CN102784645A - Metal particle combination TiO2 photocatalyst reinforcement anti-bacterial composition and preparation method thereof - Google Patents
Metal particle combination TiO2 photocatalyst reinforcement anti-bacterial composition and preparation method thereof Download PDFInfo
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- CN102784645A CN102784645A CN2011101267181A CN201110126718A CN102784645A CN 102784645 A CN102784645 A CN 102784645A CN 2011101267181 A CN2011101267181 A CN 2011101267181A CN 201110126718 A CN201110126718 A CN 201110126718A CN 102784645 A CN102784645 A CN 102784645A
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Abstract
The invention provides a metal particle combination nanometer photocatalyst TiO2 composition Ag<+>,Cu<++>,Fe<++>(<+++>)/TiO2 and a preparation method thereof, wherein the composition has characteristics of broad spectrum reinforcement and long-acting anti-bacterial effect. According to the present invention, a peroxide complexation base titanium metal oxide TiO2 anti-bactericidal composition is selected, wherein atom surfaces of the composition are modified by a peroxide, a stable anti-bacterial photocatalyst sol is formed in water, the pH value is neutral, and characteristics of film forming and long-acting anti-bacterial effect are provided; the particle size of the TiO2 particles is less than 20 nm, the crystal form of the TiO2 particles is an anatase type crystal, the electronic energy level is 3.2 eV, and an electron-hole effect is generated under an action of light, such that harmful organic matters contacting the TiO2 particles are decomposed so as to provide a harmless characteristic, and NOx and SOx are converted and removed from the atmosphere; the photocatalyst sol is added with the metal particles Ag<+>,Cu<++>,Fe<++>(<+++>)/TiO2 to produce a broad-spectrum reinforcement anti-bacterial composition, which provides strong anti-bacterial ability under visible light or in dark places, wherein the composition can form a film at a room temperature, can form a film on the surface of a high temperature resistance material, and can further be made into supplies with functions of anti-bacterial and photocatalysis.
Description
Technical field
The invention relates to and a kind ofly carry out atomic surface upgrading, anatase crystal type nano-photocatalyst TiO with peroxide
2The sterilization constituent is a main body, adds metallic and forms Ag
+, Cu
++, Fe
++ (+++)/ TiO
2The antibiotic photochemical catalyst constituent of wide spectrum enhanced type.The invention still further relates to the preparation method and the application of above-mentioned constituent colloidal sol.
Background technology
Around us, all receive the threat of the invisible various harmful substances of eyes every day.The pathogenic dwelling house syndrome that the atmosphere pollution that vehicle exhaust causes, building materials cause, the various danger of harmful mould, the pathogen of aerial infection, assorted bacterium and virus or the like exist.Because large-scale sudden health event takes place in recent years continually in the pollution of earth environment, for example SARS " bird flu " " Flu-A " " infects after the shake " or the like.
In addition, the filthy sagging, mouldy of skin, the variable color of interior decoration, new building materials in further smoking rubbish bed lavatory or the like are referred to as the stench of the dwelling house that causes a disease again.
Because bactericide and deodorant that people can select at present, great majority are the chemicals of representative for chlorine, iodine goods, often cause secondary pollution for rivers, soil, atmosphere etc. after the sterilization, and the application of this type of passive sterile products more and more is restricted.
External research also shows, owing to use disinfectant repeatedly, the phenomenon of " superbug is worked as breakfast to disinfectant " has taken place, and bacterium not only is not afraid of disinfectant, is not afraid of common antibiotic yet.
Since the later stage nineties in last century, be accompanied by the progress of nanometer technology, with Detitanium-ore-type crystal type photochemical catalyst TiO
2For representative have a photocatalytic activity semiconductor particle, the research that is applied in depollution of environment field is active, and obtains the actual effect of application.
From in essence, photocatalysis technology is to utilize light to excite semiconductors such as oxide, and the e-void effect of utilizing their to produce promotes the redox reaction that is difficult to take place at normal temperature.
But, have light and excite TiO
2Semiconductors such as oxide, illumination less than or the dark place of light use or the like, remain insoluble problem.
Has optical excitation TiO
2The semi-conductive depollution of environment such as oxide is under the condition of or the low light level relatively dark at light, with photochemical catalyst TiO
2Ag for main body
+, Cu
++, Fe
++ (+++)/ TiO
2Composition still has antibiotic by force, deodorizing, mildew-resistant ability.
Research shows that minor metallic element has the antibacterial functions of broad spectrum type, for example white gold, silver, copper, iron etc.Silver ion is a kind of broad spectrum activity sterilization material, and in metal ion known today, its anti-microbial property is the strongest.According to surveying and determination, just the common bacterias such as Escherichia coli in the water can be killed fully when containing silver ion in the water and being 0.01mg/L, fungies such as hepatitis B, tinea alba bacterium and aspergillus flavus can also be killed.
