CN103181399A - Iron injected AG/Tio2 composite anti-bacterial thin film and preparation method thereof - Google Patents

Iron injected AG/Tio2 composite anti-bacterial thin film and preparation method thereof Download PDF

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CN103181399A
CN103181399A CN2013100842467A CN201310084246A CN103181399A CN 103181399 A CN103181399 A CN 103181399A CN 2013100842467 A CN2013100842467 A CN 2013100842467A CN 201310084246 A CN201310084246 A CN 201310084246A CN 103181399 A CN103181399 A CN 103181399A
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tio
film
ion
thin film
escherichia coli
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侯兴刚
王学敏
姚琨
刘峰
王立群
李德军
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Tianjin Normal University
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Tianjin Normal University
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Abstract

The invention discloses an Ag/Tio2 composite anti-bacterial thin film and the preparation method thereof. The Ag/Tio2 composite anti-bacterial thin film mainly comprises a substrate and thin film layers with Ag ions doped to surfaces, the Ag ion dopant quantity is 1*1015 to 1*1018 ions/cm<2>, during injection, the vacuum pressure is 1*10 to 1*10 to 3 pa; and the accelerating voltage of an injection machine is 1 to 100 KV, ion beam is 0.1 to 10 mA, 3 to 4 layers of films are plated and the thickness of each thin film is 140 to 200 nm. According to the invention, by using the clearance energy level produced by Ag ions in TIO2, the recombination rate of Tio2 thin film photoproduction electron hole pairs is lowered, the TiO2 thin film photoactivating efficiency is improved, the TiO2 thin film absorption spectrum is enabled to cause red shift, the visible light absorption rate is improved, and the anti-bacterial efficiency of the TiO2 thin film is also improved. Compared with the common Ag or TiO2 composite antimicrobial agent, the Ag/ TiO2 composite anti-bacterial thin film has a higher colon bacillus killing efficiency.

Description

A kind of ion injects Ag/TiO 2The preparation method of composite antibacterial thin films
The application obtains the subsidy of the doctor of Tianjin Normal University fund (52X09003).
Technical field
The invention belongs to the inorganic antibacterial material preparing technical field, relate to a kind of novel Ag/TiO 2Complex antimicrobials more particularly, relates to a kind of employing ion and is infused in TiO 2Doping Ag ion in the film, realize unglazed with the preparation method who all has the composite antibacterial thin films of antibacterial functions under the optical condition arranged.
Background technology
Anatase TiO 2With the Ag nano material be two kinds of inorganic antiseptics commonly used.Nano-TiO 2Antibacterial activity derive from photocatalysis characteristic, its surface can produce and have extensive chemical activity very in a large number under the effect of light
Figure 221584DEST_PATH_IMAGE001
And superoxide radical, oxidation reaction takes place in two kinds of free radicals and various microorganism, just can kill microorganisms in very short time.The antibiotic mechanism of Ag ion is: since microorganism have negative electrical charge cell membrane can with Ag ion generation Coulomb interactions, final Ag ion penetration cell membrane, react with the sulfydryl on the microbial body internal protein, this reaction can make protein coagulating, the activity of destroy microorganisms synzyme, disturb the synthetic of microbial DNA, cause microorganism forfeiture schizogamy ability and death.
But anatase TiO 2The band gap width of body material is 3.2 electron-volts, and the band gap width of nano material is higher than this numerical value, so the anatase nano-TiO 2Film can only be worked under the irradiation of ultraviolet light, in addition anatase TiO 2Nano thin-film light induced electron-hole is higher to recombination rate, causes its operating efficiency very low, and this has also limited nano-TiO 2Film is in the application of antibiosis.Existingly studies show that silver element mixes and effectively to improve TiO 2Photocatalytic activity, and silver ion itself also has good antibacterial activity.Be antibacterial effect and its loading range of expansion that improves the Ag ion, we have carried out the antibacterial research of materials such as Ag ion injection TiN film, RESEARCH OF PYROCARBON, and result of study shows that ion injection method is a kind of effective Ag ion antibacterial agent preparation method.For in conjunction with TiO 2With Ag nano material antibiotic advantage separately, adopt the Ag ion to inject TiO 2Film process prepares complex antimicrobials.Anti-microbial property under visible light or lucifuge condition is mainly provided by the Ag ion, and the Ag ion that injects improves TiO 2Film under action of ultraviolet light antimicrobial efficiency and improve TiO 2The visible-light absorptivity of film.
