CN1739357A - Prepn process of nanometer composite silver carrying hydroxyapatite/titania disinfectant - Google Patents
Prepn process of nanometer composite silver carrying hydroxyapatite/titania disinfectant Download PDFInfo
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- CN1739357A CN1739357A CN 200510029892 CN200510029892A CN1739357A CN 1739357 A CN1739357 A CN 1739357A CN 200510029892 CN200510029892 CN 200510029892 CN 200510029892 A CN200510029892 A CN 200510029892A CN 1739357 A CN1739357 A CN 1739357A
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Abstract
The nanometer composite silver carrying hydroxyapatite/titania disinfectant is prepared with the inorganic salt of Ti, Ag, Ca and ammonium as material and through liquid phase co-precipitation process to prepare silver carrying hydroxyapatite, dispersing the silver carrying hydroxyapatite inside sol obtained via hydrolyzing inorganic salt of Ti, and subsequent heat treatment. The preparation process may be completed in improved common reactor and thermostatic equipment and is simple and practical. The nanometer composite silver carrying hydroxyapatite/titania disinfectant has lasting disinfectant effect, and is expected to be applied in purifying air, treating water and other fields.
Description
Technical field
That the present invention relates to is a kind of preparation method of technical field of nano material, specifically, is a kind of preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant.
Background technology
Hydroxyapatite Ca
10(PO
4)
6(OH)
2Be a kind of traditional bioceramic material, owing to have oh group in the structure of this material, it and some organic molecule have very strong adhesion as protein molecule etc., and microorganisms such as bacterium, virus are had the very strong effect of catching; Hydroxyapatite also has photo-catalysis function, can kill various bacteria under illumination condition.Simultaneously, argent is compound to the hydroxyapatite material surface, the hydroxyapatite of preparation argentiferous, silver ion just destroy some interior enzyme of bacterium body consumingly in case contact with bacterium, make the afunction of the enzyme that bacterium depends on for existence, thus kill bacteria.Because TiO
2Chemical stability, biological nontoxic and high catalytic activity, be acknowledged as first-selected semiconductor light-catalyst material.Nano-TiO
2Skin effect, bulk effect, especially the size quantum effect makes its effective band gap broadening, the electronics that optical excitation produces and the reduction-oxidation ability in hole strengthen greatly, make originally to be achieved under the nano particle effect in the light-catalyzed reaction that can not carry out on the bulk phase catalyst, slower reaction originally may accelerate.At normal temperatures and pressures, utilize solar energy and airborne oxygen, nano-TiO
2Almost all contaminants can be oxidized to CO
2, H
2O and simple inorganic matter.Prepare nanometer composite silver carrying hydroxyapatite stone/titanium dioxide (Ca by special technology
10(PO
4)
6(OH)
2/ Ag/TiO
2) antibiotic, pasteurization material is an innovation achievement.The research that utilizes argentum-carried hydroxylapatite or nano titanium dioxide photocatalysis to kill multiple virus has separately obtained significant progress.And be new significant problem with the two compound use, both are compound can to produce good composite effect, because the nano titanium dioxide photocatalysis functioning side overweights the strong oxidation of performance virus killing mineralization, and argentum-carried hydroxylapatite at viral adsorption, catch germ performance key effect aspect the sterilizing simultaneously.
