CN101374600A - Photocatalyst material, photocatalyst composition using the same and photocatalyst product - Google Patents
Photocatalyst material, photocatalyst composition using the same and photocatalyst product Download PDFInfo
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- CN101374600A CN101374600A CNA2007800038543A CN200780003854A CN101374600A CN 101374600 A CN101374600 A CN 101374600A CN A2007800038543 A CNA2007800038543 A CN A2007800038543A CN 200780003854 A CN200780003854 A CN 200780003854A CN 101374600 A CN101374600 A CN 101374600A
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Abstract
An object of the invention is to provide a photocatalyst material having a higher catalyst effect than conventional photocatalyst materials. The photocatalyst material of the invention contains, as its major component, a tungsten oxide powder excited by a light source which emits light having a wavelength of 430 to 500 nm, the photocatalyst material having a decomposition ability of 50% or more wherein the decomposition ability is given by the following equation based on the following test: [Test for decomposition ability] 1g of a tungsten oxide powder and 20 ppm of acetaldehyde (amount A) are poured into a 3-liter glass container, and acetaldehyde (amount B) is measured after light having a peak wavelength of 460 nm +- 10 nm is irradiated to the mixture for 2 hours to measure the decomposition ability (%): Decompostion ability % = acetaldehyde amount A - acetaldehyde amount B / acetaldehyde amount A 100.
Description
Technical field
The present invention relates to catalysis material, photocatalysis composition and photocatalyst product.
Background technology
As everyone knows, if catalysis material is shone the light with the energy more than the band gap, then, produce the hole in valence band because of optical excitation produces electronics at conduction band.Consequently, this electronics and hole diffuse to powder surface, by contacting with moisture with oxygen, and electronics absorbing and reducing and generate superoxide anion.On the other hand, hole oxidation moisture and generate hydroxy radical.These products show sterilizing power, organic decomposition power, hydrophily by its redox reaction.
In addition, as " light ", can exemplify for example ultraviolet ray, visible light etc. with the above energy of band gap.As " light source ", adopt for example sunshine, various lamp, light emitting diode.
At present, as catalysis material, mainly use titanium oxide (TiO
2) powder.Yet,, only can utilize about 2% of this light if wish to obtain the band-gap energy (wavelength that 380nm is following) of titanium dioxide powder by sunshine.So in recent years, titanium dioxide powder can utilize visible region (400～800nm) catalysis material, tungsten oxide (WO as the main wavelength of sunshine as an alternative
3) gazed at.
For example, put down in writing in the patent documentation 1 and to have used the oxidation tungsten film that forms by sputtering method content as photochemical catalyst.In addition, even the photochemical catalyst film also can obtain the effect of photochemical catalyst.But film can't obtain surface area, so the catalytic effect of unit volume is little.In addition, sputtering method is to use the film technique of vacuum, so the scale of device is big, and the cost height.In addition, in the sputtering method base material (by filmogen) is exposed under the high temperature, therefore only also exists and to go up film forming at the high material of hear resistance (base material).
Relative with it, if photochemical catalyst is the tungsten oxide powder, then have following advantage.That is, can be with whole powder surface as catalytic surface, so the catalytic effect of unit volume is improved.In addition, owing to can adopt the method that powder and mixed with resin are coated with, so do not need base material is exposed under the high temperature, anywhere can coated powder.Also have, powder is made particulate below the average grain diameter 1 μ m, can increase the catalytic surface of unit volume effectively.
As the method for the particulate that obtains the tungsten oxide powder, known for example patent documentation 2.Exemplified the method that ammonium paratungstate (following note is made APT) is heat-treated in the paragraph 0008,0009 of patent documentation in air.According to this method, if the BET specific area is made as 3～5m
2The ratio of/g and tungsten oxide is reset to 7.3, then can obtain the particulate of average grain diameter 0.2～0.3 μ m.
In addition, as the light source of exciting light catalyst, as previously mentioned, can exemplify sunshine, various light emitting diode, various lamps etc.Here, the wavelength that is prescribed of photochemical catalyst excites and brings into play catalytic effect.Therefore, if the excitation wavelength of the wavelength of light source and photochemical catalyst is inconsistent, then can't obtain sufficient characteristic.In order to improve such deficiency, known for example patent documentation 3.Disclosed in the patent documentation 3 by mixed light catalyst and luminescent substance (fluorophor etc.), made and emit the wavelength different, by the method for this wavelength exciting light catalyst with light source from luminescent substance.
According to the method for patent documentation 3, use the TiO that is excited hardly by visible light even disclosed
2Powder, also can be under color of sunshine (under the sunshine) demonstrate the capacity of decomposition of formaldehyde.Yet, the non-constant of its capacity of decomposition.Specifically, the formaldehyde of decomposition 50ppm needs 24 hours.
On the other hand, tungsten oxide (WO as previously mentioned
3) as (wavelength 400～800nm) uses photochemical catalyst and gazed in the visible region.If adopt this photochemical catalyst, can obtain certain catalysis characteristics reliably in the visible region.
Patent documentation 1: the Japan Patent spy opens the 2001-152130 communique
Patent documentation 2: the Japan Patent spy opens the 2002-293544 communique
Patent documentation 3: the Japan Patent spy opens the 2002-346394 communique
Patent documentation 4: the special fair 4-42057 communique of Japan Patent
The announcement of invention
Yet, also can't obtain sufficient characteristic at present.For example, disclosed among the embodiment 1 of patent documentation 4, to WO
3The characteristic that obtains 24 minutes 90% resolving times of acetaldehyde 10ppm with fluorescent lamp (ultraviolet power output 2.1W, wavelength 300～490nm, dominant wavelength 370nm) is duplicated in the powder irradiation.But, WO
3Powder needs more than the 100g.For such characteristic, a large amount of WO of place coating of deodorizing etc. must carried out
3Powder.
The object of the present invention is to provide have than in the past better the catalysis material of catalytic effect, comprise the photocatalysis composition of this catalysis material and use this catalysis material can save space and light-weighted photocatalyst product.
To achieve these goals, the photocatalysis composition and the photocatalyst product of catalysis material of the present invention and this material of use are as follows.
(1) the described catalysis material of claim 1 is that the tungsten oxide powder that the light source with the light by sending the wavelength that contains 430～500nm is excited is the catalysis material of main component, it is characterized in that capacity of decomposition shown below is more than 50%.
[capacity of decomposition test]
In the glass container made of 3 liters of volumes, put into the tungsten oxide powder of quality 1g and the acetaldehyde of 20ppm (amount A), the capacity of decomposition (%) the during acetaldehyde (measure B) of the light of measuring the long 460nm ± 10nm of irradiation spike after 2 hours:
Capacity of decomposition (%)=[(acetaldehyde amount A-acetaldehyde amount B)/acetaldehyde amount A] * 100
(2) the described catalysis material of claim 2 is above-mentioned (1), it is characterized in that, above-mentioned light source is for using the light emitting diode of blue-light-emitting semiconductor element.
(3) the described catalysis material of claim 3 is above-mentioned (1), it is characterized in that, above-mentioned light source is a sunshine.
(4) the described catalysis material of claim 4 is above-mentioned (1), it is characterized in that, above-mentioned light source is a fluorescent lamp.
(5) the described catalysis material of claim 5 is each in above-mentioned (1)～(4), it is characterized in that, the light quantity of the wavelength of 430～500nm is at 1mW/cm
2More than.
(6) the described catalysis material of claim 6 is each in above-mentioned (1)～(5), it is characterized in that, above-mentioned capacity of decomposition is 90%～100%.
(7) the described catalysis material of claim 7 is that the tungsten oxide particulate that excites with the photocatalysis by visible light radiation is the catalysis material of main component, it is characterized in that, has following capacity of decomposition: in the airtight container of 3 liters of volumes, import 10ppm acetaldehyde, to the tungsten oxide particulate irradiation blue light of the quality 0.1g in this container, the survival rate of acetaldehyde reaches below 50% after 30 minutes.
(8) the described catalysis material of claim 8 is above-mentioned (7), it is characterized in that, the light source of emission blue light is near the light emitting diode that has the GaN class of glow peak 470nm.
(9) the described catalysis material of claim 9 is each in above-mentioned (1)～(8), it is characterized in that, and with the monoclinic crystal principal phase.
(10) the described catalysis material of claim 10 is each in above-mentioned (1)～(9), it is characterized in that, average grain diameter is below 10 μ m.
(11) the described photocatalysis composition of claim 11 is characterised in that, comprises each the catalysis material in above above-mentioned (1)～(10) of 50 quality %.
(12) the described photocatalysis composition of claim 12 is above-mentioned (11), it is characterized in that, comprises the titanium dioxide powder of less than 50 quality %.
(13) the described photocatalyst product of claim 13 is characterised in that, uses each the described photocatalysis composition in above-mentioned (11) or (12).
(14) the described photocatalyst product of claim 14 is above-mentioned (13), it is characterized in that, organic matter, NOx, SOx at least a kind is had catalytic effect.
(15) the described photocatalyst product of claim 15 is above-mentioned (13) or (14), it is characterized in that, makes the photocatalysis composition bond in matrix surface by adhesive.
