CN1663388A - Microporous silicon dioxide-cladding tourmaline and titanium dioxide particle composition, its preparation and application - Google Patents
Microporous silicon dioxide-cladding tourmaline and titanium dioxide particle composition, its preparation and application Download PDFInfo
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- CN1663388A CN1663388A CN 200410006971 CN200410006971A CN1663388A CN 1663388 A CN1663388 A CN 1663388A CN 200410006971 CN200410006971 CN 200410006971 CN 200410006971 A CN200410006971 A CN 200410006971A CN 1663388 A CN1663388 A CN 1663388A
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- tourmaline
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Abstract
The invention relates to an inorganic nanometer modification functional material, which is a complex of silicon oxide coated tourmaline and titanium oxide granule with micropores and mesopores of several dozens of nanometers to several dozens of micrometers, the preparation and use, wherein the preparation comprises using nanometer or sub-micron tourmaline and titanium dioxide particles as carrier, coating a layer of mesoporous silicon dioxde on the surface, and finally adsorbing argentic salt. The complex can serve as a health functional material with the functions of antibiosis, radiating infrared light and discharging negative ions.
Description
Technical field
The invention belongs to inorganic nanometer modified functional material and application thereof, what particularly relate to tens nanometers to tens micron has micropore, mesoporous coated with silica tourmaline and complex of titanium dioxide granule and its production and use.
Background technology
Airborne anion mainly is a negative oxygen ion, after being inhaled into human body, effect to health can reduce following several (military dream pens, the development trend brief introduction of health environment-friendly type dope for inner wall of architecture, New Building Materials, 2002,12,16-17): 1. anion directly influences the current potential of cell membrane, improves the various functions of cell; Enhance metabolism, build up one's resistance to disease.2. purify the blood, bring high blood pressure down, improve the scheming function.3. stable autonomic nerve, control sympathetic nerve improve sleeper effect.4. increase oxygen absorbed.5. increase diaphoretic volume, increase brain liquid, reduce tired.6. control inflammation, analgesia, anticancer, weaken the leukaemia.7. cirrhosis, diabetes, neural paralysis, neuropathy also there is suitable curative effect.8. increase appetite, increase work efficiency.9. antibacterial action.10. fresh air.So the people claims that anion is " an airborne vitamin ".
Tourmaline is a kind of silicate mineral, English name Tourmaline, and its main component contains multiple elements such as Na, Fe, Mg, Al, Li, B, Si, and its developed by molecule formula is X
1Y
9B
3Si
6(OHF)
4, X represents one or more among Ca, Na, K, the Mn, and Y represents one or more among Mg, Fe, Al, Cr, Ti, the Li.1989, Japan scholar Kubo has found that first there is spontaneous electrode in tourmaline, has electrostatic field phenomenon (Nakamum T.andKubo T.Tourmaline group crystals reaction with water, Ferroelectrics around the tourmaline particles, 1992,137:13-31).Tourmaline has nonvolatil spontaneous electrode, and existing with the c axle around the tourmaline particles is the electrostatic field at the two poles of the earth.Under electric field action, hydrone generation electrolysis forms bioactive molecule H
3O
+, attract impurity, dirt in the water to purify water; OH-and water molecules form anion.Tourmaline has water-disintegrable, can produce the infrared rays of 4～14 micron wavebands.In addition, tourmaline also has sterilization, dedusting, deodorization.
The healthy functions material is meant the material that human body and environment are had certain specific function of positive effect, should have functions such as antibiotic, infrared radiation, release anion.Tourmaline machinery, chemical stability are good, can reuse, environmentally safe, but also satisfied the requirement of healthy functions material three aspects, therefore tourmaline is a kind of good healthy functions green material, is having broad application prospects aspect environment, the body-care.Yet tourmaline antibiotic, the deodorant function effect is slow, and its antibacterial functions needs further to strengthen.
