CN103551170A - Hydroxyl apatite layer-wrapped photocatalytic nano titanium dioxide powder and application thereof - Google Patents
Hydroxyl apatite layer-wrapped photocatalytic nano titanium dioxide powder and application thereof Download PDFInfo
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Abstract
The invention provides photocatalytic powder capable of being applied to environment purifying and atmospheric pollutant governing. Each titanium dioxide particle is wrapped by a hydroxyl apatite layer, and holes with controllable size are formed in the hydroxyl apatite layer, so that target products such as formaldehyde and benzene are selectively degraded, and other larger molecules such as methyl orange are not damaged. The photocatalytic chemical powder can be extensively applied to various organic polymer setting products, especially organic fibers, plastic products or paint.
Description
Technical field
The present invention relates to a kind of photocatalytic powder and production method thereof that can be applicable to the depollution of environment, this powder can be used for removing foul smell, removes harmful substance or pollutant in air, particularly as benzene, the small-molecule substances such as formaldehyde, and larger dye molecule is not had to destruction; This powder is applied to draining or purification of water quality simultaneously, removes the harmful substance in water, some harmful bacteria of specific elimination.By various physical means, (as mediated or embedding or mixing), this powder was particularly suitable for being admixed in organic fiber or plastics, and this powder is more suitable for adding in coating, especially the exploitation of aldehydes removal coating and application.
Background technology
Room air pollution has become the environmental problem of countries in the world extensive concern, and indoor major pollutants have the volatile organic matters such as sulfide, nitrogen oxide, formaldehyde and benzene.For existence better, people have higher requirement to the air quality of its life, and the method for more purification toxic gases also receives the concern of each side.Because traditional purification method just shifts pollutant as filtered absorption etc., fundamentally pollution abatement, the research of therefore carrying out the technology of purifying air has strategic importance.Nano photo catalyzed oxidation is considered to most promising pollution control of indoor air technology.
Nano photo catalyzed oxidation generally adopts TiO
2photochemical catalyst is removed pollutant.TiO
2photochemical catalyst is that a kind of under the irradiation of light, self does not change, and but can promote the material of chemical reaction.Concrete operation principle is TiO
2nano particle is under the light of certain wavelength irradiates, generation hole-electron pair is stimulated, the water of hole decomposition catalyst adsorption, produce hydroxyl free radical, electronics makes hydrogen reduction around become active ion-oxygen, thereby possesses extremely strong oxidation-reduction, the various pollutants of photocatalyst surface are destroyed, photocatalysis can be oxidized to nontoxic material by airborne organic pollution at normal temperatures, and can not produce secondary pollution, on not impact of environmental and human health impacts.The method is compared with the bioremediation of microorganism, is not subject to various reaction conditions as the restriction of temperature, pH, air pressure etc., more can remove the very difficult material decomposing of bioanalysis as compound or organic phosphorus compound containing organic halogen.
Adopt TiO
2photochemical catalyst is removed pollutant, in processing or use, has many difficulties, as the photochemical catalyst of using is difficult to reclaim; As photocatalysis titanium dioxide, the application in coating is mainly to do and be coated with a TiO at exterior wall
2glue-line, acts on singlely, and purposes is narrower.Especially the emulsion that forms coating has macromolecular compound polyethylene ethyl ester, acrylate, propyl benzene emulsion etc., TiO
2these emulsions are had to very strong photocatalytic degradation effect, thereby the film forming matter of coating is had to destruction, cause coating fast degradation, efflorescence; This problem is present in titanium dioxide simultaneously mediates in fiber or plastics, aging to fiber or plastics itself of titanium dioxide under high light catalytic action.Therefore novel nano TiO is prepared in research
2powder is added in photocatalysis, and isolated photocatalysis component is a problem that must solve to the destruction of resin.
The apatite family mineral such as hydroxyapatite (HAP) are owing to having special cavernous structure and surface chemical property, thereby there is good ionic adsorption and exchangeability, to heavy metal ion, micro-molecular gas has good absorption fixation, is a kind of novel environmental functional mineral material.
Chinese patent literature CN-1286649A(is for photocatalytic powder, the polymer composition that contains described powder and molded article and the production method of the depollution of environment) a kind of preparation method of photocatalytic powder of the particle that wraps up titanium dioxide proposed.But the larger molecules such as the little molecule such as this photocatalytic powder PARA FORMALDEHYDE PRILLS(91,95) and methyl orange coloring agent do not have the difference of degraded.Organic coloring agent extensive use coating, in the industry such as organic fiber or plastics, so we control the micropore size of coated photocatalytic powder, and the Organic Hazardous Compounds of optionally degrading has improved range of application and the practicality of photocatalytic powder.