The chemical constitution of silver has determined silver to have higher catalytic capability, and the reduction potential of high oxidation state silver is high, is enough to make its surrounding space to produce elemental oxygen.Elemental oxygen has strong oxidizing property and can sterilize Ag
+Can attract the sulfydryl on the protease in the bacterial body (SH), to combine with it rapidly, make the protease loss of activity, cause bacterial death consumingly.When bacterium by Ag
+After killing, Ag
+By dissociating out in the bacterium corpse, contact with other bacterium colony more again, carry out said process again and again, this also is the persistent reason of silver-colored sterilization.
Copper ion is a metal ion antibacterial agent (seeing table 1) the strongest except that silver ion; Have wide spectrum antibiotic property, (seeing table 2) has no drug resistance; Its antibacterial action shows as late effect property (seeing table 3), as long as promptly copper ion maintains finite concentration and certain time can effectively antibacterial and sterilization.
Table 1, influence the minimum concentration of metal ions (MIC) that the typhoid fever bacterium grows
| Metal ion | Ag 1+ | Cu 2+ | Au 1+ | Fe 2+ | Zn 2+ | Mn 2+ |
| MIC | 2.0 * 10 -6 | 1.5 * 10 -5 | 1.2 * 10 -4 | 1.0 * 10 -3 | 1.0 * 10 -3 | 0.12 |
The bactericidal properties of table 2, antibiotic and metal relatively
| Antibiotic | Metal ion (silver, copper) | Metal surface (alkali copper) | |
| The mechanism of action | Only suppress some biochemical reactions | Protein is lost activity | Let respiratory chain lose efficacy |
| Antimicrobial spectrum | Narrow antimicrobial spectrum | Broad-spectrum antiseptic | Broad-spectrum antiseptic |
| The resistance to the action of a drug | Be prone to produce | Do not produce | Do not produce |
The anti-microbial property of table 3, copper ion (mg/kg)
| Project | The MIC value of bacterium | The MIC value of mould | Quick-acting bactericidal properties (10min to 1h) to bacterium | To the quick-acting bactericidal properties of mould (10min to 1h) | Bacterium is imitated bactericidal properties (24h to 48h) late | Mould is imitated bactericidal properties (24h to 48h) late |
| Cu 2+ | 200-400 | 200 | No | No | 0.5-1 | No |
(document: trace element and total the 79th phase of phase of intestinal health Beijing Huamu Great Exploit Sci&tech Co., Ltd. Liu Quan 2008-06-13 Sai Er feed industry)
Summary of the invention
Presoma hydrolyzate solution for titanium adds the modifier peroxide, makes liquid become light yellow transparent solution, regulates the pH value and removes excessive modifier.
To solution heating, carry out crystallization and handle through upgrading.Sterilization, deodorizing, mildew-resistant photocatalysis depollution of environment constituent that formation project 1 requires.Be anatase crystal type photocatalysis TiO
2Colloidal sol.
At anatase crystal type photocatalysis TiO
2Add metallic or ion that Ag, Cu, Fe etc. have sterilization in the colloidal sol, form Ag
+, Cu
++, Fe
++ (+++)/ TiO
2Enhanced type is antibiotic, deodorizing, mildew-resistant depollution of environment photocatalysis constituent.
About anatase TiO of the present invention
2The manufacturing approach of colloidal sol further specifies.
TiO
2Colloidal sol can be raw material with the presoma of titanium, and the titanium hydroxide that for example disperses in titanic hydroxide gel or the water etc. contains the material of titanium.Ti (OH)
4Colloidal sol can be that the raw material warp makes with alkali reaction by inorganic titanium compounds such as titanium sulfate, titanium chlorides.
The anatase crystal type TiO that obtains
2In the colloidal sol, add copperization and things such as Schweinfurt green, copper carbonate, copper sulphate, or add silver compound, or add iron compound in same ratio in same ratio.Generally with TiO
20.60-0.80% be advisable.
Description of drawings: Fig. 1 is the exploded view of the Ag+/TiO2 colloidal sol of main body for C.I. alkali blue 9 for photochemical catalyst TiO2 under the UV ultraviolet light.Absorbance A BS obviously drops to-0.2800 by initial value 0.0000 under the UV UV-irradiation.Fig. 2 is the exploded view of the Ag+/TiO2 colloidal sol of main body for C.I. alkali blue 9 for photochemical catalyst TiO2 under the visible light.Visible light illumination is penetrated down absorbance A BS and is obviously dropped to-0.2700 by initial value 0.0000.
[working of an invention form]
Presoma hydrolyzate solution through for titanium adds the modifier peroxide, makes liquid become light yellow transparent solution, regulates the pH value and removes excessive modifier.To solution heating, carry out crystallization and handle through upgrading.Sterilization, deodorizing, mildew-resistant depollution of environment constituent that formation project 1 requires.Be the neutral TiO of anatase crystal type photocatalysis
2Colloidal sol.
