CN1812837A - Photocatalyst material being activated by visible light, raw material for the same and method for producing the same - Google Patents

Photocatalyst material being activated by visible light, raw material for the same and method for producing the same Download PDF

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CN1812837A
CN1812837A CN200480014680.7A CN200480014680A CN1812837A CN 1812837 A CN1812837 A CN 1812837A CN 200480014680 A CN200480014680 A CN 200480014680A CN 1812837 A CN1812837 A CN 1812837A
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photochemical catalyst
catalyst body
titanium
metal oxide
copper
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CN100431706C (en
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森川健志
铃木宪一
正木英之
大脇健史
多贺康训
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Toyota Central R&D Labs Inc
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Toyota Central R&D Labs Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B01D53/885—Devices in general for catalytic purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds

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Abstract

The present invention provides a method for producing a photocatalyst material, which comprises a step of adding at least one of nitrogen, sulfur, carbon and phosphorus to a metal oxide or a precursor thereof, and a step of incorporating at least one of vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum and a lanthanoid onto the surface or into the interior of the metal oxide or a precursor thereof, in the state wherein it is bound with an oxygen atom or in the state of a hydroxide or a salt.

Description

Photochemical catalyst body, its raw material and manufacture method thereof that visible light activity is arranged
Technical field
The present invention relates under radiation of visible light, have the photochemical catalyst body and the manufacture method thereof of photocatalyst activity.
Background technology
Metal oxides such as titanium oxide, tin oxide, zinc oxide produce electronics and hole because of light stimulus when irradiating ultraviolet light, work as the photochemical catalyst body that presents strong reducing power and oxidizing force.This photochemical catalyst body is widely used in decomposing, purifying, deodorizing, sterilization of harmful substance etc.
By supporting fixedly metal such as iron or copper or their oxide on the surface that ultraviolet region has the metal oxide of photocatalyst activity, improve the technology of the photocatalyst activity of ultraviolet region open (for example spy open flat 6-39285 communique, spy open flat 7-303835 communique, spy and open flat 9-227319 communique, spy and open flat 11-244709 communique, spy and open 2000-95976 communique, spy and open that 2000-205103 communique, spy are opened the 2003-135974 communique, the spy opens 2003-190811 communique etc.) at these.
Known on the other hand: in the crystal of metal oxides such as titanium oxide, tin oxide, zinc oxide, by replace the part of its oxygen with nitrogen, sulphur, carbon, phosphorus, or at the gap of its lattice doping nitrogen, sulphur, carbon, phosphorus, or nitrogen, sulphur, carbon, phosphorus are contained in the grain boundary that makes its polycrystalline aggregate, not only at ultraviolet light, even under radiation of visible light, also present high photocatalyst activity (for example the spy opens the 2000-205103 communique).
; the photochemical catalyst body in past; the absorbance of visible region is lower than ultraviolet region, and the quantum efficiency ratio that becomes the pointer of the light utilization ratio that is illustrated under the UV-irradiation and under the radiation of visible light is about ultraviolet light/visible light=5/1, can not obtain sufficient reaction speed at visible region.Therefore, with the occasion of these photochemical catalyst body and functions in furniture, walling, ligthing paraphernalia, electrical article, bathroom member, washstand articles for use, kitchen articles, disposable paper, automobile inside member, other indoor members, dental material etc., can not be reacted fully.
In addition, above-mentioned prior art, though can improve the photocatalyst activity of metal oxide at ultraviolet region, the photocatalyst activity that has active photochemical catalyst body at visible region can not be improved.In addition, in the photochemical catalyst body, support the technology of platinum noble metals such as (Pt), the high problem of raw material valency is arranged.
Summary of the invention
The present invention is a kind of surface that makes the metal oxide that contains among nitrogen, sulphur, carbon and the phosphorus at least a kind or inner state or the state of the salt photochemical catalyst body that presents photocatalyst activity under radiation of visible light that contains among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind with the state that combines with oxygen atom, hydroxide.
At this, in the photochemical catalyst body of the invention described above, preferred above-mentioned metal oxide is at least a kind a oxide among titanium, tin, the zinc.
In addition, in the photochemical catalyst body of the invention described above, preferred above-mentioned metal oxide contains among nitrogen and the sulphur at least a kind.Further, preferably its content is in all 0.01-13% by atomic ratio measuring.More preferably 0.01%-2.00% is with in the interior scope.
In addition, in the photochemical catalyst body of the invention described above, preferably contain among the vanadium that is in the state lower, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind than the maximum valence that in atmosphere, can stably exist as oxide.
In addition, in the photochemical catalyst body of the invention described above, preferably the scope below 6.0 weight % more than the 0.01 weight % contains vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, lanthanide series.
In addition, in the photochemical catalyst body of the invention described above, preferably contain among iron and the copper at least a kind, and in the 2p of XPS layer spectrum respectively below the above 710eV of 709eV and locate to have maximum peak below the above 933eV of 932eV.
In addition, in the photochemical catalyst body of the invention described above, preferably contain Cu 2Among O and the FeO at least a kind.
In addition, in the photochemical catalyst body of the invention described above, preferably contain among nitrate, carbonate, sulfate, phosphate, acetate and the chloride of iron or copper at least a kind.
In addition, in the photochemical catalyst body of the invention described above, preferred primary particle size is below the above 50nm of 5nm.
Other mode of the present invention is a kind of photochemical catalyst body raw material, it comprises among metal oxide and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind salt or ion, and described metal oxide contains among nitrogen, sulphur, carbon, the phosphorus at least a kind.
Other mode of the present invention is a kind of photochemical catalyst body raw material, and it comprises among metal oxide or its precursor and ammonium salt or ammoniacal liquor and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind salt or ion.
Other mode of the present invention is a kind of photochemical catalyst body raw material, its comprise among metal oxide or its precursor and urea, thiocarbamide, titanium dioxide urea and the thiourea dioxide at least a kind, and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, lanthanide series among at least a kind salt or ion.
At this, in the photochemical catalyst body raw material of the invention described above, preferred above-mentioned metal oxide is a titanium oxide.