Summary of the invention
Consider the variety of issue of conventional production photocatalytic powder, the photocatalytic nanometer titania powder that provides a kind of controlled hydroxyapatite layer in aperture that is applied to the depollution of environment to wrap up is provided one of object of the present invention, this powder can be used for removing foul smell, remove harmful substance or pollutant in air, particularly as benzene, the small-molecule substances such as formaldehyde, and large molecular dye is not had to destruction as methyl orange etc.; This powder is applied to draining or purification of water quality simultaneously, removes the harmful substance in water, some little molecule harmful bacteria of specific elimination.By various physical means, (as mediated or embedding or mixing etc.), this powder was particularly suitable for being admixed in organic fiber or plastics, and this powder is more suitable for adding in coating, especially the Application and Development of aldehydes removal coating.
Two of object of the present invention is to provide the production method of the photocatalytic nanometer titania powder of the controlled hydroxyapatite layer parcel in a kind of aperture that is applied to the depollution of environment.
Three of object of the present invention is to provide a kind of organic composite that is wherein mixed with the photocatalytic powder of this depollution of environment.
Four of object of the present invention is to provide polymer molded article in a kind of organic composite of the photocatalytic powder that is wherein mixed with this depollution of environment, and this molded article can adopt various organic coloring agents.
Five of object of the present invention is to provide a kind of coating that is wherein mixed with the photocatalytic powder of this depollution of environment, and this coating can be the coating that contains all kinds emulsion, and the coating of all colours, is not limited to whitewash.
The described coating that is mixed with the photocatalytic powder of this depollution of environment, can remove formaldehyde, removes the harmful substances such as benzene class, and there is the stink of removal effect, this coating has the ultraviolet effect of absorption.
For realizing above various objects, after conducting in-depth research, we find, to under photocatalysis titanium dioxide nano particle and certain pH value, add anion surfactant, by autotelic deposited hydroxyl apatite, and the method for pore-creating can obtain durability enhancing, selective clear and definite micropore hydroxyapatite shell, and this shell can be selectively by little molecule harmful substance, relatively large molecule color dye can't pass, and makes the photo-catalysis function of nano titanium oxide not weakened.When by this particle with physical method load or be combined in organic polymer medium or coating system, the durability of organic media is obviously improved, the durability of coating is not also received impact or is improved, based on these, we have completed the present invention.
Therefore function of the present invention has met aforementioned all object requirements.
The preparation method of the photocatalytic nanometer titania powder of hydroxyapatite parcel of the present invention, comprises following steps:
1) adopt nano titanium oxide to mix mutually with pH cushioning liquid, after add anion surfactant, concussion dispersion.Adding of anion surfactant is in order to strengthen the adhesive effect of titanium dioxide and integument, and improves the monodispersity of titanium dioxide.
2) by certain metering ratio, calcium salt and phosphide are dissolved in respectively in distilled water and organic solvent, fully concussion mixes after dissolving mutually, adds alkali lye and is adjusted to certain pH value.
3) mixed solution step 1) being obtained joins step 2) mixed solution that obtains, after more above-mentioned solution is poured in polytetrafluoroethylene (PTFE) reactor, at different temperature, carry out respectively hydro-thermal reaction, by deionized water washing and precipitating repeatedly, suction filtration, obtains solid mixture.
4) solid mixture step 3) being obtained is dry at a certain temperature, after roasting at a certain temperature obtain the hydroxyapatite outer wrapping layer of different pore size size.
For light-catalysed nano titanium dioxide crystal form, may be wherein anatase titanium dioxide, may be rutile-type, or mix crystal formation.Wherein mix crystal formation and can form pn knot, its anatase: when rutile-type mixed proportion is 8:2, effect is best.
For the average grain diameter of light-catalysed nano titanium oxide, preferably in 0.001～0.3 micrometer range, if being less than 0.001 micron, the average grain diameter diameter of nano titanium oxide is unfavorable for disperseing and follow-up parcel, and inapplicable in production practices; And if the average grain diameter diameter of nano titanium oxide is less than 0.3 micron, more preferably average primary particle diameter is in the scope of 0.005～0.05 micron.