Through literature search plan to prior art, Chinese patent publication number CN1586202A, open day is 2005.03.02, patent name is: a kind of preparation method of composite inorganic antibacterial agent, this patent readme is: " the titanium dioxide granule surface portion with photocatalytic activity supports the loose structure clad; the loose structure of this clad supports the antibiotic property silver ion; described loose structure clad is the calcium hydroxy phosphate powder; the technical process of its preparation is as follows: in the microcosmic mixing reactor with nano titanium oxide and ammonium dihydrogen phosphate (ADP) and nitrate of lime mixing stirring reaction; composite granule suspension; and then the silver nitrate deionized water solution is added drop-wise in the above-mentioned composite granule suspension, make at composite particles surface ion switching part silver ion, the thermal treatment under 400-500 ℃ of temperature of silver-colored composite particles will be carried then and composite inorganic antimicrobial agent can be made after 1 hour.The inorganic antibacterial scavenging material that makes has the novel product of the synergistic effect of photocatalysis and metal ion antibacterial functions." but this method need disperse nano titanium oxide in the mixing reactor of particular design, that equipment requires is high, operation is loaded down with trivial details.And titanium dioxide coated by argentum-carried hydroxylapatite, weakened the performance of the strong oxidation virus killing mineralization of titanium dioxide.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant is provided, make argentum-carried hydroxylapatite and nano titanium oxide better bring into play composite effect, and make the pasteurization material good weatherability, uniform particles, the virus killing Disinfection Effect that obtain lasting.
The present invention is achieved by the following technical solutions, and the present invention is a raw material with the mineral salt of titanium, silver, calcium, ammonium, adopts liquid-phase coprecipitation, the preparation argentum-carried hydroxylapatite; Then argentum-carried hydroxylapatite is scattered in the colloidal sol that the mineral salt hydrolysis of titanium obtains,, obtains argentum-carried hydroxylapatite/nano titanium oxide composite granule in conjunction with subsequent heat treatment.
The present invention includes following steps:
(1) solution preparation: titanium chloride is dissolved in deionized water, be made into the solution of 1mol/l; The nitrate of silver, calcium is dissolved in deionized water, be made into the solution of 1mol/l; Diammonium hydrogen phosphate is dissolved in deionized water, be made into the solution of 1mol/l;
(2) liquor argenti nitratis ophthalmicus is added in the calcium nitrate solution, mix, 20% ammonia spirit is joined in the ammonium dibasic phosphate solution;
(3) silver, the nitrate mixed solution of calcium, ammonium dibasic phosphate solution are put into 80 ℃ Water Tank with Temp.-controlled heating 10 minutes, ammonium dibasic phosphate solution dropwise are added in the nitrate mixed solution of silver, calcium, treat that precipitation fully after, ageing 10 ~ 20 hours;
(4) sedimentation and filtration, after washed with de-ionized water, drying is 8 hours in 120 ℃ baking oven, obtains argentum-carried hydroxylapatite.
(5) 20% ammoniacal liquor is added the TiCl of 1.0mol/L
4In the aqueous solution, add polybasic carboxylic acid, ratio is [polybasic carboxylic acid]/[TiCl
4]=2.5: 1 obtain little blue peptizate; With the above-mentioned argentum-carried hydroxylapatite that makes, be dispersed in the sol solution, 70 ~ 95 ℃ of following hydrolysis 2 hours, obtain white suspension, ageing 10 ~ 24 hours; After the precipitation and centrifugal separation, handled 6 hours, make argentum-carried hydroxylapatite/nano titanium oxide composite granule at 400 ~ 600 ℃.
The present invention proposes to prepare argentum-carried hydroxylapatite/nano titanium oxide composite granule with liquid-phase coprecipitation, and the equipment of employing is simple, only needs just to be improved on common response device and thermostatic equipment and can use, and technological operation simultaneously is simple.The particle that obtains, little, the epigranular of size, the virus killing Disinfection Effect is lasting.The prepared powder of the present invention is expected to be applied in sterilizing fields such as air cleaning, water treatments.The evaluation of the nanometer composite silver carrying hydroxyapatite stone/titanium dioxide powder bacteriostasis rate that makes for the present invention is to utilize the Escherichia coli culture experiment to investigate bacteriostasis rate 〉=99% under the illumination condition of laboratory.
Embodiment
Embodiment 1
At the Ca of 1.0mol/L (NO
3)
2Among the aqueous solution 500mL, add the AgNO of 1.0mol/l
3500ml.Both mix.Other gets 1.0mol/L (NH
4)
2HPO
4Aqueous solution 300mL is added on (NH with 20% ammoniacal liquor 100ml
4)
2HPO
4In the solution, after mixing, solution dilution is arrived 500ml.
