CN101596460A - Photocatalyst dispersion liquid and manufacture method thereof - Google Patents

Photocatalyst dispersion liquid and manufacture method thereof Download PDF

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Publication number
CN101596460A
CN101596460A CNA2009101455893A CN200910145589A CN101596460A CN 101596460 A CN101596460 A CN 101596460A CN A2009101455893 A CNA2009101455893 A CN A2009101455893A CN 200910145589 A CN200910145589 A CN 200910145589A CN 101596460 A CN101596460 A CN 101596460A
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dispersion liquid
tungsten oxide
oxide particle
photocatalyst
titanium particles
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酒谷能彰
奥迫显仙
村田诚
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Abstract

The invention provides a kind of photocatalyst dispersion liquid and manufacture method thereof.Described photocatalyst dispersion liquid contains Titanium particles, tungsten oxide particle, phosphoric acid (salt) and decentralized medium, and wherein, the content of phosphoric acid (salt) is 0.001～0.2 mole times with respect to Titanium particles.In this photocatalyst dispersion liquid, the aggegation of particle is suppressed and the difficult Separation of Solid and Liquid that takes place.The manufacture method of this photocatalyst dispersion liquid is dispersed in Titanium particles to be dissolved with in the decentralized medium of phosphoric acid (salt) and obtains the Titanium particles dispersion liquid, and with resulting Titanium particles dispersion liquid and tungsten oxide mix particles.

Description

Photocatalyst dispersion liquid and manufacture method thereof
Technical field
The present invention relates to contain the photocatalyst dispersion liquid and the manufacture method thereof of Titanium particles and tungsten oxide particle.
Background technology
When the light time that has the energy more taller than band gap to the semiconductor irradiation, the electronics of valence band is excited to conduction band, generates the hole at valence band, generates electronics at conduction band.This hole and electronics have strong oxidizing force and reducing power respectively, so that the molecular species that contacts with semiconductor suffers redox.This redox is called as photocatalysis, can show that the semiconductor of this photocatalysis is called as photochemical catalyst.As such photochemical catalyst, known have emboliform materials such as Titanium particles or tungsten oxide particle.
Photocatalyst oxidizes titanium particle, photocatalyst oxidizes tungsten particle are scattered in the decentralized medium usually, be used to form photocatalyst layer as photocatalyst dispersion liquid, for example disclose the photocatalyst dispersion liquid (spy opens the 2005-231935 communique) that Titanium particles and tungsten oxide particle is scattered in obtain in the decentralized medium.Be coated with this photocatalyst dispersion liquid by surface, can easily form the photocatalyst layer that contains Titanium particles and tungsten oxide particle and display light catalytic action at substrate surface at base material.
Summary of the invention
But, make Titanium particles and tungsten oxide particle be scattered in the photocatalyst dispersion liquid in the past that obtains in the decentralized medium, there is the mutual aggegation of so-called particle and the shortcoming of Separation of Solid and Liquid takes place easily.For example, if during carrying, taking care of photocatalyst dispersion liquid, particle generation aggegation in this dispersion liquid and Separation of Solid and Liquid occurs, then in that dispersion liquid to be applied to base material first-class and when forming photocatalyst layer, can't form good film, its result can cause the problem that what is called can't be given sufficient photocatalytic activity.
The objective of the invention is to, the aggegation that a kind of particle is provided is suppressed and is difficult for causing the photocatalyst dispersion liquid and the manufacture method thereof of Separation of Solid and Liquid.
The inventor etc. concentrate on studies repeatedly in order to address the above problem.Its result, if find Titanium particles and tungsten oxide particle being scattered in the decentralized medium in the dispersion liquid that obtains, make with respect to Titanium particles to be phosphoric acid (salt) coexistence of specified quantitative, then the aggegation of particle is suppressed.And then also find, at this moment, phosphoric acid (salt) is present near the Titanium particles, this is effective suppressing aspect the particles aggregate, so be present near the dispersion liquid of Titanium particles in order to obtain phosphoric acid (salt), as long as before mixed oxidization titanium particle and tungsten oxide particle, Titanium particles is scattered in phosphoric acid (salt) solution gets final product.The present invention just is being based on these viewpoints and the invention finished.
That is, photocatalyst dispersion liquid of the present invention contains Titanium particles, tungsten oxide particle, phosphoric acid (salt) and decentralized medium, it is characterized in that, the content of phosphoric acid (salt) is 0.001 mole times～0.2 mole times with respect to Titanium particles.
The manufacture method of photocatalyst dispersion liquid of the present invention is characterized in that, Titanium particles is scattered in be dissolved with in the decentralized medium of phosphoric acid (salt) and obtains the Titanium particles dispersion liquid, and with resulting Titanium particles dispersion liquid and tungsten oxide mix particles.
Photocatalyst functional product of the present invention is the photocatalyst functional product that possesses photocatalyst layer on the surface, it is characterized in that, photocatalyst layer is to use photocatalyst dispersion liquid of the present invention to form.
By the present invention, the aggegation that particle can be provided is suppressed and is difficult for causing the photocatalyst dispersion liquid and the manufacture method thereof of Separation of Solid and Liquid.And, if use this photocatalyst dispersion liquid, then can easily form the photocatalyst layer that shows highlight catalytic active.
The specific embodiment
(photocatalyst dispersion liquid)
Photocatalyst dispersion liquid of the present invention contains Titanium particles, tungsten oxide particle, phosphoric acid (salt) and decentralized medium.That is to say that photocatalyst dispersion liquid of the present invention is to be dispersed in the dispersion liquid that forms in the decentralized medium as Titanium particles and tungsten oxide particle with photochemical catalyst of photocatalysis in the presence of phosphoric acid (salt).At this moment, near the phosphoric acid that exists Titanium particles (salt) becomes the state on the surface that is adsorbed on Titanium particles.The Titanium particles of this state is difficult for and tungsten oxide particle generation aggegation, so photocatalyst dispersion liquid of the present invention becomes the dispersion liquid that particles aggregate is inhibited.In addition, phosphoric acid (salt) is present near the photocatalyst dispersion liquid the Titanium particles, for example can easily obtain by the manufacture method of photocatalyst dispersion liquid of the present invention described later.
Constitute the Titanium particles of photocatalyst dispersion liquid of the present invention, so long as demonstrate the emboliform titanium oxide of photocatalysis, just be not particularly limited, for example can enumerate the metatitanic acid particle, the crystal type is the titanium dioxide [TiO of Detitanium-ore-type, brookite type, rutile-type etc. 2] particle etc.It should be noted that Titanium particles can use separately, also two or more kinds may be used.
The metatitanic acid particle can make the method for its hydrolysis obtain by the aqueous solution that for example heats titanyl sulfate.
TiO 2 particles for example can obtain by method as follows etc.,, (i) does not heat the aqueous solution of titanyl sulfate or titanium chloride that is, to wherein adding alkali, obtains sediment thus, the method that the sediment that obtains is burnt till; The aqueous solution that (ii) adds water, aqueous acid or alkali in alkoxytitanium obtains sediment, the method that the sediment that obtains is burnt till; The (iii) method that metatitanic acid is burnt till.By the TiO 2 particles that these methods obtain, firing temperature or firing time in the time of can burning till by adjusting, and form the crystal type that Detitanium-ore-type, brookite type, rutile-type etc. need.
In addition, constitute the Titanium particles of photocatalyst dispersion liquid of the present invention, also can obtain by method as follows etc., that is, titanium compound and alkali are reacted, in the product that obtains, add ammonia, after the slaking, carry out Separation of Solid and Liquid, solid constituent is burnt till.In the method, as titanium compound, for example can use titanium trichloride [TiCl 3], titanium tetrachloride [TiCl 4], titanium sulfate [Ti (SO 4) 2MH 2O, 0≤m≤20], titanyl sulfate [TiOSO 4NH 2O, 0≤n≤20], titanium oxychloride [TiOCl 2] etc.Alkali as reacting with titanium compound for example can use NaOH, potassium hydroxide, sodium carbonate, potash, ammonia, hydrazine, hydroxylamine, MEA, non-ring type amines, ring type aliphatic amine compound etc.
Being reflected in the scope that above, the preferred pH3 of pH2 is above and pH7 is following, preferred pH5 is following of titanium compound and alkali carried out.In addition, the reaction temperature of this moment is generally below 90 ℃, and is preferred below 70 ℃, further preferred below 55 ℃.About the reaction of titanium compound and alkali,, also can in the presence of hydrogen peroxide, carry out in order to improve the comminuted of resulting titanium oxide.Slaking can followingly be carried out, for example, stir the product that is added with ammonia on the limit, the limit more than 0 ℃, preferred more than 10 ℃ and below 110 ℃, preferred below 80 ℃, more preferably the temperature range below 55 ℃ keep more than 1 minute, preferred more than 10 minutes and 10 hours with in interior, preferred 2 hours.The total amount of the alkali (ammonia) that uses in reaction and the slaking, get final product so long as surpass the amount that in the presence of water, makes titanium compound become the stoichiometry of the necessary alkali of titanium hydroxide, but the amount of alkali is many more, can become the photochemical catalyst that shows highlight catalytic active by the irradiation visible light more, so be generally more than 1.1 moles times, more preferably more than 1.5 moles times.On the other hand,, can not obtain and measure corresponding effects even if the amount of alkali is too much yet, thus be limited on it 20 moles doubly following and then to be 10 moles be suitable below doubly.
