CN1454481A - Rare-earth-carrying nano titanium dioxide antibacterial agent and preparation method thereof - Google Patents
Rare-earth-carrying nano titanium dioxide antibacterial agent and preparation method thereof Download PDFInfo
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- CN1454481A CN1454481A CN 03117960 CN03117960A CN1454481A CN 1454481 A CN1454481 A CN 1454481A CN 03117960 CN03117960 CN 03117960 CN 03117960 A CN03117960 A CN 03117960A CN 1454481 A CN1454481 A CN 1454481A
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Abstract
The invention discloses a rare-earth load type nano-TiO2 antimicrobial and making method, a new antimicrobial which uses the rare-earth ions as the antibacterial active component and the rare-earth activate nano-anatase type TiO2 and optically catalyzes antibacterial activity, composed of rare-earth element and semiconductor carrier. The nano-anatase type TiO2 80-99 shares, Re(NO3)3 10.7-0.3 share, and HNO3, the concentration 85%, 9.3-0.7 share. It makes mixing, constant-temperature blending, filtering, drying, baking and grinding to get the product, average particle diameter being not more than 1 micron m, the content of nano-anatase type TiO2 being 75-98%, and that of Re2O3 being 0.2-2%.
Description
One, technical field
The present invention relates to a kind of rare earth loaded type nano titanium dioxide anti-bacterial agent and preparation method thereof, belong to the material field of inorganic antiseptic.
Two, background technology
European patent 937398, Antibacterial and deodorant materials and method for theirmanufacture by adhering metallic silver and (or) copper on titanium oxide particles, reported antibiotic and deodoring materials and argent or copper have been loaded on preparation method on the Titanium particles, this antibacterial agent is the cost height not only, and has problems such as variable color.Soga M etc., Ag/TiO
2Composite ultra-fine particle studied withFE-SAM, J.Surf.Anal., 1999,5 (2): P326, reported that silver loads on the TiOx nano particle and prepared inorganic antiseptic, but its cost height is easy to change.Zhoul Xu and Kuroda Koichi etc., Antibacterial effect ofrutile form of titanium oxide carrying nanoscale particles of platinum, Seikatsu Eisei, 2000,44 (1): P21, report the antibacterial action of nanometer platinum particles load Titanium Dioxide Rutile Top grade, under fluorescence, had the TiO of Pt nano particle
2Can have antibacterial action to Escherichia coli and staphylococcus aureus, but cost an arm and a leg, the scope of application is limited.Zhou Deshan, two kinds of nanometer new materials are tested and appraised in Anhui, modern chemical industry, 2002,22 (12): P60, reported that nanoscale carries silver-bearing copper inorganic antiseptic new material, but anti-microbial property is still not ideal.Yao Aihua and Li hall are superfine, anti-biotic material and application, world's geology, 2001,20 (2): P171, introduced the character of silver-series antibacterial agent and titanium dioxide photocatalyst series antibacterial agent and antibiotic mechanism, method, think that present antibacterial agent cost is higher, performance a little less than.Hu Yaojun, the mineral-type anti-biotic material, the rare metal wall bulletin, 2000, (2): P10 has introduced the research comparative maturity, and three kinds of inorganic antibacterial materials of certain applications have been obtained, be Ag-carried antibacterial material, cupric stainless steel anti-biotic material and photocatalysis titanium dioxide anti-biotic material, but the scope of application is limited, and antibacterial ability is relatively poor.Chinese patent CN1300804, porous powder material that activating oxide coats and its production and use, relate to coated porous powder of high activity oxide and its production and use, its powder comprises Nano titanium dioxide, aluminium oxide, chrome green, nickel oxide, the mixture 25%~65% of any part by weight of iron oxide and two or more these materials, alkaline earth oxide 5%~60%, silicide and/or boride and/or rare earth oxide 5%~45%, this powder is used for the production environment air cleaning, self-cleaning, deodorization, the coating of antibiotic and antiscale, its antibacterial effect is not ideal.