Select copper sulphate and anatase crystal type TiO
2Neutral aqueous solution.TiO
2Averaged particles directly distribute below the 20nm, content is 0.85 weight %.At TiO
2Press TiO in the neutral aqueous solution
2Ratio 0.80 weight % add copper sulphate, form homogeneous transparent with photochemical catalyst TiO
2Cu for main body
++/ TiO
2Colloidal sol.
Embodiment 2
Selective chlorination iron and anatase crystal type photochemical catalyst TiO
2Neutral aqueous solution.TiO
2Averaged particles directly distribute below the 20nm, content is 0.85 weight %.At TiO
2Press TiO in the neutral aqueous solution
2Ratio 0.80 weight % add iron chloride (trivalent iron salt), form homogeneous transparent with photochemical catalyst TiO
2Fe for main body
+++/ TiO
2Colloidal sol.
Embodiment 3
Select silver nitrate and anatase crystal type TiO
2Neutral aqueous solution.TiO
2Averaged particles directly distribute below the 20nm, content is 0.85 weight %.At TiO
2Press TiO in the neutral aqueous solution
2Ratio 0.80 weight % add the inorganic salts of silver, form homogeneous transparent with photochemical catalyst TiO
2Ag for main body
+/ TiO
2Colloidal sol.
Embodiment 4
Use same copper sulphate and same anatase crystal type TiO
2Neutral aqueous solution.Investigation changes the influence of the addition of copper sulphate for the solution stability.Result such as table 4.
Table 4: the addition of copper sulphate is for the influence of solution stability
| Addition (Wt%) is for TiO 2The ratio | The solution stability |
| 0.1 | ◎ |
| 0.8 | ◎ |
| 1.6 | Zero |
| 3.0 | △ |
| 5.0 | * |
| 7.0 | * |
◎: excellent zero: good △: can *: poor
[0027]
Embodiment 5
Select same anatase crystal type TiO
2Neutral aqueous solution.Investigate of the influence of different additives for the solution stability.Result such as table 5.
Table 5: different additives is for the influence of solution stability
| Add the material name | The solution stability |
| Schweinfurt green | Zero |
| Copper carbonate | ◎ |
| Copper sulphate | ◎ |
| Copper chloride | Zero |
| Copper ( | △ |
| Copper ( | * |
| Cupric oxide | * |
| Cuprous oxide | △ |
| Iron chloride | Zero |
| Ferric trichloride | ◎ |
| Platinum is black | * |
| The acid of chlorination platinum | ◎ |
| Palladium black | * |
| Palladium bichloride | ◎ |
| Chlorination is pluged with molten metal | ◎ |
| Nickel chloride | ◎ |
| Silver nitrate | ◎ |
| Do not have and add | ◎ |
◎: excellent zero: good △: can *: poor
[0029]
Embodiment 6
Compare photochemical catalyst TiO
2Neutral aqueous solution and silver ion add the Ag that forms
+/ TiO
2Colloidal sol is photocatalytic activity under UV and visible light.
Experimental technique:
1. sneak into photochemical catalyst TiO in the whitewash
2Neutral aqueous solution and Ag
+/ TiO
2Colloidal sol.
2. be coated onto microscope with on the glass slide.
3. coat C.I. alkali blue 9 in the above.
4. irradiation (luminous ray, UV ultraviolet light) under light is write down volume reflection by certain hour with voltage.Be converted into absorbance (ABS).
Judgment criteria: the curve longitudinal axis is an absorbance, and its numerical value is got over the low absorbance moon low (permeability is high more), and promptly C.I. alkali blue 9 is decomposed.
Result such as Fig. 1 (UV ultraviolet light), Fig. 2 (visible light).Absorbance (ABS) is through after 28 hours, and absorbance A BS obviously drops to-0.2700 by initial value 0.0000 under the UV UV-irradiation.Absorbance A BS is obviously reduced to about-0.2900 by initial value 0.0000 under the radiation of visible light.Show photochemical catalyst TiO of the present invention
2Be main body A g
+, Cu
++, Fe
++ (+++)/ TiO
2The effect of decomposing organic matter.(experimental unit: the Ou Lin of Co., Ltd. of Japan).
Claims (6)
1. sterilization photochemical catalyst constituent, this constituent is the aqueous solution, it basic composition is the oxide TiO of titanium elements
2Particle, Ag
+, Cu
++, Fe
++ (+++)Metal ion and water.
2. in the project 1 in the desired Photocatalyst Composite, utilize peroxide modified, atomic surface is by O
2-The TiO that modifies
2The depollution of environment photochemical catalyst constituent of particle, this constituent is because O
2-The existence of modification group stably is dispersed in the aqueous solution by the repulsion of negative electrical charge, forms two caryogamy position compound Ti
2O
5(OH)
X (X-2)Transparent long-acting TiO
2Colloidal sol.
