CN101406836A - Photocatalyst dispersion liquid and process for producing the same - Google Patents

Photocatalyst dispersion liquid and process for producing the same Download PDF

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Publication number
CN101406836A
CN101406836A CNA2008101488873A CN200810148887A CN101406836A CN 101406836 A CN101406836 A CN 101406836A CN A2008101488873 A CNA2008101488873 A CN A2008101488873A CN 200810148887 A CN200810148887 A CN 200810148887A CN 101406836 A CN101406836 A CN 101406836A
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China
Prior art keywords
catalytic oxidation
dispersion liquid
photochemical catalytic
particle
photocatalyst dispersion
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CNA2008101488873A
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Chinese (zh)
Inventor
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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Publication of CN101406836A publication Critical patent/CN101406836A/en
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Abstract

The present invention provides a photocatalyst dispersion liquid obtained by dispersing titanium oxide photocatalyst particles and tungsten oxide photocatalyst particles in a dispersion medium, where the surfaces of both titanium oxide photocatalyst particles and tungsten oxide photocatalyst particles are charged positively or negatively. In the photocatalyst dispersion liquid, the titanium oxide photocatalyst particles and the tungsten oxide photocatalyst particles, which are dispersed in the dispersion medium, are not aggregated easily, and a solid-liquid separation is not generated.

Description

Photocatalyst dispersion liquid and manufacture method thereof
Technical field
The present invention relates to photocatalyst dispersion liquid, specifically relate to and contain photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle photocatalyst dispersion liquid as photocatalysis body.
Background technology
Irradiation has the light time of the above energy of band gap to semiconductor, and the electronics of valence band is excited to conduction band, generates the hole in valence band respectively, generates free electron at conduction band.Therefore this hole and free electron produce redox to the molecular species that contacts with semiconductor owing to have strong oxidability and reducing power respectively.This redox is called as photocatalysis, and the semiconductor that can demonstrate this photocatalysis is called as photocatalysis body.As such photocatalysis body, be known that photochemical catalytic oxidation titanium particle, the epigranular material of photochemical catalytic oxidation tungsten particle.
Also knownly this photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle are scattered in the decentralized medium and the photocatalyst dispersion liquid that obtains (spy opens the 2005-231935 communique).By this photocatalyst dispersion liquid being coated the surface of base material, can easily comprise photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle photocatalysis body layer, that demonstrate photocatalysis in substrate surface formation.
Summary of the invention
Yet, photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle are scattered in the decentralized medium and the photocatalyst dispersion liquid in the past that obtains, there is the inter coagulation of particle phase and the problem of Separation of Solid and Liquid easily.
Therefore, the inventor etc. are difficult for cohesion in order to develop the photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle that are scattered in the decentralized medium, and photocatalyst dispersion liquid that can Separation of Solid and Liquid, through research with keen determination, found that, because photocatalytic titanium oxide particle surface positively charged in the past, photochemical catalytic oxidation tungsten particle surperficial electronegative, so cohesion easily in decentralized medium, surface charging by making photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is an identical polar, i.e. positively charged all, perhaps all electronegative, then can suppress cohesion, can Separation of Solid and Liquid, thus finished the present invention.
That is, the invention provides a kind of photocatalyst dispersion liquid, it is characterized in that, dispersed light catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle form in decentralized medium, and the surface charging of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is an identical polar.
Photocatalyst dispersion liquid of the present invention is identical polar because the photochemical catalytic oxidation titanium particle that disperses and photochemical catalytic oxidation tungsten particle sub-surface are charged in decentralized medium, therefore can the phase inter coagulation, and therefore can Separation of Solid and Liquid yet.In addition, owing to can under the condition that does not make photochemical catalytic oxidation titanium particle and the sub inter coagulation mutually of photochemical catalytic oxidation tungsten particle, coat on the base material, therefore by being coated with photocatalysis body that photocatalyst dispersion liquid of the present invention the forms demonstration highlight catalytic active of filming.
The specific embodiment
[photochemical catalytic oxidation titanium particle]
Constitute the so-called photochemical catalytic oxidation titanium particle of photocatalyst dispersion liquid of the present invention, be meant the granular titanium oxide of display light catalytic action, for example can enumerate the metatitanic acid particle, crystal formation is the titanium dioxide (TiO of Detitanium-ore-type, brookite type, rutile-type etc. 2) particle etc.
The metatitanic acid particle for example can obtain by following method 1.
Method 1: heat and method for hydrolysis by the aqueous solution to titanyl sulfate
TiO 2 particles for example can obtain by any method among following method 2-1～method 2-3.
Method 2-1: the aqueous solution of titanyl sulfate or the aqueous solution of titanium chloride are not heated, and by obtaining sediment to wherein adding alkali, the sedimentary method of calcining gained
Method 2-2: in the titanium alkoxide, add the aqueous solution of entry, aqueous acid or alkali and obtain sediment, the sedimentary method of calcining gained
Method 2-3: metatitanic acid is carried out calcining method
By these methods TiO 2 particles that 2-1～method 2-3 obtains,, can be used as the particle of Detitanium-ore-type, brookite type or rutile-type and obtain according to calcining heat, the calcination time difference in when calcining.
The particle diameter of photochemical catalytic oxidation titanium particle, from the angle of photocatalysis, in the average mark shot directly, 20nm～150nm normally, preferred 40nm～100nm.
The BET specific area of photochemical catalytic oxidation titanium particle, the angle from photocatalysis is generally 100m 2/ g～500m 2/ g, preferred 300m 2/ g～400m 2/ g.
[photochemical catalytic oxidation tungsten particle]
So-called photochemical catalytic oxidation tungsten particle is meant the display light catalytic action and for granular tungsten oxide, can enumerates tungstic acid (WO usually 3) particle.The tungstic acid particle for example can be by adding acid in the aqueous solution of tungstates, and obtain wolframic acid with sediment, and the wolframic acid of gained is carried out calcining method and obtains.In addition, also can the method for thermal decomposition obtains by ammonium metatungstate, ammonium paratungstate are heated.
The particle diameter of photochemical catalytic oxidation tungsten particle, from the angle of photocatalysis, in the average mark shot directly, 50nm～200nm normally, preferred 80nm～130nm.
The BET specific area of photochemical catalytic oxidation tungsten particle, the angle from photocatalysis is generally 5m 2/ g～100m 2/ g, preferred 20m 2/ g～50m 2/ g.
The use amount of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is generally 4: 1～1: 8 than by quality ratio, is preferably 2: 3～3: 2.
[decentralized medium]
As decentralized medium, use with the aqueous medium of water usually as main component, particularly, can use the decentralized medium that contains water with the water use amount more than the 50 quality %, also can make water separately, can also be the mixed solvent of water and water-miscible organic solvent.As water-miscible organic solvent, for example can enumerate water-soluble alcohol solvent, acetone, methyl ethyl ketones etc. such as methyl alcohol, ethanol, propyl alcohol, butanols.
As the use amount of decentralized medium, with respect to the total amount of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, be generally 5 quality doubly～200 quality doubly, preferred 10 quality doubly～100 quality doubly.When the use amount of decentralized medium during less than 5 quality times, photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle be precipitation easily, and when surpassing 200 quality times, is disadvantageous from the angle of volumetric efficiency.
[photocatalyst dispersion liquid]
The hydrogen ion concentration of photocatalyst dispersion liquid of the present invention is pH0.5～pH8.0 normally, preferred pH1.0～pH7.0.Hydrogen ion concentration is during less than pH0.5, acidly crosses strong and complex operation; When surpassing pH8.0, photochemical catalytic oxidation tungsten particle may dissolve.The hydrogen ion concentration of photocatalyst dispersion liquid can be regulated by adding acid usually.As acid, for example can use nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetate, oxalic acid etc.
[surperficial is charged]
In photocatalyst dispersion liquid of the present invention, the surface charging of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is an identical polar, and particularly all positively charged or surface are all electronegative.
The metatitanic acid particle that obtains by said method 1, by the TiO 2 particles that said method 2-1～method 2-3 obtains, its surperficial positively charged usually.