Three, summary of the invention
The objective of the invention is provides a kind of rare earth loaded type nano titanium dioxide anti-bacterial agent and preparation method thereof at the deficiencies in the prior art, is characterized in utilizing rare earth ion as antibacterial activity component and rare earth activated nano Detitanium-ore-type TiO
2Photocatalysis antibacterial activity, thereby the antibacterial functions of raising material.
Material of the present invention is to have fully utilized rare earth ion and oxide antimicrobial technology and photocatalysis antibacterial technology and rare-earth activated technology, and the antibacterial functions of material is further improved.
Nano-anatase TiO is adopted in photocatalysis
2(particle diameter is 10~100nm)
Antibacterial action adopts (Ce, Pr, Nd, La) ion and oxide thereof of rare earth element
Activation adopts (Ce, Pr, Nd, the La) of rare earth element
The present inventor finds to utilize the rare earth loaded nano-anatase TiO that makes
2Light absorption bands of a spectrum generation red shift rule, and successfully this technology is used for the exploitation of inorganic antiseptic.
The atomic structure characteristics of rare earth element are: the outermost electron structure of atom identical (all being 2 electronics), inferior outer electronic structure is similar, and on the layer 4f track third from the bottom unpaired electron is arranged.Just because of the atomic structure of this uniqueness of rare earth element, it all is widely used at industry-by-industry.Especially in the catalytic field application of having succeedd.The research of this project utilizes the catalytic action of rare earth just, and the system generation catalytic reaction that antibacterial agent and water, air are formed produces O
2 -With the OH active oxygen radical.Then active oxygen radical further with the bacterial cell membrane interaction, reach the purpose that suppresses bacterium.
Rare earth element makes the light absorption bands of a spectrum red shift of material, increases the photoresponse scope of material, improves the photocatalytic activity of material, by our UV-Vis experiment confirm.
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of rare earth loaded type nano titanium dioxide anti-bacterial agent is:
Nano-anatase TiO
2Particle diameter is 80~99 parts of 10~100nm
Re (NO
3)
310.7~0.3 part
HNO
3Concentration is 85% 9.3~0.7 part
The final index of product:
Average grain diameter≤1 μ m
Nano-anatase TiO
2: 75~98%
Re
2O
3:?????????????0.2~2%
Rare earth Re is at least a among Ce, Pr, Nd, the La.
The preparation method of rare earth loaded type nano titanium dioxide anti-bacterial agent:
(1) with particle diameter is 10~100nm nano-anatase TiO
2It is that 40~60 ℃, concentration are 35~45% aqueous solution of nitric acid that 10.7~0.3 parts of 80~99 parts of powders and rare-earth salts are put into temperature, stirs while feeding in raw material;
(2) reaction is 4~6 hours, filters then, removes the acid ion in the solution;
(3) 150~250 ℃ of dryings of temperature 1~2 hour, slough slurry moisture;
(4), the rare earth ion of load is fastened on the TiO2 400~650 ℃ of roastings of temperature 3~6 hours;
(5) grind in ultra-fine grinding mill, classification detects packing.
Final products particle diameter≤1 μ m, nano-anatase TiO
2Content is 75~98%, Re
2O
3Content is 0.2~2%.
The present invention has following advantage and good effect:
(1) material of the present invention is to use rare earth ion and the antibiotic and rare-earth activated expansion nano-TiO of oxide thereof
2The new material with antibacterial functions of spectral response range principle preparation.Because the application of rare earth element, this material has overcome TiO
2Deficiency and the still more weak shortcoming of anti-microbial property that catalysis material needs ultraviolet light to participate in also have excellent antibacterial effect in the dark.
(2) antibacterial effect excellence, the inhibition zone maximum reached 16.20mm in 24 hours.
(3) be widely used in fields such as coating, plastics, fiber and construction material.
