CN109380304A - A kind of oxide-based nanomaterial of anti-plant decay disease, preparation method and applications - Google Patents
A kind of oxide-based nanomaterial of anti-plant decay disease, preparation method and applications Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- A—HUMAN NECESSITIES
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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Abstract
A kind of oxide-based nanomaterial of anti-plant decay disease, preparation method and applications, belong to technical field of nano material.The preparation and application that the present invention provides a kind of using nanoparticles such as antimony-doped tin oxide (ATO), indium doping tin oxide (ITO), aluminium-doped zinc oxide (AZO), the indium doping cadmium oxides (ICO) modified through mercaptopyridine as antibacterial agent, this kind of material the surface of nanoparticle generate it is close, in infrared plasmon resonance phenomenon.The present invention is synthesized and has studied a kind of novel inorganic antimicrobial agent and modified using nanoparticles such as ATO, ITO, AZO, ICO as main component through mercaptopyridine, and other auxiliary agents are added, and novel anti-rot sick medicament is made using nanostructure characteristic.The present invention is based on plasmon resonance mechanism, it can be achieved that long term sterilizing resistant effect.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to it is a kind of it is through mercaptopyridine modification, have in infrared region
The oxide-based nanomaterial of the anti-plant decay disease of plasmon resonance property, preparation method and applications.
Background technique
The rot disease of plant is always to perplex a kind of common disease of peasant.Rot disease is also known as decay, bark rot, is fruit tree
A kind of common disease that class plant pole is also easy to produce, there is generation all over the world.
The fungi and bacterium that rot disease is mainly carried by several hundred kinds by soil cause, and it is corrupt to be characterized in that plant is disintegrated.It is rotten
It is can be hard, dry, spongiform or more water, congee gruel shape or stickiness.For root-rot caused by many fungies, root-rot is rotten simultaneously
It is covered with the black threadiness beam of mould layer.Foxiness is also to be invaded timber caused by fungi and often change colour or colour, soft corruption is frangible
It or is in powder mustiness.Rot disease ordinary loss is slow, often through for many years.It infects and nearly all occurs through wound.The shape of a hoof and layer frame shape
Entity is developed along limb, or forms bacterium gill fungus in butt or wound.Early stage is not easy to identify from appearance, raises limb
Epidermis, can see crineous to bronzing moisten stigma or isabelline dry spot, sometimes, internal lesion area is
It is larger but still not easy to identify from outside.Cortex is easily detached from after lesion, and rotten cortex is in bronzing, and there is vinasse taste in when web rot shape.
It falls ill the later period, sick portion's dehydration drying shrinkage becomes dark brown and sink, and generates dark brown dot grain, i.e. point of germ in top
Raw spore device, becomes the infection sources of recurrence.
Rot disease main harm limb fructiferous, treelet and nursery stock may also be encroached on, but it is less to fall ill.Because of morbidity
It is difficult to early period discover, so preventing and controlling are difficult to carry out.
It is existing prevention and treatment plant decay disease method spray insecticide antibiotic and sterilizing, rationally control plant spacing, cut in time
It cuts down morbidity limb, no matter any all time-consuming consumptive material and can not eradicate.The use of antimicrobial agent is to realize prevention and treatment plant decay
One of sick most efficient method.By adding the antibacterial agent that there are antibacterial functions and can be stabilized in a solvent, through certain work
After skill processing, the medicament with antibacterial and sterilizing function is made, it is not only free from environmental pollution, but also antibiotic and sterilizing can be kept for a long time
Effect.