The Separation of Solid and Liquid of the product that has been ripened can be undertaken by pressure filtration, filtration under diminished pressure, centrifugation, decant etc.In Separation of Solid and Liquid, preferably carry out the operation that resulting solid constituent is cleaned altogether.About burning till through the solid constituent of Separation of Solid and Liquid, can use air-flow firing furnace, car tunnel furnace, revolving burner etc., usually more than 250 ℃, preferred more than 270 ℃ and below 600 ℃, preferred below 500 ℃, more preferably carry out in the temperature range below 400 ℃.Firing time is different because of the difference of the kind of firing temperature or burning apparatus, but is generally more than 10 minutes, is preferably more than 30 minutes, and in 30 hours, is preferably in 5 hours.In addition, for titanium oxide through being fired into, as required, can make the compound of the demonstration solid acid of its oxide that supports tungsten, niobium, iron, nickel or hydroxide etc. and so on, the compound of the demonstration solid alkaline of the oxide of lanthanum, cerium, calcium or hydroxide etc. and so on, the metallic compound of the absorption luminous ray of indium oxide, bismuth oxide and so on etc.
As the Titanium particles that constitutes photocatalyst dispersion liquid of the present invention, except above-mentioned, can also use the spy to open the 2001-72419 communique, the spy opens the 2001-190953 communique, the spy opens the 2001-316116 communique, the spy opens the 2001-322816 communique, the spy opens the 2002-29749 communique, the spy opens the 2002-97019 communique, the open text in the WO01/10552 world, the spy opens the 2001-212457 communique, the spy opens the 2002-239395 communique, the open text in the WO03/080244 world, the open text in the WO02/053501 world, the spy opens the 2007-69093 communique, ChemistryLetters, Vol.32, No.2, P.196-197 (2003), Chemistry Letters, Vol.32, No.4, P.364-365 (2003), Chemistry Letters, Vol.32, No.8, P.772-773 (2003), Chem.Mater., 17, the Titanium particles of record in (2005) etc. P.1548-1552.In addition, also can use by open 2001-278625 communique, spy the spy and open 2001-278626 communique, spy and open 2001-278627 communique, spy and open 2001-302241 communique, spy and open 2001-335321 communique, spy and open 2001-354422 communique, spy and open 2002-29750 communique, spy and open 2002-47012 communique, spy and open 2002-60221 communique, spy and open 2002-193618 communique, spy and open the Titanium particles that the method for record in the 2002-249319 communique etc. obtains.
Particle diameter to above-mentioned Titanium particles is not particularly limited, but from the viewpoint of photocatalysis, in the average mark shot directly, is generally 20nm～150nm, is preferably 40nm～100nm.
BET specific area to above-mentioned Titanium particles is not particularly limited, but from the viewpoint of photocatalysis, is generally 100m 2/ g～500m 2/ g, preferred 300m 2/ g～400m 2/ g.
Constitute the tungsten oxide particle of photocatalyst dispersion liquid of the present invention,, for example can enumerate tungstic acid [WO so long as the emboliform tungsten oxide of display light catalytic action just is not particularly limited 3] particle etc.It should be noted that the tungsten oxide particle can use separately, can also be also with more than 2 kinds.
The tungstic acid particle for example can obtain by method as follows etc., that is, (i) obtain as sedimentary wolframic acid and method that the wolframic acid that obtains is burnt till by add acid in the aqueous solution of tungstates; The (ii) method of carrying out thermal decomposition by heating ammonium metatungstate, ammonium paratungstate.
Particle diameter to above-mentioned tungsten oxide particle is not particularly limited, but from the viewpoint of photocatalysis, in the average mark shot directly, is generally 50nm～200nm, preferred 80nm～130nm.
BET specific area to above-mentioned tungsten oxide particle is not particularly limited, but from the viewpoint of photocatalysis, is generally 5m 2/ g～100m 2/ g, preferred 20m 2/ g～50m 2/ g.
In photocatalyst dispersion liquid of the present invention, the ratio of above-mentioned Titanium particles and above-mentioned tungsten oxide particle (Titanium particles: the tungsten oxide particle) by quality ratio, be generally 4: 1～1: 8, be preferably 2: 3～3: 2.
As the phosphoric acid (salt) that constitutes photocatalyst dispersion liquid of the present invention, can enumerate phosphoric acid or its ammonium salt, sodium salt, sylvite etc., ammonium phosphate salts such as wherein special preferably phosphoric acid ammonium dihydrogen, diammonium hydrogen phosphate.It should be noted that phosphoric acid (salt) can use separately, can also be also with more than 2 kinds.
In photocatalyst dispersion liquid of the present invention, the content of above-mentioned phosphoric acid (salt) is 0.001～0.2 mole times with respect to above-mentioned Titanium particles.Be preferably 0.01 mole doubly above and 0.1 mole doubly below.If the content of phosphoric acid (salt) less than 0.001 mole doubly, then can't fully suppress the aggegation of the particle in the dispersion liquid, on the other hand,, can not obtain and its amount effect further accordingly, so be disadvantageous economically even if surpass 0.2 mole doubly.
Constitute the decentralized medium of photocatalyst dispersion liquid of the present invention,, just be not particularly limited, use with the aqueous solvent of water usually as principal component so long as dissolve the solvent of above-mentioned phosphoric acid (salt).Particularly, decentralized medium can be that water is a kind of separately, also can be the mixed solvent of water and water-miscible organic solvent.Under the situation of the mixed solvent that makes water and water-miscible organic solvent, the content of preferred water is more than the 50 quality %.As water-miscible organic solvent, for example can enumerate water-soluble alcohol solvents such as methyl alcohol, ethanol, propyl alcohol, butanols, acetone, methyl ethyl ketone etc.It should be noted that decentralized medium can use separately, also two or more kinds may be used.
The content of above-mentioned decentralized medium is generally 5～200 quality doubly with respect to the total amount of Titanium particles and tungsten oxide particle, and preferred 10～100 quality doubly.If decentralized medium less than 5 quality doubly, then Titanium particles and the easy sedimentation of tungsten oxide particle on the other hand, if surpass 200 quality doubly, is disadvantageous aspect volume efficiency then, so all not preferred.
Photocatalyst dispersion liquid of the present invention preferably also contains electrophilic material or its precursor.The electrophilic material is meant the surface that is supported on photochemical catalyst (being Titanium particles and tungsten oxide particle) and the compound that can bring into play electrophilic, and the precursor of electrophilic material is meant the compound (for example penetrating the compound that can be reduced into the electrophilic material by illumination) that can be transformed into the electrophilic material on the surface of photochemical catalyst.If the electrophilic material is supported on the surface of photochemical catalyst and exists, then the irradiation by light is excited to the electronics of conduction band and the compound of hole that generate at valence band is suppressed, and can further improve photocatalysis.
Above-mentioned electrophilic material or its precursor contain preferably that more than one the metallic atom selected forms from Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and Co.Be more preferably that more than one the metallic atom that contains among Cu, Pt, Au and the Pd forms.For example, as above-mentioned electrophilic material, can enumerate oxide, hydroxide of the metal that constitutes by above-mentioned metallic atom or these metals etc., as the precursor of electrophilic material, can enumerate nitrate, sulfate, halide, acylate, carbonate, phosphate of the metal that constitutes by above-mentioned metallic atom etc.
As the preferred object lesson of electrophilic material, can enumerate metals such as Cu, Pt, Au, Pd.In addition, as the preferred object lesson of the precursor of electrophilic material,, can enumerate copper nitrate [Cu (NO as the precursor that contains Cu 3) 2], copper sulphate [CuSO 4], copper chloride [CuCl 2, CuCl], copper bromide [CuBr 2, CuBr], cupric iodide [CuI], cupric iodate [CuI 2O 6], copper ammonium chloride [Cu (NH 4) 2Cl 4], basic copper chloride [Cu 2Cl (OH) 3], copper acetate [CH 3COOCu, (CH 3COO) 2Cu], copper formate [(HCOO) 2Cu], copper carbonate [CuCO 3], cupric oxalate [CuC 2O 4], copper citrate [Cu 2C 6H 4O 7], cupric phosphate [CuPO 4] etc.; As the precursor that contains Pt, can enumerate platinum chloride [PtCl 2, PtCl 4], platinic bromide [PtBr 2, PtBr 4], platinum diiodide [PtI 2, PtI 4], potassium chloroplatinite [K 2(PtCl 4)], chloroplatinic acid [H 2PtCl 6], sulfurous acid platinum [H 3Pt (SO 3) 2OH], platinum oxide [PtO 2], chlorination four ammino platinum [Pt (NH 3) 4Cl 2], four ammino bicarbonate platinum [C 2H 14N 4O 6Pt], four ammino phosphoric acid hydrogen platinum [Pt (NH 3) 4HPO 4], four ammino platinic hydroxide [Pt (NH 3) 4(OH) 2], four ammino platinum nitrate [(Pt (NO 3) 2(NH 3) 4], four ammino platinum platinum tetrachloride [(Pt (NH 3) 4) (PtCl 4)] etc.; As the precursor that contains Au, can enumerate chlorauride [AuCl], gold bromide [AuBr], auric iodide [AuI], gold hydroxide [Au (OH) 2)], tetra chlorauric acid [HAuCl 4], gold potassium chloride [KAuCl 4], gold potassium bromide [KAuBr 4], gold oxide [Au 2O 3] etc.; As the precursor that contains Pd, for example can enumerate acid chloride [(CH 3COO) 2Pd], palladium bichloride [PdCl 2], palladium bromide [PdBr 2], palladium iodide [PdI 2], palladium dydroxide [Pd (OH) 2], palladium nitrate [Pd (NO 3) 2], palladium oxide [PdO], palladium sulfate [PdSO 4], tetrachloro-palladium potassium chlorate [K 2(PdCl 4)], tetrabromo palladium acid potassium [K 2(PdBr 4)], four ammino palladium chloride [Pd (NH 3) 4Cl 2], four ammino palladium bromide [Pd (NH 3) 4Br 2], four ammino palladium nitrate [Pd (NH 3) 4(NO 3) 2], four ammino palladium tetrachloro-palladium acid [(Pd (NH 3) 4) (PdCl 4)], tetrachloro-palladium acid ammonium [(NH 4) 2PdCl 4] etc.It should be noted that electrophilic material or its precursor can be distinguished separately uses, and also two or more kinds may be used.In addition, can certainly and use electrophilic material more than a kind and the precursor more than a kind.