Four, embodiment
Below by example the present invention is specifically described; be necessary to be pointed out that at this this example only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
1, the recipe ingredient of rare earth loaded type nano titanium dioxide anti-bacterial agent is:
Example one:
Nano-anatase TiO
2: 850Kg
Ce(NO
3)
3:????????????????20Kg
HNO
3: concentration 85% 110ml
Example two:
Nano-anatase TiO
2: 900Kg
Pr(NO
3)
3:????????????????15Kg
HNO
3: concentration 85% 100ml
Example three:
Nano-anatase TiO
2: 950Kg
Nd(NO
3)
3:????????????????10Kg
HNO
3: concentration 85% 90ml
2, the preparation method of rare earth loaded type nano titanium dioxide anti-bacterial agent
(1) with nano-anatase TiO
2It is that 40~60 ℃, concentration are about 35~45% aqueous solution of nitric acid that powder and rare-earth salts are put into temperature, stirs while feeding in raw material;
(2) reaction is 4~6 hours, filters then, removes the acid ion in the solution;
(3) 150~250 ℃ of dryings of temperature 1~2 hour, slough slurry moisture;
(4), the rare earth ion of load is fastened on the TiO2 400~650 ℃ of roastings of temperature 3~6 hours;
(5) grind in ultra-fine grinding mill, classification detects packing.
The particle diameter of final products≤1 μ m, nano-anatase TiO
2Content is 75~98%, Re
2O
3Content is 0.2~2%.
3, performance indications
(1) test method
An amount of inorganic antiseptic powder is pressed into the sample of the cylinder of diameter 10mm, thick 5mm as the anti-microbial property evaluation on tablet press machine.Sterile working is injected the mixed bacteria liquid of staphylococcus aureus, Escherichia coli and withered grass brood cell bar about 0.2ml on medium, use the scraper drawout, the inorganic antiseptic sample is placed on culture dish central authorities is placed on insulating box (37 ℃) cultivation 24h, take out back working sample inhibition zone size on every side.Use the same method blank sample control group is carried out the anti-microbial property evaluation.(2) result of the test is detailed is shown in Table 1.
The anti-microbial property of the rare earth loaded type nano titanium dioxide anti-bacterial agent of table 1
Laboratory sample | Example one | Example two | Example three | Blank |
Inhibition zone size (mm) | ????16.20 | ????14.10 | ????13.84 | ????- |
Claims (3)
1, rare earth loaded type nano-TiO
2Antibacterial agent is characterized in that the recipe ingredient (by weight) of described inorganic antiseptic is:
Nano-anatase TiO
2Particle diameter is 10~100nm:80~99 part
Re (NO
3)
3: 10.7~0.3 parts
HNO
3Concentration is 85%:9.3~0.7 part
The particle diameter of final products≤1 μ m, nano-anatase TiO
2Content is 75~98%, Re
2O
3Content is 0.2~2%;
2, according to the described rare earth loaded type nano-TiO of claim 1
2Antibacterial agent is characterized in that rare earth Re is at least a among Ce, Pr, Nd and/or the La.
3, according to claim 1 or 2 described rare earth loaded type nano-TiOs
2The preparation method of antibacterial agent is characterized in that:
(1) with particle diameter is 10~100nm nano-anatase TiO
280~99 parts of powders and 10.7~0.3 parts of addings of rare-earth salts have in the reactor of thermometer and agitator, are 40~60 ℃ and to add concentration be in 35~45% the aqueous solution of nitric acid in temperature, stir while feeding in raw material;
(2) reaction is 4~6 hours, filters then, removes the acid ion in the solution;
(3) 150~250 ℃ of dryings of temperature 1~2 hour, slough slurry moisture;
(4) 400~650 ℃ of roastings of temperature 3~6 hours, make the rare earth ion of load be fastened on TiO
2On;
(5) grind in ultra-fine grinding mill, classification detects packing.