Inorganic porous material because have bigger specific surface area and adsorption capacity, and is widely used in catalyzer and the absorption carrier, (Cai Wei is flat, Zhang Lide, mesoporous solid and mesic hole compound between 2～50nm in the aperture of mesoporous material, physics, 1997,26 (4): 213-216).The hole of mesoporous solid is interconnected and contacts with surrounding environment, and the quantity in its hole can be up to 10
9/ g, specific surface are generally at 600m
2More than/the g, so skin effect is very remarkable.An important application of mesoporous solid is as the artificial heterogeneous assembly system of preparing carriers, is about to form mesic hole compound in the hole that heterogeneous nano particle or group of molecules be contained in mesoporous solid, can obtain multiple material with property like this.From 1992 so far, people have reported the Metaporous silicon dioxide material of numerous metallic ion-doping modifications.According to the difference of doping ion, mesoporous silicon oxide can have different structures and reactivity, and is used for different catalytic process.
Summary of the invention
One of purpose of the present invention provides a kind of surface with functions such as antibiotic, infrared radiation, release anions and is coated with the tourmaline particle of little mesoporous silicon oxide and the Heterogeneous Composite body of titanium dioxide granule, this complex purity height, good dispersion, narrow diameter distribution, uniform particles.
Two of purpose of the present invention provides a kind of little mesoporous silicon oxide and is coated on area load the tourmaline particle of silver salt and the Heterogeneous Composite body of titanium dioxide granule are arranged.
Three of purpose of the present invention provides the preparation method that a kind of surface with functions such as antibiotic, infrared radiation, release anions is coated with the Heterogeneous Composite body of the tourmaline of little mesoporous silicon oxide and titanium dioxide granule.
Four of purpose of the present invention provides a kind of little mesoporous silicon oxide and is coated on the preparation method that area load has the Heterogeneous Composite body of the tourmaline particle of silver salt and titanium dioxide granule.
Five of purpose of the present invention provides a kind of surface with functions such as antibiotic, infrared radiation, release anions and is coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body of titanium dioxide granule, and little mesoporous silicon oxide is coated on the purposes that area load has the Heterogeneous Composite body of the tourmaline particle of silver salt and titanium dioxide granule.
The objective of the invention is to realize by following technical scheme:
Complex of the present invention is to coat one deck mesoporous silicon oxide at tourmaline particle, titanium dioxide granule powder surface, then in the mesoporous silica particles hole and shallow surface on compound one deck silver salt, to strengthen the anti-microbial property of tourmaline, reach the requirement of the functions such as antibiotic, infrared radiation, release anion of healthy functions material comprehensively.
Surface of the present invention is coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body of titanium dioxide granule, be as kernel with nanometer or sub-micron tourmaline particle and titanium dioxide granule, coat the little mesoporous silicon oxide of one deck on its surface, in the hole of little mesoporous silica particles,, make it give full play to the high-efficiency antimicrobial effect of titanium dioxide photochemical activity and/or silver salt with surface recombination one deck silver salt.
The weight ratio of titanium dioxide granule and tourmaline particle is 0.005: 1～0.2: 1 in the described complex, is preferably 0.01: 1～0.1: 1.
The particle diameter of described tourmaline particle is 100nm～2000nm.
The particle diameter of described titanium dioxide granule is 1nm～100nm.
The structure of described little mesoporous silicon oxide is a kind of loose and porous structure, and particle diameter is between 200nm～2000nm; Little mesoporous silica particles coating thickness is 200nm～2000nm.
The preparation method that surface of the present invention is coated with the Heterogeneous Composite body of the tourmaline of little mesoporous silicon oxide and titanium dioxide granule may further comprise the steps:
(1). with TiCl
4Slowly drop in the water of continuous stirring, make its hydrolysis, the molar concentration of TiO 2 sol is 0.1～5mol/L, is preferably 0.5～2mol/L.
(2). the preparation aqueous solution of urea, its molar concentration is 0.4～10mol/L, is preferably 0.8～5mol/L; Determine the molar concentration and the consumption thereof of urea according to the formaldehyde usage amount.
(3). preparating acid solution, its molar concentration is 0.1～5mol/L, is preferably 0.5～3mol/L; The thickness of the mesoporous silicon oxide of the required coating of foundation is determined the molar concentration and the consumption thereof of acid.
(4). the preparation silver salt solution, its molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L.
