CN1784974A - Composite photocatalitic germicide - Google Patents
Composite photocatalitic germicide Download PDFInfo
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- CN1784974A CN1784974A CN 200510110218 CN200510110218A CN1784974A CN 1784974 A CN1784974 A CN 1784974A CN 200510110218 CN200510110218 CN 200510110218 CN 200510110218 A CN200510110218 A CN 200510110218A CN 1784974 A CN1784974 A CN 1784974A
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Abstract
A composite photolytic antibacterial agent for antibacterial polymer, fiber and fabrics contains proportionally the nanoparticles of TiO2, SiO2 and Ag. It features that the TiO2 and Ag nanoparticles are wrapped by SiO2 nanoparticles to form a special porous layer.
Description
Technical field
What the present invention relates to is a kind of product of chemical technology field, specifically is a kind of composite photocatalitic germicide.
Background technology
Nano-TiO
2Under ultraviolet irradiation, electronics transits on the conduction band from valence band, forms hole-electron pair, and absorption is dissolved in nano-TiO
2The oxygen trapped electron of face forms active oxygen O
2 -, the hole then will be adsorbed on nano-TiO
2The OH on surface
-And H
2O is oxidized to free radical HO
The active oxygen O that generates
2 -With free radical HO
Can penetrate the cell wall of bacterium, enter thalline, stop the transmission of film forming matter, block its respiratory system and electric transmission system, thus effective kill bacteria.Nano-TiO
2Another advantage of sterilization is the noxious material that its energy bacterium for degrading discharges when dead.Free radical HO
Has very high oxidability, effectively degradation of organic substances and environmental contaminants.Common photocatalitic germicide has wide spectrum, durable, safe characteristics, obtains extensive use aspect textile, amenities, but nano-TiO
2Can only absorb excitation wavelength is that the following light of 385nm (ultraviolet wavelength) reacts, thereby common photocatalitic germicide must be at ultraviolet irradiation competence exertion antibacterial action, and this makes the application of common photocatalitic germicide be subjected to certain limitation.
Find through literature search prior art, the article that is published in the 34th the 1st phase of volume of " application chemical industry " January in 2005 " carries the research of silver-colored titanium oxide photocatalysis disinfectant performance ", this article will be in the deficiency of competence exertion antibacterial action under the ultraviolet irradiation in order to overcome nano titanium oxide, with the metatitanic acid is presoma, flood certain density liquor argenti nitratis ophthalmicus, prepare year silver-colored titanium dioxide with the heat deposition method, and the anti-microbial property of silver-colored titanium dioxide is carried in research.But year silver-colored titanium dioxide particle diameter that adopts the heat deposition method to prepare is thicker, the photocatalysis antibacterial poor-performing; Titanium dioxide surface does not pass through modification, can not be used to prepare fiber and textile with anti-microbial property.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of composite photocatalitic germicide is provided, make its anti-microbial property that can improve common photocatalitic germicide, overcoming common photocatalitic germicide will be in the limitation of competence exertion antibacterial action under the ultraviolet irradiation.Titanium dioxide nano-particle particle diameter of the present invention is less, the photocatalysis antibacterial better performances, adopt silica that titanium dioxide nano-particle is carried out modification, this antibacterial agent has good antibiotic, antifouling, deodorization functions, can be used to prepare have textile and amenities antibiotic, antifouling, deodorization functions.
The present invention is achieved by the following technical solutions, composite photocatalitic germicide of the present invention, and its component and percentage by weight are: TiO
273.7 ~ 87.0%, SiO
210.7 ~ 22.6%, Ag 2.3 ~ 3.7%, TiO
2, SiO
2Be nanoscale with the Ag particle size.The present invention makes by the following method: prepare TiO 2 sol, silicon dioxide gel at first respectively, then TiO 2 sol is mixed with silicon dioxide gel, mix silver again, after ageing, drying, grinding, roasting obtain composite photocatalitic germicide of the present invention.