Production method for light-catalysed nano titanium oxide of the present invention is not particularly limited, sulfuric acid process, chloridising all can, but the titanium dioxide of a kind of high degree of dispersion of AEROSIL200 explained hereafter is good method, wherein by certain dispersion means, can use scanning electron microscopic observation to its coherent condition.
The 1st) can be by adding alkali lye in individual step, as sodium carbonate, NaOH, sodium acid carbonate, ammoniacal liquor, urea etc. are controlled its pH value, after in aqueous solution, add anion surfactant.The effect of anion sub-surface activating agent is to control interfacial phenomenon, and causes electrodissolution, is conducive to the parcel of titanium dioxide, and it can be removed by the method for roasting.
The object lesson of anion surfactant has various carboxylates, as fatty acid sodium soap, and oleic acid potash soap; Various sulfonate, as neopelex, alpha-olefin sodium sulfonate, Negel, alpha-sulfo monocarboxylate, aliphatic acid sulfoalkyl ester, succinate sodium sulfonate, alkyl glycerylether sodium sulfonate; Various phosphate ester salts, as the mono phosphoric acid ester of the phosphate mono-ester/diester sodium salt of calgon, AEO and APES, dibasic acid esters sylvite; Various sulfate, as lauryl sodium sulfate, higher alcohol sulfate.These anion surfactants can be used separately, or are used in combination.
Step 2) in, select phosphide to be dissolved in organic solvent as methyl alcohol, ethanol as phosphorus pentoxide, calcium phosphide, zinc phosphide, aluminum phosphate, phosphorized copper, acetonitrile, acetone etc. is conducive to form mixture of phospholipids.Calcium salt needs to add alkali lye after mixing with mixture of phospholipids, as NaOH, ammoniacal liquor etc. regulate pH to 7.0～9.0.
The hydrothermal temperature of step 3) is 150～250 ℃, and the Best Times of reaction is preferably 10～20h.
The baking temperature of step 4) is that 100～150 ℃ of sintering temperatures are 200～400 ℃, and the time keeps 2～4h.
The titanium dioxide of the hydroxyapatite parcel finally obtaining there is unbodied hydroxyapatite hole layer, this coating can cover titanium dioxide surface particle uniformly.This coating is because even formation can have the aperture of 1～10nm, and wherein 3nm is best.
Weight based on titanium dioxide is calculated, if the amount of the hydroxyapatite of deposition of titanium oxide is preferably the very few effectively cladding titanium dioxide of the amount of 1～90%. porous hydroxyapatite, starting is to the effect of protection organic polymer and pigment.Otherwise the amount of porous hydroxyapatite is too large, make coated hole too little or sealing, light-catalysed activity does not reach requirement.
Finally complete after the controlled hydroxyapatite layer parcel titanium dioxide in aperture, can obtain the controlled photocatalytic powder of micropore.This powder can be used for removing foul smell, removes harmful substance or pollutant in air, particularly as benzene, and the small-molecule substances such as formaldehyde, and there is suitable micropore large molecular dye is not had to destruction as methyl orange etc.; This powder is applied to draining or purification of water quality simultaneously, removes the harmful substance in water, some little molecule harmful bacteria of specific elimination.
Especially when by various physical means (as kneading, embedding, simple mixing etc.), this powder is admixed to organic polymer medium as in fiber or plastics, adopt fluorescent lamp, incandescent lamp, black light, uviol lamp, mercury lamp, xenon lamp, Halogen lamp LED sunshine to irradiate continuously or fast, can remove airborne various harmful substance as foul smell H
2s, NO
x, or benzene etc., and organic fiber or plastic products itself can not decompose.
This photocatalytic powder is more suitable for adding in coating.By formula, adjust, this powder can be applied in coating for internal and external wall formula: exterior wall can be the exploitation of colorful texture coating, makes coating and has and prevent that outer linear light is self-cleaning, removes the effect of airborne various pernicious gas materials.Interior wall can be applied to be applicable to aldehydes removal coating, can be to form coating, good endurance by macromolecular compound as polyethylene acetic acid, acrylate, propyl benzene emulsion etc.