In addition, in the photochemical catalyst body raw material of the invention described above, the precursor of preferred above-mentioned metal oxide contains among oxidation titanium sulfate, titanium sulfate, oxidizing aqueous titanium, titanium hydroxide, alkyl dioxide, metatitanic acid, ortho-titanic acid, hydrous titanium oxide, titanium chloride and the organic titanic compound at least a kind.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, and it comprises: the 1st operation of adding among nitrogen, sulphur, carbon and the phosphorus at least a kind in metal oxide or its precursor; Make surface or the inner state or the state of salt the 2nd operation that contains among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind with the state that combines with oxygen atom, hydroxide of above-mentioned metal oxide or above-mentioned precursor.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, it is characterized in that, to the surface or inner with the state that combines with oxygen atom, hydroxide state or the state of the salt metal oxide that contains among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind or its precursor in add among nitrogen, sulphur, carbon and the phosphorus at least a kind.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, it is characterized in that, make the surface of the metal oxide that added among nitrogen, sulphur, carbon and the phosphorus at least a kind or its precursor or the inner state or the state of salt with the state that combines with oxygen atom, hydroxide contain among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, comprising: the 1st operation of mixing among the metal oxide contain among nitrogen, sulphur, carbon, the phosphorus a kind and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind salt at least; With 2nd operation of this mixture in the heating of the temperature below 600 ℃ more than 80 ℃.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, comprising: in the 1st operation that contains heating of metal oxide under the atmosphere of ammonia or its precursor; Be blended among the product that obtains in above-mentioned the 1st operation and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series the 2nd operation of at least a kind salt; Heat the 3rd operation of the mixture that in above-mentioned the 2nd operation, obtains in the temperature below 600 ℃ more than 80 ℃.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, comprising: with at least a kind blend heated the 1st operation among metal oxide or its precursor and urea, thiocarbamide, titanium dioxide urea, thiourea dioxide, melamine, guanidine, cyanuric acid, biuret, uracil and other acid amides and the acid imide; Be blended among the product that obtains in above-mentioned the 1st operation and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series the 2nd operation of at least a kind salt; Heat the 3rd operation of the mixture that in above-mentioned the 2nd operation, obtains in the temperature below 600 ℃ more than 80 ℃.
At this, in the invention described above, the precursor of preferred above-mentioned metal oxide is among oxidation titanium sulfate, titanium sulfate, oxidizing aqueous titanium, titanium hydroxide, alkyl dioxide, metatitanic acid, ortho-titanic acid, hydrous titanium oxide, titanium chloride and the organic titanic compound at least a kind.
Other mode of the present invention is a kind of manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light, comprising: the precursor of mixed-metal oxides and nonmetallic sulfide or the 1st operation of the organosulfur compound of SH base is arranged; In the 2nd operation that contains the product that heating obtains under the atmosphere of aerobic in above-mentioned the 1st operation; Be blended among the product that obtains in above-mentioned the 2nd operation and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series the 3rd operation of at least a kind salt; Heat the 4th operation of the mixture that in above-mentioned the 3rd operation, obtains in the temperature below 600 ℃ more than 80 ℃.
At this, in the invention described above, the precursor of above-mentioned metal oxide preferably comprises among organic compound, halide and the oxyhalogenation thing of metal at least a kind.
And in the invention described above, preferred above-mentioned metal oxide is a titanium oxide.
Description of drawings
Fig. 1 is the flow chart of the manufacture method of the photochemical catalyst body in the expression embodiment of the present invention.
Fig. 2 is the result's that measures of the XPS of the photochemical catalyst body that obtains among the embodiment 1 of expression figure.
Fig. 3 is the result's that measures of the XPS of the photochemical catalyst body that obtains among the embodiment 2 of expression figure.
Fig. 4 is the curve map of the minimizing of the acetaldehyde concentration that causes of expression radiation of visible light.
Fig. 5 is the curve map of the increase of the gas concentration lwevel that causes of expression radiation of visible light.
The specific embodiment
About embodiments of the present invention, describe with reference to accompanying drawing.Fig. 1 represents the flow process of the manufacturing process of the photochemical catalyst body that has photocatalyst activity under radiation of visible light in the present embodiment.
In step S10, with the same metal oxide that generates the responsive to visible light type of past.Metal oxide can be titanium oxide (Ti-O), tin oxide (Sn-O), zinc oxide (Zn-O).At this moment, contain among nitrogen (N), sulphur (S), carbon (C), the phosphorus (P) at least a kind, can be formed in the metal oxide that presents photocatalyst activity under the radiation of visible light by making these metal oxides.
It is believed that this moment, nitrogen, sulphur, carbon, phosphorus by comprise with metal oxide crystal in the state, at least a kind of state that is entrained in the state in the interstitial void of metal oxide crystal and is entrained in the state in the grain boundary of metal oxide crystal of oxygen atom displacement, can under radiation of visible light, present photocatalyst activity.In addition, the occasion of above-mentioned nitrogen, sulphur, carbon, phosphorus replace oxygen atom site also comprises the situation that they further combine with hydrogen atom or oxygen atom.That is, lift nitrogen (N) and be the example explanation, also can take the mode replace oxygen atom site of N-H, N-O.
Be the occasion of titanium oxide at metal oxide particularly, preferably have Detitanium-ore-type, rutile-type, brookite type and amorphous among at least a kind of structure.When particularly in X-ray diffraction is measured, showing Detitanium-ore-type or rutile-type, under radiation of visible light, present high photocatalyst activity.
In addition, contain the occasion of the titanium oxide of nitrogen, in the time of in the mensuration wave spectrum of X-ray photoelectron spectroscopy (XPS), near 400eV, can seeing the peak, under radiation of visible light, present high photocatalyst activity.Particularly preferably in seeing the peak near the 396eV-397eV.It is believed that the titanium atom of titanium oxide and the nitrogen-atoms that is contained have chemical bond this moment.For example can think the structure that the part in site with oxygen atom is replaced by nitrogen-atoms.
Metal oxide can be by obtaining metal oxide or its precursor and nitrogen compound while mixing to heat.At this, can use titanium oxide, tin oxide or zinc oxide as metal oxide.As the precursor of metal oxide, for example can use the zinc compound of the tin compound of titanium compound, STANNOUS SULPHATE CRYSTALLINE, stannic chloride etc. of oxidation titanium sulfate, titanium sulfate, titanium chloride, organic titanic compound etc. or zinc sulfate, zinc chloride etc.In addition, as nitrogen compound, can use urea, thiocarbamide, titanium dioxide urea, thiourea dioxide, melamine, guanidine, cyanuric acid, biuret, uracil.Used the occasion of the precursor and the nitrogen compound of these metal oxides, heating is preferably carried out 200 ℃-500 ℃ temperature range.In addition, use acid or alkali or the clean surperficial reaction residues of high-temperature vapor such as NaOH, ammoniacal liquor such as sulfuric acid, hydrochloric acid, nitric acid after the heat treated, also can handle as required for obtaining higher activity sometimes.
Illustrate that heating also can be to carrying out with the aqueous solution of slaine and the slurry that stirred in step S14.
In addition, dissolve in solvent, and add organosulfur compound and obtain precursor, thereby this precursor of heating can access metal oxide under the atmosphere of aerobic containing by organic compound, halide or oxyhalogenation thing with metal.
