CN106178008B - A kind of ultrasound-piezoelectricity Synergistic biocidal technology - Google Patents
A kind of ultrasound-piezoelectricity Synergistic biocidal technology Download PDFInfo
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- CN106178008B CN106178008B CN201610526389.2A CN201610526389A CN106178008B CN 106178008 B CN106178008 B CN 106178008B CN 201610526389 A CN201610526389 A CN 201610526389A CN 106178008 B CN106178008 B CN 106178008B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
- A61L2/025—Ultrasonics
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
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- C01G23/006—Alkaline earth titanates
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Abstract
The invention discloses a kind of ultrasound-piezoelectricity Synergistic biocidal technologies.It is related to receiving minute-pressure electric material tetragonal phase BaTiO3、BaxY1‑ xTiO3、M@BaTiO3Or M@BaxY1‑xTiO3And preparation method thereof and the application in terms of sterilization, wherein Y Sr2+、Sn2+Or Ce4+Deng M Ag, Au, Pt or Pd etc., they are strengthened piezoelectricity germicidal efficiency by moving peak and class the effects of silver.The technology is sterilized outer in addition to the cavitation using ultrasonic wave itself, is also excited using it and is received minute-pressure electric material generation hole and active oxygen radical, has the function that Synergistic biocidal.The present invention can convert mechanical energy to the chemical energy effectively sterilized using simple piezoelectric material and composite piezoelectric material, it can not only can greatly increase the efficiency of ultrasonic sterilization, also it can be widely present in the low-frequency vibration mechanical energy of natural environment using other, be a kind of environmentally protective sterilization technology.
Description
Technical field
The invention belongs to sterilization technology fields.More particularly, to a kind of ultrasound-piezoelectricity Synergistic biocidal technology.
Background technique
With going deep into microbe research, people produce more understandings for the disease that numerous microorganisms cause,
The research and development of effective sterilization technology becomes very important project.
Ultrasonic wave is a kind of new physical sterilization method, and when ultrasonic wave is propagated in medium, it is a series of special to cause
Effect destroys eucaryotic cell structure such as mechanics effect and cavitation effect, and a small amount of free radical formed in cavitation effect can also be broken
The biological substance of bad DNA etc keeps microorganism dead.But the germicidal efficiency of ultrasonic wave, especially low-frequency ultrasonic waves is not high, therefore
It often needs and other methods is used in combination.
Piezoelectric effect is a kind of effect that mechanical energy can be mutually converted with electric energy, and in recent decades, piezoelectric effect is especially
The research and application of nanometer piezoelectric effect have obtained significant development, can be converted into 90% mechanical energy using piezoelectric effect
Electric energy stores, and is used widely in fields such as daily necessities, information, biology, military affairs and new energy.In addition, we note that
It can be by live effectively benefit to that other than it can convert mechanical energy into electric energy, mechanical energy can also be converted to by piezoelectric effect
Chemical energy, degradable organic pollutant.But it there are no the relevant report for being applied to sterilization about piezo technology at present.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiency of sterilization technology in the prior art and ultrasonic sterilization skills
The defect of art provides a kind of ultrasound-piezoelectricity Synergistic biocidal technology.The technology in addition to be related to ultrasonic wave itself cavitation sterilize other than,
Ultrasonic wave is further related to as receiving the excitation energy of minute-pressure electric material piezoelectricity chemical effect, excitation receives minute-pressure electric material for mechanical vibrational energy
It is converted into hole and the active oxygen radical of electrochemical energy and scene generation strong disinfecting, realizes ultrasonic wave-piezoelectric effect collaboration
The effect of sterilization.
The object of the present invention is to provide a kind of piezoelectricity to sterilize new technology.
It is a further object of the present invention to provide a kind of piezoelectricity sterilization materials.
Still a further object of the present invention is to provide a kind of ultrasound-piezoelectricity Synergistic biocidal technology.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
Receive minute-pressure electric material tetragonal phase BaTiO3、BaxY1-xTiO3、M@BaTiO3Or M@BaxY1-xTiO3In terms of sterilization
Using or preparing application in terms of fungicide, wherein Y Sr2+、Sn2+Or Ce4+Deng M Ag, Au, Pt or Pd etc..