Summary of the invention
The objective of the invention is to overcome anatase TiO in the prior art 2The low shortcoming of antimicrobial efficiency under effect no antibiotic effect down, the action of ultraviolet light provides a kind of preparation method with nano thin-film of high antimicrobial efficiency under nano thin-film lucifuge and the visible light.
Purpose of the present invention is achieved by following technical proposals:
A kind of Ag/TiO 2Composite antibacterial thin films is characterized in that the Ag/TiO that is made up of the thin layer of substrate, top layer doping Ag ion 2The THIN COMPOSITE rete; Described Ag ion doping dosage is 1 * 10 15-1 * 10 18Ions/cm 2
The present invention further discloses Ag/TiO 2The preparation method of composite antibacterial thin films is characterized in that carrying out according to following step:
(1) absolute ethyl alcohol and acetylacetone,2,4-pentanedione are mixed and stir, butyl titanate is poured in the mixed liquor by drainage, obtain mixed liquor 1; Absolute ethyl alcohol wherein: acetylacetone,2,4-pentanedione: the mol ratio of butyl titanate is 10-14:1:5-7;
(2) deionized water, absolute ethyl alcohol and nitric acid are mixed the even drainage in back and pour in the mixed liquor 1, stir and obtain mixed liquor 2, put into container lucifuge ageing 24h then, the clear gel that obtains stable yellow is standby; Absolute ethyl alcohol wherein: the mol ratio of nitric acid is 10-20:1;
(3) adopting quartz glass is used the sol evenning machine plated film as substrate, and the sol evenning machine rotating speed is 3000 r/min-5000 r/min, dries 15-20 minute at 60-80 ℃ with drying baker behind every plating skim, plates the 3-4 tunic altogether; Film thickness is 140-200nm.
(4) the good TiO of plating 2Film is placed on and slowly is warming up to 450-500 ℃ in the Muffle furnace, is incubated 1-2 hour;
(5) adopt metal vapor vacuum arc source ion implanter to TiO 2Film injects the Ag ion; Wherein Ag is negative electrode, and vacuum pressure is 1 * 10 during injection -1– 1 * 10 -3Pa; The accelerating potential of implanter is 1 –, 100 kV, and ion beam current is 0.1 –, 10 mA; The Ag ion implantation dosage is 1 * 10 15-1 * 10 18Ions/cm 2
TiO of the present invention 2Method for manufacturing thin film also should comprise chemical vapour deposition technique, liquid phase deposition or aerosol gel deposition method except above-mentioned collosol and gel is sent out.
Substrate of the present invention also comprises the substrate of chemical methodes such as the various Rong of being applicable to Jiao – gel methods, chemical vapour deposition technique, liquid phase deposition, aerosol gel deposition method except above-mentioned quartz glass.
Thin layer of the present invention is the various TiO by the preparation of chemical methodes such as molten glue – gel method, chemical vapour deposition technique, liquid phase deposition, aerosol gel deposition method 2Film.
Ag/TiO of the present invention 2The Ag ion distribution is at TiO in the THIN COMPOSITE rete 2In the film top layer, do not have obvious Ag cluster and produce, ion concentration distribution begins to increase gradually from the top layer, and peak value is about 100 nm, reach peak value after, concentration reduces gradually.
Preferred embodiment of the invention preparation method is as follows:
(1) acetylacetone,2,4-pentanedione of the absolute ethyl alcohol of 344ml and 25ml is mixed and stir, the butyl titanate of 170ml is poured in the mixed liquor by drainage, obtain mixed liquor 1, and use magnetic stirrer.
(2) deionized water of 9ml, the absolute ethyl alcohol of 173ml and the even drainage in nitric acid mixing back of 10ml are poured in the mixed liquor 1, obtain mixed liquor 2.
(3) with magnetic stirring apparatus mixed liquor 2 is stirred 30min, put into container lucifuge ageing 24h, standby.
(4) the general adopting quartz glass of described film-substrate.Normally base material is not put into each ultrasonic cleaning of acetone, absolute ethyl alcohol and deionized water 5 minutes.
(5) adopt the sol evenning machine plated film, the sol evenning machine rotating speed is 3000 r/min-5000 r/min.Dried 15-20 minute at 60-80 ℃ with drying baker behind every plating skim, plate the 3-4 tunic altogether.Film thickness is 150nm.
(6) will plate good TiO 2Film is placed in the Muffle furnace and at the uniform velocity heats up, and is upgraded to 450-500 ℃ by room temperature behind the 140-160min, insulation 30-50 min.