At this,, can use the alkoxide of metal and pentanedione thing etc. as the organic compound of metal.For example the occasion of titanium can be used tetraisopropoxy titanium as organic compound.Also exemplify out in addition: titanium butoxide, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate, metatitanic acid four monooctyl esters, titanium chelate, pentanedione close titanium, ethohexadiol closes titanium, tetra-acetylated acetone titanium, ethylacetoacetate titanium, acidylate titanium, multi-hydroxy stearic acid titanium, lactic acid titanium, triethanolamine titanium tetraisopropoxy titanium, two (ethyl acetoacetate) titaniums of diisopropoxy, two (acetoacetate) titaniums of diisopropoxy, two (acetylacetone,2,4-pentanedione) titaniums of diisopropoxy.
In addition, as sulfur-containing compound, can use nonmetallic sulfide or the organosulfur compound of SH base is arranged.Nonmetallic sulfide is the compound of sulphur and the nonmetalloid that more is positive than sulphur preferably.For example, can be hydrogen sulfide (H 2S) or carbon disulfide (CS 2).The preferred especially good hydrogen sulfide of reactivity that uses.As the organosulfur compound that the SH base is arranged, (R-SH:R is organic groups such as alkyl preferably to use thio-alcohol.Below identical), carbodithioic acid class (R-CSSH).In addition, these organosulfur compounds also can have functional group beyond the SH, for example amino etc.
In addition, solvent preferably uses the non-protonic solvent of the protonic solvent that is not ethanol and methyl alcohol and so on.For example preferably use acetonitrile and dimethyl formamide, especially preferably use acetonitrile.This be because, the H of hydrogen sulfide +Easily, can generate reactive high HS expeditiously with metallo-organic compound (for example tetraisopropoxy titanium) attached on the solvent molecule -In addition, solvent is not limited to a kind of, also can use the mixture that has mixed multiple solvent.For example can use the mixture of non-polar solvens such as benzene and acetonitrile.
In addition,, be necessary to make the metal oxide crystallization, preferably precursor burnt till in the temperature range more than at least 300 ℃ in order to manifest photocatalyst activity.On the other hand, when reaching a high temperature, easily deviate from sulphur, therefore preferably burn till in the temperature range below 700 ℃ from metal oxide.Burning till of precursor is to need only oxygen containing atmosphere, for example heats in dry air or in the wet air to get final product.In wet air, because water (H 2O) promote the removal of residual organic matter, therefore in than dry air, make the metal oxide crystallization under the low temperature.Set out by above situation, in dry air, preferably burn till, in wet air, preferably burn till in the temperature range below 500 ℃ more than 350 ℃ in the temperature range below 550 ℃ more than 450 ℃.
And, supply with to titanium oxide, tin oxide or zinc oxide and will lead to as the nitrogen of carrier gas in the solvent that has dissolved sulphur compound and the mist that generates by the arrival treatment temperature that heats up from room temperature and be heated to defined, also can access metal oxide.At this moment, as sulphur compound, can use carbon disulfide (CS 2) or hydrogen sulfide (H 2S).In addition, the arrival treatment temperature of defined preferably sets below 400 ℃.Be preferably especially more than 100 ℃ below 300 ℃.
In addition, the synthesis example of nitrogenous titanium oxide as other has: 400-700 ℃ scope, the method for burning till precursor dry mixed urea and tetraisopropoxy titanium in ethanol after in oxidizing atmosphere.Treatment temperature is preferred 450-600 ℃ scope further.In addition, also can replace urea to use thiocarbamide, thiourea dioxide, in addition,, also can use various alcohol such as isopropyl alcohol about solvent.
In addition, by heat treated titanium carbide in oxidizing atmosphere, can access the titanium oxide that contains carbon.The preferred 300-700 of heat treatment temperature ℃ the scope of this moment.And then more preferably in 450 ℃-600 ℃ the scope.In addition, titanium oxide, tin oxide, zinc oxide or their precursor are put in the reaction vessel, under the state that vacuum is forced down than atmosphere, enclosed carbonaceous gas such as methane,, can make the metal oxide that contains carbon by the irradiation electromagnetic wave.As the pressure of this moment, the scope of preferred 0.1-10Torr.The more preferably scope of 0.5-5Torr.In addition, for example when using 2.45GHz, handle as electromagnetic frequency than being easier to.In addition, when in reaction vessel, enclosing the gas of reproducibilities such as hydrogen and ammonia simultaneously, can adjust Production Time according to its ratio.
In addition, by heat treatment titanium oxide in the atmosphere that contains phosphorus compound gas, tin oxide, zinc oxide or their precursor, can make the oxide that has added P.
The metal oxide that adopts these methods to generate is dissolved in the high solvent of purity such as ion exchange water.At this moment, in order to obtain suitable viscosity, preferred solid component concentration is about 10%.By this solution of dispersion such as employing mechanical type dispersion machines, make the low slurry of settleability.
At this moment, add as among the polyacrylic acid of dispersant, former phosphoric acid, pyrophosphoric acid, the hexa metaphosphoric acid at least a kind for slurry is preferred.In addition, also can use dispersants such as these sour alkali metal salts, sodium orthosilicate, sodium metasilicate.
In step S12, generate the solution of the slaine of defined.Contained metal can be vanadium (V), manganese (Mn), chromium (Cr), iron (Fe), cobalt (Co), copper (Cu), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), lanthanide series in the slaine.Nitrate, sulfate, carbonate, phosphate, acetate or the chloride of slaine by being decided to be these metals can access same effect.With among these slaines at least a kind be dissolved in the high solvent of purity such as ion exchange water and generate the aqueous solution.At this moment, also can mix these slaines multiple and use.
In step S14, mix and be stirred in the aqueous solution of slurry that contains metal oxide that generates among the step S10 and the slaine that in step S12, generates.The slurry that generates in this step becomes the raw material of the photochemical catalyst body in the present embodiment.
In step S16, burn till after making the mixture drying that in step S14, generates.Preferred drying is carried out about 100 ℃ in atmosphere.The dry back of end is ground into powdery with mortar and burns till.Preferably in atmosphere, burn till in the temperature range below 600 ℃ more than 80 ℃.Burn till particularly preferably in the temperature range below 450 ℃ more than 150 ℃,, present extra high photocatalyst activity by burning till in the temperature range below 350 ℃ more than 250 ℃.This be because, if be low temperature, then raw material do not need composition remaining, and if be high temperature, the nitrogen or the sulphur that then become in the powder of matrix are deviate from.
In addition, carried out X-ray diffraction mensuration about resulting several photochemical catalyst bodies.X-ray diffraction is measured and is used Cu-K α line to carry out.By its diffracted ray, half-peak breadth β (radian) and peak position 2 θ (radian) by the diffracted ray that uses this Cu-K alpha ray (wavelength X nm) to measure, use following Scherrer formula D=0.94 λ/(β cos θ), calculate the result of following primary particle size D, the primary particle size D of metal oxide is below the above 100nm of 5nm, distinguish most particle coacervations, formed the following aggregated particle of the above 50 μ m of 0.01 μ m.