(5). with the tourmaline particle dispersed with stirring in the aqueous solution of urea of step (2), and then slowly join in the colloidal sol of titanium dioxide of step (1) preparation, the weight percent concentration of the tourmaline particle in the gained final solution is 0.1～20%, the weight ratio of titanium dioxide granule and tourmaline particle is 0.005: 1～0.2: 1, is preferably 0.01: 1～0.1: 1.
(6). the sour mixed liquor of commercially available Ludox and formaldehyde and step (3) preparation is injected into respectively in step (5) liquid mixture prepared, and constantly stirs the gained mixed liquor; Wherein, Ludox: formaldehyde: the mol ratio of urea is 1: 0.1: 0.6～1: 10: 30, is preferably 1: 1: 1.5～1: 6: 5, and the pH that adds acid accent solution is 1～4; Make Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, the weight ratio of mesoporous silicon oxide and tourmaline is 1: 0.02～1: 1.After the sedimentation 1～5 hour, at a high speed it is broken up.Washing then, dry, calcining obtain the mesoporous silicon oxide clad material.
(7). in the aqueous solution of the silver salt that the mesoporous silicon oxide clad material dispersed with stirring of step (6) preparation is prepared to step (4).Wherein, the weight percent concentration of mesoporous coated with silica material is 5～40% in the final solution, is preferably 5～25%; The molar concentration of silver salt solution is 0.01～1mol/L, is preferably 0.01～0.3mol/L; 10～60 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying.The surface that promptly obtains having functions such as antibiotic, infrared radiation, release anion is coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule.
Described silver salt can be silver nitrate or silver thiosulfate etc.
Described Ludox can be selected from the 90-II Ludox that Changhong chemical plant, Beijing produces.
Described acid is nitric acid, hydrochloric acid or sulfuric acid.
Described calcining heat is 500～900 ℃.
The product purity height that method of the present invention is prepared, good dispersion, and the size of particle can be controlled by reaction condition.
What the present invention was significantly different with other anti-biotic material technology of preparing is, method of the present invention is to coat the loose porous mesoporous preparing spherical SiO 2 particle of one deck at tourmaline and titanium dioxide granule surface, adsorb silver salt then, make particle have very strong antibacterial properties, and have the effect that discharges anion.
The present invention is a carrier with tourmaline powder, titanium dioxide granule, carries out mesoporous silicon oxide on its surface and coats, and mesoporous silicon oxide is carried out silver mix, and can strengthen the antibacterial action of tourmaline significantly, obtains mesoporous silicon oxide healthy functions material.
Surface of the present invention is coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body of titanium dioxide granule adds among fabric, coating, pottery, plastics or the elastomeric material, can build a kind of good ecotope, reduces transmission of disease and generation.
The Heterogeneous Composite body and function way that surface with functions such as antibiotic, infrared radiation, release anions of the present invention is coated with the tourmaline of little mesoporous silicon oxide and titanium dioxide granule extensively, be a kind of novel high function fine inorganic material, this complex can be entrained in coating, textile, pottery, rubber, plastics, paper or the fibers material and use as anti-biotic material.Complex material purity height of the present invention, good dispersion, and the size of particle is controlled.
The anti-microbial property experiment of complex material of the present invention is with reference to GB15981-1995, and Q/HDHKH002-2000 detection method and standard are carried out.Behind the testing sample sterilization and drying, 0.2ml bacterium bacterium to be measured liquid is evenly dripped on sample respectively, cover with film, put in the sterilization container, after placing 24 hours under 36 ℃ of temperature, the humidity 90%RH, add the 20ml eluent respectively, wash-out fully vibrates, switching NA medium carries out count plate, calculates its bacteriostasis rate with antibiotic sample and common recovery bacterium number in the same old way.Test result shows that antibiotic paint all reaches more than 96% the antibiotic rate of Escherichia coli and staphylococcus aureus, has good antibacterial performance.
The healthy functions complex material of strong antibacterial functions of the present invention, release anion has:
1. prepare simplely, be easy to apply.
2. mesoporous silicon oxide is made the compound silver of carrier, and the method that preparation has very strong antibacterial action material is a very economical and superior.
3. by adjusting the Ludox addition, and the mol ratio of Ludox and formaldehyde, urea, the size of mesoporous silicon oxide and the product that surface state is easy to make different field purposes required size can be controlled.