(7) utilizing and carry out the Ag ion on the metal vapor vacuum arc source ion implanter and inject, is negative electrode with metal A g, 1 * 10 -2-5 * 10 -3Inject under the condition of Pa.The accelerating potential of implanter is 40 kV, and ion beam current is set at 0.5 mA, Ag +Implantation dosage is 3 * 10 16Ions/cm 2
The present invention has carried out a large amount of experiments to the concentration of Ag ion doping:
(1) mainly investigated ion implantation energy and two influence factors of implantation dosage in the experiment, wherein injected energy by the estimation of SRIM program, determined that at last injecting energy is 40 kV.Whether suitable implantation dosage is is determined by antibiotic rate experiment under the action of ultraviolet light.
(2) in the antibacterial experiment implantation dosage to choose scope be 1 * 10 15-1 * 10 18Ions/cm 2, experimental result as shown in Figure 1, when implantation dosage less than 5 * 10 15The time Ag/TiO 2Laminated film is lower than TiO 2The antibacterial effect of film itself does not mark on the figure.
Conclusion: Ag ion doping concentration is more high, and energy level is easy overlapping more, and it is more few that electron transition absorbs photon institute energy requirement, causes the red shift phenomenon more obvious,
The present invention further discloses prepared Ag/TiO 2Composite antibacterial thin films is the application aspect long acting antibiotic (the killing Escherichia coli) thin-film material under preparation lucifuge and visible light.
The antibiotic property of film is measured, and is by test Ag/TiO 2Nano thin-film and TiO 2Film is under the irradiation of uviol lamp of 8W at power, kills colibacillary ability.
(1) the single spot of Escherichia coli of picking in the LB of 50ml liquid nutrient medium (do not contain antibiotic, PH=7), 37 ℃ of following constant temperature culture 12 hours.Be that 2000rpm separate 5min with centrifuge at rotating speed with Escherichia coli solution, it is separated with the LB liquid nutrient medium.After removing the suspension supernatant, clean centrifugal 3 times with dual distilled water, make LB also medium separate with Escherichia coli fully.With the Escherichia coli that distilled water diluting as above separates, recording the Escherichia coli initial concentration solution by the plating technology is 4.46 * 10 8CFU/ml.
(2) the Escherichia coli solution of 10mL is poured into the beaker bottom of 50mL.The beaker that bacterium liquid is housed is placed on uviol lamp 5cm place apart from 8W, draws Escherichia coli 15 μ l every 20s, and dilution records the Escherichia coli solution concentration with the plating technology.The beaker place that the Escherichia coli solution of getting 10mL is poured 50 mL into is placed on dark place, also takes a sample once every 20s, in contrast experiment.More than experiment is all operated under gnotobasis.Behind 80 s, the direct sterilization rate of ultraviolet light is 50%.
(3) TiO 2Film is placed on the beaker bottom of 50mL respectively, pours the Escherichia coli solution of 10mL into.The beaker that film and bacterium liquid are housed is placed on uviol lamp 5cm place apart from 8W, draws Escherichia coli 15 μ l every 20s, and dilution records the Escherichia coli solution concentration with the plating technology.The beaker place that the Escherichia coli solution of getting 10mL is poured 50 mL into is placed on dark place, also takes a sample once every 20s, in contrast experiment.More than experiment is all operated under gnotobasis.Behind 80 s, TiO 2The sterilization rate of film is 75%.
(4) Ag/TiO 2Film is placed on the beaker bottom of 50mL respectively, pours the Escherichia coli solution of 10mL into.The beaker that film and bacterium liquid are housed is placed on uviol lamp 5cm place apart from 8W, draws Escherichia coli 15 μ l every 20s, and dilution records the Escherichia coli solution concentration with the plating technology.The beaker place that the Escherichia coli solution of getting 10mL is poured 50 mL into is placed on dark place, also takes a sample once every 20s, in contrast experiment.More than experiment is all operated under gnotobasis.Behind the 80s, Ag/TiO 2The film sterilization rate is relevant with the dosage that injects the Ag ion, and concrete data see Table one.
(5) Ag/TiO 2The Escherichia coli solution of film and 10mL is put into each hole of aseptic vacuum box (cultivation box), and it is 150 r.m.p that the cultivation box is put into rotating speed, and the constant temperature lucifuge is cultivated in 37 ℃ the shaking table.Draw Escherichia coli 15 μ l after 24 hours, and dilution records the Escherichia coli solution concentration with the plating technology.Ag/TiO 2The film sterilization rate is relevant with the dosage that injects the Ag ion, and concrete data see Table two.