Current main sterilization material can be divided into inorganic sterilization material and organic bactericide material.Due to consideration that environment and
Tissue safety has no toxic side effect and the problem of biocompatibility, inorganic sterilization material is relatively limited.Inorganic sterilization material
Metal ion type (silver, copper, zinc etc.) and oxide photocatalyst-type (titanium dioxide, zinc oxide, magnesia etc.) can be divided into, made
After nanoscale, specific surface area increases, and can preferably adsorb microorganism with good antibacterial effect.Metal ion type is inorganic
It is typically bactericidal nano-silver material in sterilization material, after the advantage is that thallus inactivation, Ag ion and therefrom separate out, weight
Multiple sterilization, effect is lasting, that is, has long-term effect.Be disadvantageous in that be easy discoloration and it is at high cost.The antibacterial effect light of Ag ion
Very big with the influence of heat, unstable, long-time service is easy to be reduced and reduce antibacterial effect.Oxide photocatalyst-type mainly with
TiO2To represent, it the advantage is that its chemical property is stable, anti-microbial property is wide, acid and alkali-resistance, nontoxic, raw material sources are abundant.Disadvantage
It is to be difficult to settle, is not easily recycled.More representational a few class organic bactericides are chitosan, flavone compound, antibiotic, season
Ammonium (phosphorus) salt and macromolecular bactericide.Its advantage is that good biocompatibility, at low cost, and it is nontoxic, there is good anti-microbial property.
The disadvantage is that poorly water-soluble, it is highly difficult to use it as additive, needs acidic environment.
In order to overcome existing antibacterial agent to be applied to the disadvantage in the prevention and treatment of plant decay disease, sight is now focused on into novel inorganic
Antibacterial agent makes it have outstanding advantage in all various aspects such as persistence, broad spectrum antibacterial and fast light heat resistance.
This patent has researched and developed a kind of novel inorganic antiseptic, includes the antimony-doped tin oxide modified through mercaptopyridine
(ATO), indium doping tin oxide (ITO), aluminium-doped zinc oxide (AZO), indium doping cadmium oxide (ICO) etc. have infrared phasmon
The nano material of resonance characteristics plays plant decay disease using infrared plasmon resonance characteristic and effectively prevents.
These materials have low cost of material, processing easy to produce, broad-spectrum antibacterial property height, light shine, few photoetch etc. excellent
Point.The experimental results showed that such anti-biotic material is with the mediation of infrared plasmon resonance characteristic or combination mercaptopyridine molecule
For Antibacterial Mechanism, inhibit spore germination and hyphal development.Currently, there is no relevant commodity circulation and reported literatures in the market.
Summary of the invention
Morbidity germ and environmental requirement for plant decay disease, the present invention provides a kind of to modify through mercaptopyridine
The nanometers such as antimony-doped tin oxide (ATO), indium doping tin oxide (ITO), aluminium-doped zinc oxide (AZO), indium doping cadmium oxide (ICO)
Preparation and application of the particle as antibacterial agent, this kind of material the surface of nanoparticle generate it is close, in infrared phasmon
Covibration.The present invention synthesizes and has studied a kind of novel inorganic antimicrobial agent, is with nanoparticles such as ATO, ITO, AZO, ICO
Main component is modified through mercaptopyridine, and other auxiliary agents are added, and novel anti-rot sick medicament is made using nanostructure characteristic, grinds
Study carefully the inhibiting effect after it is applied to plant decay disease.
For most of fungies, main Antibacterial Mechanism is to destroy cell tissue to inhibit germ sprouting and hyphal development.This
Class anti-biotic material Antibacterial Mechanism are as follows: due to the special level structure of nano material, under sunlight irradiation, ATO, ITO, AZO,
The nanoparticle surfaces such as ICO generate infrared plasmon resonance phenomenon, using the conversion of infrared light plasmon resonance energy, lead to
The protein for crossing the numerator mediated conversion of mercaptopyridine or directly conversion, generated energy and fungal cell and its spore is made
With, make cell cortex protein, lipid etc. and be activated, aoxidize and even destroy, further destroy its internal structure, while also inhibiting
Mycelium germination and growth, to reach antibacterial action.Meanwhile this kind of nano material has great specific surface area, is easier to and disease
The contact of bacterium occurrence of large-area is also conducive to clear up it.
The mass fraction of nanoparticle and germ action time are to antibacterial in the doping level of nanoparticle, antimicrobial agent
Rate has apparent influence.We by antimony-doped tin oxide (ATO), indium doping tin oxide (ITO), aluminium-doped zinc oxide (AZO),
The doping level of the synthetic method control nanoparticle of the nanoparticles powders such as indium doping cadmium oxide (ICO), by the way that sulfydryl pyrrole is added
Pyridine modifies nanoparticle powder to enhance anti-plant decay disease effect, and obtained nano-powder is distributed to specific organic solvent
In, the nanoparticle antimicrobial agent for anti-plant decay disease is made, and other auxiliary components are added and improve nanoparticle antibacterial
The stability and effect of medicament in the environment.