The above-mentioned preparation method for receiving minute-pressure electricity sterilization material, includes the following steps:
S1. butyl titanate is slowly dripped to slowly to hydrolyze in acetic acid solution and obtains high-purity titanium hydroxide；
S2. by titanium hydroxide and Ba (OH)2·8H2O is added in NaOH solution, molten by gel after magnetic agitation is uniform
Glue method or hydrothermal synthesis method, which are prepared, receives micro- tetragonal phase BaTiO3。
Alternatively, further, step S2 is: by titanium hydroxide and Ba (OH)2·8H2After O is added in NaOH solution, then
Be added move peak agent after, then carry out magnetic agitation it is uniform after, Ba is prepared by sol-gel process or hydrothermal synthesis methodxY1- xTiO3, wherein Y Sr2+、Sn2+Or Ce4+Deng M Ag, Au, Pt or Pd etc.；The shifting peak agent is SrCl2、Sn(NO3)2、
SnCl2·2H2O、SnCl4、Ce(NO3)3·6H2O、(NH4)2Ce(NO3)6、CeCl3Or Ce (SO4)2·4H2O etc., wherein metal from
Son enters tetragonal phase BaTiO in synthesis process in a manner of adulterating3Lattice, keep its dielectric Curie peak mobile and moved to low temperature direction
It is dynamic, so as to improve its germicidal efficiency.
Preferably, the dosage for moving peak agent is according to following criterion calculation: being equivalent to the amount of Ti molar ratio 2%.
Furthermore it is preferred that the specific method of above-mentioned steps S1 is: butyl titanate is slowly dripped to the second of 0.5~2mol/L
In acid solution, at room temperature after 60~80h of magnetic agitation, it is centrifuged 5~20min with 3000~8000rpm/min, abandons supernatant；
Precipitating successively crosses 100~300 meshes with 50~70 DEG C of drying, grinding after ultrapure water, washes of absolute alcohol to neutrality, and hydrogen is made
Titanium oxide.
Preferably, the volume ratio of the butyl titanate and acetic acid solution is 1~2:10~20.
It is highly preferred that the concentration of the acetic acid solution is 1mol/L.
It is highly preferred that the time of the magnetic agitation at room temperature is 72h.
It is highly preferred that the centrifugation is 5000rpm/min centrifugation 10min.
It is highly preferred that the drying is 60 DEG C of drying.
It is highly preferred that the sieve is 200 meshes.
Preferably, titanium hydroxide described in step S2 and Ba (OH)2·8H2The ratio of O is according to molar ratio Ti:Ba=1~2:1
~2 calculate.
It is highly preferred that titanium hydroxide described in step S2 and Ba (OH)2·8H2The ratio of O is according to molar ratio Ti:Ba=1:1
It calculates.
Preferably, the concentration of NaOH solution described in step S2 is 0.2~0.3mol/L；Described in step S2 by titanium hydroxide and
Ba(OH)2·8H2The dosage of O is according to following criterion calculation: by titanium hydroxide and Ba (OH)2·8H2O is added to NaOH solution extremely
Its concentration is 0.05~0.07mol/L.
It is highly preferred that the concentration of NaOH solution described in step S2 is 0.25mol/L, it is described by titanium hydroxide and Ba
(OH)2·8H2The dosage of O is according to following criterion calculation: by titanium hydroxide and Ba (OH)2·8H2O be added to NaOH solution to its
Concentration is 0.06 mol/L.
