CN105980056B - Include the antimycotic and anti microbial materials of the tungsten oxide photcatalyst added with bismuth - Google Patents
Include the antimycotic and anti microbial materials of the tungsten oxide photcatalyst added with bismuth Download PDFInfo
- Publication number
- CN105980056B CN105980056B CN201480074748.4A CN201480074748A CN105980056B CN 105980056 B CN105980056 B CN 105980056B CN 201480074748 A CN201480074748 A CN 201480074748A CN 105980056 B CN105980056 B CN 105980056B
- Authority
- CN
- China
- Prior art keywords
- tungsten oxide
- bismuth
- added
- photcatalyst
- oxide photcatalyst
- 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.)
- Active
Links
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims abstract description 55
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 43
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 230000001857 anti-mycotic effect Effects 0.000 title claims abstract description 20
- 239000002543 antimycotic Substances 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 19
- 230000000845 anti-microbial effect Effects 0.000 title claims abstract description 11
- 239000004599 antimicrobial Substances 0.000 title claims abstract description 11
- 241000894006 Bacteria Species 0.000 claims abstract description 20
- 239000010409 thin film Substances 0.000 claims abstract description 4
- 230000000843 anti-fungal effect Effects 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 23
- 230000000844 anti-bacterial effect Effects 0.000 claims description 22
- 239000010408 film Substances 0.000 claims description 19
- 230000001699 photocatalysis Effects 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 16
- 238000007146 photocatalysis Methods 0.000 claims description 12
- 241000228245 Aspergillus niger Species 0.000 claims description 9
- 238000002474 experimental method Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 241000191967 Staphylococcus aureus Species 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000005259 measurement Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 16
- 210000004215 spore Anatomy 0.000 description 19
- 238000012360 testing method Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 241000606507 Talaromyces pinophilus Species 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 241000191940 Staphylococcus Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011081 inoculation Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241000228150 Penicillium chrysogenum Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 210000004666 bacterial spore Anatomy 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XOBGMVXXJIHFNI-UHFFFAOYSA-N bismuth;oxotungsten Chemical compound [Bi].[W]=O XOBGMVXXJIHFNI-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
- B01J37/0223—Coating of particles by rotation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
It improves that tungsten oxide is antimycotic and bacteria resistance the present invention relates to a kind of offer, there is excellent antimycotic, bacteria resistance material, antimycotic and anti microbial materials to be characterized in that including the photochemical catalyst for the tungsten oxide for being added to bismuth under thin film shape.
Description
Technical field
The present invention relates to a kind of comprising the tungsten oxide photcatalyst added with bismuth, in antifungal activity and antibacterial activity
Upper excellent material.
Background technology
In recent years, environmental pollutants are adsorbed and are closed by the semiconductor light-catalyst of sunlight or indoor photodegradation removal
Note, and it is studied energetically.Titanium oxide shows strong photocatalytic activity as its representative species.But
There are it is following the problems such as：It, can to accounting for that sunlight is most although can show activity under ultraviolet light since titanium oxide band gap is big
It is light-exposed there is no absorbability, it does not show the catalytic activity to visible light, sunlight can not be made full use of to have, and ultraviolet
The low interior of optrode does not work yet.As the countermeasure for it, carry out making titanium oxide by adulterating nitrogen, sulphur, metal etc.
The Upgrading of visible light etc. can be absorbed, or has been carried out to showing active chemical combination as photochemical catalyst under visible light
The exploratory development etc. of object semiconductor.
On the other hand, also report has the tungsten as photocatalytic activity semiconductor more higher than titanium oxide base under visible light
Oxide system.Tungsten oxide, especially tungsten oxide are by loading the suitable co-catalyst such as copper compound or noble metal, and energy
Enough photocatalyst material (referenced patent document 1- to have a great attraction that various organic matters are completely oxidized to carbon dioxide
2)。
In addition, tungsten oxide on the basis of with photocatalysis, be reported show it is unrelated with the presence or absence of illumination
Antibacterial activity is also further reported with antifungal activity (referenced patent document 3).Learn the antibacterium of tungsten oxide powder
Activity depends on its physical property and preparation method, and the physical property of its powder of wider range has been recorded in patent document 3.But about
The antibacterial activity, antifungal activity, expression mechanism are not known, therefore are effective for what kind of structure of tungsten oxide
The problems such as almost without detailed information.If also, tungsten oxide is made into the small thin film shape of surface area, even by phase
The tungsten oxide of same manufacturing method manufacture, it has also been found that there are antibacteriums compared with the filter shape for being considered as surface area bigger
The trend that activity is lower.