In addition, about these photochemical catalyst bodies, carried out XPS mensuration.Adopt the PHI-5500MC of Ulvao-phi company, use Mg-K α line to measure.In addition, before mensuration, do not implement the pre-treatments such as corrosion of sample, under the state of former state, measured sample surfaces.It found that following possibility: the surface from the aqueous solution of slaine to metal oxide or can be added with metallic compound with the inside of about 3nm of XPS analysis.The chemical shift of measuring wave spectrum from XPS can be judged with the state that combines with oxygen atom or the state of hydroxide and contains metallic compound.Think especially: but to contain the possibility height that has than the state as the low valence of the valence of the maximum of oxide stable existence in atmosphere.Can think in addition, exist with nitrate, carbonate, sulfate, phosphate, acetate or the muriatic state of metal.
In addition, when being identified by the wave spectrum that the photochemical catalyst that presents high photocatalyst activity at visible region is carried out XPS mensuration, the content of slaine preferably is converted into metal 0.0005 weight %-10 weight %.Particularly in order under radiation of visible light, to obtain high photocatalyst activity, below the above 6 weight % of preferred 0.001 weight %, more preferably below the above 3 weight % of 0.05 weight %, most preferably below the above 1.5 weight % of 0.1 weight %.
Under radiation of visible light, demonstrate the reason of high photocatalyst activity as the photochemical catalyst body that obtains in the present embodiment, think that reason is: Cu in the inside of the surface near surface that support or that be doped to above-mentioned metal oxide of metal oxides such as titanium oxide, oxynitriding titanium, sulphur titanium oxide 2The metal oxide of O and FeO etc. promotes to betide the electronics of photochemical catalyst inside or the separation of charge in hole by visible light radiation.Think in addition because prolonged the cause of penetrating the life-span in the electronics that encourages or hole by illumination.
Below demonstrate the embodiments of the invention and the comparative example corresponding of above-mentioned embodiment with each embodiment.Wherein, these embodiment only represent the part of present embodiment, and present embodiment is not limited by the scope of these embodiment.
(comparative example 1)
As the comparative example relative 1, prepared the ultraviolet ray of Millenmium chemical company system and replied type titania photocatalyst (model PC500) with the present invention.In the comparative example 1, handle especially.
(comparative example 2)
(the former industry corporate system of stone: ST01) 250g puts in the quartz container, on one side with the 1000sccm flow ammonia that circulates in container, on one side 600 ℃ of heat treated 180 minutes with titanium oxide.Generated the oxynitriding titanium of the responsive to visible light type that is yellow thus.The powder 10g of this oxynitriding titanium is mixed among the ion exchange water 90g, has generated the slurry of solid component concentration 10%.And then use the mechanical type dispersion machine to make the low slurry of settleability.
Behind dry slurry under 100 ℃ the heating atmosphere, will in atmosphere, burn till 1 hour with the crushed material that mortar is pulverized at 300 ℃.Burn till the back by pulverizing once again, obtained the powder of photochemical catalyst body.
(comparative example 3)
(the former industry corporate system of stone: ST01) 250g puts in the quartz container, on one side with the 1000sccm flow ammonia that circulates in container, on one side 600 ℃ of heat treated 180 minutes with titanium oxide.Generated the oxynitriding titanium of the responsive to visible light type that is yellow thus.The powder 10g of this oxynitriding titanium is mixed among the ion exchange water 90g, has generated the slurry of solid component concentration 10%.And then use the mechanical type dispersion machine to make the low slurry of settleability.
In this slurry, add 10% nitric acid 15.5g, stirred 1 hour.Then, behind dry slurry under 100 ℃ the heating atmosphere, will in atmosphere, burn till 1 hour with the crushed material that mortar is pulverized at 300 ℃.Burn till the back by pulverizing once again, obtained the powder of photochemical catalyst body.
(comparative example 4)
Generated the solution that mixes and dissolved acetonitrile and tetraisopropoxy titanium with mol ratio 20/1.This solution is at room temperature supplied with hydrogen sulfide (H 2S) gas bubbles.After solution becomes black, continue again to bubble 3 hours, stop to supply with hydrogen sulfide gas.Then, by filtration under diminished pressure solution, obtain the black precipitate.
And then after making precipitate be scattered in the ethanol again, filter.To and filter the dispersion again of ethanol carry out 3 times repeatedly after, clean and make it air-dry, obtained precursor powder.In wet air under 400 ℃ with this precursor powder heat treated 6 hours.
(comparative example 5)
(the former industry corporate system of stone: ST01) 100g and urea (with the pure medicine of light) 125g put in the quartz container, 450 ℃ of heat treated 1 hour with titanium oxide.Use sulfuric acid scrubbing then, again with making it dry after the ion-exchange washing.Generated the oxynitriding titanium of the responsive to visible light type that is yellow thus.
The powder 12g of this oxynitriding titanium is mixed with the isopropyl alcohol of 80cc, and the silicon Acrylote that has added as adhesive is emulsion (a Daicel chemistry system).At this moment, carried out adjust making and reached the ratio that oxynitriding titanium/silicon Acrylote is emulsion=8/2 as solid constituent.Then, use the mechanical type dispersion machine to carry out case of wet attrition, make with isopropanol to reach solid component concentration 4%, thereby generated photocatalyst coating liquid.Use spin coater that this coating liquid is coated on the glass substrate surface of 40mm * 40mm, make it 110 ℃ of dryings 3 minutes.
(comparative example 6)
Obtained titanium tetrachloride aqueous solution by in the frozen water (being converted into water is 2 liters) of pure water, adding titanium tetrachloride 500g and stirring.On one side stir this aqueous solution 200g with agitator, on one side the ammoniacal liquor that adds as nitrogenous source rapidly (contain 13 weight %NH 3) about 50 milliliters.The addition adjustment of ammoniacal liquor makes the pH of the final aqueous solution become about 8.Stir this stock white after 15 minutes, use suction filter to filter.The ammoniacal liquor that makes the sediment that filters and obtain be dispersed in 20 milliliters (contains 6 weight %NH 3) in, after 20 hours, carry out suction strainer with the agitator stir about once again, obtain the hydrolysate of white.Resulting hydrolysate is put in the crucible, used electric furnace in atmosphere, to heat 1 hour, obtained powder at 400 ℃.
Adopt X-ray diffraction to measure it.Distinguish that by the X-ray diffraction peak photochemical catalyst body contains the titanium oxide of Detitanium-ore-type.And by the result that the half-peak breadth of the anatase (101) of x-ray diffraction line uses the Scherrer formula to calculate, the primary particle size of photochemical catalyst body is about 13.5nm.