Preferably, the specific method of hydrothermal synthesis method described in step S2 is: by titanium hydroxide and Ba (OH)2·8H2O is added
To NaOH solution, after magnetic agitation is uniform, it is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, in high-precision baking oven
In with 2~4 DEG C/min(be preferably 3 DEG C/min) heating rate rise to 180~220 DEG C of (preferably 200 DEG C) hydro-thermal reactions 60~
70h(is preferably 68h)；Be preferably again 3 DEG C/min with 2~4 DEG C/min() be cooled to room temperature after, with 3000~8000rpm/min
5~20min(of centrifugation is preferably 5000rpm/min centrifugation 10min), liquid is discarded supernatant, then precipitating is successively used into deionized water, nothing
It dries after water-ethanol is cleaned to neutrality, grinding, cross 100~300 meshes (preferably 200 mesh) for 50~70 DEG C (preferably 60 DEG C),
It is made and receives micro- tetragonal phase BaTiO3；
Or further, the specific method of the hydrothermal synthesis method is: by titanium hydroxide and Ba (OH)2·8H2O is added to
In NaOH solution, adds and move peak agent, after magnetic agitation is uniform, be transferred to the hydrothermal reaction kettle with polytetrafluoroethyllining lining
In, with 2~4 DEG C/min(it is preferably 3 DEG C/min in high-precision baking oven) heating rate rises to 180~220 DEG C (preferably 200
DEG C) 60~70h(of hydro-thermal reaction is preferably 68h)；Be preferably again 3 DEG C/min with 2~4 DEG C/min() be cooled to room temperature after, use
It is preferably 5000rpm/min centrifugation 10min that 3000~8000rpm/min, which is centrifuged 5~20min(), liquid is discarded supernatant, then will precipitating
It successively dried with 50~70 DEG C (preferably 60 DEG C) after deionized water, washes of absolute alcohol to neutrality, grinding, cross 100~300 mesh
It sieves (preferably 200 mesh), Ba is madexY1-xTiO3。
In addition, further, by BaTiO made from step S23Or BaxY1-xTiO3It is mixed with containing class by the solution of argentum reagent
It closes, and by means such as UV illumination, can be prepared by M@BaTiO3Or M@BaxY1-xTiO3(tetragonal phase BaTiO3Composite piezoelectric material
Material)；The class is AgNO by argentum reagent3、HAuCl4、K2(PtCl4) or PdCl2Deng, metal ion therein by photocatalysis also
Former or electronation generates nano-noble metal simple substance, in tetragonal phase BaTiO3Surface forms the micro- bath of electronics, accelerates hole and pressure causes
The separation of electronics can strengthen its germicidal efficiency.
Specifically by BaTiO made from step S23Or BaxY1-xTiO3It is mixed with containing class by the solution of argentum reagent, in light
10~20min(of magnetic agitation is preferably 15min under non-illuminated conditions in chemical reactor) after, with 300W Hg lamp irradiation 30min
(preferably 300W Hg lamp irradiation 30min)；Being centrifuged 5~20min(with 3000~8000rpm/min later is preferably 5000rpm/
Min is centrifuged 10min), discard supernatant liquid, then will precipitating successively with deionized water, washes of absolute alcohol for several times after 50~70 DEG C it is (excellent
It is selected as 60 DEG C) drying, and grind, cross 100~300 meshes (preferably 200 mesh), M@BaTiO is made3Or M@BaxY1-xTiO3。
Preferably, the class is calculated by the dosage of argentum reagent according to following standard: by silver content and BaTiO3Mole
Than for 1:10000.
It is highly preferred that it is described containing class by the concentration of the solution of argentum reagent be 0.2mol/L, it is described containing class by the molten of argentum reagent
The dosage of liquid is 25mL.
In addition, the above method be prepared receive minute-pressure electric material tetragonal phase BaTiO3、BaxY1-xTiO3、M@BaTiO3Or
M@BaxY1-xTiO3, also all within protection scope of the present invention.
A kind of ultrasound-piezoelectricity Synergistic biocidal technology is that above-mentioned minute-pressure electric material of receiving is added in solution to be processed, magnetic force
Stir the preferred 30min of 20~40min(), after reaching adsorption equilibrium, place under Ultrasonic Conditions that (such as low-frequency ultrasonic waves are clear
Wash in device) carry out ultrasound-piezoelectricity sterilization.
By taking the water containing E. coli as an example, these are received into micro- piezo-electric material powder and is added to containing Escherichia coli
In E.coli water, 30 min of magnetic agitation after reaching adsorption equilibrium, is placed into low-frequency ultrasonic waves washer and is surpassed
Clean aqua sterilisa can be obtained in sound-piezoelectricity sterilization, filtering.