Relative therewith, obtain wolframic acid and the wolframic acid of gained is carried out the tungsten oxide particle that calcining method obtains with sediment by in the aqueous solution of tungstates, adding acid, the tungsten oxide particle that thermal decomposition obtains by ammonium metatungstate, ammonium paratungstate etc. is heated, its surface is electronegative.
Therefore, at the electronegative above-mentioned photochemical catalytic oxidation tungsten particle period of the day from 11 p.m. to 1 a.m of above-mentioned photochemical catalytic oxidation titanium particle that uses surperficial positively charged and surface, for example can make the surperficial electronegative of photocatalytic titanium oxide particle, thereby in photocatalyst dispersion liquid of the present invention, use.
Want to make photochemical catalytic oxidation titanium particle surperficial electronegative of surperficial positively charged, it is scattered in decentralized medium, is dissolved with in the solution that can make the electronegative surface conditioning agent of this photocatalytic titanium oxide particle surface.As this surface conditioning agent, for example can enumerate polybasic carboxylic acid, phosphoric acid of dicarboxylic acids, tricarboxylic acids etc. and so on etc.As dicarboxylic acids, for example can enumerate oxalic acid etc.; For example can enumerate citric acid etc. as tricarboxylic acids.As polybasic carboxylic acid and phosphoric acid, can use free acid, also can use salt.As salt, for example can enumerate ammonium salt etc.As this surface conditioning agent, preferably can enumerate oxalic acid, ammonium oxalate etc.
The use amount of above-mentioned surface conditioning agent is with respect to TiO 2The photochemical catalytic oxidation titanium particle that converts from making fully charged angle of surface, is generally more than 0.001 mole times, and is preferred more than 0.02 mole times; From the angle of economy, be generally below 0.5 mole times, preferred below 0.3 mole times.
Be scattered in the solution that in decentralized medium, is dissolved with above-mentioned surface conditioning agent by the photochemical catalytic oxidation titanium particle that makes surperficial positively charged, the surface conditioning agent that dissolves in the surface processing solution just is adsorbed in the surface of photochemical catalytic oxidation titanium particle, can make the surface electronegative thus.
Photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle sub-surface charged can be measured by the Zeta potential when being scattered in solvent separately.The solvent that uses in the mensuration as Zeta potential can use to add hydrochloric acid and make hydrogen ion concentration be the sodium-chloride water solution of pH3.0 (0.01 mole of sodium chloride concentration/L).The use amount of solvent is generally 10000 mass parts～1000000 mass parts with respect to photochemical catalytic oxidation titanium particle or tungsten oxide particle.
[preparation of photocatalyst dispersion liquid]
Make the photochemical catalytic oxidation titanium particle of surperficial positively charged be scattered in that above-mentioned surface conditioning agent is dissolved in the decentralized medium and solution in, then by mixing, thereby can obtain photocatalyst dispersion liquid of the present invention with surface electronegative photochemical catalytic oxidation tungsten particle.
The photochemical catalytic oxidation titanium particle of surface behind the positively charged, also can be in being scattered in above-mentioned solution after, implement again after the dispersion treatment, mix with surface electronegative photochemical catalytic oxidation tungsten particle.Dispersion treatment can be undertaken by for example using the usual method of media-agitation type dispersion machine.
Photochemical catalytic oxidation tungsten particle can directly mix, but mixes with the state that is dispersed in the decentralized medium usually, and preferred further enforcement mixed after the dispersion treatment.Dispersion treatment can be undertaken by for example using the usual method of media-agitation type dispersion machine.
[electrophilic material or its precursor]
Photocatalyst dispersion liquid of the present invention can also contain electrophilic material or its precursor that can bring into play electrophilic by being supported on the photocatalysis body surface.The electrophilic material is by supporting in the photocatalysis body surface, suppresses to penetrate combining again of the hole that generates in the electronics that is excited to conduction band and the valence band by illumination, can further improve photocatalysis.
As this electrophilic material, for example can enumerate metals such as Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh, Co, preferred Cu, Pt, Au, Pd etc.In addition, can also enumerate the oxide and the hydroxide of these metals.
As the precursor of electrophilic material, be meant the compound that can be transformed into the electrophilic material on the surface of photocatalysis body.As this precursor, for example can enumerate nitrate, sulfate, halide, acylate, carbonate, phosphate of above-mentioned metal etc., particularly,, can enumerate copper nitrate (Cu (NO for example as the precursor of Cu 3) 2), copper sulphate (Cu (SO 4) 2), 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), copper oxychloride (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 of Pt, can enumerate platinum chloride (PtCl 2, PtCl 4), platinic bromide (PtBr 2, PtBr 4), platinum diiodide (PtI 2, PtI 4), potassium chloroplatinate (K 2(PtCl 4)), chloroplatinic acid (H 2(PtCl 6), sulfurous acid platinum (H 3(Pt (SO 3) 2OH), platinum oxide (PtO 2), dichloro 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), tetramino platinum closes platinum tetrachloride ((Pt (NH 3) 4) (PtCl 4)) etc.As the precursor of Au, can enumerate chlorauride (AuCl), gold bromide (AuBr), auric iodide (AuI), gold hydroxide (Au (OH) 2), tetra chlorauric acid (HAuCl 4), potassium chloroaurate (KAuCl 4), potassium auric bromide (KAuBr 4), gold oxide (Au 2O 3) etc.In addition, as the precursor of Pd, 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)) etc.
These electrophilic materials or its precursor can be used singly or in combination of two or more respectively.
When using these electrophilic materials or its precursor, its use amount converts with metallic atom, total with respect to photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is measured 100 mass parts, is generally 0.005 mass parts～0.6 mass parts, preferred 0.01 mass parts～0.4 mass parts.During use amount less than 0.005 mass parts, the raising of the photocatalytic activity that is obtained by the use of electrophilic material is insufficient, and when surpassing 0.6 mass parts, it is insufficient that photocatalysis becomes on the contrary easily.
The photocatalyst dispersion liquid that contains this electrophilic material or its precursor for example can be with similarly above-mentioned, and after photocatalytic titanium oxide dispersion liquid and photochemical catalytic oxidation tungsten dispersion liquid were mixed, the method that adds electrophilic material or its precursor obtained.And, under the situation that adds precursor, also can carry out illumination after this and penetrate.As the light of irradiation, can be visible light, also can be ultraviolet ray.Penetrate by carrying out illumination, just precursor can be transformed into the electrophilic material.Irradiation can the phot-luminescence catalytic body light time of wavelength, precursor is supported in the photocatalysis body particle surface as the electrophilic material by the electron reduction that generates through optical excitation.
[additive]
Photocatalyst dispersion liquid of the present invention can also contain additive in the charged scope that does not change photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle sub-surface.
As additive, for example can enumerate the additive that adds so that photocatalysis rises to purpose, particularly can enumerate silicon compounds such as amorphous silicon oxide, silica sol, waterglass, organopolysiloxane; Aluminium compounds such as amorphous alumina, alumina sol, aluminium hydroxide; The aluminosilicate of zeolite, kaolin and so on; Alkaline-earth metals oxide or alkaline-earth metal hydroxide 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.These additives can be distinguished use separately, also can make up two or more uses.
In addition, (spy opens flat 8-67835 communique can also to enumerate adhesive that photochemical catalytic oxidation titanium particle in order to be coated on photocatalyst dispersion liquid on the substrate surface and photochemical catalytic oxidation tungsten particle remain on substrate surface more firmly etc., 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 the 2007-161824 communique).
The photocatalyst dispersion liquid that contains this additive can be by for example obtaining photocatalytic titanium oxide dispersion liquid and photochemical catalytic oxidation tungsten dispersion liquid being mixed the method for adding additive in the photocatalyst dispersion liquid that obtains.
[formation of photocatalysis body layer]
By photocatalyst dispersion liquid of the present invention being coated the surface of base material, make the decentralized medium volatilization, thereby can be manufactured on the photo-catalysis function goods that substrate surface is formed with the photocatalysis body layer, this photocatalysis body layer contains photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, and the display light catalytic action.
When photocatalyst dispersion liquid contains electrophilic material or its precursor, electrophilic material or its precursor are supported in the surface of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, during body, the precursor that is supported is transformed into the electrophilic material after supporting before use.
