 4 and comparative example 1 ~ 4, flooding mass area ratio with this mixed liquor (coating) is 150g/m
2the flat fabric made of polyester, make the polyester fiber being attached with visible-light-responsive photocatalyst thus.Cut the sample of 5 × 10cm from each fiber, adopt method similar to the above respectively, evaluate photocatalysis performance under visible light illumination.Its results verification, be impregnated with the photocatalyst dispersion liquid using comparative example 1 ~ 4 to make coating fiber compared with, the resolution ratio of polyester fiber to aldehydes gas being attached with the photochemical catalyst of embodiment 1 ~ 4 is high.And then prepare 10 samples made equally, the fluctuation of assess performance, results verification, the dispersion liquid of embodiment is owing to having excellent dispersiveness, and therefore photochemical catalyst is stablized the adhesion amount of fiber.Also confirm in addition, polyester fiber maintains uniform feel.
Photocatalyst dispersion liquid due to above-described embodiment has excellent dispersiveness, therefore can obtain uniform photocatalyst film.In addition, based on the photocatalysis performance of photocatalyst film, stably can obtain the decomposability to organic gas such as acetaldehyde, nor easily produce the unequal problem of visual shade.Therefore, be applicable to the parts used in the interior space of automobile, the building materials, interior material, household electrical appliances etc. that use in factory, shop, school, communal facility, hospital, welfare facility, lodging facilities, house etc.In addition, even if the photochemical catalyst of embodiment is in the environment that the illumination of visible ray is low, except visible ray is with in the environment of external Ultraviolet radiation and in the environment that gas concentration is low, also can give play to high gas decomposability.By using the dispersion liquid or coating that contain this photochemical catalyst, the interior material in indoor or upholstery etc. forming photocatalyst film, excellent deodorization, deodorizing effect can be obtained.The characteristic that this film or goods can effectively utilize the photochemical catalyst of embodiment to have and be applicable to various uses.
Be explained, in the present invention, describe several embodiment, but these embodiments just propose as an example, are not used to limit scope of the present invention.These new embodiments also can be implemented in other various modes, without departing from the scope of the subject in the invention, can carry out various omission, replacement and change.These embodiments and distortion be all included in the scope of the invention and purport, meanwhile, be also included within claim record invention and equivalency range in.
Claims (15)
1. photochemical catalyst, it possesses tungsten oxide base particulate, wherein contains the tungsten oxide of more than 5 quality % to the scope of below 100 quality %,
In the Raman spectrum that above-mentioned photochemical catalyst adopts Raman spectroscopy to measure, at 920cm
-1above to 950cm
-1the intensity X at the peak that following scope is observed with at 800cm
-1above to 810cm
-1the ratio (X/Y) of the intensity Y at the peak that following scope is observed is for being greater than below 0 to 0.04.
2. photochemical catalyst according to claim 1, wherein, above-mentioned tungsten oxide base particulate contains the metallic element except tungsten except of more than 0.001 quality % to the following scope of 50 quality %.
3. photochemical catalyst according to claim 2, wherein, above-mentioned metallic element is be selected from least a kind in titanium, zirconium, manganese, iron, ruthenium, nickel, palladium, platinum, copper, silver, cerium and aluminium.
4. photochemical catalyst according to claim 3, wherein, the content of above-mentioned metallic element is in the scope of more than 0.005 quality % to below 10 quality %.
5. photochemical catalyst according to claim 1, wherein, above-mentioned tungsten oxide base particulate contains the metal oxide except tungsten oxide except of more than 0.01 quality % to the following scope of 70 quality %.
6. photochemical catalyst according to claim 5, wherein, above-mentioned metal oxide is be selected from least a kind in zirconia, titanium oxide and ruthenium-oxide.
7. photochemical catalyst according to claim 1, wherein, the average grain diameter (D50) of above-mentioned tungsten oxide base particulate is for more than 1nm is to less than 30 μm.
8. photocatalyst dispersion liquid, it possess decentralized medium and in above-mentioned decentralized medium with the scope of more than 0.001 quality % to below 50 quality % disperse, photochemical catalyst according to claim 1.
9. photocatalyst dispersion liquid according to claim 8, wherein, above-mentioned decentralized medium is be selected from least a kind in water and alcohol.
10. photocatalyst dispersion liquid according to claim 9, wherein, the pH value of above-mentioned photocatalyst dispersion liquid is more than 1 to less than 9.
11. photocatalyst coatings, it contains photocatalyst dispersion liquid according to claim 8 and is selected from least a kind of adhesive ingredients in inorganic bond and organic bond.
12. photocatalyst films, it is formed by being coated on base material by photocatalyst dispersion liquid according to claim 8.
13. photocatalyst films, it is formed by being coated on base material by photocatalyst coating according to claim 11.
14. goods, it possesses photocatalyst film according to claim 12.
15. goods, it possesses photocatalyst film according to claim 13.
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