TiO of the present invention
2Nano particle is through SiO
2Modification, SiO
2Coat TiO
2Nanoparticle surface forms the special perforated membrane of one deck, has overcome TiO
2The agglomeration traits of nano particle in polymer improved TiO
2The dispersiveness of nano particle in polymer, thus make this composite photocatalitic germicide can be used to prepare antibiotic macromolecular material and textile.Ag itself has very strong anti-microbial property, and it meets water can stripping Ag
+, attract strongly in the bacterium body and the thin base of breathing relevant zymoprotein, and lump together by chemical bonded refractory, its respiratory metabolism is obstructed, make bacterium death, thereby make this composite photocatalitic germicide not have also have good antibacterial performance under the situation of ultraviolet irradiation.Ag can promote TiO
2Change mutually to rutile from anatase, and the anatase that contains certain proportion rutile phase has higher catalytic activity, thereby Ag can improve the anti-microbial property of photocatalitic germicide.The present invention is not having to bring into play good antibacterial performance under the situation of ultraviolet irradiation yet.
Composite photo catalyst antimicrobial powder particle diameter distribution uniform of the present invention, particle diameter is less than 100nm, under ultraviolet irradiation, to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate greater than 99%, do not having under the ultraviolet irradiation, to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate greater than 90%.Composite photocatalitic germicide preparation method technology provided by the invention is simple, does not need special installation, and industrialization prospect is good.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
Composite photocatalitic germicide, its component and percentage by weight are: TiO
2(87.0%), SiO
2(10.7%) and Ag (2.3%), its preparation process is as follows:
Metatitanic acid four fourth liposoluble are gone in the absolute ethyl alcohol, the metatitanic acid four fourth fat ethanolic solutions of preparation 10%, ratio preparation deionized water, alcohol mixeding liquid in 1: 5, splashing into a small amount of glacial acetic acid, to make the pH value of deionized water, alcohol mixeding liquid be 4, isopyknic deionized water, alcohol mixeding liquid are splashed into metatitanic acid four fourth fat ethanolic solutions, stir while splashing into, solution temperature remains on 15 ℃.After treating that deionized water, alcohol mixeding liquid add metatitanic acid four fourth fat ethanolic solutions, stirred 6 hours, obtain the TiO 2 sol of homogeneous transparent.
Tetraethoxysilance is dissolved in the absolute ethyl alcohol, the tetraethoxysilance ethanolic solution of preparation 10%, prepare deionized water, alcohol mixeding liquid in 1: 3 ratio, isopyknic deionized water, alcohol mixeding liquid are splashed into the tetraethoxysilance ethanolic solution, stir while splashing into, solution temperature remains on 15 ℃, stirs 16 hours, obtains the silicon dioxide gel of homogeneous transparent.With volume ratio is that 10: 1 TiO 2 sol, silicon dioxide gel mixes, and stirs 4 hours, and collosol temperature remains on 15 ℃, obtains the mixed sols of homogeneous transparent.
The preparation weight percent concentration is 2.5% liquor argenti nitratis ophthalmicus, and the silver nitrate aqueous solution of mixed sols volume 1.8% is splashed in the mixed sols, stirs while splash into, and collosol temperature remains on 15 ℃, stirs 2 hours.Form and do not have behind the gel of flowability, put only 3 days, be warming up to 100 ℃ under vacuum, programming rate is 1 ℃/min, be incubated 12 hours, after the grinding, in air atmosphere, be warming up to 600 ℃, programming rate is 3 ℃/min, is incubated 3 hours, obtains the composite photo catalyst antimicrobial powder.
The composite photo catalyst antimicrobial powder that present embodiment makes, under ultraviolet irradiation, to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate is 99.99%, not having under the ultraviolet irradiation, is 90.5% to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate.
Embodiment 2:
Composite photocatalitic germicide, its component and percentage by weight are: TiO
2(80.6%), SiO
2(16.5%) and Ag (2.9%), its preparation process is as follows:
Metatitanic acid four fourth liposoluble are gone in the absolute ethyl alcohol, the metatitanic acid four fourth fat ethanolic solutions of preparation 10%, ratio preparation deionized water, alcohol mixeding liquid in 1: 3, splashing into a small amount of glacial acetic acid, to make the pH value of deionized water, alcohol mixeding liquid be 4.5, isopyknic deionized water, alcohol mixeding liquid are splashed into metatitanic acid four fourth fat ethanolic solutions, stir while splashing into, solution temperature remains on 25 ℃, after treating that deionized water, alcohol mixeding liquid add metatitanic acid four fourth fat ethanolic solutions, stirred 5 hours, and obtained the TiO 2 sol of homogeneous transparent.