These photo-catalysis function goods maintain photocatalysis body on its surface can tolerate practical intensity usually.Photocatalysis body used herein can use different shapes such as particle, fiber, thin slice, and its size can suitably be selected according to purposes, surface texture.In addition, when the surface filming of photo-catalysis function goods, its thickness also can suitably be selected and forms at number 100nm～number mm with photocatalysis body.Photocatalysis body preferably remains on the inner surface of the photo-catalysis function goods that the material by plastics, metal, pottery, timber, concrete, paper and so on forms and the face that visible light shone in the outer surface, and be with the position that produces odorant continuously or the face that spatially links to each other intermittently.
[photo-catalysis function goods]
As the example of photo-catalysis function goods, can be listed below goods.
Clothes (underwear, pajamas, suits, kimonos, aprons), clothing items (socks, hat, collar Belts, handkerchiefs, belts), belongings (umbrellas, walking sticks, fan, fan, accessories, eyewear, Wig), bags, portable bags, shoes, smoking paraphernalia (pipes, pipe racks, pipe cleaners, tobacco Bags, tobacco bags (ta ば ko into slightly), ashtrays, lighters, desktop lighters, playing with clock Lighters, matchboxes, gas igniter), make-up beauty salon equipment (compact, perfume bottles, perfume Sprayers, pocket mirror, with the child's mirror, shaving brush, brushes, combs, hair brushes, Nail clippers, hair curlers, curling iron, hair dryer, manicure knife, manicure with cuticle, Manicure with a file, Hair clipper, electric hair clipper, Western razor, Japanese razors, safety razor, safety razor Spare blades, portable razor, electric razor, hairdressing chairs, buttons, zippers), flooring Loaded material (carpet, tatami surface, tatami edge material, flowers seats, cushions, cushions cover, cushion, cushion Cover, bath mats, door mats, blankets), bedding (futon, futon covers, blankets, sheets, pillows, Pillowcases, sleeping bags, mattresses), curtains, blinds, louver blades, bottom rail shutters, blinds Windows ladder, curtain, curtain shop, beaded curtains, tablecloths, napkins, table cloth heart, placemats, interior Accessories (vases, ornaments, decorative frames, columns hanging, wall, arts and crafts hanging dish, artificial flowers), Wallpaper, deodorants, washing and cleaning supplies (pots, washboard, washing machine, washing machine with dryer Machine, washing machine drain, rods, rods supports, rods pillar, hangers, clothesline, Laundry folder, dryers, drying is dryer, iron, ironing board, ironing board, trouser press, automatic laundry Machines, brooms, cleaning brush, clothes brush, dustpan, dusters, rags, mop, hand cleaners, garbage Dustbin, electric vacuum cleaners, electric floor polishing machines, electric floor polishing machine brush, electric shoe polisher), Household hygiene supplies (toothbrush, toothbrush box, toothbrush holder, electric toothbrush, electric toothbrush brush Head, tweezers, digging Ershao, Cuozao towel, bath brush, soap, wash basin, towels, towels, eye Doser, eyewash, electric mosquito traps, insect repellent container, deodorant container), cooking and eating Appliances (wash basin, drain basket, wash rice devices, cooking material is soaked, kettle, rice cooker, electric warmers, Pot, boiled egg, the lid, the lid with Tiniu, inner pot with a lid (na bell with a drop expands shabu ta), put the pot Children, kettle, electric kettle, warm wine, steamer, steamer, frying pan, omelette pans, coffee machine, burning Grill, grill plates), cooking appliances (furnace, stove, microwave, oven, toaster, toasted Bread oven, oven, cooker, peeler, fruit to heart devices, grinding machine, home meat grinder, cut Machine, ice machine, dried bonito shavings device (cut ri lator), pulp machine (juicer mixer), juice Machine, lemon juicer, food mixers, hand blenders, whipped cocktail shakers, ice Ice cream machine, coffee grinder, spices grinder, sesame grinders, ice picks, nuts, pliers, household Pasta machine, made cake machine, cooking filters, tea strainer, drain rack, cooking squeezer, open cans Device, Bottle Opener, sushi mold, dessert molds, ice cube tray, handle, food clip, cheese cutter, Egg cutter, dishwasher, tableware dryer, heat storage boxes, refrigerators, freezers, ice machines, water Coolers, beverage vending machines, metering meter boxes, household water purifiers, cup holder, dish rack, knife, Cup holder, bottle holder, wine holder, tray, dining table, coffee table, cup holder, pot holder, tray mats, mugs Paul Wen sets, oven hood, napkins holder, napkin ring, seasoning bottle rack, chopsticks boxes, chopsticks frame, chopstick, Toothpick Holder), weddings and funerals supplies (shrines, incense drawer, seeking Qiantong, statues, shrines, with canopy Ornaments, statues, rosaries, the volume table, with a bell ceremonies, altars, tombstones, tomb standard, coffin, funeral Burial ritual vases, funeral ritual incense, funeral ritual lighting, funeral ritual candelabra, (Buddha) with seat square wooden tray, amulets, pray bags, palanquin, red packets, white packet signing ceremony, Gift rope, Christmas tree, Christmas tree ornaments, Christmas ribbon), supplies (sewing with a spatula, draw Powder, sewing spools, sewing needles, inserted, sewing box, thimble, knitting needles, jewelry boxes, ring Boxes, home nebulizer, home nebulizer nozzle), furniture (beds, hammocks, chairs, benches, Sofa Bed, legless chairs, chair covers, stools, benches, chairs errands, child walker, table, Table with chairs, reading books, kang table, dining table, dining table errands, desk, TV table, flower pot holder Children, table car, closet, cabinets, corner cabinets, bookcases, sideboards, chest of drawers, sorting racks, Cabinet, shoe, clothes sorting boxes, no cover boxes, daily necessities cabinets, safes, laptop safes, insurance Cabinet locks, lockers, dressing basket, dresser, mirror, wall mirror, desk stand mirrors, screens, Folding screen, hat racks, furniture hinges, furniture locks, furniture handles, furniture handles, furniture With Tiniu, resting seat furniture, furniture with shelves, furniture, decorative metal parts, furniture, doors controller), Indoor lap finishing boxes (hanging hooks, hangers, skirt racks, tie racks, towel racks, cloth hanger, hanging Matter hooks, magazine storage boxes, newspaper racks, umbrella stands, slipper rack, under-floor storage cabinets), according to Ming appliances (incandescent, incandescent decorative, closed bulbs, infrared bulbs, halogen bulbs, fluorescent Light, fluorescent starter, sodium lamps, xenon lamps, ceiling lamps, ceiling lamps lampshades, chandeliers, Chandelier hangings, ceiling chandeliers, ceiling pendant lamp, ceiling lamp hanging, ceiling, ceiling Lamp shade, embedded ceiling lights, ceiling lights blinds, ceiling lights through the mask, wall, wall lamp, Wall lights, wall into the sky lights (wall direct mounting light), the wall into the sky lamp shade, table lamps, floor Lamps, lamp shade, lamp, lamppost, street lamp sets, garden lights, door lights, flashlights, hand Torch cover, pocket lamps, portable lamps, oil lamps, lanterns, candlesticks, lanterns, stone lanterns, germicidal lamp, Searchlight, spotlight), heating and cooling devices (heaters, stoves, gas stoves, kerosene heaters, heaters With a combustion cylinder, radiator guards, heaters, panel heaters, air conditioners, indoor coolers, air Call the outdoor unit, solar water heaters, solar water heater tank, brazier, fireplace, charcoal baskets, electric Kotatsu, kotatsu electric heaters, foot warmers, hot water bottle, warmer, foot warmer, electric fans, ceiling fans, changing Air fan, ventilation fan filters, fan cover, Hoods, dehumidifiers, humidifiers, air net Equalizer), kitchen and sanitary appliances (cooking sets, sink, sink with sink, sink with garbage Rubbish box, sink with drip plates, straw broom boxes, garbage disposal, stove, drain rack, wall heater, Wall heater with a heat exchanger, heating tub, heated tub with exhaust pipes, heated tub Heat exchangers, bathtub, children bathtub, bathroom with shower at Bath, Bath cover, bathtub aprons, shower Bath head, bathroom with a shower the bathroom floor drain, bath mats, soap, wall mounted wash basin, wall Style hand-washing, wash dresser, washstand drain plug, pre-wash sink or laundry tub, water fountains, wall Style toilet, toilet seat, toilet seat covers, wall-mounted urinals, bidets, waste tanks, septic tanks, Toilet