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Cited By (13)
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CN100508757C (en) * | 2006-12-29 | 2009-07-08 | 上海师范大学 | Kernel-shell structured rare-earth nanometer antibiotic agent, prepn. method and application thereof |
CN101983569A (en) * | 2010-11-25 | 2011-03-09 | 中国地质大学(武汉) | Titanium dioxide nano antibacterial agent taking halloysite as carrier and preparation method thereof |
CN101423647B (en) * | 2007-11-03 | 2011-06-22 | 上海晨光文具股份有限公司 | Nano modified bamboo charcoal plastic, and production method thereof and stationary produced thereby |
CN104001490A (en) * | 2014-05-08 | 2014-08-27 | 亿利资源集团有限公司 | Photocatalyst composition for air purifier and preparation method thereof |
CN105037870A (en) * | 2015-06-10 | 2015-11-11 | 苏州宏恒化工有限公司 | Preparation method of polyethylene composite material for storage tanks |
CN106752950A (en) * | 2016-11-28 | 2017-05-31 | 杭州金知科技有限公司 | A kind of architectural paints |
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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 |
CN111470814A (en) * | 2020-04-14 | 2020-07-31 | 广东盖特奇新材料科技有限公司 | Antibacterial and disinfectant inorganic high-performance composite fiber material and preparation method thereof |
CN111875995A (en) * | 2020-07-15 | 2020-11-03 | 天津包钢稀土研究院有限责任公司 | Novel rare earth nano composite cleaning antibacterial antifogging agent and preparation method and application thereof |
CN112544632A (en) * | 2020-12-31 | 2021-03-26 | 代思炜 | Cerium bromide doped titanium dioxide visible sterilization preparation |
CN115005233A (en) * | 2022-07-07 | 2022-09-06 | 辽宁石油化工大学 | Preparation method of platinum-loaded titanium-containing blast furnace slag photocatalytic antibacterial material |
CN115474611A (en) * | 2022-10-20 | 2022-12-16 | 代思炜 | Cesium iodide doped titanium dioxide visible strong-effect sterilization preparation |
-
2003
- 2003-05-29 CN CN 03117960 patent/CN1203767C/en not_active Expired - Fee Related
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100508757C (en) * | 2006-12-29 | 2009-07-08 | 上海师范大学 | Kernel-shell structured rare-earth nanometer antibiotic agent, prepn. method and application thereof |
CN101423647B (en) * | 2007-11-03 | 2011-06-22 | 上海晨光文具股份有限公司 | Nano modified bamboo charcoal plastic, and production method thereof and stationary produced thereby |
CN101983569A (en) * | 2010-11-25 | 2011-03-09 | 中国地质大学(武汉) | Titanium dioxide nano antibacterial agent taking halloysite as carrier and preparation method thereof |
CN101983569B (en) * | 2010-11-25 | 2014-01-01 | 中国地质大学(武汉) | Titanium dioxide nano antibacterial agent taking halloysite as carrier and preparation method thereof |
CN104001490A (en) * | 2014-05-08 | 2014-08-27 | 亿利资源集团有限公司 | Photocatalyst composition for air purifier and preparation method thereof |
CN104001490B (en) * | 2014-05-08 | 2016-04-06 | 亿利资源集团有限公司 | A kind of light catalyst composition for air purifier and preparation method thereof |
CN105037870A (en) * | 2015-06-10 | 2015-11-11 | 苏州宏恒化工有限公司 | Preparation method of polyethylene composite material for storage tanks |
CN106752950A (en) * | 2016-11-28 | 2017-05-31 | 杭州金知科技有限公司 | A kind of architectural paints |
CN110157267A (en) * | 2019-05-30 | 2019-08-23 | 廊坊师范学院 | The preparation method of energy-saving and emission-reduction functional paint and processing method to core plate with holes |
CN110157267B (en) * | 2019-05-30 | 2021-02-26 | 廊坊师范学院 | Preparation method of energy-saving emission-reducing functional coating and treatment method of core plate with holes |
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 |
CN111470814A (en) * | 2020-04-14 | 2020-07-31 | 广东盖特奇新材料科技有限公司 | Antibacterial and disinfectant inorganic high-performance composite fiber material and preparation method thereof |
CN111875995A (en) * | 2020-07-15 | 2020-11-03 | 天津包钢稀土研究院有限责任公司 | Novel rare earth nano composite cleaning antibacterial antifogging agent and preparation method and application thereof |
CN112544632A (en) * | 2020-12-31 | 2021-03-26 | 代思炜 | Cerium bromide doped titanium dioxide visible sterilization preparation |
CN115005233A (en) * | 2022-07-07 | 2022-09-06 | 辽宁石油化工大学 | Preparation method of platinum-loaded titanium-containing blast furnace slag photocatalytic antibacterial material |
CN115474611A (en) * | 2022-10-20 | 2022-12-16 | 代思炜 | Cesium iodide doped titanium dioxide visible strong-effect sterilization preparation |
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