4. mesoporous silicon oxide is made the healthy functions material of carrier, just has very strong antibacterial action under very weak visible light effect.
Embodiment
Embodiment 1
With particle diameter is that the tourmaline particle of 100nm～1500nm is distributed in the aqueous solution of urea that molar concentration is 3mol/L, and the weight percent concentration of tourmaline particle is 3% in the solution.Adding particle diameter is the Ti0 of 1nm～15nm
2Colloidal sol, the weight ratio that makes titanium dioxide granule and tourmaline particle is 0.005: 1, fully stir the mixed liquor that drips Ludox and formaldehyde and hydrochloric acid down simultaneously, make Ludox: formaldehyde: the mol ratio of urea is 1: 3: 9, Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, and the weight ratio of mesoporous silicon oxide and tourmaline is 1: 0.02.With hydrochloric acid the pH value of solution is adjusted to 2.1.After the sedimentation 4 hours, wash 3 times, drying, and, obtain pale powder 600 ℃ of calcinings down, the coating thickness of its mesoporous silicon oxide is about 2000nm.In the aqueous solution of silver nitrate, the weight percent concentration that makes mesoporous coated with silica material in the final solution is 25% with this canescence particle dispersed with stirring, and the molar concentration of silver nitrate is 0.1mol/L.10 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying.Obtain the surface and be coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule, this material can be used as the filler of rubber, can improve the quality of product.
Embodiment 2
With particle diameter is that 50～1000nm tourmaline particle is distributed in the aqueous solution of urea that molar concentration is 3mol/L, and the weight percent concentration of tourmaline particle is 0.2% in the solution.Adding particle diameter is 15nm～50nm TiO
2Colloidal sol, the weight ratio that makes titanium dioxide granule and tourmaline particle is 0.2: 1, fully stir the mixed liquor that drips Ludox and formaldehyde and hydrochloric acid down simultaneously, make Ludox: formaldehyde: the mol ratio of urea is 1: 10: 10, Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, and the weight ratio of mesoporous silicon oxide and tourmaline is 1: 1.With sulfuric acid the pH value of solution is adjusted to 1.8.After the sedimentation 3 hours, wash 3 times, drying, and, obtain pale powder 550 ℃ of calcinings down, the coating thickness of its mesoporous silicon oxide is about 200nm.In the aqueous solution of silver thiosulfate, the weight percent concentration of mesoporous coated with silica material is 20% in the final solution with this canescence particle dispersed with stirring, and the molar concentration of silver thiosulfate is 0.1mol/L.60 ℃ of constant temperature, lucifuge, stirring 4.5 hours, washing, drying.Obtain the surface and be coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule, this material can be used as the filler of coating, improves the quality of product.
Embodiment 3
With particle diameter is that 200～2000nm tourmaline particle is distributed in the aqueous solution of urea that molar concentration is 8mol/L, and the weight percent concentration of tourmaline particle is 20% in the solution.Adding particle diameter is 20nm～80nm TiO
2Colloidal sol, the weight ratio that makes titanium dioxide granule and tourmaline particle is 0.01: 1, fully stir the mixed liquor that drips Ludox and formaldehyde and hydrochloric acid down simultaneously, make Ludox: formaldehyde: the mol ratio of urea is 1: 2: 5, Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, and the weight ratio of mesoporous silicon oxide and tourmaline is 1: 0.1.With hydrochloric acid the pH value of solution is adjusted to 1.6.After the sedimentation 3.5 hours, wash 3 times, drying, and, obtain pale powder 500 ℃ of calcinings down, the coating thickness of its mesoporous silicon oxide is about 800nm.In the aqueous solution of silver nitrate, the weight percent concentration of mesoporous coated with silica material is 30% in the final solution with this canescence particle dispersed with stirring, and the molar concentration of silver nitrate is 0.1mol/L.20 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying.Obtain the surface and be coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule, this material can be used as the filler of plastics, improves the quality of product.