with sink), to close the milk box, mailbox, mail recipient mouth metal parts, to close the newspaper boxes, Ladders pedal, foot ride, double ladder, toys (dolls, toy boat, toy cars, toy planes, Educational toys, talking toys, toy boxes (jack-in-the-box), pacifiers, toys fireworks, gas Balls, toy windmill), video games and supplies (trojans, jungle gym, swings, seesaws, slides, Children tricycle, children's car, three skates, skipping, stilts, shuttlecock board, shuttlecock board, chess, Bamboo dragonfly, sword jade ball, kite, ball, water ball, games with buoys, rings, yo-yo, pinball Games, slot machines, a pool table, board, chess board, chess piece, double six, baseball tour Game machine, mahjong, poker, assembling wooden toys, assembling toys, nine rings, blocks, insert play Tools, paper cutting, origami, drawing paper), athletic goods (baseball, baseball glove, baseball player sheath (Mitt), baseball mask, a baseball bat, tennis racket, tennis racket, tennis racket, table tennis, Badminton, badminton rackets, badminton pat boxes, golf clubs, golf clubs with a handle, Gower Cardiff club with head, golf clubs with head cover, golf clubs with bag, golf tees, slip Skis, ski poles, ski poles with a ring fixator skis, snowboards bags, four skates, transport Action athletic sled, water skiing, surfboards, scuba diving regulator, scuba diving snorkel, diving fins, Western-style bows, arrows, bamboo sword, sword with a breastplate, sword with armband, gymnastics horizontal bar, ice ax, wedge nails, Dumbbells, chest, shotguns, air guns), musical instruments (keyboards, wind instruments, stringed instruments to combat Musical instruments, synthesizers, music box, rhythm generator, metronome, pitch pipe, music stand), Fun Flavored entertainment supplies (cage, insect cage, dog houses, collars, ornamental fish tank), calligraphy utensils (town Paper, ink stone, ink stone boxes, canvas, paint boxes, chisel, clay craft knife, map, globe Meter, star charts), stationery (pen, pencil, ball pen, ballpoint pen with mechanical pencil, Pencil, brush, pen, marker, cap, pen holder, chalk boxes, ink bottle, electric pencil sharpener, Erasers, pads, seals, rotary seals, stamp pad, abacus, drawing board, drawing tables, write-through units (tracing stand), plotter, compass, Wire Gauge, protractor, like rules, regulations triangle, curve regulations, letters Sealing machines, letter opening machines, shredders, staplers, electric stapler, office punch, do Public electric punch, paper cutter, drilling machine, paper cutter, office paper clip, office stud Pin, pushpin, awl, tape racks, filing cabinets, books, bookends, pen, mail, letter inserted, pen Disk, penholder, stamp boxes, sealed boxes, telephone number summary table, desk, blackboard, blackboard eraser), do Common Paper Products (invoices, envelopes, magnetic cards, graph paper, notes, photo albums mount, slide mount, Tag, card mount, greeting cards, postcards, art postcards, Christmas cards, birthday cards, complex Write papers, drafts, checks, business cards, frames, scrapbook, manuals, diaries, books, folders, files, Folder with metal parts, paper clips, paper clip with metal parts, hanging folders, stationery scissors, notebooks, Sketchbook, letter books, photo albums, film bags, checkbook, book covers, books, brochures, calendars, Catalogs, posters, flyers, bookmarks, ticket, ticket, ticket shoe storage, house, brand name, Price list), packaging supplies (cans, bottles, boxes, drums, packaging boxes, packaging Plastic squeeze tubes, packaging tray, ampoule packaging, packaging sprayers, bags, straw bags, bag Equipped with containers, packaging container replacement plug, packaging container lid, cap, packaging guard, Wrapping paper, labels, packaging labels, packaging curtain, Eli sign, packaging mount), for advertising Tools (advertising equipment, advertising boards, billboards, advertising lights, advertising balloons, signs, photoelectric display, Scoreboard, banners, pennants, streamers chess, flagpoles, commodity showcase, display rack, merchandise Chan Column table, refrigerator showcase, display mannequins with plastic), apparatus handling equipment (cranes, transfer Belt, screw conveyor, conveyor chains, winches, cranes, chain block, lifts, escalators, Jacks, container, transport pallets, transport gas cylinders, pulleys, handling equipment with tracks), Vehicles (locomotives, buses, trolleys, trains, seats, ride with cars, buses, trucks, Dumpers, trucks loading station, truck sideboard, tractors, trailers, fire trucks, garbage Cars, trucks, snowmobiles, fork lift trucks, car headlamp, car taillights, auto With the steering wheel, automotive consoles, automotive gear lever, car wheels, car wheels, steam Car hubcaps, wheel covers for automobiles, automotive muffler, automotive bumpers, automobile dashboards, Car locks, car wipers, car alarm, car heater, automotive air-conditioning, Vehicle side mirror, automotive rear-view mirror, car seat, car radiator, snow chains, car Fenders, side window flashings, car sun visor, roof rack, motorcycles, motorcycle Car, motor tricycle, motorcycle headlight, taillight locomotive, locomotive shock absorbers, motorcycle fuel tank, Motorcycle muffler, motorcycle mirrors, motorcycle seats, motorcycle windshield, bike, bike rack, since Roading fenders, bike and wheeled, bicycle brake levers, bicycle brake caliper, self- Car foot pedals, bicycle car seat, car seat bicycle seat cover, bicycle alarm, self- Car headlight, taillight bicycle, bicycle with rear rack, bicycle frame, bicycle Locks, bicycle fork, bicycle rain gear, two trailers, child car exhaust, strollers, linear hair Motive traction trains), ships (passenger ships, cargo ships, motor boats, sailboats, sailing with a mast, rowing Boats, canoes, fishing boats, outboard motors, aircraft, airship), electrical components (batteries, storage Pool, solar cells, socket, table socket, plugs, lights with jack socket electron tubes, Printed wiring connectors, high frequency coaxial connectors, plug boxes, plugs, crimp terminal, then Contactors, grounding rods, terminal blocks, terminal blocks, electrical with handle), distribution (distribution mechanical appliances, Control mechanical appliances, cables, wires installation tools, rotary motor), communication electronics equipment (telephone Machines, public telephones, cell phones, telephone switches, radio, telegraph, teletype, Biography True, photo fax machines, communication relay exchanger, a radio communication equipment, antennas, parabolic antennas, Radio receivers, radio tuners, tape recorders, graphic equalizer, headphones, headsets , Microphones, microphone stand, a speaker, a speaker box, a television receiver, video tape recorder, DVD player, TV cameras, video cameras with tape recorders, television cameras used to take Viewfinder, cassette tapes, video tapes, records, compact disc (CD), DVD, magneto-optical, digital Word tapes, digital versatile disc (DVD)), computer, electronics applications, mechanical appliances, measuring Instrument (tape measure, vernier caliper, height gauge, micrometer, dial gauge, gauge blocks, scales, bathroom scales, Thermometer, thermometers), watches (watches, bracelet, watch, stopwatch, clock, wall clock), optical Equipment appliances (telescopes, binoculars, microscopes, magnifying glass, camera, overhead projector), Office equipment appliance (desktop computer, copiers, microfilm with readers, microfilm Read the printer chip used), Vending Machine (drinks vending machines, frozen food vending machines, Cigarette vending machines, ticket vending machines, stamp vending machines, vending machine money counter, Conversion machines, automatic teller machines, automatic ticket machines), security equipment appliances (dust mask, protective face Tools, helmets, life buoy, life jackets, fire hydrants, fire sensors, rotating warning lights, traffic signal Number machine, road reflector, road reflectors, hair chimney, oil boom), medical mechanical appliances (diagnosis Spa facilities with mechanical appliances, physiotherapy machinery, medical steel appliances, diagnostic mechanical appliances, surgical Mechanical Appliances, Disposal machinery equipment, dental mechanical appliances, functional recovery with appliances), Lee Devices and tools (knives, hand-held power tool, portable power tools, machine tools), fishery Mechanical appliances (fishing gear, fishing tackle), agricultural machinery and appliances (ground equipment used in agriculture, cultivation and management With machinery, harvesting machinery adjustment, the