CN104472543A - Preparation method of silver-titanium dioxide compound antibacterial material - Google Patents
Preparation method of silver-titanium dioxide compound antibacterial material Download PDFInfo
- Publication number
- CN104472543A CN104472543A CN201410798814.4A CN201410798814A CN104472543A CN 104472543 A CN104472543 A CN 104472543A CN 201410798814 A CN201410798814 A CN 201410798814A CN 104472543 A CN104472543 A CN 104472543A
- Authority
- CN
- China
- Prior art keywords
- silver
- preparation
- titanium
- antibacterial
- buffer solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an inorganic antibacterial agent and a preparation method thereof and particularly relates to a preparation method of silver-titanium dioxide compound antibacterial material with a multi-level structure. The preparation method comprises the steps of adopting basic magnesium carbonate for preparing the multi-level structure as a template, mixing a template agent, a titanium source and a silver source in sequence to prepare silver-titanium compound intermediate product, then introducing carbon dioxide gas, adding buffering solution to remove the template agent so as to obtain a silver-titanium compound precursor; and after the silver-titanium compound precursor is dried, carrying out high-temperature calcination under the nitrogen protection condition so as to obtain the silver-titanium-dioxide compound material. According to the preparation method, staphylococcus aureus and escherichia coli are selected to be subjected to bacteria testing experiment; the prepared material has the antibacterial performances of elemental silver and titanium dioxide, and compared with the single silver-nano antibacterial agent, the silver-titanium dioxide compound antibacterial material has better antibacterial effect.
Description
Technical field
The present invention relates to a kind of inorganic antiseptic and preparation method thereof, be specifically related to a kind of preparation method with the silver-colored titanium dioxide composite antibacterial material of multilevel hierarchy.
Background technology
Antibacterial agent be a class to kill or to suppress the preparation that growth of microorganism is major function, be mainly divided into organic material antibacterial agent and inorganic material antibacterial agent.Most of organic material antibacterial agent easily decomposes, easily produces cytotoxicity, and Long-Time Service can make bacterial resistance occurred, thus limits its application.Inorganic antibacterial material, because of its broad spectrum antibacterial, not easily produces drug resistance and becomes the focus that current people develop anti-biotic material.Silver nano antibacterial agent has better antibacterial effect relative to classical antibacterial agents, but single silver nano-grain is easily reunited, and easily oxidized under air ambient.For addressing these problems, people start to find suitable carrier material, better disperse Nano silver grain, develop new silver-colored composite antibacterial material.
As important inorganic carrier material, titanium dioxide (Ti0
2) not only itself there is antibiotic property, and particle surface is rich in hydroxyl, can strengthen its biocompatibility, prepares the application that silver-colored composite titania material has widened silver nanoparticle composite antibacterial material greatly.Chinese patent 201110092394.4 discloses titanium dioxide anti-bacterial agent of a kind of load silver and preparation method thereof, mainly utilizes water heat transfer titanium dioxide microballoon sphere carrier, then by reducing process or excessive infusion process by silver-colored load in the surface of carrier or inside.Silver particles load on the titanium dioxide granule with loose structure clad, thus is obtained composite inorganic antimicrobial agent by Chinese patent 200410052644.1.Although synthesized the composite antibacterial material of the silver-colored titanium dioxide of different-shape at present, there is the rarely seen report of technology of preparing of the silver-colored titanium dioxide composite antibacterial material of multilevel hierarchy.The present invention proposes a kind of new practical technique, and use basic magnesium carbonate is template, has prepared the silver-colored titanium dioxide composite antibacterial material with multilevel hierarchy.
Summary of the invention
The object of the invention is to synthesize a kind of silver-colored composite titania material with the excellent antibacterial performance of multilevel hierarchy.