And then dry resulting powder, powder 10g is mixed among the ion exchange water 90cc, use the mechanical type dispersion machine to carry out case of wet attrition, generated the low slurry of settleability.
On the other hand, with copper nitrate hydrate (Cu (NO 3) 23H 2O) be dissolved in the ion exchange water, generate the aqueous solution of copper concentration 5%.This aqueous solution 1g is joined in the slurry of powder, stirred 1 hour.And then 100 ℃ make this slurry drying after, pulverize with mortar, in atmosphere, burnt till 1 hour at 300 ℃.Again by pulverize the powder that has just obtained the photochemical catalyst body with mortar.
(comparative example 7)
(the former industry corporate system of stone: ST01) powder 10g and ion exchange water 90g, the slurry of making solid component concentration 10% adopts the mechanical type dispersion machine to make the low slurry of settleability to the mixed oxidization titanium again.In addition, copper nitrate (II) hydrate is dissolved in the ion exchange water, has made the aqueous solution of copper concentration 5%.Mix slurry 100g and copper nitrate aqueous solution 1g, stirred 1 hour.The conversion melting concn of the copper of this moment is 0.5 weight %.
100 ℃ make this slurry drying after, pulverize with mortar, crushed material was burnt till 1 hour at 300 ℃ in atmosphere.After burning till, by pulverizing the powder that has just obtained the photochemical catalyst body once more.
(comparative example 8)
(the former industry corporate system of stone: ST01) powder 10g and ion exchange water 90g, the slurry of making solid component concentration 10% adopts the mechanical type dispersion machine to make the low slurry of settleability to the mixed oxidization titanium again.In addition, ferric nitrate (III) hydrate is dissolved in the ion exchange water, has made the aqueous solution of concentration of iron 5%.Mix slurry 100g and iron nitrate aqueous solution 1g, stirred 1 hour.The conversion melting concn of the iron of this moment is 0.5 weight %.
After making this slurry drying under 100 ℃ the heating atmosphere, pulverize with mortar, crushed material was burnt till 1 hour at 300 ℃ in atmosphere.After burning till, by pulverizing the powder that has just obtained the photochemical catalyst body once again.
(embodiment 1)
(the former industry corporate system of stone: ST01) 1000g and urea (with the pure medicine of light) 375g puts in the rustless steel container, while mix 450 ℃ of heat treated 120 minutes with titanium oxide.Generated the oxynitriding titanium of the responding to visible light that is yellow thus.The powder 10g and the ion exchange water 90g that mix this oxynitriding titanium have generated the slurry of solid component concentration 10%.Adopt the mechanical type dispersion machine to make the low slurry of settleability again.
On the other hand, copper nitrate (II) hydrate is dissolved in the ion exchange water, has made the aqueous solution of the slaine of copper concentration 5%.
Then, the slurry 100g of mixed oxidization titanium and the aqueous solution 1g of copper nitrate stirred 1 hour, had generated the mixed solution of photochemical catalyst body metallizing thing.The melting concn of the copper of this moment is 0.5 weight %.After making this mixed solution drying under 100 ℃, pulverize with mortar, in atmosphere, burnt till 1 hour at 300 ℃.And then, obtained the powder of photochemical catalyst body by pulverizing with mortar.
Just do not corrode powder the most surperficial of having measured this photochemical catalyst body with XPS.The wave spectrum of being measured by XPS is obtained the ratio of components of the copper in the powder, for atomicity than 0.7 atom %.In addition, as shown in Figure 2, in 2p layer wave spectrum, the strongest peak has been seen in the zone below the above 933eV of 932eV.Particularly near 933eV, seen the peak.Think on the surface of titanium oxide or inner by its chemical shift with Cu 2The state of O contains the possibility height of copper.Certainly, only measure to identify it is difficult fully, the possibility that contains copper with the state of hydroxide or salt is also arranged from XPS.
In addition, adopt X-ray diffraction to measure the powder of photochemical catalyst body.Distinguish that by the peak of X-ray diffraction the photochemical catalyst body contains the titanium oxide of Detitanium-ore-type.And by the result that the half-peak breadth of the anatase (101) of x-ray diffraction line uses the Scherrer formula to calculate, the primary particle size of photochemical catalyst body is about 11.5nm.
(embodiment 2)
(the former industry corporate system of stone: ST01) 250g puts in the quartz container, on one side with the 1000sccm flow ammonia that circulates in container, on one side 600 ℃ of heat treated 180 minutes with titanium oxide.Generated the oxynitriding titanium of the responsive to visible light type that is yellow thus.Its powder is just carried out XPS mensuration without corrosion, near 396eV, observe the peak that derives from the N-Ti key.The powder 10g of this oxynitriding titanium is mixed among the ion exchange water 90g, has generated the slurry of solid component concentration 10%.And then use the mechanical type dispersion machine to make the low slurry of settleability.
On the other hand, ferric nitrate (III) hydrate is dissolved in the ion exchange water, has made the aqueous solution of the slaine of concentration of iron 5%.
Then, mix the slurry 100g of oxynitriding titanium and the aqueous solution 1g of ferric nitrate, stirred 1 hour, generated the mixed solution of photochemical catalyst body and metallic compound.The melting concn of the iron of this moment is 0.5 weight %.100 ℃ make this mixed solution drying after, pulverize with mortar, in atmosphere, burnt till 1 hour at 300 ℃.And then, obtained the powder of photochemical catalyst body by pulverizing with mortar.
Just measured powder the most surperficial of this photochemical catalyst body with XPS without corrosion.The wave spectrum of being measured by XPS is obtained the ratio of components of the iron in the powder, for atomicity than 0.8 atom %.In addition, as shown in Figure 3, in 2p layer wave spectrum, the strongest peak has been seen in the zone below the above 710eV of 709eV.Particularly near 709eV, seen the peak.Can think surface or the inner possibility height that contains iron with the state of FeO at the oxynitriding titanium by its chemical shift.Should illustrate only measure fully identify it is difficult, the possibility that contains iron with the state of hydroxide or salt is also arranged by XPS.
In addition, adopt X-ray diffraction to measure the powder of photochemical catalyst body.Distinguish that by the peak of X-ray diffraction the photochemical catalyst body contains the titanium oxide of Detitanium-ore-type.And by the result that the half-peak breadth of the anatase (101) of x-ray diffraction line uses the Scherrer formula to calculate, the primary particle size of photochemical catalyst body is about 19.0nm.
(embodiment 3)
Generated the solution that mixes and dissolved acetonitrile and tetraisopropoxy titanium with mol ratio 20/1.For this solution, at room temperature supply with hydrogen sulfide (H 2S) gas bubbles.After solution becomes black, continue again to bubble 3 hours, stop to supply with hydrogen sulfide gas.Then, by filtration under diminished pressure solution, obtained the precipitate of black.