Under the situation that also contains above-mentioned electrophilic material or its precursor, its content is pressed the metal atom and is converted, and measures 100 mass parts with respect to the total of Titanium particles and tungsten oxide particle, is generally 0.005～0.6 mass parts, preferred 0.01～0.4 mass parts.If electrophilic material or its precursor, then might fully obtain the raising effect of the photocatalytic activity that the electrophilic material brings less than 0.005 mass parts, on the other hand, if surpass 0.6 mass parts, photocatalysis might reduce on the contrary.
In the scope of not damaging effect of the present invention, photocatalyst dispersion liquid of the present invention can contain known in the past various additives.It should be noted that additive can be distinguished separately uses, and also two or more kinds may be used.
As above-mentioned additive, for example can enumerate to improve photocatalysis is the additive that purpose is added.To improve effect with photocatalysis be the additive of purpose as such, specifically can enumerate silicon compounds such as amorphous silicon di-oxide, silicon dioxide gel, waterglass, organopolysiloxane; Aluminium compounds such as amorphous state aluminium oxide, alumina sol, aluminium hydroxide; The aluminosilicate of zeolite, kaolinite and so on; Alkaline earth oxide or alkaline earth metal hydroxides such as magnesia, calcium oxide, strontium oxide strontia, barium monoxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide; The condensation polymer of calcium phosphate, molecular sieve, active carbon, organopolysiloxane compound, phosphate, fluorine based polymer, silicon based polymer, acrylic resin, mylar, melmac, polyurethane resin, alkyd resins etc.
And then, as above-mentioned additive, also can use when photocatalyst dispersion liquid is coated substrate surface, to be used to make adhesive that photochemical catalyst (Titanium particles and tungsten oxide particle) remains on substrate surface more firmly etc. (for example to open flat 8-67835 communique with reference to the spy, Te Kaiping 9-25437 communique, Te Kaiping 10-183061 communique, Te Kaiping 10-183062 communique, Te Kaiping 10-168349 communique, Te Kaiping 10-225658 communique, Te Kaiping 11-1620 communique, Te Kaiping 11-1661 communique, the spy opens the 2004-059686 communique, the spy opens the 2004-107381 communique, the spy opens the 2004-256590 communique, the spy opens the 2004-359902 communique, the spy opens the 2005-113028 communique, the spy opens the 2005-230661 communique, the spy opens 2007-161824 communique etc.).
Photocatalyst dispersion liquid of the present invention, its hydrogen ion concentration is generally pH2.0～pH7.0, preferred pH3.0～pH6.0.If hydrogen ion concentration is less than pH2.0, then acidly cross by force and cumbersome on handling, on the other hand,, then might dissolve by the tungsten oxide particle, so all not preferred if surpass pH7.0.The hydrogen ion concentration of photocatalyst dispersion liquid can be regulated by adding acid usually.As the acid that can be used to regulate hydrogen ion concentration, for example can enumerate nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetate, oxalic acid etc.
(manufacture method of photocatalyst dispersion liquid)
The manufacture method of photocatalyst dispersion liquid of the present invention is following method: Titanium particles is dispersed in is dissolved with in the decentralized medium of phosphoric acid (salt), and with resulting Titanium particles dispersion liquid and tungsten oxide mix particles.So, it is scattered in the decentralized medium that is dissolved with phosphoric acid (salt), the surface of Titanium particles becomes the state that is adsorbed with phosphoric acid (salt) thus.The Titanium particles of this state is difficult for and the tungsten oxide particles aggregate, so the particles aggregate of the photocatalyst dispersion liquid that obtains by manufacture method of the present invention is inhibited.
When obtaining the Titanium particles dispersion liquid in the decentralized medium that Titanium particles is dispersed in be dissolved with phosphoric acid (salt), preferred further enforcement dispersion treatment after both are mixed.Dispersion treatment for example can adopt known method in the past such as working medium stirring-type dispersion machine.In addition, when preparation made Titanium particles decentralized medium that disperse, that contain phosphoric acid (salt), the use amount of phosphoric acid (salt) was so long as get final product at the content range of the phosphoric acid (salt) described in (photocatalyst dispersion liquid).
Above-mentioned tungsten oxide particle can directly be mixed in the above-mentioned Titanium particles dispersion liquid, but preferably makes it be scattered in to make in the decentralized medium and mix with above-mentioned Titanium particles dispersion liquid after the tungsten oxide particle dispersion.When making the tungsten oxide particle be scattered in the decentralized medium, preferably after being mixed, both further implement dispersion treatment.Dispersion treatment for example can adopt known method in the past such as working medium stirring-type dispersion machine.
In addition, under the situation of mixed oxidization titanium particle dispersion liquid and tungsten oxide particle dispersion, about the kind of the decentralized medium that uses in two dispersion liquids, as long as mixed decentralized medium be at the decentralized medium described in (photocatalyst dispersion liquid) item, just can be identical, also can be different.In addition, about the use amount of decentralized medium in two dispersion liquids, as long as the content of decentralized medium just is not particularly limited for the scope described in (photocatalyst dispersion liquid) item in the photocatalyst dispersion liquid that finally obtains.
When mixed oxidization titanium particle dispersion liquid and tungsten oxide particle, about both use amounts, as long as the ratio of Titanium particles and tungsten oxide particle is the scope described in (photocatalyst dispersion liquid) item.
The manufacture method of photocatalyst dispersion liquid of the present invention preferably includes the operation of adding electrophilic material or its precursor.Wherein, the interpolation of electrophilic material or its precursor can be carried out above-mentioned Titanium particles dispersion liquid, can also carry out above-mentioned tungsten oxide particle dispersion, can also carry out having mixed above-mentioned Titanium particles dispersion liquid and above-mentioned tungsten oxide particle dispersion or tungsten oxide particle dispersion liquid afterwards, but from obtaining the viewpoint of highlight catalytic active, preferred electrophilic material or its precursor add in the above-mentioned tungsten oxide particle dispersion.
In addition, under the situation of adding electrophilic material or its precursor, about its addition, as long as the content of electrophilic material or its precursor is the scope described in (photocatalyst dispersion liquid) in the photocatalyst dispersion liquid that finally obtains.
Under the situation of the precursor that has added above-mentioned electrophilic material, preferably after it adds, carry out illumination and penetrate.Light as irradiation is not particularly limited, and can be luminous ray, also can be ultraviolet ray.Penetrate by carrying out illumination, the electron reduction that precursor is generated by optical excitation becomes the electrophilic material, and is supported on the surface of photocatalyst particles (Titanium particles and tungsten oxide particle).In addition, under the situation of having added above-mentioned precursor, do not penetrate, be transformed into the electrophilic material in the moment yet, so its photo-catalysis capability can be not impaired to the photocatalyst layer irradiates light that forms by the photocatalyst dispersion liquid that obtains even if do not carry out illumination.
Penetrate about above-mentioned illumination,, preferably before the mixing of Titanium particles dispersion liquid and tungsten oxide particle, carry out to good so long as after the interpolation of above-mentioned precursor, can carry out in any stage.
In addition, under the situation of the precursor that has added above-mentioned electrophilic material,, also can before penetrating, illumination in the scope of not damaging effect of the present invention, suitably add methyl alcohol, ethanol, oxalic acid etc. in order to obtain the electrophilic material more efficiently.
In addition, in the manufacture method of photocatalyst dispersion liquid of the present invention, also can be added on the various additives described in (photocatalyst dispersion liquid) item.At this moment, the interpolation of these additives can be carried out in any stage, but for example preferably carries out after mixed oxidization titanium particle dispersion liquid and tungsten oxide particle dispersion or tungsten oxide particle.