Embodiment 4
With particle diameter is that 50～2000nm tourmaline particle is distributed in the aqueous solution of urea that molar concentration is 0.5mol/L, and the weight percent concentration of tourmaline particle is 1% in the solution.Adding particle diameter is 1nm～100nm TiO
2Colloidal sol, the weight ratio that makes titanium dioxide granule and tourmaline particle is 0.05: 1, fully stir the mixed liquor that drips Ludox and formaldehyde and hydrochloric acid down simultaneously, make Ludox: formaldehyde: the mol ratio of urea is 1: 3: 3, Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, and the weight ratio of mesoporous silicon oxide and tourmaline is 1: 0.08.With nitric acid the pH value of solution is adjusted to 1.7.After the sedimentation 4 hours, wash 3 times, drying, and, obtain pale powder 550 ℃ of calcinings down, the coating thickness of its mesoporous silicon oxide is about 800nm.In the aqueous solution of silver thiosulfate, the weight percent concentration of mesoporous coated with silica material is 20% in the final solution with this canescence particle dispersed with stirring, and the molar concentration of silver thiosulfate is 0.05mol/L.40 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying.Obtain the surface and be coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule, this material can be used as the filler of chemical fibre, improves the quality of product.
Embodiment 5
With particle diameter is that 100～1000nm tourmaline particle is distributed in the aqueous solution of urea that molar concentration is 6mol/L, and the weight percent concentration of tourmaline particle is 1% in the solution.Adding particle diameter is 10nm～80nm TiO
2Colloidal sol, the weight ratio that makes titanium dioxide granule and tourmaline particle is 0.05: 1, fully stir the mixed liquor that drips Ludox and formaldehyde and hydrochloric acid down simultaneously, make Ludox: formaldehyde: the mol ratio of urea is 1: 2: 5, Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, and the weight ratio of mesoporous silicon oxide and tourmaline is 1: 0.015.With hydrochloric acid the pH value of solution is adjusted to 1.5.After the sedimentation 4 hours, wash 3 times, drying, and, obtain pale powder 600 ℃ of calcinings down, the coating thickness of its mesoporous silicon oxide is 1500nm.In the aqueous solution of silver nitrate, the weight percent concentration of mesoporous coated with silica material is 10% in the final solution with this canescence particle dispersed with stirring, and the molar concentration of silver nitrate is 0.05mol/L.40 ℃ of constant temperature, lucifuge, stirring be about 5 hours, washing, drying.Obtain the surface and be coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule, this material can be used as the filler of paper products, can improve the quality of product.
Embodiment 6
With particle diameter is that 50～2000nm tourmaline particle is distributed in the aqueous solution of urea that molar concentration is 3mol/L, and the weight percent concentration of tourmaline particle is 4% in the solution.The adding particle diameter is 1nm～100nmTiO
2Colloidal sol, the weight ratio that makes titanium dioxide granule and tourmaline particle is 0.01: 1, fully stir the mixed liquor that drips Ludox and formaldehyde and hydrochloric acid down simultaneously, make Ludox: formaldehyde: the mol ratio of urea is 1: 2: 4, Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, and the weight ratio of mesoporous silicon oxide and tourmaline is 1: 1.With hydrochloric acid the pH value of solution is adjusted to 1.7.After the sedimentation 4 hours, wash 3 times, drying, and, obtain pale powder 600 ℃ of calcinings down, the coating thickness of its mesoporous silicon oxide is 200nm.In the aqueous solution of silver thiosulfate, the weight percent concentration of mesoporous coated with silica material is 5% in the final solution with this canescence particle dispersed with stirring, and the molar concentration of silver thiosulfate is 0.15mol/L.40 ℃ of constant temperature, lucifuge, stirring be about 5 hours, washing, drying.Obtain the surface and be coated with the tourmaline of little mesoporous silicon oxide and the Heterogeneous Composite body healthy functions material of titanium dioxide granule, this material can be used as the filler of textile, can improve the quality of product.
Embodiment 7
The negative ion antibiotic nano load material of embodiment 1～6 preparation is carried out antibiotic detection.The anti-microbial property experiment is with reference to GB15981-1995, and Q/HDHKH002-2000 detection method and standard are carried out.Behind the testing sample sterilization and drying, 0.2ml bacterium bacterium to be measured liquid is evenly dripped on sample respectively, cover with film, put in the sterilization container, after placing 24 hours under 36 ℃ of temperature, the humidity 90%RH, add the 20ml eluent respectively, wash-out fully vibrates, switching NA medium carries out count plate, calculates its bacteriostasis rate with antibiotic sample and common recovery bacterium number in the same old way.Test result shows that antibiotic paint all reaches more than 96% the antibiotic rate of Escherichia coli and staphylococcus aureus, has good antibacterial performance.