The present invention is prepared using the methods of hydrothermal synthesis and sol-gel receives the tetragonal phase BaTiO of particle diameter3Piezoelectricity
Material, and compound tetragonal phase BaTiO is obtained by means such as silver by additional shifting peak agent and class3Efficient piezoelectricity sterilization material.These
Nano-micro structure piezoelectric material generates hole and electronics with regard to deformation occurs under lesser mechanical force, this pressure causes hole to have oxygen
The property changed, pressure, which sends a telegraph son, has reducing；These pressure cause holes can direct oxidation sterilization, can also be catalyzed H2O is decomposed to generate and be killed
The active oxygen radical of bacterium；It, which is pressed, sends a telegraph son and may also restore oxygen in water and generate a series of active oxygens with bactericidal activity
Substance, they include O2 -With OH etc..Meanwhile the ultrasonic wave as nano-micro structure piezoelectric material conventional machinery vibration source is also
A kind of new sterilization means, therefore, the two combination can play the effect of Synergistic biocidal.Simultaneously by moving peak and class by means such as silver
Further increase the efficiency of its Synergistic biocidal.
The invention has the following advantages:
The invention discloses a kind of ultrasound-piezoelectricity Synergistic biocidal technologies, and the technology is in addition to the cavitation using ultrasonic wave itself
Effect sterilization is outer, also excites BaTiO using it3、BaxY1-xTiO3、M@BaTiO3Or M@BaxY1-xTiO3Etc. receiving minute-pressure electric material
(wherein Y is Sr2+、Sn2+And Ce4+Deng M Ag, Au, Pt and Pd etc., they strengthen piezoelectricity by the effects of silver by moving peak and class
Germicidal efficiency) generate hole and active oxygen radical Synergistic biocidal.
In addition, the present invention using simple piezoelectric material and composite piezoelectric material can be converted mechanical energy to and effectively be sterilized
Chemical energy can dramatically increase the efficiency of ultrasonic sterilization, and it is mechanical also natural environment low-frequency vibration can be widely present in using other
In energy, such as: water flow, water is folded to be fallen, air flowing is sterilized, and is a kind of environmentally protective sterilization technology.
Detailed description of the invention
Fig. 1 is ultrasound-piezoelectricity collaboration processing sterilization front and back E.coli thallus SEM figure.
Specific embodiment
The present invention is further illustrated below in conjunction with Figure of description and specific embodiment, but embodiment is not to the present invention
It limits in any form.Unless stated otherwise, the present invention uses reagent, method and apparatus routinely try for the art
Agent, method and apparatus.
Unless stated otherwise, agents useful for same and material of the present invention are commercially available.
Embodiment 1
40 ml butyl titanates are taken slowly to drip in the acetic acid solution of 400 ml 1mol/L, at room temperature magnetic agitation 72h
Afterwards, 10 min are centrifuged with 5000 rpm/min.Liquid is discarded supernatant, precipitating is successively used into ultrapure water, washes of absolute alcohol to neutrality
200 meshes are crossed in 60 DEG C of drying afterwards, grinding, and titanium hydroxide is made.
Take this titanium hydroxide and Ba (OH)2·8H2To be added to 0.25 mol/L NaOH molten by Ti:Ba=1:1 in molar ratio by O
Liquid to its concentration is 0.06 mol/L, after magnetic agitation is uniform, is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining,
With 3 DEG C/min heating rate to 200 DEG C of 68 h of hydro-thermal reaction in high-precision baking oven.Room temperature is cooled to 3 DEG C/min again
Afterwards, 10 min are centrifuged with 5000 rpm/min, discard supernatant liquid, then precipitating is successively used into deionized water, washes of absolute alcohol extremely
It dries after neutrality, grinding, cross 200 meshes for 60 DEG C, tetragonal phase BaTiO is made3。
The tetragonal phase BaTiO3It can be used as piezoelectric material and be applied to sterilization.
Embodiment 2
50 ml butyl titanates are taken slowly to drip in the acetic acid solution of 500 ml 1mol/L, at room temperature magnetic agitation 72h
Afterwards, 10min is centrifuged with 5000 rpm/min.Liquid is discarded supernatant, by precipitating successively with after ultrapure water, washes of absolute alcohol to neutrality
200 meshes are crossed in 60 DEG C of drying, grinding, and titanium hydroxide is made.