(6) Ag/TiO 2The Escherichia coli solution of film and 10mL is put into each hole of aseptic vacuum box (cultivation box), and cultivating box under indoor natural light (the non-sunshine direct projection) condition, to put into rotating speed be 150 r.m.p, constant temperature culture in 37 ℃ shaking table.Draw Escherichia coli 15 μ l after 24 hours, and dilution records the Escherichia coli solution concentration with the plating technology.Ag/TiO 2The film sterilization rate is relevant with the dosage that injects the Ag ion, and concrete data see Table three.
(7) different implantation dosage Ag/TiO 2The UV-Vis transmitted spectrum of film records at Tianjin, island UV-160 type spectrophotometer, sees Fig. 2.
Experimental data;
Table one
Implantation dosage ions/cm 2 5×10 15 1×10 16 3×10 16 6×10 16 1×10 17
80s antibiotic rate (%) 72 85 90 78 70
Table two
Implantation dosage ions/cm 2 5×10 15 1×10 16 3×10 16 6×10 16 1×10 17
24h antibiotic rate (%) 15 70 85 95 100
Table three
Implantation dosage ions/cm 2 5×10 15 1×10 16 3×10 16 6×10 16 1×10 17
24h antibiotic rate (%) 20 82 93 98 100
Experiment conclusion:
(1) Ag/TiO under the action of ultraviolet light 2The film antibiotic rate is relevant with the injection ion dose, is lower than 5 * 10 when injecting ion 15Ions/cm 2, inject the Ag ion and do not play the effect that improves antimicrobial efficiency, along with the raising of implantation dosage, antimicrobial efficiency is also along with improve, when implantation dosage brings up to 3 * 10 16Ions/cm 2The time, the 80s antimicrobial efficiency is by TiO 275% of film brings up to 90%, continues to improve implantation dosage, and antimicrobial efficiency reduces on the contrary.But high implantation dosage helps the antimicrobial efficiency under lucifuge and the visible light condition.Implantation dosage is higher than 1 * 10 17, antibiotic rate is 100%
(2) can be with spectrum as can be known by ultraviolet, ion injects Ag/TiO 2Significantly " red shift " phenomenon takes place, and the red shift amount increases with the increase of implantation dosage.
It is the technological means of very desirable doping ion that the used ion of the present invention injects, and injects energy of ions and dosage by regulating, and can control thickness and the concentration of ion doped layer; Can distinguish the different valence state ion and avoid the doping of other kind ion to disturb.The Ag ion that utilization is mixed can be realized the long acting antibiotic under lucifuge and the visible light condition, and can reduce TiO 2The recombination rate of light induced electron in the film improves TiO 2Antimicrobial efficiency under the film ultraviolet effect.The Ag ion that mixes also can be at TiO 2Gap level between producing in being with of film makes TiO 2Significantly " red shift " phenomenon takes place in the ultraviolet-visible absorption spectroscopy of nano thin-film, increases film to the absorption of visible light.Doping content is more high, and energy level is easy overlapping more, and it is more few that electron transition absorbs photon institute energy requirement, causes the red shift phenomenon more obvious, as shown in Figure 1.
The Ag/TiO of the present invention's preparation 2The good effect that composite antibacterial thin films compared with prior art has is:
(1) doping Ag ion concentration and injection depth controlled, the doping ion only is present in the top layer of film.
(2) the Ag ion of Zhu Ruing has improved TiO 2Antimicrobial efficiency under the film ultraviolet effect.
(3) the Ag ion of Zhu Ruing has improved TiO 2Antimicrobial efficiency under the effect of film visible light.
(4) the Ag ion of Zhu Ruing has been realized TiO 2Antimicrobial efficiency under the film lucifuge condition.
Description of drawings
Fig. 1 is different implantation dosage Ag/TiO 2Antibiotic rate experimental data under the film ultraviolet effect: (1) 5 * 10 15Ions/cm 2(2) 1 * 10 16Ions/cm 2(3) 3 * 10 16Ions/cm 2(4) 6 * 10 16Ions/cm 2(5) 1 * 10 17Ions/cm 2
Fig. 2 is TiO 2With different implantation dosage Ag/TiO 2The Zi Wai – visible light transmission spectrum of film; A:TiO wherein 2B:Ag ion implantation dosage 1 * 10 16Ions/cm 2C:Ag ion implantation dosage 6 * 10 16Ions/cm 2D:Ag ion implantation dosage 1 * 10 18Ions/cm 2
Fig. 3 is that the Ag ion injects the titanium deoxid film schematic diagram; Wherein 1: substrate; 2: nano-titanium dioxide film; 3:Ag/TiO 2Laminated film; 4: the ion beam that ion implantation apparatus comes.