In order to improve the photocatalytic activity of tungsten oxide, exists and utilize the method for increasing optical absorption.Report have by
When manufacturing tungsten oxide, peroxide is added to its precursor solution, after thermally decomposing and synthesizing tungsten oxide, due to the increasing of light absorption
Big effect increases (referenced patent document 4) to its photocatalytic activity.In addition, also reporting the oxidation manufactured by this method
Tungsten also shows excellent antibacterial activity (referenced patent document 5) while photocatalytic activity is excellent.
But since tungsten oxide is easy to dissolve in alkalinity, alkali is used in bathroom, kitchen, washing basin, sink, lavatory etc.
It cannot directly be used in the place of property detergent.Therefore, in order to be utilized in the various uses of the environment of paddling of family etc., the phase
It hopes and assigns tungsten oxide in the state of fully keeping photocatalytic activity, undissolved stability in alkaline environment.Make
Method to solve the project, it was recently reported that addition alone or in combination is selected from copper, tantalum, niobium, lanthanum, bismuth, calcium, chromium, manganese in tungsten oxide
And the metallic element of zinc so that tungsten oxide improves under conditions of the photo-catalysis function under not losing visible light in alkaline condition
Under the method for environmental resistance improve the environmental resistance under alkaline condition it is also reported that by adding these metallic elements
Property also maintain or improves photocatalytic activity (referenced patent document 6).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2008-149312 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2009-061426 bulletins
Patent document 3：WO2009/110233
Patent document 4：Japanese Unexamined Patent Publication 2009-189952 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2011-200774 bulletins
Patent document 6：WO2012/111709
Invention content
The technical problems to be solved by the invention
The present invention improves the antifungal activity and bacteria resistance of tungsten oxide to provide, and with excellent for thin film shape
Antifungal activity, bacteria resistance material be project.
Solve the means of technical problem
The present inventor is thoroughly discussed in order to solve the above problems, as a result, finding by being added into tungsten oxide
Photochemical catalyst obtained from bismuth has excellent antifungal activity and bacteria resistance, also, to by tungstenic material and hydrogen peroxide system
The oxide precursor of standby tungsten carries out heat resolve, adds bismuth into thus obtained tungsten oxide and obtains photochemical catalyst,
In the photochemical catalyst, it is found that antifungal activity and bacteria resistance are especially excellent, until completing the present invention.
That is, there is provided inventions below by the application.
(1) a kind of antimycotic and anti microbial materials, which is characterized in that include the tungsten oxide photcatalyst added with bismuth.
(2) according to the antimycotic and anti microbial materials described in (1), which is characterized in that by based on JIS R's 1705
The antifungal activity value and/or measured by the bacteria resistance experiment based on JIS R 1702 anti-thin that antifungal activity experiment measures
Bacterium activity value is 1.0 or more.
(3) according to the antimycotic and anti microbial materials described in (2), which is characterized in that above-mentioned antifungal activity value and/or
Antibacterial activity value is 1.5 or more.
(4) according to the antimycotic and anti microbial materials described in (1)-(3), which is characterized in that antifungal activity is to be directed to
The activity of aspergillus niger and thermophilic loose mould, also, antibacterial activity is the activity for staphylococcus aureus.
(5) according to antimycotic and anti microbial materials above-mentioned described in (1)-(4), which is characterized in that tungsten oxide is to pass through
Heat resolve is carried out to the tungsten oxide presoma by tungstenic material and the tungsten of hydrogen peroxide preparation and is manufactured.
(6) according to antimycotic and anti microbial materials above-mentioned described in (1)-(5), which is characterized in that tungsten oxide is film
Shape.
Invention effect
According to the present invention, by adding bismuth into tungsten oxide photcatalyst, can obtain steady under alkaline environment
While determining and there is excellent photocatalysis, the material with superior antifungal activity and bacteria resistance.
When tungsten oxide is used as interior decoration building materials due to the photocatalysis of visible light-responded property, it can be expected that it is from clear
Clean function, but its excellent bacteria resistance, antifungal activity is further assigned while assigning its alkali resistance by adding bismuth,
To significantly improve its functionality.