The present invention synthesizes the antimony-doped tin oxide modified through mercaptopyridine with small particle by short-cut method
(ATO), the nanoparticles such as indium doping tin oxide (ITO), aluminium-doped zinc oxide (AZO), indium doping cadmium oxide (ICO), further
Disperse and auxiliary agent be added that antimicrobial agent is made in specific solvent.
Method of the present invention includes two steps, respectively nanoparticle preparation, the preparation of antimicrobial agent;Specifically such as
Under:
One, nanoparticle prepare (by ATO nanoparticle preparation for, the preparation of other nanoparticles need to only change metal
Element raw material)
Method 1, using hydrothermal synthesis method, steps are as follows:
(1) by total mole number be 0.1 mole soluble tin source and soluble antimony source by different ratio (soluble tin source with
Soluble antimony source is not zero, and soluble antimony source is potassium antimony tartrate, antimony chloride, nitric acid antimony etc., and further, antimony source mole is mixed
Miscellaneous amount is 5~25%) it is mixed to join in 0.8~1.2L deionized water, 1mol/L sodium hydroxide solution is added and adjusts pH 9.8
~10.2, it is uniformly mixed;
(2) clear solution uniformly mixed obtained by step (1) is warming up to 20~30h of heating at 180~220 DEG C, obtained
Black precipitate;
(3) reaction solution that step (2) obtains is cooled to room temperature, centrifuged pellet with ethanol washing 3~5 times,
It is dried in vacuo 40~60h at 50~80 DEG C, obtains the ATO nano-powder of different doping ratios, particle diameter is 10~20nm;
(4) the ATO nano-powder and 10 for obtaining step (3)-3The 4-MPY solution of M mixes, and is obtained after centrifugation through sulfydryl pyrrole
The ATO nano-powder of pyridine modification;The ATO powder of 1g uses 0.8~1.2L, 10-3The 4-MPY solution of M;
Method 2, combustion synthesis method, steps are as follows:
(1) by total mole number be 0.1 mole soluble tin source and soluble antimony source by different ratio (soluble tin source with
Soluble antimony source is not zero, and soluble antimony source is potassium antimony tartrate, antimony chloride, nitric acid antimony etc., and further, antimony source mole is mixed
Miscellaneous amount is 5~25%) it is added in 0.8~1.2L deionized water with 0.08~0.1L nitric acid, 0.08~0.1L citric acid, it mixes
Uniformly, uniformly mixed solution is obtained;
(2) 25% ammonia spirit of mass fraction is added into the obtained uniformly mixed solution of step (1), adjusts pH and exists
6.8~7.2;
(3) solution that step (2) obtains is calorified and is dried at 80~120 DEG C, obtain white colloidal;
(4) white colloidal that step (3) obtains is put into 260~360 DEG C of 10~15h of heat treatment in an oven, then 500
10~15 are calcined at~700 DEG C, obtains the ATO nano-powder of different doping ratios, and particle diameter is 10~20nm;
(5) the ATO nano-powder and 10 for obtaining step (4)-3The 4-MPY solution of M mixes, and is obtained after centrifugation through sulfydryl pyrrole
The ATO nano-powder of pyridine modification;The ATO powder of 1g uses 0.8~1.2L, 10-3The 4-MPY solution of M;
Method 1,2 obtained ATO nano-powders, are used equally for the preparation of antimicrobial agent.