whole pole machine), livestock machinery appliances (feed mill, animal Produced by automatic feeding machine, automatic water machine with livestock, milking machines), mining machinery, construction machinery, Chemical use mechanical appliances (grinder, grinding machine, sorting machine), civil engineering structures (asphalt mix Concrete roads, wood roads, bridges, lock bolts, gate, gate gate, pressure tanks, gas Tanks, towers, poles, metal parts scaffolding poles, telephone poles with tape, caissons, puzzle Brick (black), sheet piles, sheet piles interfaces, sidewalk driveway isolation block, sidewalk concrete slab, Curbs, linings, road with telescopic interfaces, road safety fences, fence panels, anti-avalanche fences, Snow fences, berms stone, solid root block, wave breakers, dock fenders pieces, floating docks, floating breakwaters, Artificial reef, artificial reef blocks access hole cover, trench cover, agricultural weir, agricultural weir column), Housing (tents, greenhouses, plastic greenhouses, bathroom, sauna, window bars, window with lattice fence, stairs, Stair railings, handrails railings, handrails railings supporting, handrails with pillars, handrails with pole, exposed Desk, balcony with a bar, porch), outdoor equipment (doors, woodwork, doors, walls, walls with horizontal Wooden wall with a crossbar supporting, fence, fence with pole, fence decorative metal parts, garden fence, High sink, high sink plate, arch, telephone booths, mail boxes), building component parts (columns, Beams, wall constituting member constituting the ceiling member, the floor constituent parts, roof component parts, water flowing Tube), doors and windows sliding door (doors, glass doors, sliding door, sliding door, screen door, transom, building partitions, Folding doors, sliding doors, windows and doors with sliding door hinges, door sliding door with a crescent locks, door closers, sliding door handle, Doors sliding door with lever handle, curtain rails, curtain lining, curtain pull, curtain drapes, curtains hanging Hooks, curtain box, door frames, door engine, sliding door frame, double sash windows, rotate the sash, housing Column with shutter doors, roller shutter door rails for housing, housing cover with shutter doors), building exterior materials (Tile, concrete blocks, tiles, mosaics, floors, ceilings, wall panels, sheathing, ropes, Chains, screws, nuts, wood screws, cotter pins, washers, nails, rivets, bolts, wedges, Hinges, locks, keys, springs, wheels, casters with wheels, piping tube, hose, hose clamps, Protective cap tube, piping supports metal parts) and so on. ...
These photo-catalysis function goods show and high catalytic action can be applied to the decomposition of organic decomposition, nitrogen oxide by penetrating from the illumination of the visible light source of fluorescent lamp, sodium vapor lamp and so on.For example, if these photo-catalysis function goods are arranged in the indoor living environment of illumination, then can decompose, remove the odorant of aldehydes in the environment, thio-alcohol, ketone, ammonia and so on simply.
Below, the present invention will be described in more detail by embodiment, but the present invention is not subjected to the qualification of this embodiment.
In addition, the determination method among each embodiment is as follows.
1.BET specific area
The BET specific area of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is used specific area measuring device (Yuasa Ionics corporate system " MONOSORB "), measures by nitrogen adsorption method.
2. average mark shot footpath (nm)
Use ultra micro particle size distribution device (Coulter corporate system " N4Plus "), the size distribution of sample is measured, go up subsidiary software by this device and carry out single decentralized model automatically and resolve, as the average mark shot directly the result that obtains.
3. crystal formation
Use X-ray diffraction device (Rigaku corporate system " RINT 2000/PC ") to measure X-ray diffraction spectrum, determine crystal formation by its spectrum.
4. the Zeta potential of photocatalysis body
The sodium-chloride water solution of hydrogen ion concentration being adjusted to pH3.0 adding hydrochloric acid is (in 0.01 mole of the sodium chloride concentration/L), photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is disperseed, use laser zeta potentiometer (the big system ELS-6000 of tomb electronics corporation) to measure Zeta potential.The use amount of sodium-chloride water solution with respect to photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle use amount separately be 250000 quality doubly.If this Zeta potential is positive, photocatalysis body surface positively charged then, if negative, then surperficial electronegative.
5. photocatalytic activity 1[acetaldehyde decomposition ability]
With airtight in the working sample adding airbag (internal capacity 1L) that obtains among each embodiment, make then to be vacuum in this airbag, the volume ratio of enclosing oxygen and nitrogen afterwards is 1: 4 mist 600ml.And then enclose the nitrogen 3ml that contains acetaldehyde with 1 capacity %, in the dark kept 1 hour under the room temperature.Then, be light source with commercially available white fluorescent lamp, so that near the illumination the working sample is the mode of 1000 Luxs (" T-10 " with Minolta company manufacturing measures) airbag is set, carry out the decomposition reaction of acetaldehyde.Near the working sample ultraviolet ray intensity is 6.5 μ W/cm 2(light receiver " UD-36 " that the said firm's manufacturing has been installed on the ultraviolet ray intensity meter " UVR-2 " of Topcon corporate system is measured).After fluorescent lamp, the gas in the airbag taken a sample in per 1.5 hours, measure the residual concentration of acetaldehyde with gas-chromatography (Shimadzu Seisakusho Ltd. makes " GC-14A "), calculate the primary first-order equation velocity constant by acetaldehyde concentration with respect to the reduction of irradiation time, with it as acetaldehyde decomposition ability.The primary first-order equation velocity constant is big more, and then the capacity of decomposition of acetaldehyde is big more.
6. photocatalytic activity 2[acetone capacity of decomposition]
With airtight in the working sample adding airbag (internal capacity 1L) that obtains among each embodiment, make then to be vacuum in this airbag, the volume ratio of enclosing oxygen and nitrogen afterwards is 1: 4 mist 600ml.And then enclose the nitrogen 1.8ml that contains acetone with 1 capacity %, in the dark under room temperature, kept 1 hour.Then, be light source with commercially available white fluorescent lamp, so that near the illumination the working sample is the mode of 1000 Luxs (" T-10 " with Minolta company manufacturing measures) airbag is set, carry out the decomposition reaction of acetone.Near the working sample ultraviolet ray intensity is 6.5 μ W/cm 2(light receiver " UD-36 " that the said firm's manufacturing has been installed on the ultraviolet ray intensity meter " UVR-2 " of Topcon corporate system is measured).After fluorescent lamp, the gas in the airbag taken a sample in per 1.5 hours, measure the residual concentration of acetone with gas-chromatography (Shimadzu Seisakusho Ltd. makes " GC-14A "), calculate the primary first-order equation velocity constant by acetone concentration with respect to the reduction of irradiation time, with it as the acetone capacity of decomposition.The primary first-order equation velocity constant is big more, and the capacity of decomposition of acetone is big more.
The preparation of reference example 1[photochemical catalytic oxidation titanium particle and dispersion liquid thereof]
As the photochemical catalytic oxidation titanium particle, use the metatitanic acid filter cake that will filter behind the aqueous hydrolysis of titanyl sulfate and get (with TiO 2Convert titaniferous composition 42 quality %).
2.70g is dissolved in the 60.2g water with oxalic acid (pure pharmaceutical worker already makes with light), obtains oxalic acid aqueous solution.In this oxalic acid aqueous solution, add above-mentioned metatitanic acid filter cake 57.1g, mix, obtain mixture.Oxalic acid use amount in this mixture is 0.1 mole with respect to 1 mole of metatitanic acid.
Working medium stirring-type dispersion machine (50 haze machinery productions made " 4TSG-1/8 ") carries out the dispersion treatment of this mixture under following condition, obtain the photocatalytic titanium oxide dispersion liquid.