  
Embodiment
Below in conjunction with embodiment the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, described these improvement and variation all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.The used all ingredients of the present invention all has commercially available.
Reference example
The TiO that utilizes in the embodiment of the invention 2According to document Hongbo. Jiang, Lian. Gao, Mater. the method for record is prepared among the Chem. Phys. 77 (2002) 878, concrete steps are for being the titanium source with the butyl titanate, colloidal sol by butyl titanate, ethanol, deionized water, nitric acid, acetylacetone,2,4-pentanedione in n (Ti (OC4H9) 4): the ratio of n (EtOH): n (H2O): n (HNO3): n (AcAc)=1:18:2:0.2:0.5 mixes.A certain amount of butyl titanate is added to by in the mixed solution of forming as the acetylacetone,2,4-pentanedione of inhibitor and absolute ethyl alcohol (volume be volume required 2/3rds), drip needed nitric acid and deionized water and 1/3rd the mixed solution of absolute ethyl alcohol then in above-mentioned solution, obtain stable TiO 2Colloidal sol, process described above is all finished under the strong agitation of magnetic stirring apparatus.Need to prove, though all multifactor impact TiO such as titanium source, strong acid, inhibitor, assembly time for example 2The preparation of gel, but do not influence final TiO 2The acquisition of gel and the preparation of subsequent thin film.
Preparation embodiment 1
(1) absolute ethyl alcohol and acetylacetone,2,4-pentanedione are mixed and stir, butyl titanate is poured in the mixed liquor by drainage, obtain mixed liquor 1; Absolute ethyl alcohol wherein: acetylacetone,2,4-pentanedione: the mol ratio of butyl titanate is 12:1:7;
(2) deionized water, absolute ethyl alcohol and nitric acid are mixed the even drainage in back and pour in the mixed liquor 1, stir and obtain mixed liquor 2, put into container lucifuge ageing 24h then, the clear gel that obtains stable yellow is standby; Absolute ethyl alcohol wherein: the mol ratio of nitric acid is 15:1;
(3) adopting quartz glass is used the sol evenning machine plated film as substrate, and the sol evenning machine rotating speed is 3000 r/min-5000 r/min, dries 20 minutes at 80 ℃ with drying baker behind every plating skim, plates 3 tunics altogether;
(4) the good TiO of plating 2Film is placed on and slowly is warming up to 500 ℃ in the Muffle furnace, is incubated 2 hours;
(5) adopt metal vapor vacuum arc source ion implanter to TiO 2Film injects the Ag ion; Wherein Ag is negative electrode, and vacuum pressure is 1 * 10 during injection -3Pa; The accelerating potential of implanter is 100 kV, and ion beam current is 1 mA; The Ag ion implantation dosage is 1 * 10 16Ions/cm 2Film thickness is about 150nm.
(6) the single spot of Escherichia coli of picking in the LB of 50ml liquid nutrient medium (do not contain antibiotic, PH=7), 37 ℃ of following constant temperature culture 12 hours.Be that 2000rpm separate 5min with centrifuge at rotating speed with Escherichia coli solution, it is separated with the LB liquid nutrient medium.After removing the suspension supernatant, clean centrifugal 3 times with dual distilled water, make LB also medium separate with Escherichia coli fully.With the Escherichia coli that distilled water diluting as above separates, recording the Escherichia coli initial concentration solution by the plating technology is 4.46 * 10 8CFU/ml.
(7) Ag/TiO 2Film is placed on the beaker bottom of 50mL respectively, pours the Escherichia coli solution of 10mL into.The beaker that film and bacterium liquid are housed is placed on uviol lamp 5cm place apart from 8W, draws Escherichia coli 15 μ l every 20s, and dilution records the Escherichia coli solution concentration with the plating technology.The beaker place that the Escherichia coli solution of getting 10mL is poured 50 mL into is placed on dark place, also takes a sample once every 20s, in contrast experiment.More than experiment is all operated under gnotobasis.Behind 80 s, the direct sterilization rate of ultraviolet light is 50%, TiO 2The sterilization rate of film is 75%, Ag/TiO 2The film sterilization rate is 85%.