Tetraethoxysilance is dissolved in the absolute ethyl alcohol, the tetraethoxysilance ethanolic solution of preparation 10%, prepare deionized water, alcohol mixeding liquid in 1: 3 ratio, isopyknic deionized water, alcohol mixeding liquid are splashed into the tetraethoxysilance ethanolic solution, stir while splashing into, solution temperature remains on 25 ℃, stirs 12 hours, obtains the silicon dioxide gel of homogeneous transparent.With volume ratio is that 6: 1 TiO 2 sol, silicon dioxide gel mixes, and stirs 3 hours, and collosol temperature remains on 25 ℃, obtains the mixed sols of homogeneous transparent.
The preparation weight percent concentration is 2.5% liquor argenti nitratis ophthalmicus, and the silver nitrate aqueous solution of mixed sols volume 2.3% is added dropwise in the mixed sols, stirs while add, and collosol temperature remains on 25 ℃, stirs 1.5 hours.Form and do not have behind the gel of flowability, put only 3 days, be warming up to 100 ℃ under vacuum, programming rate is 1 ℃/min, be incubated 12 hours, after the grinding, in air atmosphere, be warming up to 600 ℃, programming rate is 3 ℃/min, is incubated 3 hours, obtains the composite photo catalyst antimicrobial powder.
The composite photo catalyst antimicrobial powder that present embodiment makes, under ultraviolet irradiation, to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate is 99.99%, not having under the ultraviolet irradiation, is 96.6% to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate.
Embodiment 3:
Composite photocatalitic germicide, its component and percentage by weight are: TiO
2(73.7%), SiO
2(22.6%) and Ag (3.7%), its preparation process is as follows:
Metatitanic acid four fourth liposoluble are gone in the absolute ethyl alcohol, the metatitanic acid four fourth fat ethanolic solutions of preparation 10%, ratio preparation deionized water, alcohol mixeding liquid in 1: 3, splashing into a small amount of glacial acetic acid, to make the pH value of deionized water, alcohol mixeding liquid be 5, isopyknic deionized water, alcohol mixeding liquid are splashed into metatitanic acid four fourth fat ethanolic solutions, stir while splashing into, solution temperature remains on 35 ℃, after treating that deionized water, alcohol mixeding liquid add metatitanic acid four fourth fat ethanolic solutions, stirred 4 hours, and obtained the TiO 2 sol of homogeneous transparent.
Tetraethoxysilance is dissolved in the absolute ethyl alcohol, the tetraethoxysilance ethanolic solution of preparation 10%, prepare deionized water, alcohol mixeding liquid in 1: 3 ratio, isopyknic deionized water, alcohol mixeding liquid are splashed into the tetraethoxysilance ethanolic solution, stir while splashing into, solution temperature remains on 35 ℃, stirs 8 hours, obtains the silicon dioxide gel of homogeneous transparent.With volume ratio is that 4: 1 TiO 2 sol, silicon dioxide gel mixes, and stirs 2 hours, and collosol temperature remains on 35 ℃, obtains the mixed sols of homogeneous transparent.
The preparation weight percent concentration is 2.5% liquor argenti nitratis ophthalmicus, and the silver nitrate aqueous solution of mixed sols volume 3% is added dropwise in the mixed sols, stirs while add, and collosol temperature remains on 35 ℃, stirs 1 hour.Form and do not have behind the gel of flowability, put only 3 days, be warming up to 100 ℃ under vacuum, programming rate is 1 ℃/min, be incubated 12 hours, after the grinding, in air atmosphere, be warming up to 600 ℃, programming rate is 3 ℃/min, is incubated 3 hours, obtains the composite photo catalyst antimicrobial powder.
The composite photo catalyst antimicrobial powder that present embodiment makes, under ultraviolet irradiation, to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate is 99.99%, not having under the ultraviolet irradiation, is 99.5% to Escherichia coli, staphylococcus aureus, bacillus megaterium, hay bacillus (48 hours) antibiotic rate.
Claims (6)
1, a kind of composite photocatalitic germicide is characterized in that, each component and percentage by weight thereof are: TiO
273.7 ~ 87.0%, SiO
210.7 ~ 22.6%, Ag 2.3 ~ 3.7%.
2, composite photocatalitic germicide according to claim 1 is characterized in that, described TiO
2Be of a size of nanoscale.
3, composite photocatalitic germicide according to claim 1 is characterized in that, described SiO
2Be of a size of nanoscale.
4, composite photocatalitic germicide according to claim 1 is characterized in that, described Ag is of a size of nanoscale.