Take this titanium hydroxide and Ba (OH)2·8H2Ti:Ba=1:1 is added to 0.25mol/L NaOH solution to O in molar ratio
It is 0.06 mol/L to its concentration, adds the SnCl for being equivalent to Ti molar ratio 2%2·2H2O, after magnetic agitation is uniform, transfer
Into the hydrothermal reaction kettle with polytetrafluoroethyllining lining, with 3 DEG C/min heating rate to 200 DEG C of hydro-thermals in high-precision baking oven
React 68h.After being cooled to room temperature again with 3 DEG C/min, be centrifuged 10min with 5000 rpm/min, discard supernatant liquid, then will precipitating according to
It is secondary to be dried with 60 DEG C after deionized water, washes of absolute alcohol to neutrality, grinding, cross 200 meshes, Ba is made0.97Sn0.3TiO3。
The Ba0.97Sn0.3TiO3It can be used as piezoelectric material and be applied to sterilization.
Embodiment 3
60 ml butyl titanates are taken slowly to drip in the acetic acid solution of 600 ml 1mol/L, at room temperature 72 h of magnetic agitation
Afterwards, 10 min are centrifuged with 5000 rpm/min.Liquid is discarded supernatant, precipitating is successively used into ultrapure water, washes of absolute alcohol to neutrality
200 meshes are crossed in 60 DEG C of drying afterwards, grinding, and titanium hydroxide is made.
Take this titanium hydroxide and Ba (OH)2·8H2Ti:Ba=1:1 is added to 0.25mol/L NaOH solution extremely to O in molar ratio
Its concentration is 0.06 mol/L, after magnetic agitation is uniform, is transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining, in height
With 3 DEG C/min heating rate to 200 DEG C of 68 h of hydro-thermal reaction in precision baking oven.After being cooled to room temperature again with 3 DEG C/min, use
5000 rpm/min are centrifuged 10 min, discard supernatant liquid, then will precipitate successively with after deionized water, washes of absolute alcohol to neutrality
60 DEG C of drying, cross 200 meshes at grinding, and tetragonal phase BaTiO is made3。
Tetragonal-phase barium titanate (the BaTiO that will be prepared3) mixed with the silver nitrate solution of 25ml 0.2mol/L, photochemical
In reactor under non-illuminated conditions after 15 min of magnetic agitation, with 300 W Hg lamp irradiation, 30 min.Later with 5000 rpm/
Min is centrifuged 10 min, discards supernatant liquid, then precipitating is successively used the rear 60 DEG C of drying for several times of deionized water, washes of absolute alcohol,
And grind, cross 200 meshes, class is made by the piezoelectric material Ag@BaTiO of silver3, wherein by silver content and BaTiO3Molar ratio be 1:
104。
The class is by the piezoelectric material Ag@BaTiO of silver3It can be used as piezoelectric material and be applied to sterilization.
Embodiment 4
40 ml butyl titanates are taken slowly to drip in the acetic acid solution of 400 ml 1mol/L, at room temperature 72 h of magnetic agitation
Afterwards, 10 min are centrifuged with 5000 rpm/min.Liquid is discarded supernatant, precipitating is successively used into ultrapure water, washes of absolute alcohol to neutrality
200 meshes are crossed in 60 DEG C of drying afterwards, grinding, and titanium hydroxide is made.
Take this titanium hydroxide and Ba (OH)2·8H2Ti:Ba=1:1 is added to 0.25mol/L NaOH solution extremely to O in molar ratio
Its concentration is 0.06 mol/L, adds the SnCl for being equivalent to Ti molar ratio 2%2·2H2O after magnetic agitation is uniform, is transferred to tool
Have in the hydrothermal reaction kettle of polytetrafluoroethyllining lining, it is anti-to 200 DEG C of hydro-thermals with 3 DEG C/min heating rate in high-precision baking oven
Answer 68 h.After being cooled to room temperature again with 3 DEG C/min, 10 min are centrifuged with 5000 rpm/min, discard supernatant liquid, then will precipitating
It successively dried with 60 DEG C after deionized water, washes of absolute alcohol to neutrality, grinding, cross 200 meshes, Ba is made0.97Sn0.3TiO3。
The Ba that will be prepared0.97Sn0.3TiO3It is mixed with the silver nitrate solution of 25ml 0.2mol/L, in photochemical reactor
Under middle non-illuminated conditions after 15 min of magnetic agitation, with 300 W Hg lamp irradiation, 30 min.It is centrifuged later with 5000 rpm/min
10 min discard supernatant liquid, then precipitating are successively dried for latter 60 DEG C with deionized water, washes of absolute alcohol for several times, and grinds, mistake
Class is made by the piezoelectric material Ag@Ba of silver in 200 meshes0.97Sn0.3TiO3, wherein by silver content and Ba0.97Sn0.3TiO3Mole
Than for 1:104。
The Ag/Ba0.97Sn0.3TiO3It can be used as piezoelectric material and be applied to sterilization.
