CN101731270B - Method for preparing novel titanium dioxide silver-doped antibacterial agent - Google Patents
Method for preparing novel titanium dioxide silver-doped antibacterial agent Download PDFInfo
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- CN101731270B CN101731270B CN2009101550845A CN200910155084A CN101731270B CN 101731270 B CN101731270 B CN 101731270B CN 2009101550845 A CN2009101550845 A CN 2009101550845A CN 200910155084 A CN200910155084 A CN 200910155084A CN 101731270 B CN101731270 B CN 101731270B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 27
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 239000004332 silver Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008139 complexing agent Substances 0.000 claims abstract description 6
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- -1 silver ions Chemical class 0.000 abstract description 2
- 229910001923 silver oxide Inorganic materials 0.000 abstract description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 abstract 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 229940043267 rhodamine b Drugs 0.000 description 2
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- QBNKFXYJSJOGEL-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ti+4] QBNKFXYJSJOGEL-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
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Abstract
The invention relates to the preparation of an antibacterial agent and provides a method for preparing a novel titanium dioxide silver-doped antibacterial agent. The method comprises the following steps of: (1) adding a complexing agent into a silver nitrate ethanol solution, fully and uniformly stirring under the shading condition and carrying out reflux reaction under the water bath condition to obtain chelate silver-contained sol; (2) dropwise adding a mixed solution of tetrabutyl titanate and anhydrous ethanol into an aqueous solution with the pH of 1-2.5 under the stirring condition, refluxing under the water bath condition and finally adjusting the pH to 3-6 to obtain titanium dioxide grain sol; (3) dropwise adding the chelate silver-contained sol into the titanium dioxide grain solunder the stirring condition, refluxing and ageing under the water bath condition and then obtaining the titanium dioxide silver-doped antibacterial agent. The invention agglomerate silver ions on the surface of a titanium dioxide grain by adopting a wet-chemical method and utilizing a chelate technology and a sol-gel hydrolytic polymerization control technology, realizes the uniform complexing of silver and titanium dioxide at a nano size and endows materials with favorable antibacterial capability.
Description
Technical field
The present invention relates to the preparation of antibacterial agent, particularly a kind of preparation method of novel titanium dioxide silver-doped antibacterial agent.
Background technology
Antibacterial agent be one type to kill and to suppress the preparation that growth of microorganism is a major function, according to the difference of its host material, can be divided into two types of organic antibacterial agent and inorganic antiseptics.
Organic antibacterial agent is meant that with organic matters such as organic acid, phenols, quaternary ammonium salt, benzimidazoles be the antibacterial agent of antibacterial material.Organic antibacterial agent is the anti-biotic material that comes into the picture the earliest; It is of a great variety; Low production cost; But the shortcoming of organic antibacterial agent ubiquity heat resistance poor (being generally below 200 ℃), high specificity, broad spectrum activity difference, thereby organic antibacterial agent is mainly used in pharmaceutical sanitary field is used few in the field at article of manufacture etc. widely.
Sterilize two big type but inorganic antiseptic sub-oxide light activated semiconductor is antibiotic with heavy metal, they all have broad spectrum antibacterial, and are safe in utilization, and can keep good antibacterial effect for a long time.But the sterilizing efficiency of conductor oxidate is lower, and in use must have ultraviolet ray to carry out catalysis; Though the heavy metallic oxide antibacterial effect is remarkable, costs an arm and a leg, usage amount is restricted, and the discoloration problem of silver-series antibacterial agent is serious.Discover that orderly, the directed doping of silver ion in the nanometer titanium dioxide titanium oxide can improve antibacterial activity effectively.Yet traditional titanium dioxide silver-doped antibacterial agent is for the titanium dioxide that obtains crystalline state and promote both effectively compound, often needs follow-up Technology for Heating Processing, and this can consume mass energy, but also has limited range of application.
Summary of the invention
The technical problem that the present invention will solve is, overcomes deficiency of the prior art, and a kind of preparation method of novel titanium dioxide silver-doped antibacterial agent is provided.
Be the technical solution problem, the preparation method of titanium dioxide silver-doped antibacterial agent provided by the invention comprises the steps:
(1) in the silver nitrate ethanolic solution, adds complexing agent, stir under the lucifuge condition, and reacted 2～6 hours, obtain chelating type and contain silver sol in 40～80 ℃ water bath condition refluxed;
(2) under stirring condition, it is in 1～2.5 the aqueous solution that the mixed liquor of butyl titanate and absolute ethyl alcohol is added drop-wise to pH, and 50～80 ℃ water bath condition refluxed 5～10 hours, regulating pH at last was 3～6, obtains titania colloidal sol;
(3) under stirring condition, chelating type is contained silver sol be added drop-wise in the titania colloidal sol with the speed of 0.05～0.5 gram/minute, 60 ℃ water bath condition refluxed 2 hours, ageing obtained titanium dioxide silver-doped antibacterial agent after 3～7 days;
Silver nitrate ethanolic solution mass percent in the step (1) is 5%～30%, and complexing agent is sodium thiosulfate or citric acid, and wherein the mol ratio of sodium thiosulfate and silver nitrate is 0.2～1.5, and the mol ratio of citric acid and silver nitrate is 0.4～1; Butyl titanate in the step (2): absolute ethyl alcohol: the mass ratio of water is 1: 10～16: 150～185.