3. desired pH value of solution value is neutral photochemical catalyst constituent in the project 1 and 2.
4. in the project 1,2,3 in the desired photochemical catalyst constituent, nano-TiO
2The crystal type of particle is the Detitanium-ore-type crystallization, and its electron energy level is 3.2eV, and the sterilization constituent of electronics-void effect takes place under the sun or fluorescent lamp light (UV) effect.
5. the manufacturing approach basic characteristics of desired photochemical catalyst sterilization constituent are following in the project 1:
At neutral anatase crystal type colloidal sol TiO
2Middle metallic or the ion that Ag, Cu, Zn etc. have sterilization, the formation Ag of adding
+, Cu
++, Fe
++ (+++)/ TiO
2The antibiotic photochemical catalyst constituent of wide spectrum enhanced type.
6. the sterilization photochemical catalyst constituent of project 1 and 5 requirements is Ag
+, Cu
++, Fe
++ (+++)/ TiO
2The antibiotic constituent of wide spectrum enhanced type; Back formation colorless and transparent film is characterized in that constructing; Do not influence the base material outward appearance, can select cold sprayings such as building indoor wall, decoration, implements according to different substrate materials, can spray dip-coating glass ceramics surface yet; Through heat treatment, process antibiotic amenities or tableware etc.
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|---|---|---|---|
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|---|---|---|---|
| CN2011101267181A CN102784645A (en) | 2011-05-17 | 2011-05-17 | Metal particle combination TiO2 photocatalyst reinforcement anti-bacterial composition and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480396A (en) * | 2013-10-16 | 2014-01-01 | 代思炜 | Visual sterilization strength color-changing photocatalyst preparation |
| CN107285735A (en) * | 2017-08-14 | 2017-10-24 | 潮州市华中陶瓷实业有限公司 | A kind of ceramic water filter filter core and preparation method thereof |
| CN107459267A (en) * | 2017-06-27 | 2017-12-12 | 伦慧东 | The manufacture craft of photocatalyst film compound glass |
| CN107459845A (en) * | 2017-06-27 | 2017-12-12 | 伦慧东 | A kind of photocatalyst kit with antibacterial and degradation property |
| JP2018089583A (en) * | 2016-12-05 | 2018-06-14 | ナカ工業株式会社 | Coping |
| CN108392982A (en) * | 2018-05-31 | 2018-08-14 | 青岛三色源环保科技工程有限公司 | A kind of deodorant and preparation method thereof and application method |
| CN112218714A (en) * | 2018-05-30 | 2021-01-12 | 株式会社信州陶瓷 | Preparation effective in the same way as light irradiation without light irradiation and its preparation method |
| CN114097821A (en) * | 2021-11-17 | 2022-03-01 | 杭州大岸科技有限公司 | Sterilization disinfectant and preparation method and application thereof |
| US11326062B2 (en) * | 2015-06-26 | 2022-05-10 | Corning Incorporated | Colorless copper-containing material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103480396A (en) * | 2013-10-16 | 2014-01-01 | 代思炜 | Visual sterilization strength color-changing photocatalyst preparation |
| US11326062B2 (en) * | 2015-06-26 | 2022-05-10 | Corning Incorporated | Colorless copper-containing material |
| JP2018089583A (en) * | 2016-12-05 | 2018-06-14 | ナカ工業株式会社 | Coping |
| CN107459267A (en) * | 2017-06-27 | 2017-12-12 | 伦慧东 | The manufacture craft of photocatalyst film compound glass |
| CN107459845A (en) * | 2017-06-27 | 2017-12-12 | 伦慧东 | A kind of photocatalyst kit with antibacterial and degradation property |
| CN107459267B (en) * | 2017-06-27 | 2019-09-17 | 伦慧东 | The manufacture craft of photocatalyst film compound glass |
| CN107459845B (en) * | 2017-06-27 | 2020-06-16 | 伦慧东 | Photocatalyst kit with antibacterial and degradation performance |
| CN107285735A (en) * | 2017-08-14 | 2017-10-24 | 潮州市华中陶瓷实业有限公司 | A kind of ceramic water filter filter core and preparation method thereof |
| CN112218714A (en) * | 2018-05-30 | 2021-01-12 | 株式会社信州陶瓷 | Preparation effective in the same way as light irradiation without light irradiation and its preparation method |
| CN108392982A (en) * | 2018-05-31 | 2018-08-14 | 青岛三色源环保科技工程有限公司 | A kind of deodorant and preparation method thereof and application method |
| CN114097821A (en) * | 2021-11-17 | 2022-03-01 | 杭州大岸科技有限公司 | Sterilization disinfectant and preparation method and application thereof |
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