Decentralized medium: the zirconia system mill pearl of external diameter 0.05mm
Treatment temperature: 20 ℃
Processing time: 3 hours
Revolution: 2000rpm
The average mark shot of the photochemical catalytic oxidation titanium particle in the photocatalytic titanium oxide dispersion liquid of gained directly is 85nm.Hydrogen ion concentration is pH1.6.The part of the photocatalytic titanium oxide dispersion liquid of gained is carried out vacuum drying, obtain solid state component, measure the BET specific area of this solid state component, the result is 325m 2/ g.The crystal formation of the solid state component of the photocatalytic titanium oxide dispersion liquid of gained is a Detitanium-ore-type.In addition, measure the X-ray diffraction spectrum of the solid state component of mixture before the dispersion treatment and the photocatalytic titanium oxide dispersion liquid after the dispersion treatment respectively,, do not see variation by the crystalline texture due to the dispersion treatment through relatively.The Zeta potential of the photochemical catalytic oxidation titanium particle of the photocatalytic titanium oxide dispersion liquid of gained is-19.9mV.
The preparation of reference example 2[photochemical catalytic oxidation tungsten particle and dispersion liquid thereof]
In ion exchange water 4kg, add tungsten oxide powder (purity 99.99%, high-purity chemical corporate system) 1kg, obtain mixture after the mixing.Working medium stirring-type dispersion machine (KotobukiEngineering﹠amp; Manufacturing company makes, " ULTRAAPEX MILL UAM-11009 "), under following condition, carry out the dispersion treatment of this mixture, obtain photochemical catalytic oxidation tungsten dispersion liquid.
Decentralized medium: the zirconia system mill pearl 1.85kg of diameter 0.05mm
Mixing speed: peripheral speed 12.6m/ second
Flow velocity: 0.25L/min
Processing time: add up to about 50 minutes
The average mark shot of photochemical catalytic oxidation tungsten particle in the photochemical catalytic oxidation tungsten dispersion liquid of gained directly is 96nm.Hydrogen ion concentration is pH2.2.The part of this dispersion liquid is carried out vacuum drying, obtain solid state component, the BET specific area of this solid state component is 37m 2/ g.In addition, measure the X-ray diffraction spectrum of the solid state component of mixture before the dispersion treatment and the photochemical catalytic oxidation tungsten dispersion liquid after the dispersion treatment respectively, through relatively, crystal formation all is WO 3, do not see by the crystal formation due to the dispersion treatment changing.The Zeta potential of photochemical catalytic oxidation tungsten particle in the photochemical catalytic oxidation tungsten dispersion liquid is-25.5mV.
Embodiment 1
Is that the mode of 1: 3 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 1 and the reference example 2 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, obtains photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts (solid component concentration 5 quality %).Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
In glass system culture dish (external diameter 70mm, internal diameter 66mm, high 14mm, the about 48ml of capacity), drip the above-mentioned photocatalyst dispersion liquid that obtains, the dripping quantity that converts by solid state component of every bottom surface unit are is 1g/m 2, treat after launch equably the whole bottom surface of culture dish, in 110 ℃ drying machine, in atmosphere, kept 1 hour, make its drying, thereby form the photocatalysis body layer in the bottom surface of glass system culture dish.To the ultraviolet ray that this photocatalysis body layer irradiation was sent by blackout in 16 hours, making uitraviolet intensity is 2mW/cm 2, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.351h -1
Embodiment 2
The photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that will obtain in the reference example 1 and reference example 2 is the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 1, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.372h -1In addition, even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
Embodiment 3
The photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that will obtain in the reference example 1 and reference example 2 is the mode of 3: 1 (mass ratio) is mixed with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 1, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.282h -1In addition, even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
Comparative example 1
Except using commercially available titanium oxide dispersion liquid (the former industry corporate system of stone " STS-01 ", contain nitric acid, the average mark shot is directly for 50nm) beyond the photocatalytic titanium oxide dispersion liquid that replaces obtaining in the reference example 1, all the other are operated similarly to Example 1, the preparation photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.This photocatalyst dispersion liquid produces aggregated particle in the preservation process, Separation of Solid and Liquid takes place.The Zeta potential of contained Titanium particles is+40.1mV in this titanium oxide dispersion liquid (STS-01) in addition.
Comparative example 2
The photocatalytic titanium oxide dispersion liquid that the same commercially available titanium oxide dispersion liquid (STS-01) that uses in use and comparative example 1 replaces obtaining in the reference example 1, all the other are operated similarly to Example 2, the preparation photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.This photocatalyst dispersion liquid produces aggregated particle in the preservation process, Separation of Solid and Liquid takes place.
Comparative example 3
The photocatalytic titanium oxide dispersion liquid that the same commercially available titanium oxide dispersion liquid (STS-01) that uses in use and comparative example 1 replaces obtaining in the reference example 1, all the other are operated similarly to Example 3, the preparation photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.This photocatalyst dispersion liquid produces aggregated particle in the preservation process, Separation of Solid and Liquid takes place.
Embodiment 4
Is that the mode of 1: 3 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 1 and the reference example 2 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds chloroplatinic acid (H 2PtCl 6) the aqueous solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of chloroplatinic acid converts with pt atom, with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, is 0.06 mass parts.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.382h -1
Embodiment 5
The photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that will obtain in the reference example 1 and reference example 2 is the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 4, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.625h -1
Embodiment 6
The photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that will obtain in the reference example 1 and reference example 2 is the mode of 3: 1 (mass ratio) is mixed with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 4, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.380h -1
Embodiment 7
Except with chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution becomes with pt atom and convert, be beyond 0.03 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle that all the other are operated similarly to Example 5, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.451h -1
Embodiment 8
Except with chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution becomes with pt atom and convert, be beyond 0.1 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle that all the other are operated similarly to Example 5, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.551h -1
Embodiment 9
Except with chloroplatinic acid (H 2PtCl 6) use amount of the aqueous solution becomes with pt atom and convert, be beyond 0.3 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle that all the other are operated similarly to Example 5, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.451h -1
Embodiment 10
Is that the mode of 1: 3 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 1 and the reference example 2 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds copper nitrate (Cu (NO 3) 2) the aqueous solution, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts (solid component concentration 5 quality %).And the use amount of copper nitrate aqueous solution converts, is 0.03 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle with copper atom.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.407h -1
Embodiment 11
Convert, be 0.06 mass parts except the use amount with copper nitrate aqueous solution becomes with copper atom with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 10, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.408h -1
Embodiment 12
Except the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that will obtain in the reference example 1 and the reference example 2 is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and the use amount of copper nitrate aqueous solution become with copper atom convert, be beyond 0.01 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 10, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.394h -1
Embodiment 13
Convert, be 0.03 mass parts except the use amount with copper nitrate aqueous solution becomes with copper atom with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 12, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.Even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, thereby form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.396h -1
The preparation of reference example 3[photochemical catalytic oxidation titanium particle and dispersion liquid thereof]
As the photochemical catalytic oxidation titanium particle, use the metatitanic acid filter cake that will filter behind the aqueous hydrolysis of titanyl sulfate and get (with TiO 2Convert titaniferous composition 45 quality %).
158g is dissolved in the 1.88kg water with oxalic acid dihydrate (pure pharmaceutical worker already makes with light), obtains oxalic acid aqueous solution.In this oxalic acid aqueous solution, add above-mentioned metatitanic acid filter cake 2.2kg, mix, obtain mixture.The use amount of the oxalic acid in this mixture is 0.1 mole with respect to 1 mole of metatitanic acid.
Working medium stirring-type dispersion machine (Kotobuki Engineering﹠amp; Manufacturing company makes, " ULTRAAPEXMILL UAM-11009 "), under following condition, carry out the dispersion treatment of this mixture, obtain the photocatalytic titanium oxide dispersion liquid.
Decentralized medium: the zirconia system mill pearl 1.85kg of diameter 0.05mm
Mixing speed: peripheral speed 12.6m/ second
Flow velocity: 0.25L/min
The interpolation of water: handle beginning after 17 minutes.Append and add water 5kg.