The present invention's application has the photocatalytic powder of the depollution of environment applicable to polymer molded article, as organic fiber or shaping plastic goods or the coating that organic polymer formed.All organic polymers are had no particular limits, and can be the various polyolefin of mentioning as its concrete example, as polyethylene and polypropylene, polystyrene, and polyvinyl chloride, the sub-ethene of poly-1,2-dichloro; Polyamide is as nylon; Various polyalkamers, as PEO, various polyalcohols are as polyethylene glycol, polyvinyl alcohol; Various polyesters, as organic siliconresin, poly terephthalic acid diethylester, phenolic resins, vinyl acetal resin, poly-acetic acid esters, ABS resin, epoxy resin, styrene-acrylic resin, vinyl acetate resin, polyurethanes, Merlon, urea resin, fluororesin, phenol resin; Cellulose and various cellulose derivative; Chitin; Lignin; Starch.Generally speaking, in the production process of polymer molded article by various physical means (as mediated, embedding, simple mixed compaction etc.), this photocatalytic powder is admixed to organic polymer medium as in fiber or plastics, total weight based on polymeric compositions, the concentration of photocatalytic powder in polymer is generally 0.1～70%, is preferably 0.5～50%
Large molecule organic dyestuff to part has no particular limits, and as concrete example, can be phthalocyanine green, peacock blue, toluidine red, methyl orange.This photocatalytic powder can be weaved and be added in cloth by static, and formula is adjusted and to be added various coating, reaches aldehydes removal, self-cleaning effect.
The present invention compared with prior art has following features:
(1) integrate multi-functional, there is removing and harmful gas, sterilization, anti-oxidant, absorb ultraviolet effect;
(2) low, the environmental protection of cost;
(3) consumption is few, is widely used;
(4) easy to use, good dispersion, mixes easily mutually with other macromolecular material;
(5) Selective adsorption good, the little molecule of specific pernicious gas is had to effect, other the medium molecules such as pigment are had and protect not degradation.
(6) synthetic control procedure is accurate, and target material aperture is controlled.
The specific embodiment
At each following working example, will the photocatalytic powder that be applied to the depollution of environment of the present invention be described.
Embodiment 1: 100g titanium dioxide (P25-adopts the titanium dioxide of a kind of high degree of dispersion of AEROSIL200 explained hereafter, average grain diameter 21nm) is poured in 200mL water and added Na
2cO
3controlling pH value is 8.0, and adds 5.0g dodecyl sodium sulfate (Chinese traditional Chinese medicines), and fully concussion disperses.
Stoichiometric proportion by Ca/P=12 takes, Ca (NO
3)
24H
2o120g and P
2o
5852g is dissolved in respectively in 500mL distilled water and 500mL absolute ethyl alcohol, V water: V absolute ethyl alcohol=1: 1, and in ultrasonic wave, vibration is dissolved, afterwards by Ca (NO
3)
24H
2the aqueous solution of O is poured P into
2o
5ethanolic solution in, stir and regulate pH value to 9～10 with ammoniacal liquor, again above-mentioned solution is poured in polytetrafluoroethylene (PTFE) autoclave, 1 carries out hydro-thermal reaction at the temperature of 200 ℃, by deionized water washing and precipitating repeatedly, suction filtration, dry at 100 ℃ of temperature, after at a certain temperature under air atmosphere roasting obtain the hydroxyapatite outer wrapping layer that different pore size is 5nm.Measurement result is that the amount of powder of hydroxyapatite layer parcel photocatalytic nanometer titanium dioxide is to be total to 600g, and the weight ratio that wherein forms component is titanium dioxide: hydroxyapatite=1:5.
Adopt methyl orange and liquid formaldehyde method as degraded marker, measure the performance of hydroxyapatite layer parcel photocatalytic nanometer titanium dioxide:
Concrete steps are as follows: first, to the methyl orange solution that adds the 20mg/L of 500mL in reactor, then add 1g synthesis of nano TiO
2catalyst, magnetic agitation makes it to suspend.Lucifuge is filled air stirring 30min, makes methyl orange on the surface of catalyst, reach absorption/desorption balance, pipettes 10mL solution in centrifuge tube.Then open cooling water, and open to eliminate and carry out light-catalyzed reaction 25min, every 5min, pipette 10mL reactant liquor, after centrifugation, get supernatant and carry out visible spectrophotometry analysis.Adopt 722 type visible spectrophotometers, by the absorbance A of reactant liquor, measure to monitor the Photocatalytic Decoloration of methyl orange and decompose effect.Within the scope of 0～20mg/L, the absorption value at methyl orange solution concentration and its 462nm place is extremely significant positive correlation.In like manner carry out the degraded test of formaldehyde, adopt the concentration of formyl acetone photometry test formaldehyde.Wherein the size of methyl orange molecule is for approaching 6nm, and the size of formaldehyde molecule is less than 1nm.