If employing the present invention, then provide have than in the past better the catalysis material of catalytic effect, comprise the photocatalysis composition of this catalysis material and use this catalysis material can save space and light-weighted photocatalyst product.
The simple declaration of accompanying drawing
Figure 1A represents the sectional view that comprises cut-out section of fluorescent lamp of the present invention.
Figure 1B represents the medelling sectional view as the photocatalysis membrana of a kind of structure of fluorescent lamp of the present invention.
Fig. 2 A represents the simple stereogram of deodorizing of the present invention unit.
The simple side view of Fig. 2 B presentation graphs 2A.
Fig. 3 represents an example of the spectrum of blue LED 45 of the present invention.
Fig. 4 represents tungstic acid (WO
3) anorthic system and an example of monoclinic X-ray diffraction pattern.
Fig. 5 represents that the aldehydes gas under the different situation of the crystalline texture of comparison tungstic acid decomposes the performance plot of effect.
Fig. 6 represents to be used to obtain the sketch of determinator of the performance plot of Fig. 5.
Fig. 7 represents to be used to form the sketch of the manufacturing installation of catalysis material of the present invention.
Fig. 8 is the figure of the size distribution (particle diameter and frequency, the relation by composition accumulative total) after expression disperses.
Fig. 9 is expression WO
3The figure of the size distribution of dispersion paints (particle diameter and frequency, the relation by composition accumulative total).
Figure 10 represents the microphotograph of conduct by the ammonium metatungstate of the 3rd kind of granular feedstock that embodiment obtains.
Figure 11 represents the monoclinic system type WO that will obtain through the short time heat treatment of 800 ℃, 1～10 minute Fast Heating by the 3rd kind of granular feedstock that embodiment obtains
3The microphotograph of crystallization photocatalysis particulate.
Figure 12 is the performance plot of the aldehydes gas decomposability of each the tungstic acid photocatalysis particulate of expression when the firing temperature in the 4th kind of embodiment changed to 600 ℃, 700 ℃, 800 ℃, 900 ℃.
The performance plot of the aldehydes gas decomposability of each the tungstic acid photocatalysis particulate when Figure 13 illustrates expression the firing temperature in the 4th kind of embodiment is changed to 800 ℃, 900 ℃, 1000 ℃.
The performance plot of the aldehydes gas decomposability when Figure 14 illustrates expression firing time is changed to 30 seconds, 1 minute, 5 minutes, 10 minutes, 15 minutes.
Figure 15 is that the WO based on the 6th kind of embodiment is used in expression
3During photochemical catalyst, use TiO
2The figure of the wavelength during photochemical catalyst and the relation of reflectivity.
Figure 16 represents the stereogram of decomposing state of the ligthing paraphernalia of the 6th kind of embodiment.
Figure 17 represents the amplification sectional view of the major part of Figure 16.
Figure 18 represents based on the ligthing paraphernalia of the 7th kind of embodiment and band TiO
2The fluorescent lamp of photochemical catalyst, band TiO
2The fluorescent lamp of photochemical catalyst and band TiO
2The ligthing paraphernalia of photochemical catalyst and band TiO
2The relation of the time of the fluorescent lamp of photochemical catalyst and acetaldehyde survival rate.
Figure 19 represents the long example of blue spike of the blue LED that uses in the test of the present invention.
Figure 20 represents the long example of blue-green spike of the blue-green light emitting diode that uses in the test of the present invention.
The 1st capacity of decomposition test when Figure 21 represents the passing through blue LED and excite of sample 1～6 of present embodiment.
The 1st capacity of decomposition test when Figure 22 represents the passing through sunshine and excite of sample 1～6 of present embodiment.
The 1st capacity of decomposition test when Figure 23 represents the passing through fluorescent lamp and excite of sample 1～6 of present embodiment.
The 1st capacity of decomposition test when Figure 24 represents the passing through green LED and excite of sample 1～6 of present embodiment.
One example of the 1st capacity of decomposition test when Figure 25 represents that the sample 2 for present embodiment changes irradiation light quantity based on blue LED.
Figure 26 represents a kind of embodiment of the odor removal of present embodiment.
Figure 27 represents the capacity of decomposition of acetaldehyde of the odor removal of present embodiment.
Figure 28 represents a kind of embodiment of other photocatalyst product of present embodiment.
Figure 29 represents a hydrophilic example of the photocatalyst product of present embodiment.
The best mode that carries out an invention
Below, describe with reference to accompanying drawing for embodiments of the present invention.
[structure of fluorescent lamp]
Figure 1A B is the sectional view that the structure of fluorescent lamp of the present invention is represented in medelling.Specifically, Figure 1A represents to comprise the sectional view of cut-out section, and Figure 1B represents the medelling sectional view as the photocatalysis membrana of a kind of structure of described fluorescent lamp.
Described light transmission discharge vessel 11 is made of elongated glass lamp 11a and a pair of stem stem 11b.Described glass lamp 11a is formed by soda-lime glass.Described stem stem 11b possesses blast pipe, oviduct, inner lead-in wire and outside lead-in wire.Described blast pipe be communicated with light transmission discharge vessel 11 inside and outside, be used to the exhaust of inside of light transmission discharge vessel 11 and the inclosure of discharge medium.And blast pipe is sealed after enclosing discharge medium.Described oviduct is packaged on the two ends of glass lamp 11a and forms light transmission discharge vessel 11.The cardinal extremity of described inner lead-in wire is embedded in the inside of stem stem 11b airtightly, and connects outside lead-in wire.The front end of described outside lead-in wire is embedded among the stem stem 11b, and cardinal extremity exports to the outside of light transmission discharge vessel 11.
Described luminescent coating 12 is formed by three-wavelength light emitting-type fluorophor, is formed at the inner surface of light transmission discharge vessel 11.In the three-wavelength light emitting-type fluorophor, blue-light-emitting is with being BaMgAl
16O
27: Eu,, green emitting is with being LaPO
4: Ce, Tb, emitting red light is with being Y
2O
3: Eu.Pair of electrodes 13,13 is the inner leading section of a pair of inner lead-in wire of subtend at interval that connects at the two ends of light transmission discharge vessel 11.In addition, electrode 13 is formed with the electron emission material that adheres to coiled filament by the coiled filament of tungsten.
Described discharge medium is formed by mercury and argon, is enclosed the inside of light transmission discharge vessel 11.Mercury is enclosed by an amount of ground warp blast pipe.Argon is enclosed about 300Pa.Described lamp holder 14 is by cap body 14a and a pair of bayonet peg 14b, and 14b constitutes.Cap body 14a is and covers shape, is engaged in the both ends of light transmission discharge vessel 11.A pair of bayonet peg 14b, 14b in the cap body 14a time, connects outside lead-in wire with the state support of mutually insulated respectively.
Described photocatalysis membrana 30 is with tungstic acid particulate (average grain diameter: 0.1 μ m) be the film of the light catalyzed coating formation of main component.The thickness of photocatalysis membrana 30 is about 0.5～3 μ m.Described tungstic acid particulate is also kept monoclinic crystalline texture after application is finished.Described photocatalysis membrana 30 is formed by the good adhesive 22 of transmissison characteristic of ultraviolet rays such as photocatalysis particulate 21 and alumina particulate, silicon dioxide microparticle or zirconia particulate or visible light.Described photocatalysis particulate 21 is made of the calcium carbonate microparticle 21b that tungstic acid particulate 21a and interpolation are attached to the surface of this tungstic acid particulate 21a.Also have, adhesive 22 adds in the scope of 10～50 quality % with respect to tungstic acid particulate 21a.In addition, if adhesive 22 uses acrylic compounds modification silicon or siloxane resin, can be formed in the photocatalysis membrana of 20～200 ℃ of curing.In addition, calcium carbonate microparticle 21b plays a role as the material of NOx adsorption (nitrogen oxide) and SOx (oxysulfide), if do not need to suppress the deterioration of the tungstic acid particulate 21a that NOx and SOx cause, then not necessarily needs to add and adheres to calcium carbonate microparticle 21b.
[structure of deodorizing unit]
Fig. 2 AB is the key diagram that the structure of deodorizing of the present invention unit is represented in medelling.Specifically, Fig. 2 A represents the simple stereogram of described deodorizing unit, the simple side view of Fig. 2 B presentation graphs 2A.Also have, among Fig. 2 B, for the purpose of making things convenient for, not shown tungstic acid particulate.
Among the present invention, tungstic acid (WO
3) average grain diameter of particulate below 0.5 μ m, better be below the 0.1 μ m.Here, if average grain diameter surpasses 0.5 μ m, the probability that then reacts on the surface of particulate reduces, and can't obtain enough catalytic effects.In addition, the crystalline texture of described tungstic acid is monoclinic system, but it for example only becomes anorthic system by just pulverizing with mortar easily, is important so keep monoclinic system.The spectrum of the blue LED 45 that uses in the deodorizing unit of Fig. 3 presentation graphs 2.As shown in Figure 3, near the emission light of blue LED 45 specific energy about 470nm reaches peak value.