(photocatalyst functional product)
Photocatalyst functional product of the present invention possesses the photocatalyst layer that the photocatalyst dispersion liquid that uses the invention described above forms on the surface.Wherein, photocatalyst layer by the photochemical catalyst of display light catalytic action, be that Titanium particles and tungsten oxide particle form.In addition, contain at photocatalyst dispersion liquid of the present invention under the situation of electrophilic material or its precursor, this electrophilic material or its precursor are supported on the surface of Titanium particles and tungsten oxide particle.In addition, for example changed into the electrophilic material by the precursor that supported by irradiates light etc.
Above-mentioned photocatalyst layer for example can form by make known in the past film build methods such as decentralized medium volatilization after the surface that photocatalyst dispersion liquid of the present invention is coated on base material (product).Thickness to photocatalyst layer is not particularly limited, usually according to its purposes etc., as long as suitably set hundreds of nm～number mm for.About photocatalyst layer, so long as the inner surface or the outer surface of base material (product), just can be formed on arbitrary portion, for example, be preferably formed on the face as described below, that is, this face by the face of light (luminous ray) irradiation and be with the place that produces odorant continuously or the three-dimensional intermittently face that is connected.In addition, material about base material (product), as long as can keep formed photocatalyst layer with the intensity that can tolerate practical use, just be not particularly limited, can be object for example with the product that forms by all materials such as plastics, metal, pottery, timber, concrete, paper.
Object lesson as photocatalyst functional product of the present invention, for example can enumerate building goods, materials and equipments such as ceiling material, ceramic tile, glass, wallpaper, materials for wall, floor, automobile inside material (automobile instrument board, automobile sheet material, automobile ceiling material), household appliances such as refrigerator, air-conditioning, fiber products such as clothes, curtain etc.
Photocatalyst functional product of the present invention is certainly penetrated by illumination without and is demonstrated high catalytic action, even if in the environment of only accepting from the light of the visible light source of fluorescent lamp, sodium vapor lamp and so within doors, penetrates by illumination and also to demonstrate high catalytic action.Therefore, go up and make its drying if photocatalyst dispersion liquid of the present invention is coated the ceiling material, ceramic tile, glass etc. of hospital for example, by penetrating based on the illumination of illumination within doors, the concentration of odorants such as volatile organic matters such as formaldehyde, acetaldehyde, aldehydes, thio-alcohol, ammonia, nitrogen oxide is reduced, and then pathogens such as staphylococcus aureus, Escherichia coli etc. can be killed.
Below, describe the present invention in detail by embodiment, but the present invention is not limited to them.
In addition, about the mensuration of each rerum natura in embodiment and the comparative example and the evaluation of photocatalytic activity thereof, utilize following method to carry out.
＜crystal type 〉
Use X-ray diffraction device (corporate system of science " RINT2000/PC ") to measure X-ray diffraction spectrum, determine the crystal type by this spectrum.
＜BET specific area 〉
Use specific area measuring device (the shallow Ionics corporate system of soup " MONOSORB "), utilize nitrogen adsorption method to measure.
＜average mark shot footpath 〉
Use submicron particle size measure of spread device (Coulter corporate system " N4Plus ") to measure size distribution, the software that utilization is attached to this device carries out result that single decentralized model analysis obtains automatically as average mark shot footpath (nm).
The evaluation of＜photocatalytic activity: the decomposition of acetaldehyde 〉
Photocatalytic activity is to estimate by the first order reaction velocity constant in the acetaldehyde decomposition reaction under the irradiation of the light that is determined at fluorescent lamp.
At first, make the sample that photocatalytic activity is measured usefulness.That is, the dripping quantity that converts by solid constituent according to the per unit area of bottom surface is 1g/m 2Mode, drip resulting photocatalyst dispersion liquid to glass system ware (external diameter 70mm, internal diameter 66mm, height 14mm, the about 48mL of capacity), form uniform mode according to whole bottom surface and launch at ware.Then,, make its drying thus in atmosphere, form photocatalyst layer in the bottom surface of glass system ware by in 110 ℃ drying machine, this ware being kept 1 hour.According to making uitraviolet intensity become 2mW/cm 2Mode to the irradiation of this photocatalyst layer from the ultraviolet ray of black light 16 hours, it is measured as photocatalytic activity uses sample.
Then, this photocatalytic activity mensuration is connected ware with sample to be put in the airbag (internal volume 3L) also airtight together, then, in making this airbag, form after the vacuum, the volume ratio of enclosing oxygen and nitrogen is 1: 4 mist 1.8L, and then enclose the nitrogen 9mL that contains acetaldehyde with 1 capacity % therein, in the dark and at room temperature kept 1 hour.Subsequently, with commercially available white fluorescent lamp is light source, is the mode of 1000 luxs (using Minolta (Minolta) corporate system illumination photometer " T-10 " to measure) according to making mensuration with near the illumination the sample, from the light of airbag external exposure fluorescent lamp, carries out the decomposition reaction of acetaldehyde.At this moment, measuring near the ultraviolet light intensity of sample is 6.5 μ W/cm 2(measuring after Pu Kang (Topcon) corporate system ultraviolet ray intensity meter " UVR-2 " is installed the said firm's system light accepting part " UD-36 ") to opening up.After the illumination of beginning fluorescent lamp is penetrated, the gas in the airbag taken a sample in per 1.5 hours, measure the concentration of acetaldehyde with gas chromatography (Shimadzu Seisakusho Ltd.'s corporate system " GC-14A ").In addition, calculate the first order reaction velocity constant with respect to the remaining concentration of irradiation time, it is estimated as acetaldehyde decomposition ability by acetaldehyde.We can say that this first order reaction velocity constant is big more, the capacity of decomposition of acetaldehyde (being photocatalytic activity) is high more.
The evaluation of＜photocatalytic activity: the decomposition of formaldehyde 〉
Photocatalytic activity is to estimate by the first order reaction velocity constant in the formaldehyde decomposition reaction under the irradiation of the light that is determined at fluorescent lamp.
At first, make the sample that photocatalytic activity is measured usefulness.That is, the dripping quantity that converts by solid constituent according to the per unit area of bottom surface is 1g/m 2Mode, drip resulting photocatalyst dispersion liquid to glass system ware (external diameter 70mm, internal diameter 66mm, height 14mm, the about 48mL of capacity), form uniform mode according to whole bottom surface and launch at ware.Then, in 110 ℃ drying machine, this ware was kept in atmosphere 1 hour, make its drying thus, formed photocatalyst layer in the bottom surface of glass system ware.According to making uitraviolet intensity become 2mW/cm 2Mode,, it is measured as photocatalytic activity uses sample from the ultraviolet ray of black light 16 hours to the irradiation of this photocatalyst layer.
Then, this photocatalytic activity mensuration is connected ware with sample to be put in the airbag (internal volume 1L) also airtight together, then, in making this airbag, form after the vacuum, enclose oxygen 0.12L, and then enclose the nitrogen 0.48L that contains formaldehyde with concentration 100ppm therein, in the dark and at room temperature kept 45 minutes.Subsequently, be light source with commercially available white fluorescent lamp, be the mode of 6000 luxs (using Minolta corporate system illumination photometer " T-10 " to measure) according to making mensuration with near the illumination the sample, from the light of airbag external exposure fluorescent lamp, carry out the decomposition reaction of formaldehyde.At this moment, measuring near the ultraviolet light intensity of sample is 40 μ W/cm 2(measuring) to opening up general health corporate system ultraviolet ray intensity meter " UVR-2 " installation the said firm's system light accepting part " UD-36 ".After the illumination of beginning fluorescent lamp is penetrated, the gas in the airbag taken a sample in per 15 minutes, measure the concentration of formaldehyde with gas chromatography (Agilent Technologies corporate system " Agilent 3000Micro GC ").In addition, calculate the first order reaction velocity constant with respect to the remaining concentration of irradiation time, it is estimated as the formaldehyde capacity of decomposition by formaldehyde.We can say that this first order reaction velocity constant is big more, the capacity of decomposition of formaldehyde (being photocatalytic activity) is high more.
(preparation of Production Example 1-Titanium particles dispersion liquid)
To possessing the pH electrode and being connected with this pH electrode and having the reaction vessel supplying with 25 quality % ammoniacal liquor and pH is adjusted to the pH controller of constant mechanism (promptly, in this reaction vessel, if the pH of the liquid in the container is lower than setting value, then begin to supply with ammoniacal liquor, and supply reaches setting value until pH continuously), add ion exchange water 30kg, the setting value that makes the pH controller is pH4.On the other hand, making after titanyl sulfate 75kg is dissolved in ion exchange water 50kg, under cooling, in the aqueous solution that obtains, add 35% aquae hydrogenii dioxidi 30kg, the preparation mixed solution.To stirring in the above-mentioned reaction vessel, to this reaction vessel was added this mixed solution with 530mL/ minute in the limit with 42rpm on the limit, and itself and the ammoniacal liquor that offers reaction vessel by the pH controller are reacted.At this moment, reaction temperature (internal temperature of reaction vessel) is 20 ℃～30 ℃ a scope.After the interpolation of mixed solution finished, then, limit stirring reaction container inner edge kept 1 hour, then, supplied with 25 quality % ammoniacal liquor, obtained the pulpous state product.Filter resulting pulpous state product, flushing obtains solids (filter cake) after cleaning.In addition, the total amount that offers the ammoniacal liquor of reaction vessel is 90kg, is 2 times for titanyl sulfate being transformed into the necessary theoretical amount of titanium hydroxide.