5, composite photocatalitic germicide according to claim 1 is characterized in that, TiO
2Nano particle is through SiO
2Modification, SiO
2Coat TiO
2Nanoparticle surface forms one deck porous coating.
6, composite photocatalitic germicide according to claim 1 is characterized in that, particle diameter is less than 100nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510110218 CN1784974A (en) | 2005-11-10 | 2005-11-10 | Composite photocatalitic germicide |
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|---|---|---|---|
| CN 200510110218 CN1784974A (en) | 2005-11-10 | 2005-11-10 | Composite photocatalitic germicide |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566931A (en) * | 2013-10-17 | 2014-02-12 | 华中科技大学 | Photocatalytic material with visible-light response function as well as preparation method and application thereof |
| CN104872177A (en) * | 2015-04-16 | 2015-09-02 | 厦门大学嘉庚学院 | Preparation method of antibacterial deodorant material based on carbon nano silver catalyst |
| CN106172493A (en) * | 2016-07-28 | 2016-12-07 | 东莞市雄林新材料科技股份有限公司 | A kind of nano-photo catalytic antibacterial and preparation method thereof |
| CN106234413A (en) * | 2016-07-28 | 2016-12-21 | 东莞市雄林新材料科技股份有限公司 | A kind of nano antibacterial agent with infra red radiation function and preparation method thereof |
| CN106433337A (en) * | 2016-11-03 | 2017-02-22 | 张静 | Preparation method of self-cleaning waterborne fluorocarbon coating |
| CN110438801A (en) * | 2019-08-08 | 2019-11-12 | 苏州经贸职业技术学院 | A kind of fabric functional modifying agent and preparation method thereof |
| CN111357767A (en) * | 2020-04-03 | 2020-07-03 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN112690287A (en) * | 2020-12-01 | 2021-04-23 | 张晓龙 | Novel inorganic nano photocatalyst bactericide spray and preparation method thereof |
| CN113337064A (en) * | 2021-06-17 | 2021-09-03 | 广东川奥高新科技有限公司 | Antibacterial wear-resistant runway floor composite material and preparation method thereof |
-
2005
- 2005-11-10 CN CN 200510110218 patent/CN1784974A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566931A (en) * | 2013-10-17 | 2014-02-12 | 华中科技大学 | Photocatalytic material with visible-light response function as well as preparation method and application thereof |
| CN104872177A (en) * | 2015-04-16 | 2015-09-02 | 厦门大学嘉庚学院 | Preparation method of antibacterial deodorant material based on carbon nano silver catalyst |
| CN104872177B (en) * | 2015-04-16 | 2018-01-16 | 厦门大学嘉庚学院 | A kind of preparation method of the bactericidal deodoring materials based on carbon nano-silver photo-catalyst |
| CN106172493A (en) * | 2016-07-28 | 2016-12-07 | 东莞市雄林新材料科技股份有限公司 | A kind of nano-photo catalytic antibacterial and preparation method thereof |
| CN106234413A (en) * | 2016-07-28 | 2016-12-21 | 东莞市雄林新材料科技股份有限公司 | A kind of nano antibacterial agent with infra red radiation function and preparation method thereof |
| CN106433337A (en) * | 2016-11-03 | 2017-02-22 | 张静 | Preparation method of self-cleaning waterborne fluorocarbon coating |
| CN110438801A (en) * | 2019-08-08 | 2019-11-12 | 苏州经贸职业技术学院 | A kind of fabric functional modifying agent and preparation method thereof |
| CN111357767A (en) * | 2020-04-03 | 2020-07-03 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN111357767B (en) * | 2020-04-03 | 2021-02-23 | 李建勋 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN112438274A (en) * | 2020-04-03 | 2021-03-05 | 祁海强 | Preparation method of high-dispersion anti-discoloration nano-silver antibacterial agent material |
| CN112690287A (en) * | 2020-12-01 | 2021-04-23 | 张晓龙 | Novel inorganic nano photocatalyst bactericide spray and preparation method thereof |
| CN113337064A (en) * | 2021-06-17 | 2021-09-03 | 广东川奥高新科技有限公司 | Antibacterial wear-resistant runway floor composite material and preparation method thereof |
| CN113337064B (en) * | 2021-06-17 | 2022-06-10 | 广东川奥高新科技有限公司 | Antibacterial wear-resistant runway floor composite material and preparation method thereof |
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