Ammonium dibasic phosphate solution dropwise is added in the nitrate mixed solution of silver, calcium, constantly stirs, the control solution temperature is 80 ℃, ageing 10 hours.After filtration, repeatedly after the washing, the filter cake drying in 120 ℃ baking oven that obtains can be obtained argentum-carried hydroxylapatite in 8 hours.TiCl at 1.0mol/L
4Among the aqueous solution 500mL, drip 20% ammoniacal liquor 25mL, add polybasic carboxylic acid, ratio is [polybasic carboxylic acid]/[TiCl
4]=2.5: 1, obtain little blue peptizate, add argentum-carried hydroxylapatite, abundant mixing made it to be dispersed in the sol solution, 95 ℃ of following hydrolysis 2 hours, obtain white suspension, continue ageing 20 hours, will be deposited in 450 ℃ after the centrifugation and handle 6 hours, make argentum-carried hydroxylapatite/nano titanium oxide composite granule, powder diameter: 100nm, the mol ratio of nano titanium oxide and argentum-carried hydroxylapatite=10: 1.
The equipment that the present invention adopts is simple, only needs just to be improved on common response device and thermostatic equipment and can use, and technological operation simultaneously is simple.The particle that obtains, little, the epigranular of size, the virus killing Disinfection Effect is lasting.Bacteriostasis rate 〉=99%.
Embodiment 2
At the Ca of 1.0mol/L (NO
3)
2Among the aqueous solution 500mL, add the AgNO of 1.0mol/l
3500ml.Both mix.Other gets 1.0mol/L (NH
4)
2HPO
4Aqueous solution 300mL is added on (NH with 20% ammoniacal liquor 100ml
4)
2HPO
4In the solution, after mixing, solution dilution is arrived 500ml.
Ammonium dibasic phosphate solution dropwise is added in the nitrate mixed solution of silver, calcium, constantly stirs, the control solution temperature is 80 ℃, ageing 20 hours.After filtration, repeatedly after the washing, the filter cake drying in 120 ℃ baking oven that obtains can be obtained argentum-carried hydroxylapatite in 8 hours.TiCl at 1.0mol/L
4Among the aqueous solution 400mL, drip 20% ammoniacal liquor 25mL, add polybasic carboxylic acid, ratio is [polybasic carboxylic acid]/[TiCl
4]=2.5: 1, obtain little blue peptizate, add argentum-carried hydroxylapatite, abundant mixing made it to be dispersed in the sol solution, 80 ℃ of following hydrolysis 2 hours, obtain white suspension, continue ageing 24 hours, will be deposited in 600 ℃ after the centrifugation and handle 6 hours, make argentum-carried hydroxylapatite/nano titanium oxide composite granule, powder diameter: 150nm, the mol ratio of nano titanium oxide and argentum-carried hydroxylapatite=8: 1.
The equipment that the present invention adopts is simple, only needs just to be improved on common response device and thermostatic equipment and can use, and technological operation simultaneously is simple.The particle that obtains, little, the epigranular of size, the virus killing Disinfection Effect is lasting.Bacteriostasis rate 〉=99%.
Embodiment 3
In the Ca of 1.0mol/L (NO3) 2 aqueous solution 500mL, add the AgNO of 1.0mol/l
3500ml.Both mix.Other gets 1.0mol/L (NH
4)
2HPO
4Aqueous solution 300mL is added on (NH with 20% ammoniacal liquor 100ml
4)
2HPO
4In the solution, after mixing, solution dilution is arrived 500ml.