Embodiment 2
(1) absolute ethyl alcohol and acetylacetone,2,4-pentanedione are mixed and stir, butyl titanate is poured in the mixed liquor by drainage, obtain mixed liquor 1; Absolute ethyl alcohol wherein: acetylacetone,2,4-pentanedione: the mol ratio of butyl titanate is 14:1:5;
(2) deionized water, absolute ethyl alcohol and nitric acid are mixed the even drainage in back and pour in the mixed liquor 1, stir and obtain mixed liquor 2, put into container lucifuge ageing 24h then, the clear gel that obtains stable yellow is standby; Absolute ethyl alcohol wherein: the mol ratio of nitric acid is 20:1;
(3) adopting quartz glass is used the sol evenning machine plated film as substrate, and the sol evenning machine rotating speed is 3000 r/min-5000 r/min, dries 15 minutes at 60 ℃ with drying baker behind every plating skim, plates 4 tunics altogether; Film thickness is 200nm.
(4) the good TiO of plating 2Film is placed on and slowly is warming up to 450 ℃ in the Muffle furnace, is incubated 1 hour;
(5) adopt metal vapor vacuum arc source ion implanter to TiO 2Film injects the Ag ion; Wherein Ag is negative electrode, and vacuum pressure is 1 * 10 during injection -1Pa; The accelerating potential of implanter is 20 kV, and ion beam current is 3 mA; The Ag ion implantation dosage is 6 * 10 16Ions/cm 2
(6) the single spot of Escherichia coli of picking in the LB of 50ml liquid nutrient medium (do not contain antibiotic, PH=7), 37 ℃ of following constant temperature culture 12 hours.Be that 2000rpm separate 5min with centrifuge at rotating speed with Escherichia coli solution, it is separated with the LB liquid nutrient medium.After removing the suspension supernatant, clean centrifugal 3 times with dual distilled water, make LB also medium separate with Escherichia coli fully.With the Escherichia coli that distilled water diluting as above separates, recording the Escherichia coli initial concentration solution by the plating technology is 4.46 * 10 8CFU/ml.
(7) Ag/TiO 2Film is placed on the beaker bottom of 50mL respectively, pours the Escherichia coli solution of 10mL into.The beaker that film and bacterium liquid are housed is placed on uviol lamp 5cm place apart from 8W, draws Escherichia coli 15 μ l every 20s, and dilution records the Escherichia coli solution concentration with the plating technology.The beaker place that the Escherichia coli solution of getting 10mL is poured 50 mL into is placed on dark place, also takes a sample once every 20s, in contrast experiment.More than experiment is all operated under gnotobasis.Behind 80 s, the direct sterilization rate of ultraviolet light is 50%, TiO 2The sterilization rate of film is 75%, Ag/TiO 2The film sterilization rate is 78%.
Embodiment 3
(1) absolute ethyl alcohol and acetylacetone,2,4-pentanedione are mixed and stir, butyl titanate is poured in the mixed liquor by drainage, obtain mixed liquor 1; Absolute ethyl alcohol wherein: acetylacetone,2,4-pentanedione: the mol ratio of butyl titanate is 12:1:6;
(2) deionized water, absolute ethyl alcohol and nitric acid are mixed the even drainage in back and pour in the mixed liquor 1, stir and obtain mixed liquor 2, put into container lucifuge ageing 24h then, the clear gel that obtains stable yellow is standby; Absolute ethyl alcohol wherein: the mol ratio of nitric acid is 15:1;
(3) adopting quartz glass is used the sol evenning machine plated film as substrate, and the sol evenning machine rotating speed is 3000 r/min-5000 r/min, dries 20 minutes at 80 ℃ with drying baker behind every plating skim, plates 3 tunics altogether; Film thickness is 150nm.
(4) the good TiO of plating 2Film is placed on and slowly is warming up to 500 ℃ in the Muffle furnace, is incubated 1 hour;
(5) adopt metal vapor vacuum arc source ion implanter to TiO 2Film injects the Ag ion; Wherein Ag is negative electrode, and vacuum pressure is 1 * 10 during injection -3Pa; The accelerating potential of implanter is 50 kV, and ion beam current is 4 mA; The Ag ion implantation dosage is 1 * 10 17Ions/cm 2
(6) the single spot of Escherichia coli of picking in the LB of 50ml liquid nutrient medium (do not contain antibiotic, PH=7), 37 ℃ of following constant temperature culture 12 hours.Be that 2000rpm separate 5min with centrifuge at rotating speed with Escherichia coli solution, it is separated with the LB liquid nutrient medium.After removing the suspension supernatant, clean centrifugal 3 times with dual distilled water, make LB also medium separate with Escherichia coli fully.With the Escherichia coli that distilled water diluting as above separates, recording the Escherichia coli initial concentration solution by the plating technology is 4.46 * 10 8CFU/ml.