Fig. 4 is expression tungstic acid (WO
3) anorthic system and the figure of monoclinic X-ray diffraction pattern.In the mensuration of X-ray diffraction pattern, X ray use CuK alpha ray (λ=0.15418nm), make by making sample rotation θ with respect to incident X-rays when the test section that constitutes by proportional counter rotate the goniometer of 2 θ, measure the X ray intensity (CPS) of each angle of deriving (2 θ).Also have, among Fig. 4, upside is represented anorthic system WO
3Situation, downside is represented monoclinic system WO
3Situation.
As shown in Figure 4, the pattern if comparison anorthic system and monoclinic tungstic acid are respectively derived, most of similar.But, can confirm that pattern differs greatly in angle 2 θ that derive are 30～35 ° scope.Especially, ° locate to exist the distinctive a plurality of little peaks of monoclinic system distinctive high peak, anorthic system in 2 θ=34.155, its difference is obvious.In addition, can confirm under the situation of monoclinic tungstic acid that the peak is 2 places in 2 θ are 30～35 ° scope, and under the situation of triclinic tungstic acid, the peak is more than 3 places in same scope.In addition, for being that the peak value that occurs in 30～35 ° the scope is the ratio of the peak value in 30～35 ° the scope with respect to 2 θ at 2 θ, be low to moderate 50～60% under the situation of triclinic tungstic acid, and be 70～95% under the situation of monoclinic tungstic acid, the difference of peak value is little.
Fig. 5 represents that the aldehydes gas under the different situation of the crystalline texture of comparison tungstic acid decomposes the performance plot of effect.Among Fig. 5, line a represents monoclinic system WO of the present invention
3Particulate (downside of the figure of Fig. 4), line b represents anorthic system WO as a comparative example
3Particulate (upside of the figure of Fig. 4), line c represents not use photochemical catalyst also not carry out the situation of illumination.Fig. 6 represents to be used to obtain the sketch of determinator of the performance plot of Fig. 5.Numbering 1 expression drier among the figure.Take in the ware 2 of having put into photochemical catalyst in the drier 1.Dispose fan 3 in the drier 1 of the bottom of this ware 2.The top of drier 1, sidepiece are situated between and connect multifunctional gas monitor (マ Le チ ガ ス モ ニ -) with pipeline 4.In addition, the oblique top of drier 1 is equipped with the blue led light source 6 that photochemical catalyst is carried out illumination.
Also have, the specification of said determination device is as follows.
Measure BOX capacity: 3000cc
Use light source: blue led
Analyzer: multifunctional gas monitor
Import gas: about acetaldehyde 10ppm
Blue led: 0.88mW/cm
2(UV-42)
0.001mW/cm
2(UV-35)
Tungstic acid fine-particle powder amount: 0.1g
As shown in Figure 5, line a compares with line b, and gas decomposes effective.Photocatalysis better effects if during therefore, clearly based on the irradiation visible light of monoclinic system tungstic acid particulate of the present invention.
As light catalyzed coating of the present invention, can exemplify the formation that tungstic acid particulate after using described tungstic acid particulate and application to finish is kept monoclinic crystalline texture.Light catalyzed coating has the good function that comprises that light-catalysed VOC removes, so be suitable for for example employed odor removal filter of air cleaning machine.
As photocatalysis body of the present invention, can exemplify the formation of described light catalyzed coating being coated matrix surface and having formed photocatalysis membrana.,, for example can exemplify pipe ball products such as fluorescent lamp here as photocatalysis body, building materials such as glass pane, mirror, ceramic tile, amenities, the filter component of air conditioner and deodoriser, optical device etc., but purposes applicatory, category are not limited to these.
As photocatalyst product of the present invention, can exemplify described light catalyzed coating of combination and GaN blue LED element or use formation, perhaps make up described photocatalytic filter and GaN blue LED element or use formation by the white light-emitting diode of blue light excited fluorescent body by the white light-emitting diode of blue light excited fluorescent body.Here, photocatalyst product specifically is meant for example fluorescent lamp, ligthing paraphernalia or deodorizing unit.
[manufacturing installation of photocatalysis particulate]
Among the present invention, the photocatalysis particulate uses manufacturing installation for example shown in Figure 7 to make.This manufacturing installation is made of spray dryer main body A, the B of gas-liquid mixed portion, forced air introduction part C, solution introduction part D and particle recoverer E.Numbering 51 among the figure is illustrated in the hothouse that top possesses distributor 52.Here, distributor 52 plays the effect that is used for hothouse 51 is heated to 200 ℃ air introducing port.In the hothouse 51, spray nozzle 53 and the middle pipeline 55a that electromagnetic pump 54 is installed are arranged with the state configuration of passes therethrough 52.Described pipeline 55a plays the effect that only is used for pressure (hydraulic) water solution and makes the air introducing port of its atomizing.On the top of described hothouse 51, by pipeline 55b air feed.Described pipeline 55b plays the effect of the hot blast air supply opening that is used to add hydrothermal solution and air.The pipeline 55c of needle-valve 56 in the middle of branching out halfway, described pipeline 55a is installed.
The top of described pipeline 55c and spray nozzle 53 links.Be connected with on the top of spray nozzle 53 sample 57 is supplied to flexible pipe 59 in the spray nozzle 53 by pump 58.The amount that is supplied to the sample 57 in the spray nozzle 53 can suitably be regulated by pump 58.Sidepiece binding at described hothouse 51 has taking-up to be the cyclone separator 60 of the product of vaporific ejection from spray nozzle 53.In addition, cyclone separator 60 connects the product container 61 of collecting the photocatalysis particulate and the air exhauster 62 that is used for exhaust.
Not shown temperature sensor is disposed at entrance side, the outlet side of described hothouse 51.By described temperature sensor, measure the air of supplying with to hothouse 51 temperature, be sent to the atmosphere temperature of the photocatalysis particulate of cyclone separator 60.In addition, the air that is supplied in the pipeline 55c mixes with sample 57 in being supplied to flexible pipe 59 in the upper side of spray nozzle 53, is vaporific ejection from the bottom of spray nozzle 53.
Use the manufacturing installation of such structure to make under the situation of photocatalysis particulate following carrying out.At first, in forced air was delivered to spray nozzle 53, the front end from spray nozzle 53 in 200 ℃ hot blast atmosphere for example sprayed, and makes its particle diameter of spraying into 1～10 μ m, generates granular feedstock with the ammonium paratungstate aqueous solution (sample) of 1～20 weight %.At this moment, forced air is delivered to from pipeline 55a near the front end of spray nozzle 53, supplied with oxygen to the granular feedstock of being sprayed from spray nozzle 53.Then, in 700～800 ℃ of heat treated of carrying out 1～10 minute, forming with the tungstic acid particulate is that the average grain diameter of main component, this particulate is that 0.1 μ m, crystalline texture are monoclinic photocatalysis particulate in hothouse 51.Then, when carrying out exhaust in the hothouse 51, the photocatalysis particulates in the hothouse 51 are collected in the product container 61 by cyclone separator 60 by air exhauster 62.
According to inventor's etc. research, known tungsten oxide (WO
3) also there is the difference of catalysis characteristics in the powder.Specifically, the catalytic effect (capacity of decomposition) of the light time of illumination wavelength 430～500nm there are differences in the discovery tungsten oxide powder.Among the present invention, if the tungsten oxide powder is shone above-mentioned light, then the tungsten oxide powder is excited.
That is, pass through the catalytic effect (capacity of decomposition) of the light time of illumination wavelength 430～500nm among the present invention, screening tungsten oxide powder, thereby the catalysis material that can obtain to have good characteristic.In addition, have the tungsten oxide powder of good capacity of decomposition, can save space and light-weighted photocatalyst product so can provide compared with the past because use.
[catalysis material (the 1st kind of catalysis material)]
The 1st kind of catalysis material of the present invention is as described in above-mentioned (1).
Discoveries such as the inventor, by in the wavelength that shines 430～500nm, the light of the long 460nm ± 10nm of spike particularly, more significant difference appears in capacity of decomposition.
Sunshine mixes existence ultraviolet ray～visible region, and (300～800nm) light ground shines.Therefore, can't only shine the light of the scope of 430～500nm.In addition, common fluorescent lamp with mercury as excitaton source, use the calcium halophosphate fluorophor (Ba, Ca, Mg)
10(PO
4)
6C
12: Eu etc.Such fluorescent lamp has spike in these 2 scopes of 420～470nm, 550～580nm (still, do not comprise based on mercury self peak) long.Obtain white light by these 2 kinds of light.In fluorescent lamp, 2 kinds of light also mix existence.Therefore, can't only shine the light of the scope of 430～500nm.
Therefore, the catalytic effect of light time of only shining 430～500nm was not carried out any research in the past.For example, the wavelength more than 2 kinds (being wavelength blue, green, yellow, red area under this situation) mixes under the situation of existence, only can't confirm the catalytic effect that excites based on 430～500nm.
The inventor etc. find that at first the tungsten oxide powder only there are differences on the catalytic effect that excites based on 430～500nm.
As light source, better be light emitting diode.Light emitting diode is a semiconductor element, therefore uses mercury unlike fluorescent lamp.Therefore, to the environment friendliness, developing as the substitute of fluorescent lamp.Wherein, confirm that blue LED (B-LED) can stably provide blue light (wavelength 430～500nm).