Ammonium dibasic phosphate solution dropwise is added in the nitrate mixed solution of silver, calcium, constantly stirs, the control solution temperature is 80 ℃, ageing 18 hours.After filtration, repeatedly after the washing, the filter cake drying in 120 ℃ baking oven that obtains can be obtained argentum-carried hydroxylapatite in 8 hours.TiCl at 1.0mol/L
4Among the aqueous solution 300mL, drip 20% ammoniacal liquor 25mL, add polybasic carboxylic acid, ratio is [polybasic carboxylic acid]/[TiCl
4]=2.5: 1, obtain little blue peptizate, add argentum-carried hydroxylapatite, abundant mixing made it to be dispersed in the sol solution, 70 ℃ of following hydrolysis 2 hours, obtain white suspension, continue ageing 10 hours, will be deposited in 400 ℃ after the centrifugation and handle 6 hours, make argentum-carried hydroxylapatite/nano titanium oxide composite granule, powder diameter: 80nm, the mol ratio of nano titanium oxide and argentum-carried hydroxylapatite=6: 1.
The equipment that the present invention adopts is simple, only needs just to be improved on common response device and thermostatic equipment and can use, and technological operation simultaneously is simple.The particle that obtains, little, the epigranular of size, the virus killing Disinfection Effect is lasting.Bacteriostasis rate 〉=99%.
Claims (9)
1. the preparation method of a nanometer composite silver carrying hydroxyapatite stone/titania disinfectant is characterized in that, is raw material with the mineral salt of titanium, silver, calcium, ammonium, adopts liquid-phase coprecipitation, the preparation argentum-carried hydroxylapatite; Then argentum-carried hydroxylapatite is scattered in the colloidal sol that the mineral salt hydrolysis of titanium obtains,, obtains argentum-carried hydroxylapatite/nano titanium oxide composite granule in conjunction with subsequent heat treatment.
2. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 1 is characterized in that, may further comprise the steps:
(1) solution preparation: titanium chloride is dissolved in deionized water, be made into the solution of 1mol/l; The nitrate of silver, calcium is dissolved in deionized water, be made into the solution of 1mol/l; Diammonium hydrogen phosphate is dissolved in deionized water, be made into the solution of 1mol/l;
(2) liquor argenti nitratis ophthalmicus is added in the calcium nitrate solution, mix, ammonia spirit is joined in the ammonium dibasic phosphate solution;
(3) silver, the nitrate mixed solution of calcium, ammonium dibasic phosphate solution are put into Water Tank with Temp.-controlled and are heated, ammonium dibasic phosphate solution dropwise is added in the nitrate mixed solution of silver, calcium, treat that precipitation fully after, ageing;
(4) sedimentation and filtration, dry in baking oven after washed with de-ionized water, obtain argentum-carried hydroxylapatite;
(5) ammoniacal liquor is added TiCl
4In the aqueous solution, add polybasic carboxylic acid, obtain little blue peptizate; With the above-mentioned argentum-carried hydroxylapatite that makes, be dispersed in the sol solution, hydrolysis obtains white suspension, ageing; After the precipitation and centrifugal separation, make argentum-carried hydroxylapatite/nano titanium oxide composite granule.
3. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2 is characterized in that, described ammoniacal liquor, and its concentration is 20%.
4. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2, it is characterized in that, in the described step (3), the Water Tank with Temp.-controlled that silver, the nitrate mixed solution of calcium, ammonium dibasic phosphate solution are put into 80 ℃ heated 10 minutes, ammonium dibasic phosphate solution dropwise is added in the nitrate mixed solution of silver, calcium, after treating that precipitation is fully, ageing 10 ~ 20 hours.
5. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2 is characterized in that, in the described step (4), sedimentation and filtration, after washed with de-ionized water, drying is 8 hours in 120 ℃ baking oven, obtains argentum-carried hydroxylapatite.
6. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2 is characterized in that, described TiCl
4The aqueous solution, its concentration are 1.0mol/L.
7. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2 is characterized in that, described polybasic carboxylic acid, itself and TiCl
4Ratio be 2.5: 1.
8. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2, it is characterized in that, in the described step (5), with the above-mentioned argentum-carried hydroxylapatite that makes, be dispersed in the sol solution, 70 ~ 95 ℃ of following hydrolysis 2 hours, obtain white suspension, ageing 10 ~ 24 hours.