Processing time: add up to about 90 minutes
The average mark shot of the photochemical catalytic oxidation titanium particle in the photocatalytic titanium oxide dispersion liquid of gained directly is 55nm.Hydrogen ion concentration is pH1.5.The part of gained photocatalytic titanium oxide dispersion liquid is carried out vacuum drying, obtain solid state component, measure the BET specific area of this solid state component, the result is 301m 2/ g.The crystal formation of the solid state component of the photocatalytic titanium oxide dispersion liquid of gained is a Detitanium-ore-type.In addition, measure the X-ray diffraction spectrum of the solid state component of mixture before the dispersion treatment and the photocatalytic titanium oxide dispersion liquid after the dispersion treatment respectively,, do not see variation by the crystalline texture due to the dispersion treatment through relatively.The Zeta potential of the photochemical catalytic oxidation titanium particle of the photocatalytic titanium oxide dispersion liquid of gained is-10.5mV.
The preparation of reference example 4[photochemical catalytic oxidation tungsten particle and dispersion liquid thereof]
With ammonium paratungstate (Japanese inorganic chemistry system) in air in 700 ℃ the calcining 6 hours, obtain the tungsten oxide powder.In ion exchange water 4kg, add this tungsten oxide powder 1kg, obtain mixture after the mixing.Working medium stirring-type dispersion machine (Kotobuki Engineering﹠amp; Manufacturing company makes, " ULTRAAPEXMILL UAM-11009 "), under following condition, carry out the dispersion treatment of this mixture, obtain photochemical catalytic oxidation tungsten dispersion liquid.
Decentralized medium: the zirconia system mill pearl 1.85kg of diameter 0.05mm
Mixing speed: peripheral speed 12.6m/ second
Flow velocity: 0.25L/min
Processing time: add up to about 50 minutes
The average mark shot of photochemical catalytic oxidation tungsten particle in the photochemical catalytic oxidation tungsten dispersion liquid of gained directly is 114nm.Hydrogen ion concentration is pH2.6.The part of this dispersion liquid is carried out vacuum drying, obtain solid state component, the BET specific area of this solid state component is 34m 2/ g.In addition, measure the X-ray diffraction spectrum of the solid state component of mixture before the dispersion treatment and the photochemical catalytic oxidation tungsten dispersion liquid after the dispersion treatment respectively, through relatively, crystal formation all is WO 3, do not see variation by the crystal formation due to the dispersion treatment.The Zeta potential of photochemical catalytic oxidation tungsten particle in the photochemical catalytic oxidation tungsten dispersion liquid is-10.3mV.
Embodiment 14
The photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that will obtain in the reference example 3 and reference example 4 is the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, all the other are operated similarly to Example 2, obtain photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.380h -1In addition, even this photocatalyst dispersion liquid is not seen Separation of Solid and Liquid yet after preservation.
Embodiment 15
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds chloroplatinic acid (H 2PtCl 6) the aqueous solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of chloroplatinic acid converts with pt atom, is 0.1 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, bottom surface at glass system culture dish forms the photocatalysis body layer, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.622h -1
Embodiment 16
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds tetra chlorauric acid (HAuCl 4) the aqueous solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of tetra chlorauric acid converts with gold atom, is 0.1 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the result is that rate constant is 0.587h -1
Embodiment 17
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds palladium bichloride (PdCl 2) aqueous hydrochloric acid solution (with PdCl 2Powder 0.252g is dissolved in the aqueous solution of being made up of the aqueous hydrochloric acid solution 9.41g of concentration 1mol/L and 90.43g water), make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of palladium bichloride converts with the palladium atom, is 0.1 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.652h -1
Embodiment 18
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds tetra chlorauric acid (HAuCl 4) the aqueous solution and embodiment 17 in the palladium bichloride (PdCl that uses 2) aqueous hydrochloric acid solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of tetra chlorauric acid converts with gold atom, is 0.067 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle; The use amount of palladium bichloride converts with the palladium atom, is 0.033 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.662h -1
Embodiment 19
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds tetra chlorauric acid (HAuCl 4) the aqueous solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of tetra chlorauric acid converts with gold atom, is 0.1 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
30g transfers in the 100ml beaker with the photocatalysis dispersion liquid, uses ultrahigh pressure mercury lamp (Ushio motor system, light-source box: MPL-25101, ultrahigh pressure mercury lamp: USH-250BY, lamp power supply: HB-25103BY) carry out 3 hours ultraviolet ray irradiation while stir.Penetrate through illumination, tetra chlorauric acid is reduced to gold, and the color of dispersion liquid becomes lavender by cream color.The Separation of Solid and Liquid of also not seeing photocatalyst dispersion liquid after the ultraviolet ray irradiation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.750h -1
Embodiment 20
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds tetra chlorauric acid (HAuCl 4) the aqueous solution and embodiment 17 in the palladium bichloride (PdCl that uses 2) aqueous hydrochloric acid solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of tetra chlorauric acid converts with gold atom, is 0.067 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle; The use amount of palladium bichloride converts with the palladium atom, is 0.033 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
30g transfers in the 100ml beaker with the photocatalysis dispersion liquid, while stir the ultraviolet ray irradiation of carrying out 3 hours similarly to Example 19.Penetrate through illumination, tetra chlorauric acid and palladium bichloride are reduced to gold and palladium respectively, and the color of dispersion liquid becomes grey by cream color.The Separation of Solid and Liquid of also not seeing photocatalyst dispersion liquid after the ultraviolet ray irradiation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.805h -1
Embodiment 21
Is that the mode of 1: 1 (mass ratio) is mixed with the photochemical catalytic oxidation tungsten dispersion liquid that obtains in the photocatalytic titanium oxide dispersion liquid that obtains in the reference example 3 and the reference example 4 with the photochemical catalytic oxidation titanium particle and the use amount ratio of photochemical catalytic oxidation tungsten particle, and then adds tetra chlorauric acid (HAuCl 4) the aqueous solution and embodiment 17 in the palladium bichloride (PdCl that uses 2) aqueous hydrochloric acid solution, make photocatalyst dispersion liquid.Solid state component in these photocatalyst dispersion liquid 100 mass parts is 5 mass parts (solid component concentration 5 quality %).And the use amount of tetra chlorauric acid converts with gold atom, is 0.02 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle; The use amount of palladium bichloride converts with the palladium atom, is 0.01 mass parts with respect to total use amount 100 mass parts of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle.This photocatalyst dispersion liquid is not seen Separation of Solid and Liquid.
30g transfers in the 100ml beaker with the photocatalysis dispersion liquid, while stir the ultraviolet ray irradiation of carrying out 3 hours similarly to Example 19.Penetrate through illumination, tetra chlorauric acid and palladium bichloride are reduced to gold and palladium respectively, and the color of dispersion liquid becomes grey by cream color.The Separation of Solid and Liquid of also not seeing photocatalyst dispersion liquid after the ultraviolet ray irradiation.
The photocatalyst dispersion liquid that in using the above-mentioned photocatalyst dispersion liquid replacement embodiment 1 that obtains, obtains, all the other are operated similarly to Example 1, form the photocatalysis body layer in the bottom surface of glass system culture dish thus, obtain working sample, estimate photocatalytic activity (acetaldehyde decomposition ability), the bearing reaction velocity constant is 0.719h -1
Comparative example 4
The photocatalytic titanium oxide dispersion liquid that obtains except use commercially available titanium oxide dispersion liquid (STS-01) the replacement reference example 3 that uses in comparative example 1 in, all the other are operated similarly to Example 14, the preparation photocatalyst dispersion liquid.The photochemical catalytic oxidation titanium particle in these photocatalyst dispersion liquid 100 mass parts and the total amount of photochemical catalytic oxidation tungsten particle are 5 mass parts.This photocatalyst dispersion liquid produces aggregated particle in the preservation process, Separation of Solid and Liquid takes place.