In the past, photocatalysis was not attempted B-LED with light source, only not being verified based on the catalytic effect of the light of 430～500nm of tungsten oxide powder.Among the present invention, use B-LED to study the catalytic effect of tungsten oxide powder as light source.Consequently, even discoveries such as the inventor look identical tungsten oxide powder, catalytic effect also there are differences.
[catalysis material (the 2nd kind of catalysis material)]
The 2nd kind of catalysis material of the present invention is as described in above-mentioned (7).
In the 2nd kind of catalysis material,, better be near the light emitting diode that 470nm, has the GaN class of glow peak as the light source of emission blue light.Average grain diameter better is below the 10 μ m.In addition, better be to be principal phase with the monoclinic crystal.
Among the present invention, following the carrying out of capacity of decomposition test.
[finding out the capacity of decomposition test method (test of the 1st capacity of decomposition) of the 1st kind of catalysis material]
1) at first,, prepares 3 liters container as the glass container made.In addition, as the glass container made, so long as the light of air-tightness height and transmission peaks wavelength 460nm ± 10nm gets final product, being not particularly limited, better is PYREX (registration mark of Corning Incorporated (コ-ニ Application グ the society)) system that is difficult for the reaction of generation and organic matter etc.
2) then, in the glass container made, put into 1g tungsten oxide powder, 20ppm acetaldehyde (amount A).
3) then, measure the acetaldehyde (amount B) of light after 2 hours of the long 460nm ± 10nm of irradiation spike, measure capacity of decomposition (%) by following formula.
Capacity of decomposition (%)=[(acetaldehyde amount A-acetaldehyde amount B)/acetaldehyde amount A] * 100
The mensuration of acetaldehyde amount is used the multifunctional gas monitor.
Among the present invention, be benchmark, measure the remaining acetaldehyde amount (acetaldehyde amount B) of light after 2 hours of the long 460nm ± 10nm of irradiation spike with initial acetaldehyde amount A (20ppm).And, discern the powder that remaining acetaldehyde amount reaches (capacity of decomposition is below 50%) below 50%.
Importantly tungsten oxide amount of powder 1g and initially acetaldehyde amount 20ppm in the test method of the present invention.Which kind of degree affirmation can decompose to the acetaldehyde of 20ppm by a small amount of tungsten oxide powder to 1g.At this moment, if use the light of the long 460nm ± 10nm of spike, the difference of characteristic appears significantly then.
In addition, once under the situation about testing for the tungsten oxide powder of the amount that surpasses 1g, increase acetaldehyde amount according to its amount and carry out.At this moment, can strengthen the size of glass container made as required.But if once the amount of Ce Dinging is excessive, the tungsten oxide powder that then is present in the bottom of container may contact with acetaldehyde.Therefore, the amount of once measuring better is to be the upper limit with 500g.When measuring the amount that surpasses 500g, it is desirable to cut apart to 500g, better be that 100g carries out method for measuring to get off.
In addition, can deal with by the operation of carrying out 10 times (10 place) measuring the 1g of haphazard selection simply.In addition, the configuration status of powder also must below the thickness 1mm, better be to lay under the state below the 0.5mm.Also have, during tungsten oxide powder deficiency 1g, better be to use the 2nd capacity of decomposition test described later.
As the light of the long 460nm ± 10nm of spike, as long as in this scope, exist spike long, be not particularly limited, better be waveform as shown in figure 19.As the light source that waveform as shown in figure 19 is provided, can exemplify blue LED (B-LED).In addition, as waveform, better be that half width reaches the following sharp-pointed waveform of 50nm.If sharp-pointed waveform, then distinguish the quality of the capacity of decomposition when carrying out aforesaid capacity of decomposition test easily.
The power output of light better is at 1mW/cm
2More than.The not enough 1mW/cm of the power output of light
2The time, be difficult to obtain the effect of illumination, be difficult for judging exactly capacity of decomposition.The power output of light better is 2～5mW/cm
2Test the aspect, irradiation surpasses 5mW/cm
2The light of power output also no problem.But, there is not better effect, cause the waste of electric power, so better be described scope.
By the test of aforesaid capacity of decomposition, screening capacity of decomposition more than 50%, be more preferably 90%～100% powder, thereby can obtain good catalysis material.
[finding out the capacity of decomposition test method (test of the 2nd capacity of decomposition) of the 2nd kind of catalysis material]
1) at first, prepares 3 liters airtight container.This airtight container better is the glass container made, and good especially is the PYREX system.
2) then, in this container, put into the tungsten oxide particulate (for example below the average grain diameter 0.5 μ m) of quality 0.1g.
3) then, import 10ppm acetaldehyde, the tungsten oxide particulate by the irradiation blue light, is measured the remaining quantity of acetaldehyde after 30 minutes, obtain survival rate.Survival rate (%) is tried to achieve by following formula.
Survival rate=[(after 10ppm-30 minute remaining acetaldehyde amount ppm)/10ppm] * 100
Also having, as the light source that blue light takes place, better is near the light emitting diode that has the GaN class of glow peak 470nm.
Survival rate better is below 40% below 50%.Have the particulate of such characteristic by screening, can obtain good catalysis material.In the test of the 2nd capacity of decomposition, the tungsten oxide powder is on a small quantity to 0.1g, so minute was made as 30 minutes.The tungsten oxide powder is 1g and under the more situation, the acetaldehyde of 10ppm decomposes rapidly, is difficult to obtain the difference of capacity of decomposition as the 1st capacity of decomposition is tested.In addition, the survival rate of acetaldehyde uses the multifunctional gas monitor to measure.
[test of the 3rd capacity of decomposition]
Test of the 1st capacity of decomposition and the test of the 2nd capacity of decomposition are to use airtight container to measure the method for capacity of decomposition with airtight space.Relative with it, as the test of the 3rd capacity of decomposition, carry out method for measuring when also making gas flow.As the object lesson of such method, JIS-R-1701-1 (2004) is arranged.This JIS is the test of removing performance (capacity of decomposition) that is used to measure nitrogen oxide, but also goes for organic capacity of decomposition test such as acetaldehyde.
Enforcement is during based on the method for JIS-R-1701-1, and container better is to use the container that is defined as " illumination container " among this JIS.Following the carrying out of the 3rd capacity of decomposition test.
1) at first, 1g is coated on the glass plate of 50 * 100mm equably as the catalysis material of measuring sample, be accommodated in the container.
2) then, the gas supply port from container contains the air of 0.1～10ppm as the acetaldehyde of decomposition gas with constant speed (1/ minute) importing.In addition, catalysis material is shone the light of the long 460nm ± 10nm of spike.After the irradiation time of light reaches 60 minutes, measure the acetaldehyde concentration [I at container gas supply port place
0] and the acetaldehyde concentration [I] at the gas discharge outlet place of container.On this basis, obtain capacity of decomposition (μ g/m by following formula
2).
[([the I of capacity of decomposition=(K/S)
0]-[I]) * flow velocity (1/ minute) * irradiation time (60 minutes) * m]/22.4
In the formula, K is with cm
2Be converted to m
2Coefficient, K=10000.S is the area of the catalysis material on the glass plate, S=50cm
2Acetaldehyde concentration [the I at container gas supply port place
0] and the acetaldehyde concentration [I] at the gas discharge outlet place of container be respectively (volume ppm), m is the molecular weight of acetaldehyde.
Above-mentioned formula is used as the method for capacity of decomposition for the absolute value of measuring the acetaldehyde amount decomposed.In addition, (1) formula of 7. putting down in writing in a) the nitrogen oxide adsorbance of the calculating of result of the test based on JIS-R-1701-1 (2004) of this formula based on test film.Can capacity of decomposition be scaled percentage according to this absolute value.In addition, as the light source of the light that shines the long 460nm ± 10nm of spike, better be blue led.
The 3rd capacity of decomposition test is based on the JIS method, so as the reliability height of assay method.Yet it is miscellaneous that item is adjusted in the adjustment of the initial concentration of the adjustment of sample, the adjustment of flow velocity, acetaldehyde (air that contains acetaldehyde) etc.Therefore, adopt the test of the 1st or the 2nd capacity of decomposition among the present invention.Also have, the difference of the measurement result of test of the 1st capacity of decomposition and the 3rd capacity of decomposition test (being scaled percentage according to measured value) is about ± 5%.
Catalysis material better is below the average grain diameter 10 μ m, is more preferably below the average grain diameter 1 μ m, and good especially is below the 0.5 μ m.If average grain diameter is little, then the surface area of powder is big, so catalytic effect increases.
Among the present invention, better be to be the tungsten oxide powder of principal phase with the monoclinic crystal.Better be to possess that 50 quality % are above, to be more preferably 70 quality % above be the catalysis material of the tungsten oxide powder of principal phase with the monoclinic crystal.The tungsten oxide powder also has three oblique crystalline substances except monoclinic crystal.Tungsten oxide powder of the present invention (catalysis material) can mix and have anorthic system, but better is to be principal phase with the monoclinic crystal.Be that the powder of principal phase carries out the screening based on the test of the 1st and the 2nd (or even 3rd) capacity of decomposition easily with the monoclinic crystal.
[tungsten oxide manufacturing method of power]
Below, the tungsten oxide manufacturing method of power is described.Manufacture method is preferably carried out aforesaid capacity of decomposition and is tested and carry out method for screening.