Two, the preparation of antimicrobial agent
Using methylated vegetable oil as solvent, synthetic method are as follows: 230~250g vegetable oil is (including cottonseed oil, rape oil, big
Palm oil) and 4.8~5.2L sodium hydroxide methanol solution (sodium hydroxide mass fraction be 10%) mixing, at 30~50 DEG C
0.5~1h is kept, methylated vegetable oil is obtained;Obtained methylated vegetable oil, diethyl aminoethyl hexanoate (it is limited to be joined into chemical products in Zhengzhou
The diethylamino ethanol caproate DA-6 of company) 0.3~0.5g, dispersing agent (alkylnaphthalene sulfonate, including Negel
Salt, alkyl naphthalene sulfonic acid ammonium salt) 0.5~0.7g, sticker (improve the flushing of resistance to rainwater, improve lasting effect, it is mineral oil, gelatin, poly-
Vinyl alcohol etc.) 0.5~0.7g, (a kind of common coating additive for inhibiting foam to generate, selects Degussa Digao to defoaming agent
3062 defoaming agent of Foamex) the ATO nano-powder 12 obtained modified through mercaptopyridine in 0.4~0.6g and step (1)
~15g mixing, obtains mixed solution;After low speed disperses 2~5h, ATO nano-antibacterial medicament is obtained.
In the present invention, made using antimony-doped tin oxide (ATO) the plasmon resonance nano material modified through mercaptopyridine
For the application of anti-plant decay disease medicament, innovative significance are as follows: (1) develop novel pin to plant decay disease inorganic antibacterial material,
Numerator mediated based on plasmon resonance mechanism and surface modification, the phasmon that nanoparticle generates under sunlight irradiation is total
The energy damages Fungal Protein that shakes is synthesized and its is acted on, destruction fungi structure, inhibition fungi sprouts and hyphal development, to sterilize
It is disease-resistant;(2) based on plasmon resonance mechanism, it can be achieved that long term sterilizing resistant effect;(3) cost of material is low, is easy preparation, right
Environmental hazard is small, is conducive to mass production and Technique Popularizing.
Detailed description of the invention
Fig. 1: fruit tree putrefaction disease morbidity schematic diagram (a), (b).
Powder x-ray diffraction (XRD) figure of Fig. 2: ATO nanoparticle.Wherein, ATO nanoparticle is by hydro-thermal method and burning
Method is synthetically prepared, and antimony mole doping is than being respectively 5%, 10%, 15%, 20% and 25%.
Fig. 3: the made medicament (a) of ATO nanoparticle without mercaptopyridine modification and the ATO nanometer through mercaptopyridine modification
The antibiotic rate effect contrast figure of the made medicament (b) of particle (uses germ in culture medium after two kinds of ATO nanoparticle antimicrobial agents
Survival condition.Germ is Valsa mali Miyabe et Yamada, obtains from apple tree canker morbidity place, cultivates under room temperature at 25 DEG C
And tested).The result shows that: the ATO nanoparticle antibiotic rate modified through mercaptopyridine is higher, up to 99%.
The relational graph of mass fraction and antibiotic rate of Fig. 4: the ATO nanoparticle in antimicrobial agent.The result shows that: with
The continuous raising of mass fraction of the ATO nanoparticle in antimicrobial agent, antibacterial take the lead in quickly increasing, then gradually steady,
The antibiotic rate of ATO nanoparticle antimicrobial agent and its mass fraction in a medicament be not in a linear relationship;ATO nanoparticle is anti-
When mass fraction in bacterium medicament reaches 10%, ATO nanoparticle antimicrobial agent has embodied good antibiotic property.
The relational graph of Fig. 5: ATO nanoparticle antimicrobial agent and bacterium colony action time and antibiotic rate.The result shows that: with work
It is significantly improved with the antibiotic rate of the increase of time, ATO nanoparticle antimicrobial agent, saturation is reached after 12 hours.
Fig. 6: the infrared absorpting light spectra (a) and 12 hours antibacterials of its antimicrobial agent of the ATO nanoparticle of difference doping ratio
Rate curve (b).The result shows that: the surface plasmon resonance (LSPR) of the ATO nanoparticle of 5% mole of doping ratio in figure (a)
Property is poor, and the resonance energy of generation is lower, and antimicrobial agent antibiotic rate made from it is lower, such as schemes (b), mole doping ratio
Reach 10%, nanoparticle has excellent LSPR property, and the antibiotic rate of antimicrobial agent also improves, and a mole doping ratio continues to increase
Greatly, LSPR property and antibiotic rate are maintained.
Specific embodiment
Below with reference to embodiment, the invention will be further elaborated, rather than limits the invention.