Embodiment 5
1, these piezo-electric material powders prepared by Examples 1 to 4 are added separately to 20ml containing E.coli is about 107~108
In the water of cfu/ml, piezoelectric material dosage is 2g/L, and magnetic agitation 30min after reaching adsorption equilibrium, is placed into
Ultrasound-piezoelectricity is carried out in 100W, 40kHz Ultrasound Instrument sterilizes 180min.
Meanwhile measuring the sterilization of the sterilizing rate of independent ultrasonic wave and these piezoelectric materials of the preparation of separate embodiments 1 ~ 4
Rate.
2, the results are shown in Table 1.
Table 1
The results show that tetragonal phase BaTiO prepared by embodiment 13Sterilizing rate is 2.72 lg, is higher than independent ultrasonic sterilization rate
(0.70 lg) and independent BaTiO30.30 lg of sterilizing rate shows stronger Synergistic biocidal effect.
Ba prepared by embodiment 20.97Sn0.3TiO3Sterilizing rate is 2.98 lg, is higher than independent ultrasonic sterilization rate (0.70 lg)
With independent Ba0.97Sn0.3TiO30.45 lg of sterilizing rate shows stronger Synergistic biocidal effect.
Ag@BaTiO prepared by embodiment 33Sterilizing rate be 3.35 lg, be higher than independent ultrasonic sterilization rate (0.70 lg) and
Independent Ag@BaTiO31.19 lg of sterilizing rate shows strong Synergistic biocidal effect.
Ag/Ba prepared by embodiment 40.97Sn0.3TiO3Sterilizing rate is 3.55 lg, is higher than independent ultrasonic sterilization rate (0.70
) and independent Ag/Ba lg0.97Sn0.3TiO31.22 lg of sterilizing rate shows strong Synergistic biocidal effect.
In addition, the above results are also shown using shifting peak agent and class by argentum reagent to tetragonal phase BaTiO3It is handled,
Its bactericidal effect can significantly be strengthened.
3, after SEM photograph shows the processing of ultrasound-piezoelectricity collaboration, E.coli thallus by destruction very serious, cell wall,
The structure of cell membrane is no longer complete, occurs being broken and notch, can not protect to somatic cells, thus it is speculated that its sterilization mechanism is main
It is the damage (as shown in Fig. 1) to cell wall and cell membrane.
Claims (9)
1. receiving minute-pressure electric material tetragonal phase BaTiO3、BaxY1-xTiO3、M@BaTiO3Or M@BaxY1-xTiO3Answering in terms of sterilization
With or preparing application in terms of fungicide, which is characterized in that wherein, Y Sr2+、Sn2+Or Ce4+, M Ag, Au, Pt or Pd.
2. a kind of preparation method for receiving minute-pressure electricity sterilization material, which comprises the steps of:
S1. butyl titanate is slowly dripped to slowly to hydrolyze in acetic acid solution and obtains titanium hydroxide；
S2. by titanium hydroxide and Ba (OH)2·8H2O is added in NaOH solution, after magnetic agitation is uniform, passes through sol-gel process
Or hydrothermal synthesis method is prepared and receives micro- tetragonal phase BaTiO3；
Or further, step S2 is: by titanium hydroxide and Ba (OH)2·8H2After O is added in NaOH solution, shifting peak is added
After agent, then carry out magnetic agitation it is uniform after, Ba is prepared by sol-gel process or hydrothermal synthesis methodxY1-xTiO3；
S3. further, by BaTiO made from step S23Or BaxY1-xTiO3With containing being mixed by the solution of silver-colored similar reagents, and
By UV illumination, M@BaTiO is made3Or M@BaxY1-xTiO3；It is described by silver-colored similar reagents be AgNO3、HAuCl4、K2(PtCl4)
Or PdCl2；
Wherein, Y Sr2+、Sn2+Or Ce4+, M Ag, Au, Pt or Pd；The shifting peak agent is SrCl2、Sn(NO3)2、SnCl2·
2H2O、SnCl4、Ce(NO3)3·6H2O、(NH4)2Ce(NO3)6、CeCl3Or Ce (SO4)2·4H2O。
3. preparation method according to claim 2, which is characterized in that the specific method of step S1 is: butyl titanate is delayed
Slowly drip in the acetic acid solution of 0.5~2mol/L, at room temperature after 60~80h of magnetic agitation, with 3000~8000rpm/min from
5~20min of the heart abandons supernatant；Precipitating is successively with 50~70 DEG C of drying, grinding, mistake after ultrapure water, washes of absolute alcohol to neutrality
Titanium hydroxide is made in 100~300 meshes.