Tungsten oxide powder for before the screening for example can exemplify the method for (a) direct oxidation tungsten, the method that (b) obtains ammonium paratungstate tungsten compound thermal decompositions in air such as (APT) tungsten oxide.By any method, can obtain tungsten oxide (WO
3) powder.
As the method for making of using APT, can exemplify for example following method.At first, APT by pulverizing such as ball mill or planetary ball mills, is carried out classification by centrifugation.Then, this particulate is heat-treated in 400～600 ℃ in atmosphere.Thus, can generate the photocatalysis powder that the tungsten oxide particulate with monoclinic crystalline texture by average grain diameter 0.01～0.5 μ m forms.
In addition, as other method, following (1), the method for (2) are arranged.
(1) possess the operation of the APT aqueous solution of 1～20 quality % being sprayed in high-temperature atmosphere and generating granular feedstock and with this granular feedstock 700～800 ℃ of methods of operation of carrying out 1～10 minute heat treated.Thus, can obtain crystalline texture is monoclinic tungsten oxide powder.
(2) possesses the operation that APT is dissolved in be recrystallized behind the aqueous solvent and the method for operation that this crystallization is burnt till with the condition more than 600 ℃, more than 15 seconds.Thus, can obtain the tungsten oxide powder.
In any method,, can obtain the monoclinic system tungsten oxide by adjusting heat-treat condition etc.Also have, can obtain the tungsten oxide powder of average grain diameter 0.1 μ m by aforementioned method for making.But, under the big situation of the particle diameter of the tungsten oxide powder that obtains because of method for making and creating conditions, it is desirable to carry out classification obtain average grain diameter 10 μ m following, better be the following powder of 1 μ m.
Aforesaid catalysis material has good photocatalysis effect, so can decomposing organic matter, NOx, SOx etc.
[photocatalysis composition]
As described in above-mentioned (11), photocatalysis composition of the present invention comprises the above catalysis material of 50 quality %.During catalysis material less than 50 quality %, can't obtain enough photocatalysis effects.In addition, this photocatalysis composition can comprise the titanium dioxide powder of less than 50 quality %.
[photocatalyst product]
Photocatalyst product of the present invention is as described in above-mentioned (14).Above-mentioned photocatalysis composition is suitable for photocatalyst product, and organic matter, NOx, SOx at least a kind is had catalytic effect.
When catalysis material of the present invention is used for photocatalyst product, get final product, be not particularly limited so long as have the environment of the light source of the light that sends the wavelength that contains 430～500nm.As excitaton source (light source), the light with the wavelength that contains 430～500nm gets final product.As light source, can exemplify for example blue-light-emitting semiconductor element (for example blue LED, blue semiconductor laser), sunshine, various fluorescent lamp.In addition, the light quantity of the wavelength of 430～500nm better is 1mW/cm
2More than.
In addition, when making photocatalyst product, so long as the light quantity of the wavelength of 430～500nm is at 1mW/cm
2More than, be more preferably 5mW/cm
2The above big environment of light quantity, the photocatalysis composition that comprises the above catalysis material of the present invention of 50 quality % gets final product.Also have, the ratio of the catalysis material of the present invention in the tungsten oxide powder is more preferably 100% more than 90%, and it is The more the better that yes.
In addition, comprise under the situation about using under the light source of ultraviolet range, can use the titanium oxide (TiO that comprises less than 50 quality % at sunshine etc.
2) the photocatalysis composition of powder.Photocatalyst product of the present invention better is that the adhesive that possesses by regulation makes the tungsten oxide powder bonded in matrix surface and the photocatalysis membrana of film forming.The matrix carrying photocatalysis membrana of photocatalysis body originally forms for other function different with catalysis material.That is, allowing matrix is functional material.
As functional material, can exemplify for example construction materials such as ceramic tile, glass pane, ceiling panel, the equipment that for kitchen use and health is used, home appliance, illumination with equipment, deodorizing with or control of dust with various required arbitrarily members such as filters.
Use forms under the situation of photocatalysis membrana as the tungsten oxide powder of catalysis material, also can directly the photocatalysis material be burnt till, and makes it be bonded in matrix by sintering.If but use suitable adhesive to make be combined into film between matrix and the catalysis material, then make and become easy.In addition, as directly burning till, need not to be exposed under the high temperature, so also can film forming on the base material of poor heat resistance.
Use adhesive to form under the situation of photocatalysis membrana by catalysis material, adhesive can use for example silica (SiO
2), glass welding agent, glaze, low-melting-point metal, thermoplasticity synthetic resin.Also have, in order to be bonded in matrix by burning till the powder (particulate) that makes catalysis material, matrix need use the material that can tolerate firing temperature certainly.
Making the primary particle as the tungsten oxide powder of catalysis material is 0.001～0.1 μ m, can form the film of surface compact.Thus, transmission of visible light also improves.Better be even as far as possible as the size distribution of the tungsten oxide powder of catalysis material, the shape that adopts particulate is near positive spherical powder.Consequently, the radius unanimity of the pore that forms as small gap on the surface of photocatalysis membrana.Therefore, the gas molecule of the tool peculiar smell that for example acetaldehyde equimolecular radius is little is decomposed rapidly by the pore on the surface of photocatalysis membrana.If adopt this formation, also be effective for the deodorizing of formaldehyde, i.e. decomposition.Relative with it, can't enter above-mentioned pore as the polluter of wet goods particle radii more than 0.1 μ m of carbon or cigarette.But the surface of polluter contact photocatalysis membrana is decomposed by redox.
Functional material is meant that itself was endowed the equipment of the function that is used for the purpose different with photocatalysis membrana originally.As functional material, for example have construction material, health with equipment, equipment for kitchen use, equipment with filter, home appliance, illumination equipment.As construction material, can exemplify for example ceramic tile, flooring material, window material, wall covering.As health equipment, can exemplify for example washing basin, bathtub, toilet seat, urinal.As equipment for kitchen use, can exemplify for example sink, chopping board, tableware rack.
As the equipment filter, for example can exemplify air cleaning machine with filter, bathroom with circulator with filter, aircondition with filter, heating installation with filter, deodoriser filter.Can consider that with the filter with fluid flow hole be matrix, forming with the tungsten oxide powder on the surface of this matrix is the structure of the photocatalysis membrana of main component.Adopt under the situation of this structure, the air that in filter, circulates with flow through when the photocatalysis body of big as far as possible area contacts.Therefore, can improve deodorizing effect.In addition, also can play bactericidal effect.In addition, can make filter and photocatalysis body constitute odor removal independently of one another.That is, with photocatalysis body and filter dispose independently with the gas passage in, moving air is contacted with photocatalysis body gets final product.
In addition, the present invention can also make it be built in the equipment except odor removal is used separately.For example, can be built in refrigerator, aircondition, thermantidote, heating installation, aircleaning facility, humidifier, dehumidifier, play deodorization functions as odor removal.
As home appliance, refrigerator, washing machine, micro-wave oven, dish-washing machine, coffee machine, electric vacuum cleaner etc. are arranged.
Use equipment as illumination, lamp such as fluorescent lamp, ligthing paraphernalia are for example arranged with lampshade globe holder, light transmission light cover, chandelier usefulness light cover, reflecting plate, socket etc.
Ligthing paraphernalia because play can decompose the significant effect of initiation problem VOC in the room of high-air-tightness particularly, thus be suitable for indoor, but because of also having the polluter decomposition concurrently, so also be adapted to the ligthing paraphernalia of outdoor use.
If photochemical catalyst of the present invention is used for home appliance, illumination with equipment, ligthing paraphernalia, then can forms the home appliance, illumination equipment, the ligthing paraphernalia that possess photocatalysis effects such as deodorization functions.
The ligthing paraphernalia main body is meant that ligthing paraphernalia removes the remaining part beyond the lamp.As everyone knows, ligthing paraphernalia is because difference and difference home-use, office usefulness indoor, outdoor use particularly according to appearance design, are adopted various structures and shape.But, suitably select diaphragms such as reflecting plate, printing opacity light cover, louver (-vre), lampshade and globe holder to use according to it.Therefore, for the formation of control light members such as having or not of the having or not of reflecting plate, printing opacity light cover, it is unimportant whether the ligthing paraphernalia main body possesses.But the ligthing paraphernalia main body all possesses the part of the part of supporting lamp, the part that connects power supply and installation ligthing paraphernalia etc. basically.
As mentioned above, be that matrix formation is the photocatalysis membrana of main component with the tungsten oxide powder with the functional material.Therefore, photocatalysis membrana is subjected to containing the illumination of visible light at least and activates in their use.Consequently, play deodorizing, effect such as antifouling, antibiotic simultaneously, so produce effects such as the health in living space is improved, cleaning simplification.
Below, concrete embodiment of the present invention is described.
(the 1st kind of embodiment)
Following the making of photocatalysis powder of the 1st kind of embodiment.