Embodiment 1
A kind of infrared plasmon resonance nano material anti-plant decay disease effect and application, about ATO nanoparticle
Application of sub- antimicrobial agent and preparation method thereof, the preparation of preparation, antimicrobial agent comprising ATO nanoparticle.It is specific as follows:
(1) preparation of ATO nanoparticle:
(1) 0.095mol sodium stannate and 0.005mol potassium antimony tartrate are accurately weighed with balance, is added to 1L deionized water
In, it is uniformly mixed, it is 10 that 1mol/L sodium hydroxide solution, which is added, and adjusts pH;
(2) mixed solution is obtained into black precipitate as heating for 24 hours at 200 DEG C;
(3) system is cooled to room temperature, the precipitating obtained after centrifugation is put into vacuum oven, 60 with ethanol washing 4 times
Dry 50h, obtains the ATO nano-powder 13g of 5% mole of Sb doped at DEG C;
(4) by obtained ATO nano-powder 13g and 13L, 10-3The 4-MPY solution of M mixes, and shakes 12h, and centrifuge washing is dry
It is dry, obtain the ATO nano-powder 13g modified through mercaptopyridine.
(2) preparation of antimicrobial agent:
By 250g vegetable oil (cottonseed oil) and 5L sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%)
Mixing, keeps 1h at 40 DEG C, obtains methylated vegetable oil.Obtained methylated vegetable oil, diethyl aminoethyl hexanoate (are joined into chemical industry in Zhengzhou
The diethylamino ethanol caproate DA-6 of Products Co., Ltd) 0.3g, dispersing agent (dodecyl sodium naphthalene sulfonate) 0.5g, sticker
(a kind of common coating additive for inhibiting foam to generate, selects the Foamex of Degussa Digao for (mineral oil) 0.5g, defoaming agent
3062 defoaming agents) ATO nano-powder 13g mixing obtained in 0.4g and step (1), obtain antimicrobial agent.
The characterization of ATO nanoparticle antimicrobial agent includes optical characteristics, the characterization of crystal structure and antibiotic property, specifically such as
Under:
Powder x-ray diffraction (XRD) figure of ATO nanoparticle is as shown in Figure 2.Wherein, ATO nanoparticle by hydro-thermal method with
Combustion synthesis preparation, antimony mole doping is than being respectively 5%, 10%, 15%, 20% and 25%.
Medicament caused by ATO nanoparticle without mercaptopyridine modification and the ATO nanoparticle institute modified through mercaptopyridine
The antibiotic rate effect contrast figure of pharmacy agent (uses germ survival condition in culture medium after ATO nanoparticle antimicrobial agent.Germ
For Valsa mali Miyabe et Yamada, obtained from apple tree canker morbidity place, cultivate and tested under room temperature at 25 DEG C) by
Shown in Fig. 3.The result shows that: the ATO nanoparticle antibiotic rate modified through mercaptopyridine is higher, up to 99%.
The relational graph of mass fraction and antibiotic rate of the ATO nanoparticle in antimicrobial agent is as shown in Figure 4.The result shows that:
With the continuous raising of mass fraction of the ATO nanoparticle in antimicrobial agent, antibacterial takes the lead in quickly increasing, and then gradually puts down
Surely, the antibiotic rate of ATO nanoparticle antimicrobial agent and its mass fraction in a medicament be not in a linear relationship;ATO nanoparticle
When mass fraction in antimicrobial agent reaches 10%, ATO nanoparticle antimicrobial agent has embodied good antibiotic property.
ATO nanoparticle antimicrobial agent antibiotic rate and medicament are as shown in Figure 5 with the relationship of germ action time.As a result table
Bright: with the increase of action time, the antibiotic rate of ATO nanoparticle antibacterial agent is significantly improved, and saturation is reached after 12 hours.
The infrared absorpting light spectra and 12 hours antibiotic rate such as Fig. 6 of its antimicrobial agent of the ATO nanoparticle of difference doping ratio
It is shown.The result shows that: undoped ATO nanoparticle does not have antibiotic property, 5% mole of doping ratio without infrared absorption in figure (a)
ATO nanoparticle surface plasmon resonance (LSPR) property it is poor, the resonance energy of generation is lower, made from it
Antimicrobial agent antibiotic rate is lower, such as schemes (b), and than reaching 10%, nanoparticle has excellent LSPR property, antibacterial for mole doping
The antibiotic rate of medicament also improves, and a mole doping ratio continues to increase, and LSPR property and antibiotic rate are maintained.