Specific implementation mode
Bismuth is added into tungsten oxide by various methods, antifungal activity, bacteria resistance can be improved.It is preferred that can be by by oxygen
Change tungsten and be immersed in certain time in the solution containing bismuth, is added in a manner of adsorbing bismuth on the surface thereof.Or it can also be in oxygen
Change blending bismuth solution in the powder of tungsten to be sintered at a certain temperature or by the methods of spin coating that bismuth solution coating is thin in tungsten oxide
It is sintered at a certain temperature to add again on film.By sintering process, the raising meeting of antifungal activity, bacteria resistance
It is influenced by its sintering temperature, there are the tendencies of the low method of preferred sintering temperature, the method for more preferably adsorbing bismuth at normal temperatures.
In the evaluation of the antifungal activity of photochemical catalyst, using in (the light under fine ceramics-light irradiation of JIS R 1705
The antifungal activity test method of the antimycotic fabricated product of catalyst) specified in method of evaluating performance.In the test method
Antifungal activity value is on the photochemical catalyst test film of test film and evaluation performance for not carrying out photocatalysis processing (control is used)
Inoculation as subjects fungal spore and determine the surviving spores number after light irradiates, adding not carrying out photocatalysis at this time
The difference of the logarithm of work (control use) test film and the surviving spores number on the photochemical catalyst test film of performance evaluation, show by
The digit of the reduction for the surviving spores number that anti-mycotic efficiency generates.Depositing of obtaining under conditions of non-irradiation light is also contained in the value
The decrement of spore count living.In the present invention, antifungal activity value is 1.0 or more, preferably 1.5 or more.Also, it is irradiated by light
The effect Δ R of generation is the inoculated fungi spore on the photochemical catalyst test film of performance evaluation, measures the survival spore after light irradiation
Subnumber and the surviving spores number after shady place preservation when being stored in the surviving spores number after shady place and depositing after light irradiation
The difference of the logarithm of spore count living shows the part by light irradiation contribution in antifungal activity value.
In the evaluation of the antibacterial activity of photochemical catalyst, using in (the light under fine ceramics-light irradiation of JIS R 1702
Bacteria resistance test method, the anti-bacterial effect of catalyst antibacterium fabricated product) specified in method of evaluating performance.In the examination
Antibacterial activity value in proved recipe method is the photocatalysis in the test film and evaluation performance for not carrying out photocatalysis processing (control is used)
Bacterial spore of the inoculation as subjects on test film, and determine the surviving spores number after light irradiates, at this time not into
The logarithm of row photocatalysis processing (control use) test film and the surviving spores number on the photochemical catalyst test film of performance evaluation it
Difference shows the digit of the reduction of the surviving spores number generated by anti-bacterial effect.The item of non-irradiation light is also contained in the value
The decrement of the surviving spores number obtained under part.In the present invention, antibacterial activity value is 1.0 or more, preferably 1.5 or more.
Also, the effect Δ R generated by light irradiation, is the inoculated bacteria spore on the photochemical catalyst test film of performance evaluation, measures light
Surviving spores number after irradiation and the surviving spores number after shady place preservation when being stored in the surviving spores number after shady place
And the difference of the logarithm of the surviving spores number after light irradiation shows the part by light irradiation contribution in antifungal activity value.
Embodiment
Hereinafter, further the present invention is specifically described by embodiment, the present invention is not by any limit of the embodiment
It is fixed.
The preparation of tungsten oxide film, it is identical as the method for patent document 4, it is carried out by method as shown below.It first will be golden
After category tungsten is dissolved in aqueous hydrogen peroxide solution, its maturation is made while being stirred, heating on heating stirrer, generates shape
As the poly- aqueous tungstic acid solution of peroxidating of the presoma of tungsten oxide.On the electro-conductive glass for be formed as substrate spin coating (1000rpm,
15 seconds) the poly- aqueous tungstic acid solution of the peroxidating, 30 minutes are sintered at 500 DEG C to prepare tungsten oxide film.Further, each
Dipping 20 hours in the aqueous solution (1~2% aqueous solution of nitric acid) of the bismuth nitrate of kind concentration so that tungsten oxide film room temperature adsorbs
Bismuth, it is dry at 60 DEG C after washing.About antifungal activity, in assert mechanism, based on JIS R 1705 to aspergillus niger
(Aspergillus niger) and thermophilic loose mould (Penicillium pinophilum) carry out antifungal activity test evaluation.It should
Experiment passes through ultraviolet irradiation intensity 0.8mW/cm2Black light lamp carry out in advance irradiation 24 hours after in ultraviolet irradiation intensity
0.8mW/cm2Black light lamp under implement.Usually, aspergillus niger (Aspergillus niger) is melanomyces, thermophilic pine mould
(Penicillium pinophilum) is Penicillium notatum.1702 (pad pastings of JIS R are based in assert mechanism for bacteria resistance
Method) bacteria resistance examination is carried out to staphylococcus aureus (aurococcus (Staphylococcus aureus))
Test evaluation.The experiment passes through ultraviolet irradiation intensity 0.01mW/cm2Black light lamp under irradiate 8 hours to implement.