At first, para-tungstic acid ammonium salt (APT) by pulverizing such as ball mill or planetary ball mills, is carried out classification by centrifugation.Then, this particulate is heat-treated in 400～600 ℃ in atmosphere, thereby can generate the refining photocatalysis powder that forms by the tungstic acid particulate of average grain diameter 0.01～0.5 μ m with monoclinic crystalline texture.In the present embodiment,, can obtain the monoclinic tungstic acid particulate of the about 0.1 μ m of average grain diameter by in atmosphere, heat-treating in about 500 ℃.Particle size distribution data in this operation such as Fig. 8, shown in Figure 9.Here, Fig. 8 is the figure of the size distribution (particle diameter and frequency, the relation by composition accumulative total) after expression disperses, and Fig. 9 is expression WO
3The figure of the size distribution of dispersion paints (particle diameter and frequency, the relation by composition accumulative total).By Fig. 8 and Fig. 9 as can be known, by heat treatment crystalline growth is arranged slightly, it is big that granularity becomes.
If adopt the photocatalysis powder of the 1st kind of embodiment, because with average grain diameter is that the tungstic acid particulate of 0.1 μ m is a main component, crystalline texture is monoclinic system, so can obtain significantly to improve the photocatalysis powder of the visible-light response type of photocatalysis performance.
(the 2nd kind of embodiment)
Following the making of indoor light catalyzed coating of the 2nd kind of embodiment.
At first, tungstic acid particulate and micro-surface conditioning agent are mixed in the organic solvent (ethanol), carry out the dispersion treatment of a few hours by ball mill.Then, add the pure water of inanimate matter adhesive (polysiloxanes), organic solvent (alcohol) and number % with respect to tungstic acid trace 30 quality %, carry out dispersion treatment once more, make light catalyzed coating.Then, in the light catalyzed coating that obtains, after adding calcium carbonate and magnesium hydroxide with multiple amount in the scope of mole % 0.1～10%, stir and make sample with respect to tungstic acid.Then, this sample coating coated glass plate, acrylic compounds plate, fluorescent tube after, 120～180 ℃ of dryings, make the sample of filming.
They are put into 1m as original state
3Stainless steel case in, glass plate, acrylic compounds plate are with BLB light irradiation 1mW/cm
2Ultraviolet ray, fluorescent lamp is directly lighted in case, measures the decomposition effect of formaldehyde.For the sample after measuring, glass plate, acrylic compounds plate are positioned over indoor, and fluorescent lamp carries out a lantern test in common office, measures the gas decomposability week about.
If adopt the 2nd kind of embodiment, on the fluorescent lamp main body, form constituting of the photocatalysis membrana that forms by the indoor light catalyzed coating that obtains than the magnesia of tungstic acid easier absorption SOx and NOx by adopting suitably to add to the coating that contains the tungsten oxide particulate, not only can obtain sterilization, the distinctive effect of photochemical catalyst such as antifouling, the deterioration of the photocatalysis membrana in can also suppressing to use obtains long-life fluorescent lamp.
(the 3rd kind of embodiment)
At first, in forced air was sent into the spray nozzle 53 of Fig. 7, the front end from spray nozzle 53 in 200 ℃ of hot blast atmosphere sprayed, and makes its particle diameter of spraying into 1～10 μ m, generates granular feedstock with the ammonium paratungstate aqueous solution (sample) of for example 4 quality %.At this moment, forced air is delivered to from pipeline 55a near the front end of spray nozzle 53, supplied with oxygen to the photocatalysis particulate of being sprayed from spray nozzle 53.If the concentration of the aqueous solution is 4 quality %, then can obtain the granular feedstock of 0.04～0.4 μ m ammonium paratungstate.Then, in hothouse 51, carry out the short time heat treatment of Fast Heating with 800 ℃, 1～10 minute condition, described raw material is dry forcibly and make its recrystallization.Thus, forming with the tungstic acid particulate is main component, the average grain diameter of this particulate below the 0.5 μ m, better be below the 0.1 μ m, crystalline texture is monoclinic tungstic acid photocatalysis particulate.Then, when carrying out exhaust in the hothouse 51, the photocatalysis particulates in the hothouse 51 are collected in the product container 61 by cyclone separator 60 by air exhauster 62.
If adopt the 3rd kind of embodiment, supply with oxygen by next near the front end of forced air being delivered to spray nozzle 53 from pipeline 55a to the photocatalysis particulate, thereby can obtain the few WO of oxygen defect
3Crystallization photocatalysis particulate.In addition, by in hothouse 51, carrying out the short time heat treatment of Fast Heating, can obtain the few WO of crystalline growth with 800 ℃, 1～10 minute condition
3Crystallization photocatalysis particulate.
Figure 10 represents the microphotograph of conduct by the ammonium metatungstate of the 3rd kind of granular feedstock that embodiment obtains.Figure 11 represents the monoclinic system type WO that will obtain through the short time heat treatment of 800 ℃, 1～10 minute Fast Heating by the 3rd kind of granular feedstock that embodiment obtains
3The microphotograph of crystallization photocatalysis particulate.As shown in Figure 10, though variant slightly, can obtain the granular feedstock of the ammonium metatungstate of particle diameter unanimity.
(the 4th kind of embodiment)
The particulate of present embodiment be recrystallized behind the aqueous solvent commercially available ammonium paratungstate is dissolved in and raw material in atmosphere, burn till with the heating that high temperature carried out 1 minute, thereby the tungstic acid particulate of making.
Figure 12 is the performance plot of the aldehydes gas decomposability of each the tungstic acid photocatalysis particulate of expression when the firing temperature in the 4th kind of embodiment changed to 600 ℃, 700 ℃, 800 ℃, 900 ℃.Figure 13 is the same performance plot when firing temperature is changed to 800 ℃, 900 ℃, 1000 ℃.
Figure 12 and decomposability evaluation shown in Figure 13 are carried out with following condition.At first, the tungstic acid particulate of 0.1g is put into ware, be arranged in the closed container of capacity 200cc, can the condition that this photocatalysis particulate irradiation has the light of emission spectrum shown in Figure 3 being disposed blue led in container.Then, when importing aldehydes gas, light blue led, measure the variation of every gas concentration through after a while with the condition of the concentration that reaches 10ppm in the container.The mensuration of concentration is undertaken by the output that is arranged at the gas sensor in the container, by relatively estimating of this output valve.Among the figure of Figure 12 and Figure 13, the longitudinal axis is the relative value (%) of expression corresponding to the output of the sensor of the concentration of aldehydes gas.Situation is as can be known, and gas was full of through 20～30 seconds after importing in the container, and concentration constantly descends at leisure owing to the decomposition effect of photochemical catalyst again.Also have, among Figure 12 and Figure 13, represent as 100% with the maximum of sensor output for the purpose of making things convenient for.
By the result of Figure 12 and Figure 13 as can be known, make commercially available ammonium paratungstate be dissolved in water as raw material, will be by recrystallization the crystallization of grain refined best 800 ℃ of decomposition effects after burning till, preferred firing temperature is 700～900 ℃.As mentioned above, the tungsten oxide that the visible light-responded property of the catalysis material of present embodiment gets than simple commercially available product is burnt till is better, and can improve photocatalytic activity.
(the 5th kind of embodiment)
The particulate of present embodiment is, make commercially available ammonium paratungstate be dissolved in aqueous solvent earlier after, will in atmosphere, burn till by the particle that recrystallization gets in 800 ℃ of heating of carrying out the stipulated time, thus the tungstic acid particulate of making.
Figure 14 is the performance plot of the aldehydes gas decomposability of expression when firing time changed to 30 seconds (line (a)), 1 minute (line (b)), 5 minutes (line (c)), 10 minutes (line (d)), 15 minutes (line (e)).Also have, the decomposability appreciation condition of Figure 14 is identical with Figure 12 and Figure 13 with the expression content of figure.
By the result of Figure 14 as can be known, if firing time was made as 1～5 minute, then can obtain high gas decomposability.
(the 6th kind of embodiment)
The ligthing paraphernalia of the 6th kind of embodiment of the present invention is as Figure 16 and structure shown in Figure 17.Here, Figure 16 is the stereogram of the decomposing state of described ligthing paraphernalia, and Figure 17 is the amplification sectional view of the major part of Figure 16.Present embodiment relates to using at inner surface and is formed with the ligthing paraphernalia of ultraviolet shielding material as the transmittance lampshade (light cover) of the ultraviolet screener layer of main body.
In addition, the periphery of appliance body 72 is provided with 2 lamp sockets 75 and 2 bases 76.And, dispose 2 electric and mechanically be supported on the luminous tube 77 around stage portion 73 of base 76 when being connected mechanically to lamp socket 75 as the circular fluorescent lamp of light source, for example the luminous tube 77 of the mutually different fluorescent lamp of external diameter of 32W and 40W is concentric shape configuration.In addition, the part of peristome 74 is provided with socket 78, and lamp pearl lamps 79 such as (ベ PVC-balls) is installed on this socket 78.