Embodiment 2
A kind of infrared plasmon resonance nano material anti-plant decay disease effect and application, about ATO nanoparticle
Application of sub- antimicrobial agent and preparation method thereof, the preparation of preparation, antimicrobial agent comprising ATO nanoparticle.It is specific as follows:
(1) preparation of ATO nanoparticle:
(1), 0.1L nitric acid, 0.1L citric acid are added in 1L deionized water and are mixed, weigh 0.090mol nitre in the balance
Sour tin and 0.010mol citric acid antimony are added in mixed solution, obtain uniformly mixed solution;
(2), the ammonia spirit that volume ratio is 1:1 is added into uniformly mixed solution, adjusting pH is 7;
(3), the solution for regulating pH is obtained into white colloidal as 12h is dried at 100 DEG C;
(4), white colloidal is put into 300 DEG C of heat treatment 12h in an oven, then calcines 12h at 600 DEG C, obtains 10%
The ATO nano-powder 13g of mole Sb doped;
(5), ATO the nano-powder 13g and 13L 10 that will be obtained-3The 4-MPY solution of M mixes, concussion 12h, centrifuge washing,
Obtain the ATO nano-powder 13g modified through mercaptopyridine.
(2) preparation of antimicrobial agent:
By 250g vegetable oil (cottonseed oil) and 5L sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%)
Mixing, keeps 1h at 40 DEG C, obtains methylated vegetable oil.Obtained methylated vegetable oil, diethyl aminoethyl hexanoate (are joined into chemical industry in Zhengzhou
The diethylamino ethanol caproate DA-6 of Products Co., Ltd) 0.3g, dispersing agent (alkylnaphthalene sulfonate) 0.5g, sticker (mine
Object oil) 0.5g, defoaming agent (a kind of common coating additive for inhibiting foam to generate, the Foamex 3062 of selection Degussa Digao
Defoaming agent) ATO nano-powder 13g mixing obtained in 0.4g and step (1), obtain antimicrobial agent.
ATO nanoparticle antimicrobial agent sample characterization is the same as embodiment 1.
Embodiment 3
A kind of infrared plasmon resonance nano material anti-plant decay disease effect and application, about ATO nanoparticle
Application of sub- antimicrobial agent and preparation method thereof, the preparation of preparation, antimicrobial agent comprising ATO nanoparticle.It is specific as follows:
(1) preparation of ATO nanoparticle:
(1) 0.085mol sodium stannate and 0.015mol potassium antimony tartrate are accurately weighed with balance, is added to 1L and is added to 1L
It in deionized water, is uniformly mixed, it is 10 that 1mol/L sodium hydroxide solution, which is added, and adjusts pH;
(2) mixed solution is obtained into black precipitate as heating for 24 hours at 200 DEG C;
(3) system is cooled to room temperature, the precipitating obtained after centrifugation is put into vacuum oven, 60 with ethanol washing 4 times
Dry 50h, obtains the ATO nano-powder 12g of 15% mole of Sb doped at DEG C;
(4) by obtained ATO nano-powder 12g and 12L, 10-3The 4-MPY solution of M mixes, and shakes 12h, and centrifuge washing is dry
It is dry, obtain the ATO nano-powder 12g modified through mercaptopyridine.
(2) preparation of antimicrobial agent:
By 250g vegetable oil (cottonseed oil) and 5L sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%)
Mixing, keeps 1h at 40 DEG C, obtains methylated vegetable oil.Obtained methylated vegetable oil, diethyl aminoethyl hexanoate (are joined into chemical industry in Zhengzhou
The diethylamino ethanol caproate DA-6 of Products Co., Ltd) 0.3g, dispersing agent (alkylnaphthalene sulfonate) 0.5g, sticker (mine
Object oil) 0.5g, defoaming agent (a kind of common coating additive for inhibiting foam to generate, the Foamex 3062 of selection Degussa Digao
Defoaming agent) ATO nano-powder 12g mixing obtained in 0.4g and step (1), obtain antimicrobial agent.