(embodiment 1-3)
The result of the antimycotic experiment to aspergillus niger (Aspergillus niger) is shown in table 1.Compared to being not added with bismuth
Comparative example 1 in 0.7 antifungal activity value, being added to antifungal activity value in the embodiment 1 to embodiment 3 of bismuth is respectively
1.8,1.7,1.5, it is found that antifungal activity improves.
[table 1]
The antifungal activity (Aspergillus niger NBRC 105649) of tungsten oxide film
| The concentration of bismuth aqueous solution | Antifungal activity value | ΔR | |
| Comparative example 1 | (being not added with) | 0.7 | 0.8 |
| Embodiment 1 | 1×10-3M | 1.8 | 1.8 |
| Embodiment 2 | 1×10-2M | 1.7 | 1.5 |
| Embodiment 3 | 3×10-2M | 1.5 | 1.5 |
(embodiment 4-5)
The result of the antimycotic experiment to thermophilic loose mould (Penicillium pinophilum) is shown in table 2.It compares
Be not added with the antifungal activity value of 1.3 in the comparative example 2 of bismuth, be added to bismuth embodiment 4 and embodiment 5 in antifungal activity
Value is respectively 2.8,1.5, it is found that antifungal activity improves.
[table 2]
The antifungal activity (Penicillium pinophilum NBRC 6345) of tungsten oxide film
| The concentration of bismuth aqueous solution | Antifungal activity value | ΔR | |
| Comparative example 2 | (being not added with) | 1.3 | 1.3 |
| Embodiment 4 | 1×10-3M | 2.8 | 2.3 |
| Embodiment 5 | 3×10-2M | 1.5 | 0.8 |
(embodiment 6-7)
It is shown in table 3 to staphylococcus aureus (aurococcus (Staphylococcus
Aureus the result of antibacterium experiment)).Compared to the antibacterial activity value of 1.1 be not added in the comparative example 3 of bismuth, it is added to
Antibacterial activity value is respectively 2.1 and 1.9 in the embodiment 6 and embodiment 7 of bismuth, it is found that antibacterial activity improves.
[table 3]
The bacteria resistance (Staphylococcus aureus NBRC 12734) of tungsten oxide film
| The concentration of bismuth aqueous solution | Antibacterial activity value | ΔR | |
| Comparative example 3 | (being not added with) | 1.1 | 0.2 |
| Embodiment 6 | 1×10-3M | 2.1 | 0.4 |
| Embodiment 7 | 3×10-2M | 1.9 | 0.3 |
As previously discussed, antifungal activity and antibacterial activity, it is different according to the type of fungi or bacterium as object
And it is different, activity value also shows different numerical value in the case where not adding bismuth, but in each embodiment, and does not add
The case where compare, by add bismuth can improve antifungal activity value, antibacterial activity value, show 1.5 or more it is higher
Numerical value, difference according to the embodiment have reached 2.0 or more.Thus, it is shown that antimycotic by that can make to tungsten oxide addition bismuth
Activity and antibacterial activity are improved to extremely good numerical value.
Industrial availability
The antimycotic and anti microbial materials for including the tungsten oxide photcatalyst added with bismuth of the present invention, compared to being not added with bismuth
Tungsten oxide, not only there are further excellent antimycotic and antibacterial actions, also there is alkali resistance, even if in alkaline environment
Under, additionally it is possible to excellent photocatalysis is played, therefore can be under at present due to being exposed to the alkaline environment of detergent etc., nothing
Method directly uses in bathroom, kitchen, washing basin, sink, lavatory of tungsten oxide photcatalyst etc. as bacteria resistance, antifungal activity
Excellent decoration building materials use.Wherein, due to the automatically cleaning effect of photochemical catalyst effect, in the same of the pollution of organics removal etc.