Each 2.3kg of the solids (filter cake) that obtains in above-mentioned divided to open be encased in 12 stainless steel tubbing and (among the 30cm * 40cm), these 12 buckets put into box drying machine (rising sun section length of schooling " SupertempOven HP-60 ", internal volume: 216 liters), at 40m 3The dry air circulation of/hr after 115 ℃ keep 5 hours down, then kept 5 hours down at 250 ℃ down, carried out drying thus, and obtaining the BET specific area is 18.0m 2The dried powder of/g.Maximum steam partial pressure in the drying machine of this moment is 27.4kPa.Under 350 ℃ air atmosphere, the dried powder that obtains was burnt till 2 hours, subsequently, be cooled to room temperature, obtain adding up to 22kg as the titanium dioxide powder of particle shape photochemical catalyst.
Then, dissolving phosphoric acid ammonium dihydrogen 950g in ion exchange water 87.6kg (with the light special grade chemical), and then add the titanium dioxide powder 22kg that obtains in above-mentioned, obtain mixture.Working medium stirring-type dispersion machine (Sinmal Enterprises system " DYNOMILL KDL-PILOT A type ") carries out dispersion treatment with following condition to this mixture, obtains the Titanium particles dispersion liquid.
Decentralized medium: the zirconia system pearl 4.2kg of diameter 0.3mm
Treatment temperature: 20 ℃
Add up to the processing time: about 240 minutes
Mixing speed: peripheral speed 8m/ second
Flow velocity: 2L/ minute
Treatment fluid circulation: have
And then working medium stirring-type dispersion machine (the KOTOBUKI skill is ground corporate system " ULTRAAPEX MILL UAM-5 ") is implemented secondary dispersion treatment with following condition to the Titanium particles dispersion liquid that obtains in above-mentioned.
Decentralized medium: the zirconia system pearl 13kg of diameter 0.05mm
Treatment temperature: 20 ℃
Add up to the processing time: about 400 minutes
Rotating speed: 2000rpm
Flow velocity: 1L/ minute
Treatment fluid circulation: have
The content of ammonium phosphate salt is 0.03 mole times with respect to Titanium particles in the Titanium particles dispersion liquid that obtains.In addition, the dispersion liquid that obtains in above-mentioned is carried out centrifugation, remove coarse component, the average mark shot directly is 84nm.In addition, be the mode of 10 quality % according to the solid component concentration that makes the dispersion liquid that obtains, water is regulated, and the pH of this dispersion liquid is 6.9 as a result.In addition, for the solid constituent in the dispersion liquid after solid constituent in the mixture before the dispersion treatment and the dispersion treatment (above-mentioned secondary dispersion treatment), measure X-ray diffraction spectrum respectively and compare, the crystal type is Detitanium-ore-type as a result, does not see the variation of the crystal type that is caused by dispersion treatment.
(preparation of Production Example 2-tungsten oxide particle dispersion)
In air, under 700 ℃ ammonium paratungstate (Japanese inorganic chemistry system) was burnt till 6 hours, obtain tungsten oxide powder as particle shape photochemical catalyst.
Then, in ion exchange water 4kg, add the tungsten oxide powder 1kg that obtains in above-mentioned, obtain mixture.Working medium stirring-type dispersion machine (the KOTOBUKI skill is ground corporate system " ULTRAAPEX MILL UAM-1 ") carries out dispersion treatment with following condition to this mixture, obtains the tungsten oxide particle dispersion.
Decentralized medium: the zirconia system pearl 1.85kg of diameter 0.05mm
Mixing speed: peripheral speed 12.6m/ second
Flow velocity: 0.25L/ minute
Add up to the processing time: about 50 minutes
The average mark shot of tungsten oxide particle directly is 114nm in the tungsten oxide particle dispersion that obtains.In addition, be the mode of 10 quality % according to the solid component concentration that makes the dispersion liquid that obtains, water is regulated, and the pH of this dispersion liquid is 3.0.In addition, be 34m by the BET specific area of the part of this dispersion liquid being carried out the solid constituent that vacuum drying obtains 2/ g.In addition, for solid constituent in the mixture before the dispersion treatment and the solid constituent in the dispersion liquid after the dispersion treatment, measure X-ray diffraction spectrum respectively and compare, the crystal type is WO as a result 3, do not see the variation of the crystal type that causes by dispersion treatment.
(embodiment 1)
According to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), be blended in Titanium particles dispersion liquid that obtains in the Production Example 1 and the tungsten oxide particle dispersion that in Production Example 2, obtains, obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.8.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.095h as a result -1
(comparative example 1)
Use commercially available Titanium particles dispersion liquid (the former industry corporate system of stone " STS-01 ", to contain nitric acid, average mark shot footpath: 50nm), the Titanium particles dispersion liquid that replacement obtains in Production Example 1, in addition, the same with the operation of embodiment 1, obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 1.9.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, generated agglutination particle in result's keeping, Separation of Solid and Liquid has taken place.
(embodiment 2)
According to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), be blended in Titanium particles dispersion liquid that obtains in the Production Example 1 and the tungsten oxide particle dispersion that in Production Example 2, obtains.Then, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.03 mass parts with respect to total use amount 100 mass parts of Titanium particles and tungsten oxide particle by pt atom, and then, methyl alcohol added, make that its concentration is 5 quality % of whole solvents, obtains photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
And then, above-mentioned photocatalyst dispersion liquid 30g is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that extra-high-pressure mercury vapour lamp (Ushio motor system, lamp box: " MPL-25101 ", extra-high-pressure mercury vapour lamp: " USH-250BY ", lamp power supply: " HB-25103BY ") carried out 2 hours in the limit, thus the chloroplatinic acid in the photocatalyst dispersion liquid is reduced into platinum, obtains photocatalyst dispersion liquid.This pH through the postradiation photocatalyst dispersion liquid of light is 4.6.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.129h as a result -1
(embodiment 3)
Make chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution is as follows, that is, chloroplatinic acid converts, is 0.06 mass parts with respect to total use amount 100 mass parts of Titanium particles and tungsten oxide particle by pt atom, and is the same with the operation of embodiment 2 in addition, obtains photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
And then, above-mentioned photocatalyst dispersion liquid 30g is transferred to the 100mL beaker, equally with the operation of embodiment 2 carry out illumination and penetrate, thus the chloroplatinic acid in the photocatalyst dispersion liquid is reduced into platinum, obtain photocatalyst dispersion liquid.This pH through the postradiation photocatalyst dispersion liquid of light is 4.5.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.132h as a result -1
(embodiment 4)
Make chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution is as follows, that is, chloroplatinic acid converts, is 0.1 mass parts with respect to total use amount 100 mass parts of Titanium particles and tungsten oxide particle by pt atom, and is the same with the operation of embodiment 2 in addition, obtains photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
And then, above-mentioned photocatalyst dispersion liquid 30g is transferred to the 100mL beaker, equally with the operation of embodiment 2 carry out illumination and penetrate, thus the chloroplatinic acid in the photocatalyst dispersion liquid is reduced into platinum, obtain photocatalyst dispersion liquid.This pH through the postradiation photocatalyst dispersion liquid of light is 4.3.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.128h as a result -1
(embodiment 5)
Add tetra chlorauric acid (HAuCl 4) the aqueous solution replace chloroplatinic acid (H 2PtCl 6) aqueous solution, make tetra chlorauric acid convert, be 0.03 mass parts with respect to total use amount 100 mass parts of Titanium particles and tungsten oxide particle by gold atom, in addition the same with the operation of embodiment 2, obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
And then, above-mentioned photocatalyst dispersion liquid 30g is transferred to the 100mL beaker, equally with the operation of embodiment 2 carry out illumination and penetrate, thus the tetra chlorauric acid in the photocatalyst dispersion liquid is reduced into gold, obtain photocatalyst dispersion liquid.This pH through the postradiation photocatalyst dispersion liquid of light is 4.1.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.109h as a result -1
(embodiment 6)
In the tungsten oxide particle dispersion that in Production Example 2, obtains, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.03 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and then, methyl alcohol added, make its concentration become 6.5 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of chloroplatinic acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 3.3 mass parts (solid component concentration 3.3 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains chloroplatinic acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtain containing the tungsten oxide particle dispersion of platinum.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of platinum and in Production Example 1, obtain (thus, the content of platinum is pressed the pt atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.015 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.6.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.131h as a result -1
(embodiment 7)
Make chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution is as follows, that is, chloroplatinic acid converts, is 0.06 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and is the same with the operation of embodiment 6 in addition, obtains containing the tungsten oxide particle dispersion of chloroplatinic acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains chloroplatinic acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtain containing the tungsten oxide particle dispersion of platinum.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of platinum and in Production Example 1, obtain (thus, the content of platinum is pressed the pt atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.03 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.6.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.125h as a result -1
(embodiment 8)
Make chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution is as follows, that is, chloroplatinic acid converts, is 0.12 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and is the same with the operation of embodiment 6 in addition, obtains containing the tungsten oxide particle dispersion of chloroplatinic acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains chloroplatinic acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtain containing the tungsten oxide particle dispersion of platinum.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of platinum and in Production Example 1, obtain (thus, the content of platinum is pressed the pt atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.06 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.5.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.114h as a result -1
(embodiment 9)
Make chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution is as follows, that is, chloroplatinic acid converts, is 0.2 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and is the same with the operation of embodiment 6 in addition, obtains containing the tungsten oxide particle dispersion of chloroplatinic acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains chloroplatinic acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtain containing the tungsten oxide particle dispersion of platinum.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of platinum and in Production Example 1, obtain (thus, the content of platinum is pressed the pt atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.1 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.3.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.120h as a result -1
(embodiment 10)
In the tungsten oxide particle dispersion that in Production Example 2, obtains, add tetra chlorauric acid (HAuCl 4) the aqueous solution, make tetra chlorauric acid convert, be 0.03 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by gold atom, and then, methyl alcohol added, make its concentration become 6.5 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of tetra chlorauric acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 3.3 mass parts (solid component concentration 3.3 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains tetra chlorauric acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the tetra chlorauric acid in the dispersion liquid is reduced into gold, obtain containing the tungsten oxide particle dispersion of gold.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of gold and in Production Example 1, obtain (thus, the content of gold is pressed the gold atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.015 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.5.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.106h as a result -1
(embodiment 11)
Make tetra chlorauric acid (HAuCl 4) use amount of the aqueous solution is as follows, that is, tetra chlorauric acid converts, is 0.12 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by gold atom, and is the same with the operation of embodiment 10 in addition, obtains containing the tungsten oxide particle dispersion of tetra chlorauric acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains tetra chlorauric acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the tetra chlorauric acid in the dispersion liquid is reduced into gold, obtain containing the tungsten oxide particle dispersion of gold.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of gold and in Production Example 1, obtain (thus, the content of gold is pressed the gold atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.06 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.5.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.141h as a result -1
(embodiment 12)
Make tetra chlorauric acid (HAuCl 4) use amount of the aqueous solution is as follows, that is, tetra chlorauric acid converts, is 0.2 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by gold atom, and is the same with the operation of embodiment 10 in addition, obtains containing the tungsten oxide particle dispersion of tetra chlorauric acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, the above-mentioned tungsten oxide particle dispersion 22.5g that contains tetra chlorauric acid is transferred to the 100mL beaker, equally with the operation of embodiment 2 carries out illumination and penetrate, thus the tetra chlorauric acid in the dispersion liquid is reduced into gold, obtain containing the tungsten oxide particle dispersion of gold.