And then after making precipitate be scattered in the ethanol again, filter.To and filter the dispersion again of ethanol carry out 3 times repeatedly after, wash and make it air-dry, obtained precursor powder.In wet air under 400 ℃ with this precursor powder heat treated 6 hours.Obtained the powder of the oxynitriding titanium of Detitanium-ore-type thus.Just this powder is carried out XPS without corrosion and measure, near 160eV, observed the peak that derives from the S-Ti key.Then, the powder 12g of resulting oxynitriding titanium is mixed among the ion exchange water 80cc, has generated slurry.
On the other hand, generated copper nitrate hydrate (Cu (NO 3) 23H 2O) 17.2g is dissolved in the aqueous solution among the ion exchange water 82.8g.1.33g joins in the slurry of oxynitriding titanium with this aqueous solution.Then, use the mechanical type dispersion machine to carry out case of wet attrition.And then 100 ℃ make this slurry drying after, pulverize with mortar, in atmosphere, burnt till 1 hour at 300 ℃.Again by pulverize the powder that has just obtained the photochemical catalyst body with mortar.
Measured the photocatalysis characteristic of photochemical catalyst body under radiation of visible light that in above comparative example and embodiment, obtains.Photocatalysis characteristic is measured as follows.
After (1000cc) packed the powder 0.1g that makes in glass container, replace inner air with dry air.Then, at uitraviolet intensity 5.0mW/cm 2Shone black light in advance 14 hours under (opening up light intensity meter, use UVR-2 and the UD-36 of Pu Kang system).Inject aldehydes gas to moles such as each glass containers then.Specifically, (1000cc) injected the dense gas of the amount that is converted into 1000ppm with micro syringe in container.In the dark placed then 12 hours, and made the surface of gas absorption at powder.(Fuji Photo film, (concentration of having measured inner carbon dioxide and acetaldehyde over time for SUNX, FL10N) the above visible light of illumination wavelength 410nm for 10W fluorescent tube SC42) by the ultraviolet cutoff wave filter has been installed around.It the results are shown in Figure 4 and Fig. 5.
Concentration when measuring initial (constantly 0) is the concentration after the absorption of dark place, represents adsorptivity poor of each powder.In embodiments of the invention 1 and embodiment 2, the minimizing speed of the acetaldehyde concentration during radiation of visible light is brought up to more than 3 times of comparative example 1,2,6 greatly, can make the acetaldehyde that is equivalent to 1000ppm be reduced to 0ppm through 2 hours with interior radiation of visible light.In addition, in the present embodiment, final decomposition product carbon dioxide (CO 2) formation speed also be increased to more than 2 times.
In addition, the result about comparative example 6 by Fig. 4 knows that supported the occasion of Cu oxide in the titanium oxide that the employing damp process that is derived from titanium tetrachloride is made, instead photocatalyst activity is compromised.That is, as comparative example 6, the nitrogenous titanium oxide of making to adopt Hydrolyze method to make precursor contain nitrogen in advance of damp process is a matrix, has supported Cu oxide therein, and the reaction speed under visible light reduces.
Relative with it, containing by thermal response the embodiment 1 and 2 of nitrogen from face side, improve effect and further increase, reaction speed is increased to more than 2 times.Infer thus, think: the mode that the nitrogen that will contain in titania surface and sulphur etc. exist with the state that combines with titanium elements is as the occasion of carrier, and the present invention can obtain the effect that supports of higher oxide, hydroxide, salt.Think too about tin oxide and zinc oxide.Any photochemical catalyst body that obtains in the above-described embodiments and the photochemical catalyst body ratio that obtains in comparative example, the minimizing speed of its acetaldehyde and the formation speed of carbon dioxide are big.The formation speed of particularly final catabolite carbon dioxide, with comparative example than the formation speed that demonstrates more than 2 times.This situation is represented, by the processing among the embodiment, can access the photochemical catalyst body that has high photocatalyst activity under radiation of visible light.
In addition, table 1 is expressed and is injected the aldehydes gas that is equivalent to 500ppm, measures the result of the decomposition rate under the visible light.Embodiment 1 compares with 3 with comparative example 2 with 2, and the formation speed of carbon dioxide is increased to more than 2 times.Embodiment 3 compares with comparative example 4, and the formation speed of carbon dioxide also is increased to more than 2 times.On the other hand, adopt the comparative example 6 of the visible-light photocatalyst of damp process making in the past, containing the preceding reaction speed of Cu compound is 51ppm/h, sees that thus instead reaction speed reduces, and can't see the effect that supports.Know that in addition in comparative example 7,8, even make the titanium oxide that does not have responding to visible light adopt method of the present invention to contain Cu or Fe compound, the catalytic performance under radiation of visible light also almost be can't see difference.
Light-catalyzed reaction speed under table 1 radiation of visible light
Carbon dioxide formation speed (ppm/h)
Comparative example 1 2
Comparative example 2 49
Comparative example 3 52
Comparative example 4 13
Comparative example 6 43
Comparative example 7 2
Comparative example 8 4
Embodiment 1 105
Embodiment 2 112
Embodiment 3 29
On the other hand, replace visible light source use black light (Toshiba's system: BLB-A), the concentration of having measured the carbon dioxide of internal tank and acetaldehyde over time, it the results are shown in the table 2.At this moment, the luminous intensity with ultraviolet region is decided to be 5.0mW/cm 2, be about 5 times intensity of the luminous intensity of visible region.
Light-catalyzed reaction speed under table 2 UV-irradiation
Carbon dioxide formation speed (ppm/h)
Comparative example 1 342
Comparative example 2 400
Comparative example 3 403
Comparative example 4 465
Comparative example 6 372
Comparative example 7 341
Comparative example 8 355
Embodiment 1 342
Embodiment 2 393
Embodiment 3 455
The minimizing speed of the acetaldehyde of the roughly the same degree of photochemical catalyst body that any photochemical catalyst body that obtains in the above-described embodiments all demonstrates and obtains in comparative example and the formation speed of carbon dioxide.Promptly we can say: the processing among the embodiment, the photocatalyst activity under ultraviolet region to improve effect little, effective to the raising of the photocatalyst activity under visible region.In addition, in comparative example 7,8,, also can't see the effect of the reaction speed of raising under ultraviolet ray even adopt method of the present invention to make titanium oxide contain Cu, Fe.
In addition, use with embodiment 1 and 2 same methods and made the sample of the content that makes Fe compound and Cu compound respectively separately.To these sample determinations the carbon dioxide formation speed, the results are shown in the table 3.Can be known clearly that by table 3 content of Fe compound and Cu compound has been seen effect in the scope of table 3 time, particularly near 0.5 weight %, the photocatalyst activity under the visible light is the highest.