When, due to antimycotic, antibacterial actions, it can further keep its surface more to clean.
Claims (5)
1. application of the tungsten oxide photcatalyst on preparing antimycotic and anti microbial materials added with bismuth, the bismuth that is added with
Tungsten oxide photcatalyst is by the antifungal activity value of the antifungal activity experiment measurement based on JIS R 1705 and by being based on JIS
The antibacterial activity value that the bacteria resistance experiment of R1702 measures is 1.5 or more,
By on surface that tungsten oxide photcatalyst normal temperature dipping in the solution containing bismuth, is made the tungsten oxide photcatalyst
The mode of absorption bismuth is added bismuth to the tungsten oxide photcatalyst, and the tungsten oxide photcatalyst added with bismuth is film shape
Shape.
2. application according to claim 1, which is characterized in that the antifungal activity is for aspergillus niger and thermophilic loose mould
Activity, also, the antibacterial activity is the activity for staphylococcus aureus.
3. application according to claim 1, which is characterized in that the tungsten oxide photcatalyst added with bismuth passes through following
Process manufactures：
The process for manufacturing the tungsten oxide photcatalyst, by by before the oxide of tungstenic material and the tungsten of hydrogen peroxide preparation
Body is driven to carry out heat resolve and manufacture；
The process for adding bismuth to the tungsten oxide photcatalyst,
In the process of the manufacture tungsten oxide photcatalyst, the tungsten oxide photcatalyst is formed as thin film shape,
It is described by the solution containing bismuth, making tungsten oxide photcatalyst normal temperature dipping in the process of the addition bismuth
The mode of the Adsorption on Surface bismuth of tungsten oxide photcatalyst is added.
4. application according to claim 3, which is characterized in that the process of the addition bismuth is by the tungsten oxide photocatalysis
Agent is immersed in the aqueous solution of bismuth nitrate and carries out at normal temperatures.
5. application according to claim 3, which is characterized in that the process of the addition bismuth is by the tungsten oxide photocatalysis
After agent is immersed at normal temperatures in the aqueous solution of bismuth nitrate, is washed, dried.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013253306 | 2013-12-06 | ||
| JP2013-253306 | 2013-12-06 | ||
| PCT/JP2014/082297 WO2015083831A1 (en) | 2013-12-06 | 2014-12-05 | Antifungal and antibacterial material including tungsten-oxide photocatalyst having bismuth added thereto |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105980056A CN105980056A (en) | 2016-09-28 |
| CN105980056B true CN105980056B (en) | 2018-08-24 |
Family
ID=53273577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480074748.4A Active CN105980056B (en) | 2013-12-06 | 2014-12-05 | Include the antimycotic and anti microbial materials of the tungsten oxide photcatalyst added with bismuth |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6164668B2 (en) |
| CN (1) | CN105980056B (en) |
| WO (1) | WO2015083831A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107200356B (en) * | 2016-03-18 | 2019-12-17 | 纳琳威纳米科技（上海）有限公司 | preparation method of bismuth-doped tungsten oxide near-infrared high-reflection powder |
| WO2019090071A1 (en) * | 2017-11-03 | 2019-05-09 | Basf Corporation | Arsine adsorbents |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370132A (en) * | 2011-02-16 | 2013-10-23 | 独立行政法人产业技术综合研究所 | Novel visible-light-responsive photocatalyst with environmental resistance |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06293611A (en) * | 1993-04-05 | 1994-10-21 | Asahi Chem Ind Co Ltd | Antimicrobial material |
| JPH08296031A (en) * | 1995-04-24 | 1996-11-12 | Toppan Printing Co Ltd | Metal oxide coated product and its production |
| CN100475335C (en) * | 2003-09-22 | 2009-04-08 | 中国科学院化学研究所 | Photocatalyst responding to visible light, and preparation method and application thereof |
| JP2006293611A (en) * | 2005-04-08 | 2006-10-26 | Mitsubishi Electric Corp | Plant monitoring control system |
| KR100935065B1 (en) * | 2005-09-29 | 2009-12-31 | 수미도모 메탈 인더스트리즈, 리미티드 | Titanium oxide photocatalyst, its manufacturing method and use |