At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of gold and in Production Example 1, obtain (thus, the content of gold is pressed the gold atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.1 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 4.4.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.146h as a result -1
(preparation of Production Example 3-Titanium particles dispersion liquid)
Make ammonium dihydrogen phosphate (ADP) (with the light special grade chemical) the water-soluble 47.1g of 0.086g, the solids (filter cake) that mixes the metatitanic acid that the heating hydrolysis by titanyl sulfate obtains in the ammonium dihydrogen phosphate aqueous solution that obtains is (as TiO 2, solid component concentration is 46.8 quality %) and 12.82g.At this moment, the amount of ammonium dihydrogen phosphate (ADP) is 0.01 mole with respect to 1 mole of metatitanic acid.Working medium agitation type pulverizer (50 haze machinery productions made " 4TSG-1/8 ") carries out dispersion treatment with following condition to the mixture that obtains, and obtains the Titanium particles dispersion liquid.
Decentralized medium: the zirconia system pearl 190g of diameter 0.05mm
Treatment temperature: 20 ℃
Processing time: 1 hour
Rotating speed: 2000rpm
The average mark shot of Titanium particles directly is 92nm in the Titanium particles dispersion liquid that obtains, and the pH of dispersion liquid is 7.8.In addition, part to mixture before the dispersion treatment and the dispersion liquid after the dispersion treatment is carried out vacuum drying, obtain solid constituent, measure the X-ray diffraction spectrum of each solid constituent respectively and compare, the crystal type is Detitanium-ore-type as a result, does not see the variation of the crystal type that is caused by dispersion treatment.
(preparation of Production Example 4-tungsten oxide particle dispersion)
In ion exchange water 4kg, add as tungsten oxide powder (the Japanese inorganic chemistry system) 1kg of particle shape photochemical catalyst and mix, obtain mixture.Working medium stirring-type dispersion machine (the KOTOBUKI skill is ground corporate system " ULTRA APEX MILL UAM-1 ") carries out dispersion treatment with following condition to this mixture, obtains the tungsten oxide particle dispersion.
Decentralized medium: the zirconia system pearl 1.85kg of diameter 0.05mm
Mixing speed: peripheral speed 12.6m/ second
Flow velocity: 0.25L/ minute
Add up to the processing time: about 50 minutes
The average mark shot of tungsten oxide particle directly is 118nm in the tungsten oxide particle dispersion that obtains.In addition, the part of this dispersion liquid is carried out vacuum drying, obtain solid constituent, the BET specific area of the solid constituent that the result obtains is 40m 2/ g.In addition, mixture before the dispersion treatment is carried out vacuum drying equally, obtain solid constituent, for the solid constituent of the mixture before the dispersion treatment and the solid constituent of the dispersion liquid after the dispersion treatment, measure X-ray diffraction spectrum respectively and compare, the crystal type is WO as a result 3, do not see the variation of the crystal type that causes by dispersion treatment.At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
(embodiment 13)
In the tungsten oxide particle dispersion that in Production Example 4, obtains, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.12 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and then, methyl alcohol added, make its concentration become 6.25 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of chloroplatinic acid.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 11.4 mass parts (solid component concentration 11.4 quality %).
Then, the above-mentioned tungsten oxide particle dispersion 480g that contains chloroplatinic acid is transferred to the 1L beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 3 hours in the limit, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtains containing the tungsten oxide particle dispersion of platinum.This pH through the postradiation photocatalyst dispersion liquid of light is 2.4.At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of platinum and in Production Example 3, obtain (thus, the content of platinum is pressed the pt atom conversion in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.06 mass parts), obtain photocatalyst dispersion liquid.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (the total amount of Titanium particles and tungsten oxide particle) is 5 mass parts (solid component concentration 5 quality %), and pH is 3.6.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of acetaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.182h as a result -1
(embodiment 14)
The photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer that the photocatalyst dispersion liquid that use is obtained in Production Example 4 forms is estimated, and the first order reaction velocity constant is 0.644h as a result -1
(embodiment 15)
In the tungsten oxide particle dispersion that in Production Example 4, obtains, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.096 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and then, methyl alcohol added, make its concentration become 1.1 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of chloroplatinic acid.Water is adjusted to 10.2 mass parts (solid component concentration 10.2 quality %) with the solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts.
Then, the above-mentioned tungsten oxide particle dispersion 30g that contains chloroplatinic acid is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtains containing the tungsten oxide particle dispersion of platinum.
Then, in the above-mentioned tungsten oxide particle dispersion that contains platinum, add palladium bichloride (PdCl 2) aqueous hydrochloric acid solution (with PdCl 2Powder 0.252g is dissolved in the aqueous solution that is made of the aqueous hydrochloric acid solution 9.41g of concentration 1mol/L and water 90.43g), make palladium bichloride convert, be 0.024 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by the palladium atom, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the palladium bichloride in the dispersion liquid is reduced into palladium, obtains containing the tungsten oxide particle dispersion of palladium and platinum.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (with the total amount of tungsten oxide particle) is 10.0 mass parts (solid component concentration 10.0 quality %).This pH through the postradiation photocatalyst dispersion liquid of light is 2.2.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of palladium and platinum and in Production Example 3, obtain (thus, the platinum in the dispersion liquid and the content of palladium press platinum and the palladium atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are respectively 0.048 mass parts and 0.012 mass parts), obtain photocatalyst dispersion liquid.The solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts is adjusted to 5 mass parts (solid component concentration 5 quality %).PH is 3.9.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 1.05h as a result -1
(embodiment 16)
In the tungsten oxide particle dispersion that in Production Example 4, obtains, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.096 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, then, add the palladium bichloride (PdCl of embodiment 15 2) aqueous hydrochloric acid solution, make palladium bichloride convert, be 0.024 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by the palladium atom.Subsequently, further add methyl alcohol, make its concentration become 1.1 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of chloroplatinic acid and palladium bichloride.Water is adjusted to 10.0 mass parts (solid component concentration 10.0 quality %) with the solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts.
Then, the above-mentioned tungsten oxide particle dispersion 30g that contains chloroplatinic acid and palladium bichloride is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 1 hour in the limit, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, palladium bichloride is reduced into palladium, obtains containing the tungsten oxide particle dispersion of platinum and palladium.This pH through the postradiation photocatalyst dispersion liquid of light is 2.3.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of platinum and palladium and in Production Example 3, obtain (thus, the platinum in the dispersion liquid and the content of palladium press platinum and the palladium atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are respectively 0.048 mass parts and 0.012 mass parts), obtain photocatalyst dispersion liquid.The solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts is adjusted to 5 mass parts (solid component concentration 5 quality %).PH is 3.9.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.959h as a result -1
(embodiment 17)
In the tungsten oxide particle dispersion that in Production Example 4, obtains, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.048 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and then, methyl alcohol added, make its concentration become 1.1 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of chloroplatinic acid.Water is adjusted to 10.5 mass parts (solid component concentration 10.5 quality %) with the solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts.