Claims (10)
1. a surface is coated with the tourmaline of little mesoporous silicon oxide and the complex of titanium dioxide granule, it is characterized in that: described complex is as kernel with nanometer or sub-micron tourmaline particle and titanium dioxide granule, be coated with little mesoporous silicon oxide on its surface, in the hole of little mesoporous silica particles, silver salt arranged with surface recombination.
2. complex as claimed in claim 1 is characterized in that: the weight ratio of titanium dioxide granule and tourmaline particle is 0.005: 1～0.2: 1 in the described complex.
3. complex as claimed in claim 1 or 2 is characterized in that: the particle diameter of described tourmaline particle is 100nm～2000nm; The particle diameter of described titanium dioxide granule is 1nm～100nm.
4. complex as claimed in claim 1 is characterized in that: described little mesoporous silica particles coating thickness is 200nm～2000nm.
5. preparation method as each described complex of claim 1～4, it is characterized in that: described method may further comprise the steps:
(1). preparing titanium dioxide colloidal sol;
(2). the preparation aqueous solution of urea;
(3). preparating acid solution;
(4). the preparation silver salt solution;
(5). with the tourmaline particle dispersed with stirring in the aqueous solution of urea of step (2), and then slowly join in the colloidal sol of titanium dioxide of step (1) preparation, the weight percent concentration of the tourmaline particle in the final solution is 0.1～20%, and the weight ratio of titanium dioxide granule and tourmaline particle is 0.005: 1～0.2: 1;
(6). the sour mixed liquor of Ludox and formaldehyde and step (3) preparation is injected into respectively in step (5) liquid mixture prepared, and constantly stirs the gained mixed liquor; Wherein, Ludox: formaldehyde: the mol ratio of urea is 1: 0.1: 0.6～1: 10: 30, and the pH that adds acid accent solution is 1～4; Make Ludox and formaldehyde and urea reaction generate mesoporous silicon oxide, the weight ratio of mesoporous silicon oxide and tourmaline is 1: 0.02～1: 1; Sedimentation, washing, dry, calcining obtain the mesoporous silicon oxide clad material;
(7). in the aqueous solution of the silver salt that the mesoporous silicon oxide clad material dispersed with stirring of step (6) preparation is prepared to step (4), wherein, the weight percent concentration of mesoporous coated with silica material is 5～40% in the final solution, the molar concentration of silver salt solution is 0.01～1mol/L, constant temperature, lucifuge, stirring, washing, drying promptly obtain complex material.
6. method as claimed in claim 5 is characterized in that: described silver salt is silver nitrate or silver thiosulfate.
7. method as claimed in claim 5 is characterized in that: described acid is nitric acid, hydrochloric acid or sulfuric acid.
8. method as claimed in claim 5 is characterized in that: described calcining heat is 500～900 ℃.
9. method as claimed in claim 5 is characterized in that: the thermostat temperature of described step (7) is 10～60 ℃.
10. purposes as each described complex of claim 1～4, it is characterized in that: described complex is entrained in coating, textile, pottery, rubber, plastics, paper or the fibers material and uses as anti-biotic material.
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| CN102630706B (en) * | 2012-04-11 | 2014-11-05 | 宣城晶瑞新材料有限公司 | AgTiO2 core-shell structure nanometer composite material and preparation method thereof |
| CN106360880A (en) * | 2016-08-28 | 2017-02-01 | 杭州锴越新材料有限公司 | Bacteriostatic negative ion shoe pad and preparation method thereof |
| CN106360879A (en) * | 2016-08-28 | 2017-02-01 | 杭州锴越新材料有限公司 | Multifunctional healthy negative-ion insoles and making method thereof |
| CN110128905A (en) * | 2019-05-30 | 2019-08-16 | 黎明职业大学 | A kind of fiber base decorative material for wall surface |
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| CN110841098B (en) * | 2019-12-23 | 2021-02-05 | 广州飞逸生物科技有限公司 | A fragrance composition with deodorant effect |
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