Embodiment 22
In glass system culture dish (external diameter 70mm, internal diameter 66mm, high 14mm, the about 48ml of capacity), drip the photocatalyst dispersion liquid that obtains among the embodiment 14, the dripping quantity that converts by solid state component of every bottom surface unit are is 1g/m 2, treat after launch equably the whole bottom surface of culture dish, in 110 ℃ drying machine, in atmosphere, kept 1 hour, make its drying, thereby form the photocatalysis body layer in the bottom surface of glass system culture dish.To the ultraviolet ray that this photocatalysis body layer irradiation was sent by blackout in 16 hours, making uitraviolet intensity is 2mW/cm 2, obtain working sample, estimate photocatalytic activity (acetone capacity of decomposition), the bearing reaction velocity constant is 0.117h -1
Embodiment 23
In glass system culture dish (external diameter 70mm, internal diameter 66mm, high 14mm, the about 48ml of capacity), drip the photocatalyst dispersion liquid that obtains among the embodiment 19, the dripping quantity that the solid state component of every bottom surface unit are converts is 1g/m 2, treat after launch equably the whole bottom surface of culture dish, in 110 ℃ drying machine, in atmosphere, kept 1 hour, make its drying, form the photocatalysis body layer in the bottom surface of glass system culture dish.To the ultraviolet ray that this photocatalysis body layer irradiation was sent by blackout in 16 hours, making uitraviolet intensity is 2mW/cm 2, obtain working sample, estimate photocatalytic activity (acetone capacity of decomposition), the bearing reaction velocity constant is 0.127h -1
Embodiment 24
In glass system culture dish (external diameter 70mm, internal diameter 66mm, high 14mm, the about 48ml of capacity), drip the photocatalyst dispersion liquid that obtains among the embodiment 21, the dripping quantity that the solid state component of every bottom surface unit are converts is 1g/m 2, treat after launch equably the whole bottom surface of culture dish, in 110 ℃ drying machine, in atmosphere, kept 1 hour, make its drying, thereby form the photocatalysis body layer in the bottom surface of glass system culture dish.To the ultraviolet ray that this photocatalysis body layer irradiation was sent by blackout in 16 hours, making uitraviolet intensity is 2mW/cm 2, obtain working sample, estimate photocatalytic activity (acetone capacity of decomposition), the result is that rate constant is 0.160h -1
Embodiment 25
Coat on the ceiling spare respectively the photocatalyst dispersion liquid that obtains among the embodiment 1～24 and drying, carrying out illumination by room lighting penetrates, thereby can reduce the volatile organic matter concentration such as formaldehyde, acetaldehyde, acetone of the interior space, the concentration of odorant, and then can kill pathogens such as staphylococcus aureus, Escherichia coli.
Embodiment 26
Coat on the ceramic tile respectively the photocatalyst dispersion liquid that obtains among the embodiment 1～24 and drying, carrying out illumination by room lighting penetrates, thereby can reduce the concentration of the volatile organic matter such as formaldehyde, acetaldehyde, acetone of the interior space, the concentration of odorant, and then can kill pathogens such as staphylococcus aureus, Escherichia coli.
Embodiment 27
Coat the photocatalyst dispersion liquid that obtains among the embodiment 1～24 on glass and dry respectively, carrying out illumination by room lighting penetrates, thereby can reduce the concentration of the volatile organic matter such as formaldehyde, acetaldehyde, acetone of the interior space, the concentration of odorant, and then can kill pathogens such as staphylococcus aureus, Escherichia coli.
Embodiment 28
Coat on the wallpaper respectively the photocatalyst dispersion liquid that obtains among the embodiment 1～24 and drying, carrying out illumination by room lighting penetrates, thereby can reduce the concentration of the volatile organic matter such as formaldehyde, acetaldehyde, acetone of the interior space, the concentration of odorant, and then can kill pathogens such as staphylococcus aureus, Escherichia coli.
Embodiment 29
Coat on the floor respectively the photocatalyst dispersion liquid that obtains among the embodiment 1～24 and drying, carrying out illumination by room lighting penetrates, thereby can reduce the concentration of the volatile organic matter such as formaldehyde, acetaldehyde, acetone of the interior space, the concentration of odorant, and then can kill pathogens such as staphylococcus aureus, Escherichia coli.
Embodiment 30
The photocatalyst dispersion liquid that obtains among the embodiment 1～24 is coated the surface of automobile with automobile inner decorative pieces such as instrument board, automobile sheet material, roof of the vehicle spares, and make its drying, carrying out illumination by room light penetrates, thereby can reduce the concentration of the volatile organic matter such as formaldehyde, acetaldehyde, acetone of interior space, the concentration of odorant, and then can kill pathogens such as staphylococcus aureus, Escherichia coli.

Claims (17)

1, a kind of photocatalyst dispersion liquid is characterized in that, dispersed light catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle form in decentralized medium, and the surface charging of described photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is an identical polar.
2, photocatalyst dispersion liquid according to claim 1 is characterized in that, contains electrophilic material or its precursor.
3, photocatalyst dispersion liquid according to claim 2 is characterized in that, described electrophilic material or its precursor are particle or its compounds that is selected from least a metal among Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and the Co.
4, photocatalyst dispersion liquid according to claim 3, it is characterized in that, convert with metallic atom, measure 100 mass parts with respect to the total of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, described electrophilic material or its precursor are 0.005 mass parts～0.6 mass parts.
According to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that 5, the average mark shot of described photochemical catalytic oxidation titanium particle directly is 20nm～150nm.
According to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that 6, the BET specific area of described photochemical catalytic oxidation titanium particle is 100m 2/ g～500m 2/ g.
According to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that 7, the average mark shot of described photochemical catalytic oxidation tungsten particle directly is 50nm～200nm.
According to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that 8, the BET specific area of described photochemical catalytic oxidation tungsten particle is 5m 2/ g～100m 2/ g.
According to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that 9, the mass ratio of described photochemical catalytic oxidation titanium particle and described photochemical catalytic oxidation tungsten particle is 4: 1～1: 8.
According to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that 10, with respect to the total quality of photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle, the quality of described decentralized medium is 5 times～200 times.
11, according to each described photocatalyst dispersion liquid in the claim 1～4, it is characterized in that hydrogen ion concentration is pH0.5～pH8.0.
12, a kind of manufacture method of photocatalyst dispersion liquid, it is characterized in that, be that surface charging that be manufactured on that dispersed light catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle form in the decentralized medium, described photochemical catalytic oxidation titanium particle and described photochemical catalytic oxidation tungsten particle is the manufacture method of the photocatalyst dispersion liquid of identical polar
The photochemical catalytic oxidation titanium particle of surperficial positively charged is scattered in the solution, mix with surface electronegative photochemical catalytic oxidation tungsten particle then, described solution is to have dissolved the surperficial electronegative surface conditioning agent that can make described photochemical catalytic oxidation titanium particle and the solution that obtains in decentralized medium.
13, a kind of manufacture method of photocatalyst dispersion liquid, it is characterized in that, be that surface charging that be manufactured on that dispersed light catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle form in the decentralized medium, described photochemical catalytic oxidation titanium particle and described photochemical catalytic oxidation tungsten particle is the manufacture method of the photocatalyst dispersion liquid of identical polar
The photochemical catalytic oxidation titanium particle of surperficial positively charged is scattered in the solution, mix with surface electronegative photochemical catalytic oxidation tungsten particle then, and add electrophilic material or its precursor, described solution is to have dissolved the surperficial electronegative surface conditioning agent that can make described photochemical catalytic oxidation titanium particle and the solution that obtains in decentralized medium.
14, the manufacture method of photocatalyst dispersion liquid according to claim 13, it is characterized in that described electrophilic material or its precursor are particle or its compounds that is selected from least a metal among Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and the Co.
15, the manufacture method of photocatalyst dispersion liquid according to claim 14, it is characterized in that, convert with metallic atom, total with respect to photochemical catalytic oxidation titanium particle and photochemical catalytic oxidation tungsten particle is measured 100 mass parts, and the addition of described electrophilic material or its precursor is 0.005 mass parts～0.6 mass parts.
16, according to the manufacture method of each described photocatalyst dispersion liquid in the claim 13～15, it is characterized in that, after adding described electrophilic material or its precursor, carry out illumination and penetrate.
17, a kind of manufacture method of photo-catalysis function goods is characterized in that, each photocatalyst dispersion liquid makes the decentralized medium volatilization in substrate surface coating claim 1～4.
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