Then, the above-mentioned tungsten oxide particle dispersion 30g that contains chloroplatinic acid is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtains containing the tungsten oxide particle dispersion of platinum.
Then, in the above-mentioned tungsten oxide particle dispersion that contains platinum, be added on the palladium bichloride (PdCl that uses among the embodiment 15 2) aqueous hydrochloric acid solution, make palladium bichloride convert, be 0.072 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by the palladium atom, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the palladium bichloride in the dispersion liquid is reduced into palladium, obtains containing the tungsten oxide particle dispersion of palladium and platinum.The solid constituent that contains in these photocatalyst dispersion liquid 100 mass parts (with the total amount of tungsten oxide particle) is 10.0 mass parts (solid component concentration 10.0 quality %).This pH through the postradiation photocatalyst dispersion liquid of light is 2.0.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of palladium and platinum and in Production Example 3, obtain (thus, the content of platinum and palladium is pressed platinum and the conversion of palladium atom in the dispersion liquid, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are respectively 0.024 mass parts and 0.036 mass parts), obtain photocatalyst dispersion liquid.The solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts is adjusted to 5 mass parts (solid component concentration 5 quality %).PH is 3.8.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.976h as a result -1
(embodiment 18)
In the tungsten oxide particle dispersion that in Production Example 4, obtains, add chloroplatinic acid (H 2PtCl 6) the aqueous solution, make chloroplatinic acid convert, be 0.024 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by pt atom, and then, methyl alcohol added, make its concentration become 1.1 quality % of whole solvents, obtain containing the tungsten oxide particle dispersion of chloroplatinic acid.Water is adjusted to 10.7 mass parts (solid component concentration 10.7 quality %) with the solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts.
Then, the above-mentioned tungsten oxide particle dispersion 30g that contains chloroplatinic acid is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the chloroplatinic acid in the dispersion liquid is reduced into platinum, obtains containing the tungsten oxide particle dispersion of platinum.
Then, in the above-mentioned tungsten oxide particle dispersion that contains platinum, be added on the palladium bichloride (PdCl that uses among the embodiment 15 2) aqueous hydrochloric acid solution, make palladium bichloride convert, be 0.096 mass parts with respect to use amount 100 mass parts of tungsten oxide particle by the palladium atom, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the palladium bichloride in the dispersion liquid is reduced into palladium, obtains containing the tungsten oxide particle dispersion of palladium and platinum.This pH through the postradiation photocatalyst dispersion liquid of light is 2.0.The solid constituent (amount of tungsten oxide particle) that contains in these dispersion liquid 100 mass parts is 10.0 mass parts (solid component concentration 10.0 quality %).
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned Titanium particles dispersion liquid that contains the tungsten oxide particle dispersion of palladium and platinum and in Production Example 3, obtain (thus, the platinum in the dispersion liquid and the content of palladium press platinum and the palladium atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are respectively 0.012 mass parts and 0.048 mass parts), obtain photocatalyst dispersion liquid.The solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts is adjusted to 5 mass parts (solid component concentration 5 quality %).PH is 3.7.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.982h as a result -1
(embodiment 19)
In the Titanium particles dispersion liquid that in Production Example 3, obtains, be added on the palladium bichloride (PdCl that uses among the embodiment 15 2) aqueous hydrochloric acid solution, make palladium bichloride convert, be 0.12 mass parts with respect to use amount 100 mass parts of Titanium particles by the palladium atom, and then, methyl alcohol added, make its concentration become 1.1 quality % of whole solvents, obtain containing the Titanium particles dispersion liquid of palladium bichloride.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (amount of Titanium particles) that contains in these dispersion liquid 100 mass parts.
Then, the above-mentioned Titanium particles dispersion liquid 30g that contains palladium bichloride is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 1 hour in the limit, thus the palladium bichloride in the dispersion liquid is reduced into palladium, obtains containing the Titanium particles dispersion liquid of palladium.This pH through the postradiation photocatalyst dispersion liquid of light is 7.3.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned tungsten oxide particle dispersion that contains platinum that contains the Titanium particles dispersion liquid of palladium and in embodiment 13, obtain (thus, the palladium in the dispersion liquid and the content of platinum press palladium and pt atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are 0.06 mass parts), obtain photocatalyst dispersion liquid.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts.PH is 3.8.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 1.08h as a result -1
(embodiment 20)
Mode according to the ratio 3: 1 (mass ratio) that makes Titanium particles and tungsten oxide particle, be blended in Titanium particles dispersion liquid that contains palladium that obtains among the embodiment 19 and the tungsten oxide particle dispersion that contains platinum that in embodiment 13, obtains (thus, the palladium in the dispersion liquid and the content of platinum press palladium and pt atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle are respectively 0.09 mass parts and 0.03 mass parts), obtain photocatalyst dispersion liquid.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts.PH is 4.5.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 1.79h as a result -1
(embodiment 21)
In the Titanium particles dispersion liquid that in Production Example 3, obtains, be added on the palladium bichloride (PdCl that uses among the embodiment 15 2) aqueous hydrochloric acid solution, make palladium bichloride convert, be 0.06 mass parts with respect to use amount 100 mass parts of Titanium particles by the palladium atom, and then, methyl alcohol added, make its concentration become 1.1 quality % of whole solvents, obtain containing the Titanium particles dispersion liquid of palladium bichloride.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (amount of Titanium particles) that contains in these dispersion liquid 100 mass parts.
Then, the above-mentioned Titanium particles dispersion liquid 30g that contains palladium bichloride is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 1 hour in the limit, thus the palladium bichloride in the dispersion liquid is reduced into palladium, obtains containing the Titanium particles dispersion liquid of palladium.This pH through the postradiation photocatalyst dispersion liquid of light is 7.8.
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned tungsten oxide particle dispersion that contains platinum that contains the Titanium particles dispersion liquid of palladium and in embodiment 13, obtain (thus, the palladium in the dispersion liquid and the content of platinum press palladium and pt atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle, palladium is 0.03 mass parts, and platinum is 0.06 mass parts), obtain photocatalyst dispersion liquid.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts.PH is 4.0.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.901h as a result -1
(embodiment 22)
According to the ratio that makes Titanium particles and tungsten oxide particle become 3: 1 mode of (mass ratio), be blended in Titanium particles dispersion liquid that contains palladium that obtains among the embodiment 19 and the tungsten oxide particle dispersion that contains platinum that in embodiment 13, obtains (thus, the palladium in the dispersion liquid and the content of platinum press palladium and pt atom converts, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle, be respectively 0.045 mass parts and 0.03 mass parts), obtain photocatalyst dispersion liquid.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts.PH is 4.8.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.978h as a result -1
(embodiment 23)
In the Titanium particles dispersion liquid that in Production Example 3, obtains, add tetra chlorauric acid (HAuCl 4) aqueous solution, make tetra chlorauric acid convert, be 0.06 mass parts with respect to use amount 100 mass parts of Titanium particles by gold atom, and then, methyl alcohol added, make its concentration become 1.1 quality % of whole solvents, obtain containing the Titanium particles dispersion liquid of tetra chlorauric acid.The solid constituent (amount of Titanium particles) that contains in these dispersion liquid 100 mass parts is 5.1 mass parts (solid component concentration 5.1 quality %).
Then, the above-mentioned Titanium particles dispersion liquid 30g that contains tetra chlorauric acid is transferred to the 100mL beaker, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the tetra chlorauric acid in the dispersion liquid is reduced into gold, obtains containing the Titanium particles dispersion liquid of gold.
Then, contain in the golden Titanium particles dispersion liquid, be added on the palladium bichloride (PdCl that uses among the embodiment 15 to above-mentioned 2) aqueous hydrochloric acid solution, make palladium bichloride convert, be 0.06 mass parts with respect to use amount 100 mass parts of Titanium particles by the palladium atom, stir on the limit, (ultraviolet ray irradiation) penetrated with the illumination that high-pressure mercury-vapor lamp (Ushio motor system, high-pressure mercury-vapor lamp: " UM-102 ", high-pressure mercury lamp light source device: " UM-103B-B ") carried out 30 minutes in the limit, thus the palladium bichloride in the dispersion liquid is reduced into palladium, obtains containing the Titanium particles dispersion liquid of palladium and gold.This pH through the postradiation photocatalyst dispersion liquid of light is 7.7.At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.The solid constituent (amount of Titanium particles) that contains in these dispersion liquid 100 mass parts is 5.00 mass parts (solid component concentration 5.00 quality %).