Technical scheme of the present invention is the basic magnesium carbonate prepared is Template preparation silver titanium compound intermediate product; then pass into carbon dioxide and add buffer solution removing template; obtain silver-colored titanium composite precursor; after the drying of silver titanium composite precursor, under nitrogen protection condition, high-temperature calcination obtains silver-colored composite titania material.It is characterized in that the composition of buffer solution that the temperature and time of basic magnesium carbonate building-up process, the selection in titanium source, hydrolyzate composition and formula rate, template are removed and formula rate, the calcining heat of silver-colored titanium composite precursor and time are as follows:
The temperature of synthesis basic magnesium carbonate is 50 ~ 100 DEG C, and the time is 5 ~ 60min; Any one is chosen in titanium source in tetrabutyl titanate, isopropyl titanate, tetraethyl titanate; Hydrolyzate is made up of high purity water, absolute ethyl alcohol and hydrolysis inhibitor; Hydrolysis inhibitor chooses one or more mixing in glacial acetic acid, nitric acid, hydrochloric acid, ammonium acetate, ammonium nitrate, ammonium chloride; In hydrolyzate, the volume ratio of high purity water, absolute ethyl alcohol and hydrolysis inhibitor is 1:1 ~ 10:0.05 ~ 0.5; One or more mixing chosen by buffer solution in sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, sodium hydrogen phosphate-potassium phosphate buffer, potassium dihydrogen phosphate-sodium hydrate buffer solution, sodium hydrogen phosphate-citrate buffer solution, citric acid-sodium citrate buffer solution; The calcining heat of silver titanium composite precursor is 400 ~ 600 DEG C; The time of calcining is 2 ~ 6h.
The technological process of preparation is as follows:
Step 1: the aqueous sodium carbonate of the magnesium chloride brine and 0.5 ~ 2M of getting 0.5 ~ 2M is heated to 50 ~ 100 DEG C respectively.By above-mentioned two kinds of solution mixing, mechanical agitation, and keep rotating speed at 300 ~ 500r/min, stir 5 ~ 60min, then ageing 60 ~ 150min, filter, wash to obtain basic magnesium carbonate template;
Step 2: get basic magnesium carbonate template, ultrasonic disperse is in absolute ethyl alcohol, add appropriate titanium source, mechanical agitation 10 ~ 30min, slow dropping is to the hydrolyzate of the high purity water of certainty ratio, absolute ethyl alcohol, hydrolysis inhibitor composition, hydrolysis 3 ~ 8h, centrifugal, washing, dry, obtain titaniferous intermediate;
Step 3: get titaniferous intermediate ultrasonic disperse in absolute ethyl alcohol, add liquor argenti nitratis ophthalmicus, mechanical agitation 3 ~ 8h.Then in mixed liquor, pass into carbon dioxide and add buffer solution to remove template, centrifugal, wash, obtain silver-colored titanium composite precursor after drying;
Step 4: under nitrogen atmosphere, at 400 ~ 600 DEG C of temperature, calcines silver-colored titanium composite precursor 2 ~ 6h, obtains the silver-colored composite titania material with multilevel hierarchy.
Effect of the present invention and benefit are, with the basic magnesium carbonate of multilevel hierarchy for template, can the silver-colored titanium dioxide composite antibacterial material of easy synthesis multilevel hierarchy, and preparation technology is simple; Staphylococcus aureus and Escherichia coli are selected to do bacterium test experiments, result shows the Material cladding the prepared anti-microbial property of silver particles and titanium dioxide, better antibacterial effect is had compared to single silver nano antibacterial agent, lastingly antibacterial, the aspect such as biological medicine, daily necessities can be widely used in.This technology all shows significant advantage in manufacturing cost and properties of product etc.
Accompanying drawing explanation
Accompanying drawing is the scanning electron microscope diagram sheet of silver-colored composite titania material.
Embodiment
Below in conjunction with accompanying drawing and technical scheme, further illustrate the specific embodiment of the present invention.
Embodiment 1:
(1) MgCl of 100mL 1M is got
2the Na of solution and 100mL 1M
2cO
3solution, is heated to 80 DEG C respectively.Be mixed in there-necked flask by above-mentioned two kinds of solution, mechanical agitation 10min under rotating speed 300r/min, ageing 2h, filter, distilled water washing obtains basic magnesium carbonate template 2 ~ 3 times.
(2) 5g basic magnesium carbonate template ultrasonic disperse is got in absolute ethyl alcohol, 5mL tetrabutyl titanate is added in the solution after ultrasonic disperse, 400r/min mechanical agitation 10min, the mixed solution of the acetic acid of 5mL high purity water, 30mL absolute ethyl alcohol and 0.5mL is slowly dripped in above-mentioned solution, hydrolysis 4h, centrifugal, washing, dry, obtain titaniferous intermediate.