Measurement result shows that synthetic base apatite layer parcel photocatalytic nanometer titanium dioxide powder foot couple 2h can degradable formaldehyde, and for methyl orange, there is no degradation effect, nondiscolouring.
In addition this photocatalytic powder of 300g and polyethylene terephthalate resin are adopted forcing press compacting to obtain containing the bar of 30% photocatalytic powder, used the ultra violet lamp of 246nm, resin can flavescence, aging.
This photocatalytic powder of 50g is mixed mutually with water-soluble alcohol urea formaldehyde solution (the Dow Chemical Company's production), make the coating system of the photocatalytic powder that contains 30%, adopt the ultra violet lamp of 246nm, resin can variable color, aging.
Embodiment 2: by implementing program same as Example 1, difference adopts calgon (Chinese traditional Chinese medicines) as anion surfactant, and it is identical that other all conditions all keeps, and obtains for photocatalytic powder.The photocatalytic powder of gained is for degradation of formaldehyde or methyl orange, and measurement result shows that synthetic hydroxyapatite layer parcel photocatalytic nanometer titanium dioxide powder foot couple 2h can degradable formaldehyde, and for methyl orange, there is no degradation effect, nondiscolouring.
Mix and extrude mutually with plastic components polyethylene terephthalate resin, obtain containing the bar of 30% photocatalytic powder, used the ultra violet lamp of 246nm, resin can flavescence, aging.Be used in coating system water-soluble alcohol urea formaldehyde solution (the Dow Chemical Company's production), make the coating system of the photocatalytic powder that contains 30%, adopt the ultra violet lamp of 246nm, resin can variable color, aging.
Embodiment 3: by implementing program same as Example 1, difference adopts titanium dioxide (University of Fuzhou provides) particle of 15nm, and it is identical that other all conditions all keeps, and obtains for photocatalytic powder.The photocatalytic powder of gained is for degradation of formaldehyde or methyl orange, and measurement result shows that synthetic hydroxyapatite layer parcel photocatalytic nanometer titanium dioxide powder foot couple 2h can degradable formaldehyde, and for methyl orange, there is no degradation effect, nondiscolouring.
Mix and extrude mutually with plastic components polyethylene terephthalate resin, obtain containing the bar of 30% photocatalytic powder, used the ultra violet lamp of 246nm, resin can flavescence, aging.Be used in coating system water-soluble alcohol urea formaldehyde solution (the Dow Chemical Company's production), make the coating system of the photocatalytic powder that contains 30%, adopt the ultra violet lamp of 246nm, resin can variable color, aging.
Comparative example 1: adopt photocatalysis P25 to be directly used in degradation of formaldehyde or methyl orange, measurement result titanium oxide P25 powder 2h can degradable formaldehyde and methyl orange, and methyl orange becomes colourless.
P25 mixes and extrudes mutually with plastic components polyethylene terephthalate resin, obtains containing the bar of 30% photocatalytic powder, is used the ultra violet lamp of 246nm, and resin can flavescence, aging.Be used in coating system water-soluble alcohol urea formaldehyde solution (the Dow Chemical Company's production), make the coating system of the photocatalytic powder that contains 30%, adopt the ultra violet lamp of 246nm, the quick flavescence of resin, aging.
Comparative example 2: by implementing program same as Example 1, difference is not adopt anion surfactant dispersed titanium dioxide nano particle, and it is identical that other all conditions all keeps, and obtains for photocatalytic powder.The photocatalytic powder of gained is for degradation of formaldehyde or methyl orange, and measurement result shows can degradable formaldehyde and methyl orange, and methyl orange becomes colourless.
Photocatalytic powder is mixed and is extruded mutually with plastic components polyethylene terephthalate resin, obtains containing the bar of 30% photocatalytic powder, is used the ultra violet lamp of 246nm, and resin can flavescence, aging.Be used in coating system water-soluble alcohol urea formaldehyde solution (the Dow Chemical Company's production), make the coating system of the photocatalytic powder that contains 30%, adopt the ultra violet lamp of 246nm, the quick flavescence of resin, aging.