The lampshade 80 of learning device as illumination light releasably is installed on appliance body 72, the below and the side that make it cover appliance body 72 and be installed on the member of this appliance body 72.Lampshade 80 possesses the illuminating acrylic resin system light cover matrix 81 that glass or resin etc. have the curved surface shape that forms downwards bulging sleekly etc. of light transmission.Being formed with by average grain diameter at the outer surface of this matrix 81 is that 0.1 μ m, crystalline texture are the photocatalysis layer 82 that monoclinic tungstic acid particulate forms.Here, photocatalysis layer 82 following formation.That is, will be crushed to average grain diameter 0.05～0.1 μ m by ball mill or planetary ball mill etc. as the para-tungstic acid ammonium salt (APT) about the 100 commercially available μ m of raw material earlier, with this particulate in atmosphere in 500 ℃ the heating 8 hours, thereby make the tungstic acid particulate.Then, disperse mixed processing to make coating by solvent this tungstic acid particulate and adhesive ingredients, this coating is coated matrix 81 by spray gun, dry and form.
If adopt the 6th kind of embodiment,, therefore need after film forming, at high temperature not implement heat treated owing to by the coating that makes tungstic acid particulate and adhesive ingredients disperse to get photocatalysis layer 82 is set on the surface of matrix 81.Therefore, can under the situation that acrylic resin light cover outer surface is used, also can obtain enough activity to giving photo-catalysis function as the lining object of base materials such as organic base material.
Also have, in the 6th kind of embodiment, photocatalysis layer 82 is located at the outer surface of matrix 81, but is not limited to this structure, for example also can be in the resin that constitutes matrix 81 mixed light catalysis material and forming.
Figure 15 is that the WO based on the 6th kind of embodiment is used in expression
3Photochemical catalyst (line a) time, uses TiO
2The figure of the wavelength during photochemical catalyst (curve b) and the relation of reflectivity.Also have, the curve c among Figure 15 represents acrylic resin light cover transmissivity, and curve d represents from the spatial distribution of the light of three-wavelength type fluorescent lamp emission.By the figure of Figure 15 as can be known, the tungstic acid of present embodiment absorbs the blueness of 400～500nm of transmission acrylic resin light cover effectively to the energy of glaucous visible light as photocatalytic activity.
(the 7th kind of embodiment)
Present embodiment is to form WO on illuminating color steel sheet reflecting plate matrix
3The form of photocatalysis layer.The following formation of photocatalysis layer.That is, will be crushed to average grain diameter 0.05～0.1 μ m by ball mill or planetary ball mill etc. as the para-tungstic acid ammonium salt (APT) about the 100 commercially available μ m of raw material earlier, with this particulate in atmosphere in 500 ℃ the heating 8 hours, thereby make the tungstic acid particulate.Then, disperse mixed processing to make coating by solvent this tungstic acid particulate and adhesive ingredients, this coating is coated color steel sheet reflecting plate matrix by spray gun, dry and form.
If adopt the 7th kind of embodiment, then have and the 6th kind of same effect of embodiment.
Figure 18 illustrates ligthing paraphernalia and the band TiO of expression based on the 7th kind of embodiment
2The fluorescent lamp of photochemical catalyst (line a), the band TiO
2Fluorescent lamp of photochemical catalyst (line b) and band TiO
2The ligthing paraphernalia of photochemical catalyst and band TiO
2The performance plot of the time of the fluorescent lamp of photochemical catalyst (line c) and the relation of acetaldehyde survival rate.By the figure of Figure 18 as can be known, with the photocatalysis layer of the reflecting plate matrix surface that is formed at ligthing paraphernalia as in the past by TiO
2The situation that particulate forms is compared, and uses the situation of monoclinic system tungstic acid particulate more excellent aspect the photocatalysis effect.
(the 8th kind of embodiment)
At first, with the thermal decomposition and obtain oxide in air of ammonium paratungstate powder, thereby obtain tungsten oxide (WO
3) powder.Then, by it is carried out classification, thereby obtain the tungsten oxide powder of average grain diameter 0.2 μ m.Then, by carrying out the operation of burning till for several times, classification, thereby adjust the tungsten oxide powder of different batches, do not cause damage ground not mix, make it even powder, with it as sample 1～5.
Then, prepare 5 PYREX container mades (3 liters), get the 1g powder, put into 20ppm acetaldehyde from each sample.Prepare the blue LED (blue led) of the long 460nm of spike, measure the acetaldehyde amount of light after 2 hours of shining blue led, obtain capacity of decomposition (%) (adopting the test of the 1st capacity of decomposition) by the multifunctional gas monitor.
Zhi the trade name FL20SS (East of Toshiba Lighting ﹠ Technology Corp sesame ラ イ テ ッ Network (strain))), the capacity of decomposition the during green LED (spike shape is shown in Figure 20) of the long 530nm of spike in addition, also measure light source simultaneously and change sunshine, fluorescent lamp (the common fluorescent lamp of calcium halophosphate fluorophor: into.It the results are shown in following table 1.Also have, (wavelength 400～650nm) green LEDs (green LED, wavelength 530nm) are unified to be 3mW/cm to light quantity for blue LED (blue led, wavelength 460nm), fluorescent lamp
2(light quantity of wavelength 300～800nm) is 10mW/cm to sunshine
2
In addition, mensuration uses the sample of the titanium dioxide powder of average grain diameter 0.2 μ m to be used for comparison simultaneously.In the table 1, sample 1～4 is embodiments of the invention, and sample 5 is for adopting the comparative example of the tungsten oxide that does not have capacity of decomposition of the present invention, the comparative example that sample 6 is measured for the titanium dioxide powder that uses average grain diameter 0.2 μ m.
(table 1)
In addition, put down in writing respectively in Figure 21～24 by blue led, sunshine, fluorescent lamp, capacity of decomposition result of the test (transverse axis be time (minute) when green LED excites, the longitudinal axis is capacity of decomposition (%)).Also have, in Figure 21～24, line a, b, c, d, e, f represent the situation of sample 1,2,3,4,5,6 respectively.
By table 1 and Figure 21～24 as can be known, the catalysis material that obtains good characteristic by the capacity of decomposition based on blue led as sample 1～4 also obtains good characteristic under the situation of sunshine and fluorescent lamp.
On the other hand, as sample 5, as a result under the situation of less than 50%, under the situation of sunshine and fluorescent lamp, do not obtain a good result based on the capacity of decomposition of blue led yet.In addition, long by spike as green LED not at the light of 430～500nm, almost do not bring into play capacity of decomposition.In addition, though confirm that manufacture method is identical, there are differences between batch.Therefore, it is effective carrying out method for screening by capacity of decomposition test of the present invention.
(the 9th kind of embodiment)
The result that expression records by the test of the 2nd capacity of decomposition.At first, by with the 8th kind of same method of embodiment, obtain sample 7,8 as the tungsten oxide powder of average grain diameter 0.1 μ m.Then, prepare 3 PYREX container mades (3 liters), take by weighing 0.1g tungsten oxide powder from described sample and put into each container.Then, import 10ppm acetaldehyde, the tungsten oxide powder is used the blue led irradiation blue light 0.5 hour (30 minutes) of the long 470nm of spike after, by the remaining quantity of multifunctional gas monitor mensuration acetaldehyde, obtain survival rate.
Its result is shown in Figure 5 as the aforementioned.Among the figure, line a is a sample 7, and line b is a sample 8, and line c is not for to use photochemical catalyst not carry out the comparative example of illumination yet.0.5 hour survival rate, sample 7 (embodiment) is 38%, sample 8 (comparative example) is 70%, comparative example is 99%.
In addition, confirmed the X-ray diffraction pattern of sample 7,8, the principal phase of sample 7 is a monoclinic crystal, and the principal phase of sample 8 is three oblique crystalline substances.Can think that according to this result the tungsten oxide powder better is that monoclinic crystal is a principal phase.
(the 10th kind of embodiment)
Except the average grain diameter difference, use the powder identical with sample 2, similarly carry out the 1st capacity of decomposition with the 8th kind of embodiment and test.It the results are shown in following table 2.
(table 2)
As shown in Table 2, particle diameter is more little, and characteristic is good more.
(the 11st kind of embodiment)
In the present embodiment, use sample 2, the variation of capacity of decomposition is investigated in the 1st capacity of decomposition test when changing the light quantity of irradiation.It the results are shown in following table 3, table 4.
(table 3)
(table 4)
By table 3 and table 4 as can be known, light quantity better is 1mW/cm
2More than.In addition, the capacity of decomposition test during based on the irradiation light quantity of blue LED is shown among the figure with the change of table 3 among Figure 25.Line a, b, c, d, e, f light quantity (mW/cm for shining
2) be made as 0.1,1,3,5,10 measurement result.As shown in Figure 25, light quantity is big more, and the speed of decomposition is fast more.But, if surpass 5mW/cm
2, bigger difference does not then appear.
(the 12nd kind of embodiment)
At first, by WO with sample 2
3The TiO of powder and sample 6
2Powder mixes with ormal weight, preparation photocatalysis composition.Then,, carry out the 1st capacity of decomposition test when exciting, investigate the difference of ability by blue led or sunshine for each different sample of mixed proportion.It the results are shown in following table 5.
(table 5)
As shown in Table 5, and if TiO
2Powder, the capacity of decomposition when comprising the optical excitation of ultraviolet range as sunshine improves.But, if TiO
2Amount of powder is greatly to surpassing 50 quality %, then characteristic and only TiO
2Approaching during powder, therefore be difficult to obtain and WO of the present invention
3The effect of powder.