Among the present invention, before step (2) drips mixed liquor, use the nitre acid for adjusting pH value; After the end that refluxes, adopt ammoniacal liquor to regulate the pH value.
Among the present invention, the control dripping quantity makes chelating type contain the Ag in the silver sol in the step (3)
+With the Ti in the titania colloidal sol
4+Mol ratio be 1%～8%.
Compare with existing technology of preparing, the invention has the beneficial effects as follows:
The present invention adopts wet chemical method, utilizes chelating technology to make silver ion and thiosulfate anion combine to generate [Ag (S
2O
3)]
-, [Ag
2(S
2O
3)
2]
2-, [Ag (S
2O
3)
2]
3-, Ag
2C
6H
5O
7 -Etc. electronegative coordination ion; Through sol-gel hydrolytic polymerization control technology, preparation titania colloidal sol forms Ti-OH under acid liquid-phase condition simultaneously
2 +, make titanium dioxide micelle surface positively charged.Thereby utilize charge effect to make silver ion in titania surface agglomeration, realization silver and titanium dioxide are evenly compound nanoscale, give material good antibacterial ability.And the generated in-situ titania of this liquid phase is owing to exist certain crystal defect, and band structure changes thus, and it is active to discover that this titania can be produced by natural light excitation.Therefore, the present invention has compared with prior art side by side successfully solved silver-series antibacterial agent titanium dioxide silver-doped anti-biotic material need high-temperature heat treatment easy to change, traditional and must ultraviolet ray just can excite application problems such as producing activity.
Description of drawings
Fig. 1 is the absorption spectra that the different single wavelength light of 200～1000nm excite titania colloidal sol photocatalysis rhodamine B solution.
Rhodamine B by photocatalysis Decomposition after, absorption spectrum intensity can reduce.Can know that from figure such titania colloidal sol can be produced photocatalytic activity by natural light excitation.
Embodiment
Below further present invention is described through instance.
The preparation method of titanium dioxide silver-doped antibacterial agent provided by the invention comprises the steps:
(1) in the silver nitrate ethanolic solution, adds complexing agent, stir under the lucifuge condition, and reacted 2～6 hours, obtain chelating type and contain silver sol in 40～80 ℃ water bath condition refluxed;
(2) under stirring condition, it is in 1～2.5 the aqueous solution that the mixed liquor of butyl titanate and absolute ethyl alcohol is added drop-wise to pH, and 50～80 ℃ water bath condition refluxed 5～10 hours, regulating pH at last was 3～6, obtains titania colloidal sol;
(3) under stirring condition, chelating type is contained silver sol be added drop-wise in the titania colloidal sol with the speed of 0.05～0.5 gram/minute, 60 ℃ water bath condition refluxed 2 hours, ageing obtained titanium dioxide silver-doped antibacterial agent after 3～7 days.
Test data among each embodiment is seen table 1.
Table 1:
| The specific embodiment sequence number | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 |
| Silver nitrate ethanolic solution mass percent | 5％ | 10％ | 20％ | 30％ | 21％ | 14％ | 7％ | 28％ |
| Sodium thiosulfate and silver nitrate mol ratio | 0.2 | 0.5 | 1 | 1.5 | -- | -- | -- | -- |
| Citric acid and silver nitrate mol ratio | -- | -- | -- | -- | 0.4 | 0.6 | 0.8 | 1 |
| Butyl titanate and absolute ethyl alcohol mol ratio | 1∶10 | 1∶12 | 1∶14 | 1∶16 | 1∶16 | 1∶13 | 1∶11 | 1∶10 |
| Butyl titanate and water mol ratio | 1∶150 | 1∶165 | 1∶175 | 1∶185 | 1∶170 | 1∶185 | 1∶160 | 1∶150 |
| Ag +With Ti 4+Mol ratio | 1％ | 3％ | 5％ | 8％ | 1％ | 4％ | 6％ | 8％ |
| Step (1) bath temperature (℃) | 40 | 50 | 60 | 80 | 80 | 65 | 55 | 40 |
| Step (1) return time (hour) | 6 | 5 | 4 | 2 | 2 | 3.5 | 4.5 | 6 |
| Step (2) pH value of water solution | 2.5 | 2 | 1.5 | 1 | 1 | 2 | 2.5 | 2 |
| Step (2) bath temperature (℃) | 50 | 60 | 70 | 80 | 80 | 65 | 55 | 50 |
| Step (2) return time (hour) | 5 | 7 | 9 | 10 | 10 | 8 | 6 | 5 |
| Step (2) end product pH value | 6 | 4 | 4 | 3 | 5 | 4 | 3 | 6 |