Contain the Cu that is equivalent to weight ratio 0.5% and the occasion of Fe, heat treatment temperature and carbon dioxide reaction speed are shown in table 4.Can expect: do not have heat treated occasion, Cu and Fe do not become oxide, are fixed on the surface with the state of metal, hydroxide or salt.The carbon dioxide formation speed of this moment is all low.With respect to this, by implementing heat treatment, reaction speed increases.Demonstrate than comparative example 2 and 3 high reaction speeds during 100 ℃ of processing, demonstrate the highest reaction speed 250-350 ℃ temperature range.When handling for 300 ℃, think such according to the result of above-mentioned XPS, Cu and Fe mainly become Cu respectively 2The low oxide of O, FeO.In the occasion of higher Temperature Treatment, reaction speed reduces for the oxidation of the compound that further promotes Cu and Fe., during temperature below 600 ℃, kept than comparative example 2 and 3 high reaction speeds.Reaction speed reduces greatly and thinks that reason is when 700 ℃ are handled: the nitrogen that adds in the titanium oxide is deviate from, and causes responding to visible light to reduce.That is ,-600 ℃ scope heat treatment can access effect of the present invention near 100 ℃.
Light-catalyzed reaction speed under table 3 radiation of visible light (carbon dioxide formation speed)
Fe, Cu conversion loading (weight %) Fe matrix formation speed (ppm/h) Cu matrix formation speed (ppm/h)
0 49 49
0.1 51 54
0.3 75 53
0.5 111 118
0.8 91 95
1.5 52 50
6 37 16
Light-catalyzed reaction speed under table 4 radiation of visible light (carbon dioxide formation speed)
Heat treatment temperature (℃) Fe matrix formation speed (ppm/h) Cu matrix formation speed (ppm/h)
Do not have (being equivalent to carrying metal) 42 31
100 85 80
250 101 110
300 112 105
350 105 105
400 75 98
450 70 87
600 61 61
700 22 18
(embodiment 4)
(Millenmiun chemical company system: PC500) 100g and urea (with the pure medicine of light) 125g put in the quartz container, 450 ℃ of heat treated 60 minutes with titanium oxide.Use sulfuric acid scrubbing then, after cleaning with ion exchange water again, make it dry.Generated the oxynitriding titanium of the responding to visible light that is yellow thus.The powder 12g and the isopropyl alcohol 80cc that mix this oxynitriding titanium.
On the other hand, generated copper nitrate hydrate (Cu (NO 3) 23H 2O) 17.2g is dissolved in the aqueous solution among the ion exchange water 82.8g.1.33g joins in the solution of oxynitriding titanium and isopropyl alcohol with this aqueous solution.At this moment, having added silicon Acrylote as adhesive is emulsion (Diacel chemical company system: TT-105).Add silicon Acrylote and be emulsion and make by solid component meter oxynitriding titanium/silicon Acrylote to be that the ratio of emulsion reaches 8/2.
Then, use the mechanical type dispersion machine to carry out case of wet attrition.Then, up to reaching solid component concentration 4%, generated the coating liquid of photochemical catalyst body with isopropanol.Use spin coater that this coating liquid is coated on the glass substrate surface of 40mm * 40mm, 110 ℃ of dryings 3 minutes.
(embodiment 5)
With 250g titanium oxide (the former industry corporate system of stone: ST01) put in the quartz container,, handled 180 minutes at 600 ℃ on one side on one side with 1000sccm flow circulation ammonia.Generated the oxynitriding titanium photochemical catalyst of yellow responsive to visible light type thus.Mix this powder 10g and ion exchange water 90g, make the slurry of solid component concentration 10%, and then adopt the mechanical type dispersion machine to make the low slurry of settleability.Ferric nitrate (III) hydrate is dissolved in the ion exchange water, has made the aqueous solution of concentration of iron 5%.Mix above-mentioned photochemical catalyst slurry 100g and iron nitrate aqueous solution 1g, pulverize with the mechanical type dispersion machine once again and mixed 15 minutes.The conversion melting concn of the iron of this moment is 0.5 weight %.The silicon Acrylote that has added Diacel chemical company system as adhesive is emulsion (TT-105) and makes by solid component meter oxynitriding titanium/silicon Acrylote to be emulsion=8/2, has carried out case of wet attrition with the mechanical type dispersion machine then.It is diluted up to reaching solid component concentration 4% with ion exchange water, made photocatalyst coating liquid.Adopt spin coater this coating liquid to be coated on the glass substrate of 40mm * 40mm, 110 ℃ of dryings 3 minutes.
Embodiment 4 and 5, and the resolution characteristic of the methylene blue of film sample under radiation of visible light of comparative example 5 have been measured.
The 1.2W white fluorescent lamp is being rolled up under the visible light radiation of the ultraviolet wave filter (Fujiphoto) below the 410nm, measured the light decolouring of the aqueous solution of methylene blue of concentration 60 μ M.Table 5 is expressed the variable quantity that near methylene blue absorbance after 20 minutes, under the wavelength 650nm is penetrated in illumination.Present embodiment demonstrates the very high photocatalyst activity under visible light with relatively routine in the past.
The methylene blue absorbance of table 5 under visible light changes
Absorbance changes
Comparative example 5 -0.038
Embodiment 4 -0.0483
Embodiment 5 -0.121
In addition, use the sample of embodiment 4 and 5, adopt the antibacterial products technical protocol can evaluation assessment III (the film adhesion method is penetrated in illumination) implemented to use the antibacterial tests of the MRSA (mesitylene (メ シ チ リ Application) patience staphylococcus aureus) under the illumination 2000Lx of 15W white fluorescent lamp (Toshiba's system).Polyethylene film has been used in contrast as a comparison.In embodiment 4 and 5, shine after 24 hours, the bacterium number is reduced to 100,000/below, on the other hand, for polyethylene film, the reduced rate of bacterium is about 1/2.Therefore confirmed high antibiotic property of the present invention.
Be not limited to embodiment as adhesive, also can use silica sol, silicones, fluororesin, isocyanates, with epoxide, aziridine based compound, oxazoline based compound, carbodiimides based compound, cellulose-based adhesive, polysaccharide, the unbodied titanium oxide of carboxyl reaction.
In addition, solvent for use during as the making coating liquid also can use methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, TC, propylene glycol monomethyl ether, the propylidene monomethyl ether acetate, DAA, benzene, toluene, dimethylbenzene, oxolane diox, acetone, MEK, methyl iso-butyl ketone (MIBK), DIBK, ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the perhaps mixture of they and water.