(the 13rd kind of embodiment)
In the present embodiment, use the WO of sample 2
3Powder, the test of the 1st capacity of decomposition when changing sample size is measured 20ppm acetaldehyde is decomposed to time of 50%, decomposes to for 90% time.It the results are shown in following table 6.
(table 6)
As shown in Table 6, if increase the catalysis material amount, then capacity of decomposition significantly improves.In addition, if the amount of confirming increases, then capacity of decomposition is rapid-action, and 50% the time of decomposing to becomes very short.
(the 14th kind of embodiment)
Figure 26 is the concept map of a kind of embodiment of expression odor removal of the present invention.Among Figure 26, numbering 91 expression odor removal filters.Lamp 92 is disposed at the side wall side of odor removal filter 91.Described odor removal filter 91 and lamp 92 are accommodated in the odor removal main body 93 as box.
91 irradiations of 92 pairs of odor removal filters of lamp comprise the light of luminous ray and make the photocatalysis membrana activation, can use fluorescent lamp, high-pressure sodium lamp, light emitting diode etc.Described odor removal main body 93 possesses blowing unit, power supply and control module etc.Thus, when air passed through odor removal filter 91, by the photocatalysis membrana of odor removal filter 91, the gas with peculiar smell was decomposed and deodorizing by odor removal filter 1.
Figure 27 is the figure of measurement result of the photocatalysis effect of expression present embodiment.Among Figure 27, transverse axis represent the time (minute), the longitudinal axis is represented acetaldehyde (CH
3CHO) concentration (ppm).This mensuration for the decomposition of investigating acetaldehyde, be that deodorization is implemented.Condition determination is to be full of the volume 0.2m of acetaldehyde in the concentration with 500ppm
2Case in take in the odor removal of Figure 11 and it driven, in the gas in agitator tank, by (the B﹠amp of Bu Ke company; K society) 1302 type multifunctional gas monitors of system are measured the change in concentration of acetaldehyde.Line a is drawn by its result and forms.In addition, in order to compare, lamp adopts the bactericidal lamp as ultraviolet light source, with identical conditions to being that the situation (line c) that does not form photocatalysis membrana on the situation (line b) of the photocatalysis membrana of main component and the odor removal filter is measured forming with the titanium oxide on the odor removal filter.
As shown in Figure 27, under the situation of present embodiment, when bright lamp began 30 minutes, acetaldehyde was reduced to 20%.Relative with it, under the situation of titania photocatalyst (line b), when bright lamp began 30 minutes, acetaldehyde only reduced 35%, and under the situation of no photocatalysis membrana (line c), the concentration of acetaldehyde does not almost reduce.By above results verification, present embodiment with WO
3Particulate is that the irradiation of photocatalysis membrana by luminous ray of main component also has good effect for the decomposition of acetaldehyde.
(the 15th kind of embodiment)
Figure 28 represents the generalities major part amplification sectional view of other embodiment of photocatalyst product of the present invention.Among Figure 28, numbering 94 is the matrix that is formed by soda-lime glass, and numbering 95 is a photocatalysis membrana.Photocatalysis membrana 95 forms based on the tungsten oxide powder of average grain diameter 0.05～0.1 μ m, by adhesives such as silicon dioxide microparticle and on matrix 94 film forming form.Also have, the tungsten oxide powder use in the test of the 1st capacity of decomposition capacity of decomposition 90% or more and the 2nd capacity of decomposition test in remaining quantity at the powder below 40%.
If 94 irradiations comprise the light of the luminous ray more than the about 400nm of wavelength to photocatalysis membrana, then the tungsten oxide powder is by optical excitation.And, by the reaction of the electronics from valence to conduction band and airborne oxygen and form peroxide, reaction such as the hole that residues in valence band and water and generation OH base.Like this material of Sheng Chenging be attached to the organic matter generation oxidation reaction on the surface of photocatalysis membrana.The oxidized decomposition of organic matter obtains antifouling, deodorizing and sterilization effects.
In addition, about sterilization, confirm for the bacterium class that is adsorbed in photocatalyst surface that the oxidizing force by the tungsten oxide powder has the effect that suppresses propagation, this effect is proportional to the decomposition rate of pigment basically.But with the ultraviolet irradiation of wavelength 200～400nm, sterilizing power further improves by also.Wherein, near the ultraviolet effect the wavelength 250nm is best.Near the wavelength 350nm ultraviolet ray is 1/1000 of the ultraviolet ability of wavelength 250nm near.In addition, for the ultraviolet ray of wavelength 350nm, by the additional optical catalytic effect, bactericidal effect is improved.Consequently, be adsorbed in the speed decision sterilization speed of photocatalyst surface, therefore can't expect a large amount of sterilizations, so better be near the ultraviolet ray the wavelength 250nm.
Figure 29 is the hydrophilic concept map of the photocatalysis body of explanation present embodiment.Numbering 96 is for dripping to the water droplet on the photocatalysis membrana 95.The contact angle θ of photocatalysis membrana 95 and water droplet 96 confirms photocatalysis membrana 95 possess hydrophilic properties under the situation below 60 °.Also have, the L among the figure is a tangent line.
As from the foregoing, the photocatalyst product of present embodiment also is applicable to sterilizing use, because possess hydrophilic property, not only for gas componant, also going for need be to the purposes of the photocatalysis effect of the aqueous solution.
Also have, the present invention is not limited to above-mentioned embodiment, the implementation phase can change in the scope that does not exceed its main idea that to constitute unit usually specific.In addition, can form various inventions by the appropriate combination of a plurality of formation elements of being disclosed in the above-mentioned embodiment.For example, can from all the formation elements shown in the embodiment, remove several and constitute element.In addition, can make up formation element in the different embodiments.
Claims (15)
1. catalysis material, it is that the tungsten oxide powder that the light source with the light by sending the wavelength that contains 430～500nm is excited is the catalysis material of main component, it is characterized in that capacity of decomposition shown below is more than 50%;
[capacity of decomposition test]
In the glass container made of 3 liters of volumes, put into the tungsten oxide powder of quality 1g and the acetaldehyde of 20ppm (amount A), the capacity of decomposition (%) the during acetaldehyde (measure B) of the light of measuring the long 460nm ± 10nm of irradiation spike after 2 hours:
Capacity of decomposition (%)=[(acetaldehyde amount A-acetaldehyde amount B)/acetaldehyde amount A] * 100.
2. catalysis material as claimed in claim 1 is characterized in that, described light source is for using the light emitting diode of blue-light-emitting semiconductor element.
3. catalysis material as claimed in claim 1 is characterized in that, described light source is a sunshine.
4. catalysis material as claimed in claim 1 is characterized in that, described light source is a fluorescent lamp.
5. as each the described catalysis material in the claim 1～4, it is characterized in that the light quantity of the wavelength of 430～500nm is at 1mW/cm
2More than.
6. as each the described catalysis material in the claim 1～5, it is characterized in that described capacity of decomposition is 90%～100%.
7. catalysis material, it is to be the catalysis material of main component with the tungsten oxide particulate that the photocatalysis by visible light radiation excites, it is characterized in that, has following capacity of decomposition: in the airtight container of 3 liters of volumes, import 10ppm acetaldehyde, to the tungsten oxide particulate irradiation blue light of the quality 0.1g in this container, the survival rate of acetaldehyde reaches below 50% after 30 minutes.
8. catalysis material as claimed in claim 7 is characterized in that, the light source of emission blue light is near the light emitting diode that has the GaN class of glow peak 470nm.
9. as each the described catalysis material in the claim 1～8, it is characterized in that, is principal phase with the monoclinic crystal.
10. as each the described catalysis material in the claim 1～9, it is characterized in that average grain diameter is below 10 μ m.
11. the photocatalysis composition is characterized in that, comprises each the described catalysis material in the above claim 1～10 of 50 quality %.
12. photocatalysis composition as claimed in claim 11 is characterized in that, comprises the titanium dioxide powder of less than 50 quality %.
13. photocatalyst product is characterized in that, uses claim 11 or 12 described photocatalysis compositions.
14. photocatalyst product as claimed in claim 13 is characterized in that, organic matter, NOx, SOx at least a kind is had catalytic effect.
15. as claim 13 or 14 described photocatalyst products, it is characterized in that, make the photocatalysis composition bond in matrix surface by adhesive.
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| JP024918/2006 | 2006-02-01 | ||
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| CN102614865A (en) * | 2012-02-09 | 2012-08-01 | 上海师范大学 | Preparation method for nano-single crystal tungsten trioxide visible-light catalyst with controllable (001) crystal surface |
| WO2014141694A1 (en) * | 2013-03-12 | 2014-09-18 | 株式会社 東芝 | Photocatalyst and photocatalyst dispersion using same, photocatalyst coating, photocatalyst film, and product |
| JP6989421B2 (en) * | 2018-03-13 | 2022-01-05 | 株式会社東芝 | Photocatalyst dispersion, photocatalyst composite material and photocatalyst device |
| CN109126764B (en) * | 2018-09-13 | 2021-04-23 | 西北工业大学 | Preparation method of monodisperse black bismuth vanadate colloidal particles |
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| CN102266783A (en) * | 2011-06-23 | 2011-12-07 | 浙江大学 | Iron-doped tungsten trioxide photocatalyst and preparation method thereof |
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