(3) 5g titaniferous intermediate ultrasonic disperse is got in absolute ethyl alcohol, drip the liquor argenti nitratis ophthalmicus 10mL of 0.1M, mechanical agitation 4h, pass into carbon dioxide 30min, add the washing of 60mL sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution again to remove template, product is centrifugal, wash, obtain silver-colored titanium composite precursor after drying.
(4) under nitrogen atmosphere, at 500 DEG C of temperature, calcine silver-colored titanium composite precursor 4h, obtain 0.92g silver composite titania material.
The silver-colored titanium dioxide composite construction particle of preparation is flower-like structure, and specific surface area is 140m
2/ g, pore volume reaches 0.82cm
3/ g.Select staphylococcus aureus and Escherichia coli to do Bactericidal test, under 200ppm concentration, the inhibition zone preparing sample is respectively 13cm and 14cm, the inhibition zone of commercialization Nano silver grain 10cm and 11cm. respectively under comparable sodium
Embodiment 2:
(1) MgCl of 50mL 1M is got
2the Na of solution and 100mL 0.5M
2cO
3solution, is heated to 80 DEG C respectively.Be mixed in there-necked flask by above-mentioned two kinds of solution, mechanical agitation 10min under rotating speed 400r/min, ageing 2h, filter, distilled water washing obtains basic magnesium carbonate template 2 ~ 3 times.
(2) 1g multilevel hierarchy basic magnesium carbonate template ultrasonic disperse is got in absolute ethyl alcohol, 1mL isopropyl titanate is added in the solution after ultrasonic disperse, 400r/min mechanical agitation 20min, the mixed solution of 2mL high purity water, 10mL absolute ethyl alcohol and 0.1mL hydrochloric acid is slowly dripped in above-mentioned solution, hydrolysis 4h, centrifugal, washing, dry, obtain titaniferous intermediate.
(3) get 1g multilevel hierarchy intermediate ultrasonic disperse in absolute ethyl alcohol, add the liquor argenti nitratis ophthalmicus of 1m 0.3M, mechanical agitation 4h, pass into CO
2gas 30min, then add 20mL sodium hydrogen phosphate-potassium phosphate buffer washing to remove template, product is centrifugal, washing, obtains silver-colored titanium composite precursor after drying.
(4), under nitrogen atmosphere, at 500 DEG C of temperature, calcine silver-colored titanium composite precursor 4h, the silver-colored composite titania material of 0.21g multilevel hierarchy must be had.
The silver-colored titanium dioxide composite construction particle of preparation is flower-like structure, and specific surface area is 132m
2/ g, pore volume reaches 0.74cm
3/ g.Select staphylococcus aureus and Escherichia coli to do Bactericidal test, under 200ppm concentration, the inhibition zone preparing sample is respectively 12cm and 13cm, the inhibition zone of commercialization Nano silver grain 10cm and 11cm respectively under comparable sodium.
Claims (3)
1. a preparation method for silver-colored titanium dioxide composite antibacterial material, it is characterized in that, step is as follows:
Step 1: the aqueous sodium carbonate of the magnesium chloride brine of 0.5 ~ 2M and 0.5 ~ 2M is heated to 50 ~ 100 DEG C respectively; By above-mentioned two kinds of solution mixing, mechanical agitation, and keep rotating speed to be 300 ~ 500r/min, stir 5 ~ 60min, then ageing 60 ~ 150min, filter, wash to obtain basic magnesium carbonate template;
Step 2: get basic magnesium carbonate template, ultrasonic disperse, in absolute ethyl alcohol, adds titanium source, mechanical agitation 10 ~ 30min, slowly drips the hydrolyzate of high purity water, absolute ethyl alcohol and hydrolysis inhibitor composition, hydrolysis 3 ~ 8h, centrifugal, washing, dry, obtain titaniferous intermediate; In hydrolysis, the volume ratio of high purity water, absolute ethyl alcohol and hydrolysis inhibitor is 1:1 ~ 10:0.05 ~ 0.5;
Step 3: get titaniferous intermediate ultrasonic disperse in absolute ethyl alcohol, add liquor argenti nitratis ophthalmicus, mechanical agitation 3 ~ 8h; Then in mixed liquor, pass into carbon dioxide and add buffer solution to remove template, centrifugal, wash, obtain silver-colored titanium composite precursor after drying;
Step 4: under nitrogen atmosphere, at 400 ~ 600 DEG C of temperature, calcines silver-colored titanium composite precursor 2 ~ 6h, obtains the silver-colored titanium dioxide composite antibacterial material with multilevel hierarchy.
2. preparation method according to claim 1, is characterized in that, one is chosen in titanium source in tetrabutyl titanate, isopropyl titanate, tetraethyl titanate.
3. preparation method according to claim 1 and 2, is characterized in that, hydrolysis inhibitor chooses one or more mixing in glacial acetic acid, nitric acid, hydrochloric acid, ammonium acetate, ammonium nitrate, ammonium chloride; Buffer solution chooses one or more mixing in sodium hydrogen phosphate-phosphate sodium dihydrogen buffer solution, sodium hydrogen phosphate-potassium phosphate buffer, potassium dihydrogen phosphate-sodium hydrate buffer solution, Lin acid hydrogen Er Na – citrate buffer solution, Ning Meng Suan – sodium citrate buffer solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410798814.4A CN104472543B (en) | 2014-12-19 | 2014-12-19 | A kind of preparation method of silver titanium dioxide composite antibacterial material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410798814.4A CN104472543B (en) | 2014-12-19 | 2014-12-19 | A kind of preparation method of silver titanium dioxide composite antibacterial material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104472543A true CN104472543A (en) | 2015-04-01 |
| CN104472543B CN104472543B (en) | 2018-06-08 |
Family
ID=52747268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410798814.4A Expired - Fee Related CN104472543B (en) | 2014-12-19 | 2014-12-19 | A kind of preparation method of silver titanium dioxide composite antibacterial material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104472543B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107801733A (en) * | 2017-10-25 | 2018-03-16 | 安徽古尔特科技有限公司 | Titania nanoparticles suppress the New function of Escherichia coli Growth |
| CN108064881A (en) * | 2016-11-14 | 2018-05-25 | 佛山市顺德区美的电热电器制造有限公司 | A kind of argentiferous titanium dioxide composite antibacterial agent and preparation method thereof and antibiotic paint and preparation method thereof |
| CN113621181A (en) * | 2021-08-03 | 2021-11-09 | 安徽江淮汽车集团股份有限公司 | Preparation method of antibacterial agent, thermoplastic resin composite material and preparation method thereof |
| US11186493B2 (en) | 2019-09-05 | 2021-11-30 | Imam Abdulrahman Bin Faisal University | Green synthesis of noble metal/transition metal oxide nanocomposite |
| CN114946879A (en) * | 2022-06-02 | 2022-08-30 | 江苏美百加电器科技有限公司 | Preparation method of titanium oxide aerogel loaded zinc oxide antibacterial material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190458A (en) * | 2014-07-16 | 2014-12-10 | 上海工程技术大学 | Low-temperature preparation process for dual-element modified nanometer TiO2 sol |
-
2014
- 2014-12-19 CN CN201410798814.4A patent/CN104472543B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190458A (en) * | 2014-07-16 | 2014-12-10 | 上海工程技术大学 | Low-temperature preparation process for dual-element modified nanometer TiO2 sol |
Non-Patent Citations (4)
| Title |
|---|
| 张秋双: "《Ag-SiO2/TiO2微纳米复合材料的合成及其抗菌性能研究》", 《大连理工大学硕士学位论文》 * |
| 房海霞，田朋，宁桂玲: "《碳酸镁模板法制备中空分级结构N-SiO2/TiO2复合材料》", 《中国化学会第29届学术年会摘要集——第05分会：无机化学》 * |
| 田朋，叶俊伟，贡卫涛，等: "《碳酸镁模板化合成多种分级结构氧化物的研究》", 《中国化学会第28届学术年会第8分会场摘要集》 * |
| 田朋: "《碳酸镁模板化制备复杂微纳结构及性能表征》", 《大连理工大学博士学位论文》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108064881A (en) * | 2016-11-14 | 2018-05-25 | 佛山市顺德区美的电热电器制造有限公司 | A kind of argentiferous titanium dioxide composite antibacterial agent and preparation method thereof and antibiotic paint 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 |
| CN107801733A (en) * | 2017-10-25 | 2018-03-16 | 安徽古尔特科技有限公司 | Titania nanoparticles suppress the New function of Escherichia coli Growth |
| US11186493B2 (en) | 2019-09-05 | 2021-11-30 | Imam Abdulrahman Bin Faisal University | Green synthesis of noble metal/transition metal oxide nanocomposite |
| US11661349B2 (en) | 2019-09-05 | 2023-05-30 | Imam Abdulrahman Bin Faisal University | Method for making coffee husk reducing agent |
| CN113621181A (en) * | 2021-08-03 | 2021-11-09 | 安徽江淮汽车集团股份有限公司 | Preparation method of antibacterial agent, thermoplastic resin composite material and preparation method thereof |
| CN114946879A (en) * | 2022-06-02 | 2022-08-30 | 江苏美百加电器科技有限公司 | Preparation method of titanium oxide aerogel loaded zinc oxide antibacterial material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104472543B (en) | 2018-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104472543A (en) | Preparation method of silver-titanium dioxide compound antibacterial material | |
| Gao et al. | Construction of durable antibacterial and anti-mildew cotton fabric based on P (DMDAAC-AGE)/Ag/ZnO composites | |
| CN105498689B (en) | Graphene-supported nano-ZnO/Ag composites and preparation method thereof | |
| Kannan et al. | Biosynthesis of Yttrium oxide nanoparticles using Acalypha indica leaf extract | |
| CN105478792B (en) | A kind of environment-friendly preparation method thereof of modification of chitosan nano silver colloidal sol | |
| CN104145993B (en) | A kind of chitosan and silver-bearing copper are blended the method preparing complex antimicrobials | |
| CN106622128B (en) | A kind of composite nano materials and preparation method thereof for air purification | |
| CN103798289A (en) | Preparation method of silver-loaded mesoporous silicon dioxide antibacterial agent | |
| CN104264450B (en) | A kind of silk fabric antibacterial finishing agent and preparation method thereof | |
| CN106192074B (en) | A kind of preparation method of the graphene oxide being loaded with nano silver particles/seaweed composite fibre | |
| CN104311864A (en) | High-efficiency visible light antibacterial fresh-keeping plastic packaging material and preparation method thereof | |
| CN103783079A (en) | Preparation method of silver-loaded mesoporous inorganic antibacterial agent | |
| CN104872177B (en) | A kind of preparation method of the bactericidal deodoring materials based on carbon nano-silver photo-catalyst | |
| CN106424753B (en) | A kind of MnO2The preparation and its application of-Ag nanocomposite | |
| CN102391573B (en) | Modified polypropylene plastic and preparation method and use thereof | |
| Rilda et al. | Pseudomonas aeruginosa antibacterial textile cotton fiber construction based on ZnO–TiO2 nanorods template | |
| CN111849282B (en) | Monoatomic antibacterial and disinfectant interior wall coating and preparation method thereof | |
| CN105061632B (en) | The preparation method and bacteriostasis property of a kind of curdlan quaternary ammonium salt | |
| CN106800375A (en) | TiO2Modify the preparation method of dopamine antimicrobial coating | |
| US9961902B2 (en) | Method of synthesizing a graphene-based antibacterial and using the same | |
| Zhou et al. | Synthesis and characterization of size-controlled nano-Cu2O deposited on alpha-zirconium phosphate with excellent antibacterial property | |
| CN107935374A (en) | A kind of preparation method and applications method of Graphene antibiosis sterile transparent glaze | |
| CN103980665A (en) | Waterborne antibacterial composite material and preparation method thereof | |
| CN105794841B (en) | Antibacterial composite material and manufacturing method thereof | |
| CN106633829B (en) | A kind of anti-bacteria nylon and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180608 Termination date: 20201219 |