(7) Ag/TiO 2The Escherichia coli solution of film and 10mL is put into each hole of aseptic vacuum box (cultivation box), and cultivating box under the lucifuge condition, to put into rotating speed be 150 r.m.p, constant temperature culture in 37 ℃ shaking table.Draw Escherichia coli 15 μ l after 24 hours, and dilution records Escherichia coli solution concentration, Ag/TiO with the plating technology 2The film sterilization rate is 100%.
Embodiment 4
(1) absolute ethyl alcohol and acetylacetone,2,4-pentanedione are mixed and stir, butyl titanate is poured in the mixed liquor by drainage, obtain mixed liquor 1; Absolute ethyl alcohol wherein: acetylacetone,2,4-pentanedione: the mol ratio of butyl titanate is 14:1:5;
(2) deionized water, absolute ethyl alcohol and nitric acid are mixed the even drainage in back and pour in the mixed liquor 1, stir and obtain mixed liquor 2, put into container lucifuge ageing 24h then, the clear gel that obtains stable yellow is standby; Absolute ethyl alcohol wherein: the mol ratio of nitric acid is 12:1;
(3) adopting quartz glass is used the sol evenning machine plated film as substrate, and the sol evenning machine rotating speed is 3000 r/min-5000 r/min, dries 20 minutes at 80 ℃ with drying baker behind every plating skim, plates 3 tunics altogether; Film thickness is 200nm.
(4) the good TiO of plating 2Film is placed on and slowly is warming up to 500 ℃ in the Muffle furnace, is incubated 1 hour;
(5) adopt metal vapor vacuum arc source ion implanter to TiO 2Film injects the Ag ion; Wherein Ag is negative electrode, and vacuum pressure is 1 * 10 during injection -3Pa; The accelerating potential of implanter is 40 kV, and ion beam current is 10 mA; The Ag ion implantation dosage is 5 * 10 15Ions/cm 2
(6) the single spot of Escherichia coli of picking in the LB of 50ml liquid nutrient medium (do not contain antibiotic, PH=7), 37 ℃ of following constant temperature culture 12 hours.Be that 2000rpm separate 5min with centrifuge at rotating speed with Escherichia coli solution, it is separated with the LB liquid nutrient medium.After removing the suspension supernatant, clean centrifugal 3 times with dual distilled water, make LB also medium separate with Escherichia coli fully.With the Escherichia coli that distilled water diluting as above separates, recording the Escherichia coli initial concentration solution by the plating technology is 4.46 * 10 8CFU/ml.
(7) Ag/TiO 2The Escherichia coli solution of film and 10mL is put into each hole of aseptic vacuum box (cultivation box), and cultivating box under the natural daylight condition, to put into rotating speed be 150 r.m.p, constant temperature culture in 37 ℃ shaking table.Draw Escherichia coli 15 μ l after 24 hours, and dilution records Escherichia coli solution concentration, Ag/TiO with the plating technology 2The film sterilization rate is 20%.
Embodiment 5
Comparative experiments:
(1) film-substrate adopting quartz glass.Backing material is not put into each ultrasonic cleaning of acetone, absolute ethyl alcohol and deionized water 5 minutes.
(2) employing lifts thin films, and the speed that substrate proposes gel is 0.3 mm/s.Dried 15 minutes at 80 ℃ with drying baker behind every plating skim, plate six tunics altogether.
(3) will plate good TiO 2Film is placed in the Muffle furnace and at the uniform velocity heats up, and is upgraded to 450 ℃ by room temperature behind 140 min, is incubated 30 min.
(4) utilizing and carry out the Ag ion on the metal vapor vacuum arc source ion implanter and inject, is negative electrode with metal A g, 3 * 10 -3Inject under the condition of Pa.The accelerating potential of implanter is 40 kV, and ion beam current is set at 0.5 mA, Ag +Implantation dosage is 3 * 10 16Ions/cm 2
(5) the single spot of Escherichia coli of picking in the LB of 50ml liquid nutrient medium (do not contain antibiotic, PH=7), 37 ℃ of following constant temperature culture 12 hours.Be that 2000rpm separate 5min with centrifuge at rotating speed with Escherichia coli solution, it is separated with the LB liquid nutrient medium.After removing the suspension supernatant, clean centrifugal 3 times with dual distilled water, make LB also medium separate with Escherichia coli fully.With the Escherichia coli that distilled water diluting as above separates, recording the Escherichia coli initial concentration solution by the plating technology is 4.46 * 10 8CFU/ml.