Then, according to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), mix the above-mentioned tungsten oxide particle dispersion that contains platinum that contains the Titanium particles dispersion liquid of palladium and gold and in embodiment 13, obtain (thus, the content of the gold in the dispersion liquid, palladium and platinum, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle, gold and palladium are scaled 0.03 mass parts by atom, platinum is scaled 0.06 mass parts by atom), obtain photocatalyst dispersion liquid.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts.PH is 4.2.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 1.20h as a result -1
(embodiment 24)
According to the ratio that makes Titanium particles and tungsten oxide particle become 3: 1 mode of (mass ratio), be blended in Titanium particles dispersion liquid that contains palladium and gold that obtains among the embodiment 21 and the tungsten oxide particle dispersion that contains platinum that in embodiment 13, obtains (thus, the content of the gold in the dispersion liquid, palladium and platinum, total use amount 100 mass parts with respect to Titanium particles and tungsten oxide particle, the gold and palladium by atom be scaled 0.045 mass parts, platinum is scaled 0.03 mass parts by atom), obtain photocatalyst dispersion liquid.Water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in these photocatalyst dispersion liquid 100 mass parts.PH is 5.1.
Under 20 ℃, the photocatalyst dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 1.89h as a result -1
(embodiment 25)
According to the ratio that makes Titanium particles and tungsten oxide particle become 1: 1 mode of (mass ratio), be blended in Titanium particles dispersion liquid that obtains in the Production Example 3 and the tungsten oxide particle dispersion that in Production Example 4, obtains.Then, in this dispersion liquid, add chloroplatinic acid (H 2PtCl 6) aqueous solution and the palladium chloride aqueous solution that in embodiment 15, uses, make chloroplatinic acid and palladium bichloride convert, be respectively 0.048 mass parts and 0.012 mass parts, obtain containing the Titanium particles and the tungsten oxide particle dispersion of chloroplatinic acid and palladium bichloride with respect to total use amount 100 mass parts of Titanium particles and tungsten oxide particle by platinum and palladium atom.
In this dispersion liquid, add water, water is adjusted to 5 mass parts (solid component concentration 5 quality %) with the solid constituent (the total amount of Titanium particles and tungsten oxide particle) that contains in photocatalyst dispersion liquid 100 mass parts, obtains Titanium particles and tungsten oxide particle dispersion.PH is 3.8.At this constantly, under 20 ℃, the dispersion liquid that obtains was taken care of 3 hours, do not seen Separation of Solid and Liquid in result's keeping.In addition, the photocatalytic activity (decomposition of formaldehyde) that uses the photocatalyst layer that resulting photocatalyst dispersion liquid forms is estimated, the first order reaction velocity constant is 0.813h as a result -1
(reference example 1)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is applied to respectively on the ceiling material, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on the illumination of illumination within doors, can reduce the concentration of volatile organic matter such as formaldehyde, acetaldehyde, acetone, toluene in the space within doors, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 2)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on the ceramic tile respectively, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on the illumination of illumination within doors, can reduce the concentration of volatile organic matter such as formaldehyde, acetaldehyde, toluene, acetone in the space within doors, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 3)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on glass respectively, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on the illumination of illumination within doors, can reduce the concentration of volatile organic matter such as formaldehyde, acetaldehyde, toluene, acetone in the space within doors, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 4)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on the wallpaper respectively, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on the illumination of illumination within doors, can reduce the concentration of volatile organic matter such as formaldehyde, acetaldehyde, toluene, acetone in the space within doors, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 5)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on the floor respectively, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on the illumination of illumination within doors, can reduce the concentration of volatile organic matter such as formaldehyde, acetaldehyde, toluene, acetone in the space within doors, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 6)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on automobile with on instrument board, the surface of automobile with automobile inside materials such as sheet material, roof of the vehicle materials, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, penetrate by the illumination based on room light this moment, can reduce the concentration of volatile organic matters such as formaldehyde in the interior space, acetaldehyde, toluene, acetone, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 7)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on respectively on the surface of air-conditioning, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on the illumination of illumination within doors, can reduce the concentration of volatile organic matter such as formaldehyde, acetaldehyde, toluene, acetone in the space within doors, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.
(reference example 8)
The photocatalyst dispersion liquid that will obtain in embodiment 1～25 is coated on the refrigerator respectively, subsequently, dry and make the decentralized medium volatilization, form photocatalyst layer on the surface, this moment is by penetrating based on illumination within doors, the illumination of light source in the refrigerator, can reduce the concentration of volatile organic matter such as ethene in the refrigerator, the concentration of odorant, and then, pathogens such as staphylococcus aureus, Escherichia coli can be killed.

Claims (19)

1. a photocatalyst dispersion liquid contains Titanium particles, tungsten oxide particle, phosphoric acid (salt) and decentralized medium, it is characterized in that,
The content of described phosphoric acid (salt) is 0.001 mole times～0.2 mole times with respect to described Titanium particles, and wherein, described phosphoric acid (salt) is phosphoric acid and/or phosphate.
2. photocatalyst dispersion liquid according to claim 1, wherein,
Also contain electrophilic material or its precursor.
3. photocatalyst dispersion liquid according to claim 2, wherein,
Described electrophilic material or its precursor contain the metallic atom of selecting more than a kind from Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and Co.
4. photocatalyst dispersion liquid according to claim 2, wherein,
Described electrophilic material or its precursor are pressed the metal atom and are converted, and measuring 100 mass parts with respect to the total of described Titanium particles and tungsten oxide particle is 0.005 mass parts～0.6 mass parts.
5. photocatalyst dispersion liquid according to claim 1, wherein,
Described phosphoric acid (salt) is selected from phosphoric acid, ammonium phosphate salt, sodium ascorbyl phosphate and potassium phosphate.
6. photocatalyst dispersion liquid according to claim 1, wherein,
The average mark shot of described Titanium particles directly is 20nm～150nm.
7. photocatalyst dispersion liquid according to claim 1, wherein,
The BET specific area of described Titanium particles is 100m 2/ g～500m 2/ g.
8. photocatalyst dispersion liquid according to claim 1, wherein,
The average mark shot of described tungsten oxide particle directly is 50nm～200nm.
9. photocatalyst dispersion liquid according to claim 1, wherein,
The BET specific area of described tungsten oxide particle is 5m 2/ g～100m 2/ g.
10. photocatalyst dispersion liquid according to claim 1, wherein,
The mass ratio of described Titanium particles and described tungsten oxide particle is 4: 1～1: 8.
11. photocatalyst dispersion liquid according to claim 1, wherein,
The quality of described decentralized medium is 5 times～200 times with respect to the total quality of described Titanium particles and tungsten oxide particle.
12. photocatalyst dispersion liquid according to claim 1, wherein,
Hydrogen ion concentration is pH2.0～pH7.0.
13. the manufacture method of a photocatalyst dispersion liquid is characterized in that,
Titanium particles is scattered in be dissolved with in the decentralized medium of phosphoric acid (salt) and obtains the Titanium particles dispersion liquid, and with resulting Titanium particles dispersion liquid and tungsten oxide mix particles.
14. the manufacture method of photocatalyst dispersion liquid according to claim 13, wherein,
Described tungsten oxide particle is dispersed in the decentralized medium and becomes after the tungsten oxide particle dispersion, mix with described Titanium particles dispersion liquid.
15. the manufacture method of photocatalyst dispersion liquid according to claim 13, wherein,
Comprise the operation of adding electrophilic material or its precursor.
16. the manufacture method of photocatalyst dispersion liquid according to claim 14, wherein,
Comprise and add electrophilic material or its precursor in the described tungsten oxide particle dispersion operation.
17. the manufacture method of photocatalyst dispersion liquid according to claim 15, wherein,
After the precursor that has added described electrophilic material, carry out illumination and penetrate.
18. the manufacture method of photocatalyst dispersion liquid according to claim 17, wherein,
Described light carries out before being radiated at mixed oxidization titanium particle dispersion liquid and tungsten oxide particle.
19. a photocatalyst functional product that possesses photocatalyst layer on the surface, wherein,
Described photocatalyst layer uses the described photocatalyst dispersion liquid of claim 1 to form.
CNA2009101455893A 2008-06-05 2009-06-03 Photocatalyst dispersion liquid and manufacture method thereof Pending CN101596460A (en)

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JP2008148404 2008-06-05
JP2008265422 2008-10-14
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102527416A (en) * 2011-12-18 2012-07-04 浙江大学 Semiconductor photochemical catalyst with copper phosphate modified surface and preparation method thereof
CN104226341A (en) * 2014-09-18 2014-12-24 太原理工大学 Aqueous-phase dispersed photocatalyst as well as preparation method and application thereof
CN104941645A (en) * 2015-06-27 2015-09-30 江苏兰谷环保科技股份有限公司 Preparation method of high-performance composite photocatalyst dispersed solution
CN107899561A (en) * 2017-11-22 2018-04-13 张萍 Car inner top ornament materials photooxidation catalytic plate and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102527416A (en) * 2011-12-18 2012-07-04 浙江大学 Semiconductor photochemical catalyst with copper phosphate modified surface and preparation method thereof
CN104226341A (en) * 2014-09-18 2014-12-24 太原理工大学 Aqueous-phase dispersed photocatalyst as well as preparation method and application thereof
CN104226341B (en) * 2014-09-18 2016-06-29 太原理工大学 A kind of Aqueous dispersions type photochemical catalyst and its preparation method and application
CN104941645A (en) * 2015-06-27 2015-09-30 江苏兰谷环保科技股份有限公司 Preparation method of high-performance composite photocatalyst dispersed solution
CN107899561A (en) * 2017-11-22 2018-04-13 张萍 Car inner top ornament materials photooxidation catalytic plate and preparation method thereof

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Application publication date: 20091209