In addition, as making the nitrogen that contains of the present invention, sulphur, carbon, solvent during the oxide of phosphorus, except being limited in an embodiment, can also use methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, TC, propylene glycol monomethyl ether, the propylidene monomethyl ether acetate, DAA, benzene, toluene, dimethylbenzene, oxolane diox, acetone, MEK, methyl iso-butyl ketone (MIBK), DIBK, ethyl acetate, propyl acetate, butyl acetate, propylene carbonate, methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc.
It should be noted that the present invention is not limited to above-mentioned embodiment, various changes in addition in the scope that does not break away from purport of the present invention.

Claims (24)

1. photochemical catalyst body that presents photocatalyst activity under radiation of visible light makes the surface of the metal oxide that contains among nitrogen, sulphur, carbon and the phosphorus at least a kind or the inner state or the state of salt with the state that combines with oxygen atom, hydroxide contain among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind.
2. photochemical catalyst body according to claim 1, wherein, above-mentioned metal oxide is at least a kind a oxide among titanium, tin, the zinc.
3. photochemical catalyst body according to claim 1, wherein, above-mentioned metal oxide contains among nitrogen or the sulphur at least a kind.
4. photochemical catalyst body according to claim 1, wherein, contain among the vanadium that is in the state lower, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind than the maximum valence that in atmosphere, can stably exist as oxide.
5. photochemical catalyst body according to claim 1, wherein, the scope below 6.0 weight % more than the 0.01 weight % contains vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, lanthanide series.
6. photochemical catalyst body according to claim 4 wherein, contains among iron and the copper at least a kind, and in the 2p layer spectrum of measuring by XPS respectively below the above 710eV of 709eV and locate to have maximum peak below the above 933eV of 932eV.
7. photochemical catalyst body according to claim 4 wherein, contains Cu 2Among O and the FeO at least a kind.
8. photochemical catalyst body according to claim 4 wherein, contains among nitrate, carbonate, sulfate, phosphate, acetate and the chloride of iron or copper at least a kind.
9. photochemical catalyst body according to claim 4, wherein, primary particle size is below the above 50nm of 5nm.
10. photochemical catalyst body raw material comprises among the metal oxide that contains among nitrogen, sulphur, carbon, the phosphorus a kind and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind salt at least.
11. a photochemical catalyst body raw material, comprise metal oxide or its precursor and ammonium salt or ammoniacal liquor, and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, lanthanide series among at least a kind salt.
12. a photochemical catalyst body raw material, comprise among metal oxide or its precursor and urea, thiocarbamide, titanium dioxide urea and the thiourea dioxide at least a kind, and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, lanthanide series among at least a kind salt.
13. photochemical catalyst body raw material according to claim 10, wherein, above-mentioned metal oxide is a titanium oxide.
14. photochemical catalyst body raw material according to claim 11, wherein, the precursor of above-mentioned metal oxide contains among oxidation titanium sulfate, titanium sulfate, oxidizing aqueous titanium, titanium hydroxide, alkyl dioxide, metatitanic acid, ortho-titanic acid, hydrous titanium oxide, titanium chloride and the organic titanic compound at least a kind.
15. a manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light is characterized in that, comprising: the 1st operation of in metal oxide or its precursor, adding among nitrogen, sulphur, carbon and the phosphorus at least a kind; Make surface or the inner state or the state of salt the 2nd operation that contains among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind with the state that combines with oxygen atom, hydroxide of above-mentioned metal oxide or above-mentioned precursor.
16. manufacture method that under radiation of visible light, has the photochemical catalyst body of photocatalyst activity, it is characterized in that, to the surface or inner with the state that combines with oxygen atom, hydroxide state or the state of the salt metal oxide that contains among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind or its precursor in add among nitrogen, sulphur, carbon and the phosphorus at least a kind.
17. manufacture method that under radiation of visible light, has the photochemical catalyst body of photocatalyst activity, it is characterized in that, make the surface of the metal oxide that added among nitrogen, sulphur, carbon and the phosphorus at least a kind or its precursor or the inner state or the state of salt with the state that combines with oxygen atom, hydroxide contain among vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind.
18. manufacture method that under radiation of visible light, has the photochemical catalyst body of photocatalyst activity, it is characterized in that, comprise: the 1st operation of mixing among the metal oxide contain among nitrogen, sulphur, carbon, the phosphorus a kind and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series at least a kind salt at least; With 2nd operation of this mixture in the heating of the temperature below 600 ℃ more than 80 ℃.
19. a manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light is characterized in that, comprising: in the 1st operation that contains heating of metal oxide under the atmosphere of ammonia or its precursor; Be blended among the product that obtains in above-mentioned the 1st operation and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series the 2nd operation of at least a kind salt; Heat the 3rd operation of the mixture that in above-mentioned the 2nd operation, obtains in the temperature below 600 ℃ more than 80 ℃.
20. manufacture method that under radiation of visible light, has the photochemical catalyst body of photocatalyst activity, it is characterized in that, comprising: with metal oxide or its precursor, with acid amides, acid imide, urea, thiocarbamide, titanium dioxide urea, thiourea dioxide, melamine, guanidine, cyanuric acid, biuret and uracil among at least a kind blend heated the 1st operation; Be blended among the product that obtains in above-mentioned the 1st operation and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series the 2nd operation of at least a kind salt; Heat the 3rd operation of the mixture that in above-mentioned the 2nd operation, obtains in the temperature below 600 ℃ more than 80 ℃.
21. a manufacture method that has the photochemical catalyst body of photocatalyst activity under radiation of visible light is characterized in that, comprising: the precursor of mixed-metal oxides and nonmetallic sulfide or the 1st operation of the organosulfur compound of SH base is arranged; In the 2nd operation that contains the product that heating obtains under the atmosphere of aerobic in above-mentioned the 1st operation; Be blended among the product that obtains in above-mentioned the 2nd operation and vanadium, manganese, chromium, iron, cobalt, copper, yttrium, zirconium, niobium, molybdenum, the lanthanide series the 3rd operation of at least a kind salt; Heat the 4th operation of the mixture that in above-mentioned the 3rd operation, obtains in the temperature below 600 ℃ more than 80 ℃.
22. the manufacture method of photochemical catalyst body according to claim 15, wherein, above-mentioned metal oxide is a titanium oxide.
23. the manufacture method of photochemical catalyst body according to claim 15, wherein, the precursor of above-mentioned metal oxide is among oxidation titanium sulfate, titanium sulfate, oxidizing aqueous titanium, titanium hydroxide, alkyl dioxide, metatitanic acid, ortho-titanic acid, hydrous titanium oxide, titanium chloride and the organic titanic compound at least a kind.
24. the manufacture method of photochemical catalyst body according to claim 21, wherein, the precursor of above-mentioned metal oxide comprises among the organic compound of metal, halide and the oxyhalogenation thing at least a kind.
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