(6) Ag/TiO 2Film is placed on the beaker bottom of 50mL respectively, pours the Escherichia coli solution of 10mL into.The beaker that film and bacterium liquid are housed is placed on uviol lamp 5cm place apart from 8W, draws Escherichia coli 15 μ l every 20s, and dilution records the Escherichia coli solution concentration with the plating technology.The beaker place that the Escherichia coli solution of getting 10mL is poured 50 mL into is placed on dark place, also takes a sample once every 20s, in contrast experiment.More than experiment is all operated under gnotobasis.
(7) Ag/TiO 2The Escherichia coli solution of film and 10mL is put into each hole of aseptic vacuum box (cultivation box), and cultivating box under the lucifuge condition, to put into rotating speed be 150 r.m.p, constant temperature culture in 37 ℃ shaking table.Draw Escherichia coli 15 μ l after 24 hours, and dilution records the Escherichia coli solution concentration with the plating technology.
(8) Ag/TiO 2The Escherichia coli solution of film and 10mL is put into each hole of aseptic vacuum box (cultivation box), and cultivating box under the natural daylight condition, to put into rotating speed be 150 r.m.p, constant temperature culture in 37 ℃ shaking table.Draw Escherichia coli 15 μ l after 24 hours, and dilution records the Escherichia coli solution concentration with the plating technology;
? 24h lucifuge sterilization rate 80s ultraviolet light sterilization rate 24h natural daylight sterilization rate
TiO 2Film 0 75% 25
Ag/TiO 2 85 90% 93

Claims (3)

1. Ag/TiO 2Composite antibacterial thin films is characterized in that being made up of the thin layer of substrate, top layer doping Ag ion, and described Ag ion doping dosage is 1 * 10 15-1 * 10 18Ions/cm 2, vacuum pressure is 1 * 10 during injection -1– 1 * 10 -3Pa; The accelerating potential of implanter is 1 –, 100 kV, and ion beam current is 0.1 –, 10 mA, plates the 3-4 tunic altogether, and film thickness is 140-200nm.
2. the described Ag/TiO of claim 1 2The preparation method of composite antibacterial thin films is characterized in that carrying out according to following step:
(1) absolute ethyl alcohol and acetylacetone,2,4-pentanedione are mixed and stir, butyl titanate is poured in the mixed liquor by drainage, obtain mixed liquor 1; Absolute ethyl alcohol wherein: acetylacetone,2,4-pentanedione: the mol ratio of butyl titanate is 10-14:1:5-7;
(2) deionized water, absolute ethyl alcohol and nitric acid are mixed the even drainage in back and pour in the mixed liquor 1, stir and obtain mixed liquor 2, put into container lucifuge ageing 24h then, the clear gel that obtains stable yellow is standby; Absolute ethyl alcohol wherein: the mol ratio of nitric acid is 10-20:1;
(3) adopting quartz glass is used the sol evenning machine plated film as substrate, and the sol evenning machine rotating speed is 3000 r/min-5000 r/min, dries 15-20 minute at 60-80 ℃ with drying baker behind every plating skim, plates the 3-4 tunic altogether; Film thickness is 140-200nm;
(4) the good TiO of plating 2Film is placed on and slowly is warming up to 450-500 ℃ in the Muffle furnace, is incubated 1-2 hour;
(5) adopt metal vapor vacuum arc source ion implanter to TiO 2Film injects the Ag ion; Wherein Ag is negative electrode, and vacuum pressure is 1 * 10 during injection -1– 1 * 10 -3Pa; The accelerating potential of implanter is 1 –, 100 kV, and ion beam current is 0.1 –, 10 mA; The Ag ion implantation dosage is 1 * 10 15-1 * 10 18Ions/cm 2
3. the described Ag/TiO of claim 1 2Composite antibacterial thin films is killed the application aspect the Escherichia coli thin-film material under preparation lucifuge and visible light.
CN2013100842467A 2013-03-18 2013-03-18 Iron injected AG/Tio2 composite anti-bacterial thin film and preparation method thereof Pending CN103181399A (en)

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CN102330051A (en) * 2011-09-30 2012-01-25 中国科学院上海硅酸盐研究所 Surface modifying method for improving antibacterial property and biological activity of medicinal titanium
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