| WO2007122651A1 (en) * | 2006-04-24 | 2007-11-01 | Nm Tech Ltd. Nanomaterials And Microdevices Technology | Functional nanomaterials with antibacterial and antiviral activity |
| EP2255878B1 (en) * | 2008-03-04 | 2017-12-27 | Kabushiki Kaisha Toshiba | Antibacterial material and antibacterial film and antibacterial member using the same |
| CN101618322A (en) * | 2009-07-30 | 2010-01-06 | 中国科学院上海硅酸盐研究所 | Photocatalysis antibacterial material excited by visible light and application thereof |
| JP5544618B2 (en) * | 2010-03-25 | 2014-07-09 | 独立行政法人産業技術総合研究所 | Tungsten oxide secondary structure with antibacterial action |
| CN103285891B (en) * | 2013-06-05 | 2014-10-29 | 河北工业大学 | Preparation method of bismuth oxide halide-titanium oxide nanotube array composite photo-catalytic membrane |
-
2014
- 2014-12-05 WO PCT/JP2014/082297 patent/WO2015083831A1/en active Application Filing
- 2014-12-05 CN CN201480074748.4A patent/CN105980056B/en active Active
- 2014-12-05 JP JP2015551585A patent/JP6164668B2/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370132A (en) * | 2011-02-16 | 2013-10-23 | 独立行政法人产业技术综合研究所 | Novel visible-light-responsive photocatalyst with environmental resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6164668B2 (en) | 2017-07-19 |
| WO2015083831A1 (en) | 2015-06-11 |
| CN105980056A (en) | 2016-09-28 |
| JPWO2015083831A1 (en) | 2017-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Treatment of coliphage MS2 with palladium-modified nitrogen-doped titanium oxide photocatalyst illuminated by visible light | |
| CN102202789B (en) | Photocatalytic material, method of decomposing organic substance, interior member, air cleaner, and device for producing oxidizing agent | |
| CA2718999C (en) | Photocatalyst material, method for decomposition of organic material, interior member, air purification device, and apparatus for preparation of oxidizing agent | |
| EP2255878B1 (en) | Antibacterial material and antibacterial film and antibacterial member using the same | |
| JP6568630B2 (en) | Photocatalytic material and method for producing the same | |
| JP6995334B2 (en) | Photocatalyst and how to use it | |
| WO2013002151A1 (en) | Titanium oxide photocatalyst having copper compounds supported thereon, and method for producing same | |
| US20100193449A1 (en) | Materials and methods for removing arsenic from water | |
| KR20150101156A (en) | A home appliance including photocatalyst for visible rays | |
| KR102219256B1 (en) | Visible light-responsive photocatalytic composition and lighting device using the same | |
| US20160107145A1 (en) | Photocatalyst material | |
| CN105980056B (en) | Include the antimycotic and anti microbial materials of the tungsten oxide photcatalyst added with bismuth | |
| JP5946096B2 (en) | A novel visible light responsive photocatalyst with environmental resistance | |
| KR101910930B1 (en) | Visible Light-responsive Photocatalytic Composition, Method for Preparing the Same and Lighting Device Containing the Same | |
| KR20150101151A (en) | Coating composition comprising photocatalyst for visible rays and articles comprising same | |
| JP2013126623A (en) | Catalyst body holding positive hole in light irradiation non-receiving state, method for producing the same, and antiviral/antibacterial cloth | |
| US11906157B2 (en) | Photocatalyst formulations and coatings | |
| KR101046313B1 (en) | Preparation method of nano-metal doped metal oxides catalysts and thereof catalysts | |
| KR100883669B1 (en) | Method of coating lighting device | |
| JP4644812B2 (en) | Antibacterial agent using zeolite | |
| KR20180075719A (en) | Visible Light-responsive Photocatalyst and Visible Light-responsive Photocatalyst Film Using the Same | |
| Del Cacho et al. | Nanotechnology in manufacturing paints for eco-efficient buildings | |
| KR20150087095A (en) | Photocatalyst composite for odor deodorizing, photocatalyst fixing unit including the same and preparing method of the same, and non-contact odor deodorizing system including the same | |
| KR20180073541A (en) | Visible Light-responsive Photocatalyst and Visible Light-responsive Photocatalyst Film Using the Same | |
| KR20230114819A (en) | Fan type air cleaner comprising visible light-activated photocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |