CN104472543B - A kind of preparation method of silver titanium dioxide composite antibacterial material - Google Patents
A kind of preparation method of silver titanium dioxide composite antibacterial material Download PDFInfo
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- CN104472543B CN104472543B CN201410798814.4A CN201410798814A CN104472543B CN 104472543 B CN104472543 B CN 104472543B CN 201410798814 A CN201410798814 A CN 201410798814A CN 104472543 B CN104472543 B CN 104472543B
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Abstract
The present invention relates to a kind of inorganic antiseptics and preparation method thereof, and in particular to a kind of preparation method of the silver-colored titanium dioxide composite antibacterial material with multilevel hierarchy.To prepare multilevel hierarchy basic magnesium carbonate as template; template, titanium source and silver-colored source are mixed with the compound intermediate product of silver-colored titanium successively; it then passes to carbon dioxide gas and adds in buffer solution and remove template; obtain silver-colored titanium composite precursor; after the drying of silver-colored titanium composite precursor, under nitrogen protective condition high-temperature calcination obtain silver-colored composite titania material.Staphylococcus aureus and the Escherichia coli are selected to do bacterium test experiments, the Material cladding of the preparation anti-microbial property of silver-colored simple substance and titanium dioxide has better antibacterial effect compared to single silver nano antibacterial agent.
Description
Technical field
The present invention relates to a kind of inorganic antiseptics and preparation method thereof, and in particular to a kind of silver-colored dioxy with multilevel hierarchy
Change the preparation method of titanium composite antibacterial material.
Background technology
Antiseptic is a kind of to kill or suppress growth of microorganism the preparation for major function, is broadly divided into organic material and resists
Microbial inoculum and inorganic material antiseptic.Most of organic material antiseptics easily decompose, are also easy to produce cytotoxicity, and long-time service can make carefully
Bacterium develops immunity to drugs, thus limits its application.Inorganic antibacterial material is not likely to produce drug resistance and becomes because of its broad spectrum antibacterial
Current people develop the focus of anti-biotic material.Silver nano antibacterial agent has better antibacterial effect relative to classical antibacterial agents, still
Single silver nano-grain is easily reunited, and is easily aoxidized under air environment.To solve these problems, people begin look for properly
Carrier material, preferably disperse Nano silver grain, develop new silver-colored composite antibacterial material.
As important inorganic carrier material, titanium dioxide (Ti02) not only itself there is antibiotic property, but also particle surface
Rich in hydroxyl, its biocompatibility can be enhanced, it is compound anti-that the silver-colored composite titania material of preparation has greatly widened silver nanoparticle
The application of bacterium material.Chinese patent 201110092394.4 discloses a kind of titanium dioxide anti-bacterial agent for loading silver and its preparation side
Method, it is mainly microsphere supported using hydro-thermal method synthesis of titanium dioxide, then silver is supported on carrier with reduction method or excessive infusion process
Surface or inside.Silver particles are supported on the titanium dioxide with porous structure clad by Chinese patent 200410052644.1
On grain, so as to obtain composite inorganic antimicrobial agent.Although the composite antibacterial material of the silver-colored titanium dioxide of different-shape has been synthesized at present
Material, but the technology of preparing of the silver-colored titanium dioxide composite antibacterial material with multilevel hierarchy is rarely reported.The present invention proposes a kind of new
Practical technique, using basic magnesium carbonate be template, be prepared for the silver-colored titanium dioxide composite antibacterial material with multilevel hierarchy.
Invention content
The purpose of the present invention is synthesize a kind of silver-colored composite titania material of the excellent antibacterial performance with multilevel hierarchy.
The technical scheme is that prepare the compound intermediate product of silver-colored titanium, Ran Houtong by template of the basic magnesium carbonate of preparation
Enter carbon dioxide gas and add in buffer solution and remove template, obtain silver-colored titanium composite precursor, silver-colored titanium composite precursor drying
Afterwards, high-temperature calcination obtains silver-colored composite titania material under nitrogen protective condition.It is characterized in that basic magnesium carbonate building-up process
Temperature and time, titanium source selection, hydrolyzate composition and formula rate, template removal buffer solution composition and recipe ratio
Example, the calcination temperature of silver-colored titanium composite precursor and time are as follows：
The temperature for synthesizing basic magnesium carbonate is 50~100 DEG C, and the time is 5~60min；Titanium source is in tetrabutyl titanate, metatitanic acid
Any one is chosen in isopropyl ester, tetraethyl titanate；Hydrolyzate is made of high purity water, absolute ethyl alcohol and hydrolysis inhibitor；Hydrolysis suppression
Preparation chooses one or more kinds of 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；Buffer solution is in disodium hydrogen phosphate-phosphorus
Acid dihydride sodium buffer solution, disodium hydrogen phosphate-potassium phosphate buffer, potassium dihydrogen phosphate-sodium hydrate buffer solution, phosphoric acid hydrogen two
One or more kinds of mixing are chosen in sodium-citrate buffer solution, citric acid-sodium citrate buffer solution；Silver-colored titanium composite precursor
Calcination temperature be 400~600 DEG C；The time of calcining is 2~6h.
The technological process of preparation is as follows：
Step 1：The magnesium chloride brine of 0.5~2M and the aqueous sodium carbonate of 0.5~2M is taken to be separately heated to 50~100
℃.Above two solution is mixed, mechanical agitation, and keep rotating speed in 300~500r/min, stirring 5~60min, Ran Houchen
Change 60~150min, filter, wash to obtain basic magnesium carbonate template；
Step 2：Basic magnesium carbonate template is taken, ultrasonic disperse adds in suitable titanium source, mechanical agitation in absolute ethyl alcohol
10~30min is slowly added dropwise to the hydrolyzate of high purity water, absolute ethyl alcohol, the hydrolysis inhibitor composition of certainty ratio, hydrolyzes 3~8h,
Centrifugation, washing, drying, obtain titaniferous intermediate；
Step 3：Titaniferous intermediate ultrasonic disperse is taken in absolute ethyl alcohol, adds in silver nitrate solution, 3~8h of mechanical agitation.
Then carbon dioxide gas is passed through into mixed liquor and adds in buffer solution to remove removing template, silver-colored titanium is obtained after centrifugation, washing, drying
Composite precursor；
Step 4：Under nitrogen atmosphere, at a temperature of 400~600 DEG C, silver-colored titanium 2~6h of composite precursor is calcined, is had
The silver-colored composite titania material of multilevel hierarchy.
The invention has the advantages that using the basic magnesium carbonate of multilevel hierarchy as template, it can the easy multistage knot of synthesis
The silver-colored titanium dioxide composite antibacterial material of structure, preparation process are simple；Staphylococcus aureus and Escherichia coli is selected to do bacterium survey
Examination experiment, the results showed that the Material cladding of the preparation anti-microbial property of silver particles and titanium dioxide, compared to single silver nanoparticle
Antiseptic has better antibacterial effect, and antibacterial is lasting, can be widely applied to biological medicine, daily necessities etc..This skill
Art all shows significant advantage in manufacture cost and properties of product etc..
Description of the drawings
Attached drawing is the scanning electron microscope diagram piece of silver-colored composite titania material.
Specific embodiment
Below in conjunction with attached drawing and technical solution, the specific embodiment further illustrated the present invention.
Embodiment 1：
(1) MgCl of 100mL 1M is taken2The Na of solution and 100mL 1M2CO3Solution is separately heated to 80 DEG C.By above-mentioned two
Kind solution is mixed in there-necked flask, the mechanical agitation 10min under rotating speed 300r/min, is aged 2h, and water washing 2~3 is distilled in filtering
It is secondary to obtain basic magnesium carbonate template.
(2) 5g basic magnesium carbonate template ultrasonic disperses is taken to add in 5mL into the solution after ultrasonic disperse in absolute ethyl alcohol
Tetrabutyl titanate, 400r/min mechanical agitation 10min, be slowly added dropwise into above-mentioned solution 5mL high purity waters, 30mL absolute ethyl alcohols and
The mixed solution of the acetic acid of 0.5mL, hydrolyzes 4h, and centrifugation, washing, drying obtain titaniferous intermediate.
(3) 5g titaniferous intermediate ultrasonic disperses is taken the silver nitrate solution 10mL of 0.1M to be added dropwise, machinery stirs in absolute ethyl alcohol
4h is mixed, is passed through carbon dioxide gas 30min, adds 60mL disodium hydrogen phosphates-phosphate sodium dihydrogen buffer solution washing to remove mould
Plate obtains silver-colored titanium composite precursor after product centrifugation, washing, drying.
(4) under nitrogen atmosphere, at a temperature of 500 DEG C, silver-colored titanium composite precursor 4h is calcined, obtains 0.92g silver titanium dioxide
Composite material.
The silver-colored titanium dioxide composite construction particle of preparation be flower-like structure, specific surface area 140m2/ g, pore volume reach
0.82cm3/g.Staphylococcus aureus and Escherichia coli is selected to do Bactericidal test, under 200ppm concentration, prepare the suppression of sample
Bacterium circle is respectively 13cm and 14cm, the inhibition zone difference 10cm and 11cm. of commercialization Nano silver grain under comparable sodium
Embodiment 2：
(1) MgCl of 50mL 1M is taken2The Na of solution and 100mL 0.5M2CO3Solution is separately heated to 80 DEG C.It will be above-mentioned
Two kinds of solution are mixed in there-necked flask, the mechanical agitation 10min under rotating speed 400r/min, are aged 2h, and water washing 2 is distilled in filtering
~3 times basic magnesium carbonate template.
(2) 1g multilevel hierarchy basic magnesium carbonate template ultrasonic disperses are taken in absolute ethyl alcohol, toward the solution after ultrasonic disperse
In add in 1mL isopropyl titanates, 2mL high purity waters, 10mL is slowly added dropwise in 400r/min mechanical agitation 20min in above-mentioned solution
The mixed solution of absolute ethyl alcohol and 0.1mL hydrochloric acid, hydrolyzes 4h, and centrifugation, washing, drying obtain titaniferous intermediate.
(3) 1g multilevel hierarchy intermediate ultrasonic disperses are taken in absolute ethyl alcohol, add in the silver nitrate solution of 1m 0.3M, machine
Tool stirs 4h, is passed through CO2Gas 30min adds 20mL disodium hydrogen phosphates-potassium phosphate buffer washing to remove mould
Plate, product centrifugation, washing, silver-colored titanium composite precursor is obtained after dry.
(4) under nitrogen atmosphere, at a temperature of 500 DEG C, silver-colored titanium composite precursor 4h is calcined, is obtained with 0.21g multilevel hierarchies
Silver-colored composite titania material.
The silver-colored titanium dioxide composite construction particle of preparation be flower-like structure, specific surface area 132m2/ g, pore volume reach
0.74cm3/g.Staphylococcus aureus and Escherichia coli is selected to do Bactericidal test, under 200ppm concentration, prepare the suppression of sample
Bacterium circle is respectively 12cm and 13cm, the inhibition zone difference 10cm and 11cm of commercialization Nano silver grain under comparable sodium.
Claims (2)
1. a kind of preparation method of silver titanium dioxide composite antibacterial material, which is characterized in that the step of preparation is as follows：
Step 1：The magnesium chloride brine of 0.5~2M and the aqueous sodium carbonate of 0.5~2M is taken to be separately heated to 50~100 DEG C；
Above two solution is mixed, mechanical agitation, and rotating speed is kept then to be aged 60 in 300~500r/min, 5~60min of stirring
~150min is filtered, is washed to obtain basic magnesium carbonate template；
Step 2：Basic magnesium carbonate template is taken, ultrasonic disperse is in absolute ethyl alcohol, addition titanium source, 10~30min of mechanical agitation,
The hydrolyzate of high purity water, absolute ethyl alcohol, hydrolysis inhibitor composition is slowly added dropwise, hydrolyzes 3~8h, centrifugation, washing, drying obtain
Titaniferous intermediate；The volume ratio of high purity water, absolute ethyl alcohol and hydrolysis inhibitor is 1 in hydrolyzate:1~10:0.05~0.5；
Step 3：Titaniferous intermediate ultrasonic disperse is taken in absolute ethyl alcohol, adds in silver nitrate solution, 3~8h of mechanical agitation；Then
Carbon dioxide gas and addition buffer solution are passed through into mixed liquor to remove removing template, it is compound to obtain silver-colored titanium after centrifugation, washing, drying
Presoma；
Step 4：Under nitrogen atmosphere, at a temperature of 400~600 DEG C, silver-colored titanium 2~6h of composite precursor is calcined, obtaining has multistage
The silver-colored composite titania material of structure；
Hydrolysis inhibitor is chosen in glacial acetic acid, nitric acid, hydrochloric acid, is one or more of they；Buffer solution is in phosphoric acid
Disodium hydrogen-phosphate sodium dihydrogen buffer solution, disodium hydrogen phosphate-potassium phosphate buffer, potassium dihydrogen phosphate-sodium hydroxide buffer
Chosen in liquid, disodium hydrogen phosphate-citrate buffer solution, citric acid-sodium citrate buffer solution, be one or both of they with
On.
2. according to the method described in claim 1, it is characterized in that, titanium source is in tetrabutyl titanate, isopropyl titanate, tetraethyl titanate
It is middle to choose one kind.
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| 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 |
| 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 |
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| 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 |
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| 《Ag-SiO2/TiO2微纳米复合材料的合成及其抗菌性能研究》;张秋双;《大连理工大学硕士学位论文》;20131231;第18页第1段、第30页第1段、第41页第3段、第42页倒数第1段、第50页第1段 * |
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