| Step (3) contains silver sol drop rate (gram/minute) | 0.05 | 0.1 | 0.2 | 0.5 | 0.3 | 0.5 | 0.4 | 0.05 |
| Step (3) assembly time (my god) | 3 | 4 | 5 | 7 | 6 | 7 | 5 | 3 |
At last, it is also to be noted that what more than enumerate only is practical implementation example of the present invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (2)
1. the preparation method of a titanium dioxide silver-doped antibacterial agent comprises the steps:
(1) in the silver nitrate ethanolic solution, adds complexing agent, stir under the lucifuge condition, and reacted 2～6 hours, obtain chelating type and contain silver sol in 40～80 ℃ water bath condition refluxed;
(2) under stirring condition, it is in 1～2.5 the aqueous solution that the mixed liquor of butyl titanate and absolute ethyl alcohol is added drop-wise to pH, and 50～80 ℃ water bath condition refluxed 5～10 hours, regulating pH at last was 3～6, obtains titania colloidal sol;
(3) under stirring condition, chelating type is contained silver sol be added drop-wise in the titania colloidal sol with the speed of 0.05～0.5 gram/minute, 60 ℃ water bath condition refluxed 2 hours, ageing obtained titanium dioxide silver-doped antibacterial agent after 3～7 days;
Silver nitrate ethanolic solution mass percent in the step (1) is 5%～30%, and complexing agent is sodium thiosulfate or citric acid, and wherein the mol ratio of sodium thiosulfate and silver nitrate is 0.2～1.5, and the mol ratio of citric acid and silver nitrate is 0.4～1; Butyl titanate in the step (2): absolute ethyl alcohol: the mass ratio of water is 1: 10～16: 150～185;
The control dripping quantity makes chelating type contain the Ag in the silver sol in the step (3)
+With the Ti in the titania colloidal sol
4+Mol ratio be 1%～8%.
2. the preparation method of titanium dioxide silver-doped antibacterial agent according to claim 1 is characterized in that, before step (2) drips mixed liquor, uses the nitre acid for adjusting pH value; After the end that refluxes, adopt ammoniacal liquor to regulate the pH value.
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| CN2009101550845A CN101731270B (en) | 2009-12-17 | 2009-12-17 | Method for preparing novel titanium dioxide silver-doped antibacterial agent |
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| CN101731270A CN101731270A (en) | 2010-06-16 |
| CN101731270B true CN101731270B (en) | 2012-08-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103980625B (en) * | 2014-01-17 | 2016-04-20 | 安徽万兴实业有限公司 | A kind of preparation method of antibacterial PVC matrix material |
| CN104293178B (en) * | 2014-04-28 | 2016-10-26 | 南昌奥倍克纳米技术有限公司 | Concrete product long acting antibiotic waterproofing agent and preparation method thereof |
| CN105113263A (en) * | 2014-05-14 | 2015-12-02 | 青岛蓝农谷农产品研究开发有限公司 | Antibacterial fiber dipping composition |
| CN103977830B (en) * | 2014-05-21 | 2016-02-17 | 江苏科技大学 | The method for making of visible light activity doped nano titanium dioxide and the method for making of visible light photocatalysis photocatalyst glazing emulsion |
| CN104045853A (en) * | 2014-05-22 | 2014-09-17 | 上海施迈尔精密陶瓷有限公司 | Ag, Cu and Zn doped nanometer titanium dioxide composite antibacterial agent and preparation method thereof |
| CN104190458B (en) * | 2014-07-16 | 2016-08-24 | 上海工程技术大学 | A kind of low temperature preparation technology of dual element modified nano-titanium dioxide colloidal sol |
| CN106259445A (en) * | 2015-05-26 | 2017-01-04 | 东莞市昊天化工有限公司 | A kind of fine silver antibacterial |
| CN106702728A (en) * | 2016-07-13 | 2017-05-24 | 东莞市恩科化工有限公司 | Ag-TIO2 composite antibacterial agent and preparation method thereof |
| CN108064881B (en) * | 2016-11-14 | 2024-02-13 | 佛山市顺德区美的电热电器制造有限公司 | Silver-containing titanium dioxide composite antibacterial agent and preparation method thereof, and antibacterial coating and preparation method thereof |
| CN110063340B (en) * | 2018-01-23 | 2022-02-18 | 合肥杰事杰新材料股份有限公司 | Silver-doped titanium dioxide nano antibacterial agent and preparation method thereof |
| CN108902177A (en) * | 2018-06-27 | 2018-11-30 | 徐涌涛 | A kind of preparation method of argentiferous titanium dioxide anti-bacterial agent |
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