Comparative example 3: by implementing program same as Example 1, adopt higher temperature as 400 ℃ when difference is air roasting, it is identical that other all conditions all keeps, and obtains for photocatalytic powder.Now the aperture of hydroxyapatite becomes large, is 14nm, partial rupture.The photocatalytic powder of gained is for degradation of formaldehyde or methyl orange, and measurement result shows can degradable formaldehyde and methyl orange, and methyl orange becomes colourless.
Photocatalytic powder is mixed and is extruded mutually with plastic components polyethylene terephthalate resin, obtains containing the bar of 30% photocatalytic powder, is used the ultra violet lamp of 246nm, and resin can flavescence, aging.Be used in coating system water-soluble alcohol urea formaldehyde solution (the Dow Chemical Company's production), make the coating system of the photocatalytic powder that contains 30%, adopt the ultra violet lamp of 246nm, the quick flavescence of resin, aging.
Claims (10)
1. a photocatalytic nanometer titania powder for hydroxyapatite layer parcel, is characterized in that: comprise titania nanoparticles, at least coated one deck hydroxyapatite layer in the titanium dioxide granule surface disperseing separately at each; Wherein hydroxyapatite layer is the equilibrium surface coverage with the aperture of 1～10nm.
2. the photocatalytic nanometer titania powder that hydroxyapatite layer according to claim 1 wraps up, it is characterized in that: the average grain diameter of described titanium dioxide is 0.001～0.3 micron, described titanium dioxide crystal form can be anatase titanium dioxide, also can be rutile-type, or any mixing of two types.
3. the photocatalytic nanometer titania powder of hydroxyapatite layer parcel according to claim 1, is characterized in that: in described titania powder, the mass ratio of hydroxyapatite and titanium dioxide is 1:100～1:9.
4. the photocatalytic nanometer titania powder that hydroxyapatite layer according to claim 2 wraps up, it is characterized in that: when described titanium dioxide crystal form adopts two kinds to mix, wherein mix crystal formation and can form pn knot, when its anatase titanium dioxide and rutile-type mixed proportion are 8:2, effect is best.
5. a preparation method for the photocatalytic nanometer titania powder that hydroxyapatite layer as claimed in claim 1 wraps up, is characterized in that comprising the following steps:
1) adopt nano titanium oxide to mix mutually with pH cushioning liquid, after add anion surfactant, concussion dispersion; In described homogeneous mixture, the content of titanium dioxide is 50～200g/L, and the mass ratio of anion surfactant and titanium dioxide is 1:500～1:5; The concentration of pH cushioning liquid is 0.1mol/L～0.5mol/L;
2) calcium salt and phosphide are dissolved in respectively in distilled water and organic solvent, fully concussion mixes after dissolving mutually, adds alkali lye and is adjusted to certain pH value; In described homogeneous mixture, the concentration of calcium salt soln is 0.1～50mol/L, and the concentration of phosphide is 0.1～150mol/L;
3) mixed solution step 1) being obtained joins step 2) mixed solution that obtains, after more above-mentioned solution is poured in polytetrafluoroethylene (PTFE) reactor, at different temperature, carry out respectively hydro-thermal reaction, by deionized water washing and precipitating repeatedly, suction filtration, obtains solid mixture;
4) solid mixture step 3) being obtained is through super-dry, after at high temperature roasting, obtain having the photocatalytic nanometer titania powder of the hydroxyapatite outer wrapping layer of different pore size size.
6. the preparation method of the photocatalytic nanometer titania powder of hydroxyapatite layer according to claim 5 parcel, is characterized in that: step 1) and step 2) pH cushioning liquid be alkaline range, pH value is 7.0～8.0.
7. in the preparation method of the photocatalytic nanometer titania powder of hydroxyapatite layer parcel according to claim 5, it is characterized in that: the hydrothermal temperature of step 3) is preferably 150～250 ℃.
8. in the preparation method of the photocatalytic nanometer titania powder of hydroxyapatite layer parcel according to claim 5, the sintering temperature of step 4) is preferably 200～400 ℃.
9. a coating with the photocatalytic nanometer titania powder of the parcel of the hydroxyapatite layer described in any one in claim 1-4.
10. an organic polymer medium with the photocatalytic nanometer titania powder of the parcel of the hydroxyapatite layer described in any one in claim 1-4, total weight based on polymeric compositions, the concentration of the photocatalytic nanometer titania powder of described ferric phosphate parcel in polymer is generally 0.1～70%, is preferably 0.5～50%.
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