9. the preparation method of nanometer composite silver carrying hydroxyapatite stone/titania disinfectant according to claim 2, it is characterized in that, in the described step (5), after the precipitation and centrifugal separation, handled 6 hours at 400 ~ 600 ℃, make argentum-carried hydroxylapatite/nano titanium oxide composite granule.
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|---|---|---|---|
| CNB2005100298929A CN100336450C (en) | 2005-09-22 | 2005-09-22 | Prepn process of nanometer composite silver carrying hydroxyapatite/titania disinfectant |
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|---|---|---|---|
| CNB2005100298929A CN100336450C (en) | 2005-09-22 | 2005-09-22 | Prepn process of nanometer composite silver carrying hydroxyapatite/titania disinfectant |
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| CN1739357A true CN1739357A (en) | 2006-03-01 |
| CN100336450C CN100336450C (en) | 2007-09-12 |
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|---|---|---|---|
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| CN100549109C (en) * | 2007-06-15 | 2009-10-14 | 中国科学院上海硅酸盐研究所 | A kind of anti-bacterial carboxy apatite composite coating, preparation method and application |
| CN101588715B (en) * | 2006-10-12 | 2013-07-10 | Nm技术纳米材料微型装置技术有限公司 | Material, item and products comprising a composition having anti-microbial properties |
| CN104893444A (en) * | 2015-05-29 | 2015-09-09 | 江苏恒智纳米科技有限公司 | Multifunctional aqueous nano-coating |
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| CN107281555A (en) * | 2017-06-22 | 2017-10-24 | 江苏沥泽生化科技有限公司 | Preparation method of silver-carrying nano hydroxyapatite of potent long acting antibiotic and products thereof |
| CN112919881A (en) * | 2021-03-15 | 2021-06-08 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral dark-red enameled pottery and preparation method thereof |
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| JP3448896B2 (en) * | 1992-05-21 | 2003-09-22 | 東亞合成株式会社 | Manufacturing method of antibacterial agent |
| JPH08165208A (en) * | 1994-12-09 | 1996-06-25 | Sintokogio Ltd | Antimicrobial, mildewproofing and deodorizing spraying agent |
| CN1277889C (en) * | 2003-05-15 | 2006-10-04 | 深圳市成殷高新技术有限公司 | Prepn and use of nano level composite calcium hydroxy phosphate/titania grain |
| CN1264407C (en) * | 2004-07-08 | 2006-07-19 | 上海大学 | Process for preparing compound inorganic germicide |
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2005
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| CN100549109C (en) * | 2007-06-15 | 2009-10-14 | 中国科学院上海硅酸盐研究所 | A kind of anti-bacterial carboxy apatite composite coating, preparation method and application |
| CN104893444A (en) * | 2015-05-29 | 2015-09-09 | 江苏恒智纳米科技有限公司 | Multifunctional aqueous nano-coating |
| CN104893444B (en) * | 2015-05-29 | 2017-05-17 | 江苏恒智纳米科技有限公司 | Multifunctional aqueous nano-coating |
| CN106747402A (en) * | 2016-12-23 | 2017-05-31 | 江南大学 | A kind of preparation method of novel antibacterial bioceramic porous material |
| CN106987230A (en) * | 2017-03-30 | 2017-07-28 | 佛山市安齿生物科技有限公司 | A kind of abrasive material handled for implant surface and its preparation method and application |
| CN107258812A (en) * | 2017-06-22 | 2017-10-20 | 安徽省德邦瓷业有限公司 | A kind of preparation method of composite modified zeolite with carrying silver for domestic ceramics glaze slip |
| CN107281555A (en) * | 2017-06-22 | 2017-10-24 | 江苏沥泽生化科技有限公司 | Preparation method of silver-carrying nano hydroxyapatite of potent long acting antibiotic and products thereof |
| EP3808180A4 (en) * | 2018-05-25 | 2022-03-16 | Dr. C Medical Medicine Co., Ltd. | Method for controlling harmful insects |
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