4. preparation method according to claim 2, which is characterized in that titanium hydroxide described in step S2 and Ba (OH)2·8H2O
Ratio according to molar ratio Ti:Ba=1~2:1~2 calculate.
5. preparation method according to claim 2, which is characterized in that the concentration of NaOH solution described in step S2 be 0.2~
0.3mol/L；By titanium hydroxide and Ba (OH) described in step S22·8H2The dosage of O is according to following criterion calculation: by titanium hydroxide
With Ba (OH)2·8H2It is 0.05~0.07mol/L that O, which is added to NaOH solution to its concentration,.
6. preparation method according to claim 2, which is characterized in that the specific method of hydrothermal synthesis method described in step S2
It is: by titanium hydroxide and Ba (OH)2·8H2O is added to NaOH solution, after magnetic agitation is uniform, is transferred to polytetrafluoroethylene (PTFE)
In the hydrothermal reaction kettle of liner, 180~220 DEG C of hydro-thermal reactions 60 are risen to 2~4 DEG C/min heating rate in high-precision baking oven
~70h；After being cooled to room temperature again with 2~4 DEG C/min, it is centrifuged 5~20min with 3000~8000rpm/min, discards supernatant liquid,
Precipitating is successively dried with 50~70 DEG C after deionized water, washes of absolute alcohol to neutrality, grinding, crosses 100~300 meshes again,
It is made and receives micro- tetragonal phase BaTiO3；
Or further, the specific method of the hydrothermal synthesis method is: by titanium hydroxide and Ba (OH)2·8H2O is added to NaOH
In solution, adds and move peak agent, after magnetic agitation is uniform, be transferred in the hydrothermal reaction kettle with polytetrafluoroethyllining lining,
180~220 DEG C of 60~70h of hydro-thermal reaction are risen to 2~4 DEG C/min heating rate in high-precision baking oven；Again with 2~4 DEG C/min
After being cooled to room temperature, it is centrifuged 5~20min with 3000~8000rpm/min, discards supernatant liquid, then precipitating is successively used into deionization
It dries after water, washes of absolute alcohol to neutrality, grinding, cross 100~300 meshes for 50~70 DEG C, Ba is madexY1-xTiO3。
7. preparation method according to claim 2, which is characterized in that specific method is by BaTiO made from step S23Or
BaxY1-xTiO3With containing being mixed by the solution of silver-colored similar reagents, in photochemical reactor magnetic agitation 10 under non-illuminated conditions~
After 20min, with 300W Hg lamp irradiation 30min；It is centrifuged 5~20min with 3000~8000rpm/min later, discards supernatant liquid,
Precipitating is successively dried for latter 50~70 DEG C with deionized water, washes of absolute alcohol for several times again, and grinds, cross 100~300 meshes,
M@BaTiO is made3Or M@BaxY1-xTiO3。
What 8. any the method for claim 2~7 was prepared receive minute-pressure electric material tetragonal phase BaTiO3、BaxY1-xTiO3、M@
BaTiO3Or M@BaxY1-xTiO3。
9. a kind of ultrasound-piezoelectricity Synergistic biocidal technology, which is characterized in that be will be received described in claim 8 minute-pressure electric material addition
Into solution to be processed, 20~40min of magnetic agitation after reaching adsorption equilibrium, is placed under Ultrasonic Conditions and is surpassed
Sound-piezoelectricity sterilization.
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