ATO nanoparticle antimicrobial agent sample characterization is the same as embodiment 1.
Embodiment 4
A kind of infrared plasmon resonance nano material anti-plant decay disease effect and application, about ATO nanoparticle
Application of sub- antimicrobial agent and preparation method thereof, the preparation of preparation, antimicrobial agent comprising ATO nanoparticle.It is specific as follows:
(1) preparation of ATO nanoparticle:
(1), 0.1L nitric acid, 0.1L citric acid are added in 1L deionized water and are mixed, weigh 0.080mol nitre in the balance
Sour tin and 0.020mol citric acid antimony are added in mixed solution, obtain uniformly mixed solution;
(2), the ammonia spirit that volume ratio is 1:1 is added into uniformly mixed solution, adjusting pH is 7;
(3), the solution for regulating pH is obtained into white colloidal as 12h is dried at 100 DEG C;
(4), white colloidal is put into 300 DEG C of heat treatment 12h in an oven, then calcines 12h at 600 DEG C, obtains 20%
The ATO nano-powder 14g of mole Sb doped;
(5), ATO the nano-powder 14g and 14L 10 that will be obtained-3The 4-MPY solution of M mixes, concussion 12h, centrifuge washing,
Obtain the ATO nano-powder 14g modified through mercaptopyridine.
(2) preparation of antimicrobial agent:
By 250g vegetable oil (cottonseed oil) and 5L sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%)
Mixing, keeps 1h at 40 DEG C, obtains methylated vegetable oil.Obtained methylated vegetable oil, diethyl aminoethyl hexanoate (are joined into chemical industry in Zhengzhou
The diethylamino ethanol caproate DA-6 of Products Co., Ltd) 0.3g, dispersing agent (alkylnaphthalene sulfonate) 0.5g, sticker (mine
Object oil) 0.5g, defoaming agent (a kind of common coating additive for inhibiting foam to generate, the Foamex 3062 of selection Degussa Digao
Defoaming agent) ATO nano-powder 14g mixing obtained in 0.4g and step (1), obtain antimicrobial agent.
ATO nanoparticle antimicrobial agent sample characterization is the same as embodiment 1.
Embodiment 5
A kind of infrared plasmon resonance nano material anti-plant decay disease effect and application, about ATO nanoparticle
Application of sub- antimicrobial agent and preparation method thereof, the preparation of preparation, antimicrobial agent comprising ATO nanoparticle.It is specific as follows:
(1) preparation of ATO nanoparticle:
(1) 0.075mol sodium stannate and 0.025mol potassium antimony tartrate are accurately weighed with balance, is added to 1L and is added to 1L
It in deionized water, is uniformly mixed, it is 10 that 1mol/L sodium hydroxide solution, which is added, and adjusts pH;
(2) mixed solution is obtained into black precipitate as heating for 24 hours at 200 DEG C;
(3) system is cooled to room temperature, the precipitating obtained after centrifugation is put into vacuum oven, 60 with ethanol washing 4 times
Dry 50h, obtains the ATO nano-powder 12g of 25% mole of Sb doped at DEG C;
(4) by obtained ATO nano-powder 12g and 12L, 10-3The 4-MPY solution of M mixes, and shakes 12h, and centrifuge washing is dry
It is dry, obtain the ATO nano-powder 12g modified through mercaptopyridine.
(2) preparation of antimicrobial agent:
By 250g vegetable oil (cottonseed oil) and 5L sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%)
Mixing, keeps 1h at 40 DEG C, obtains methylated vegetable oil.Obtained methylated vegetable oil, diethyl aminoethyl hexanoate (are joined into chemical industry in Zhengzhou
The diethylamino ethanol caproate DA-6 of Products Co., Ltd) 0.3g, dispersing agent (alkylnaphthalene sulfonate) 0.5g, sticker (mine
Object oil) 0.5g, defoaming agent (a kind of common coating additive for inhibiting foam to generate, the Foamex 3062 of selection Degussa Digao
Defoaming agent) ATO nano-powder 12g mixing obtained in 0.4g and step (1), obtain antimicrobial agent.
ATO nanoparticle antimicrobial agent sample characterization is the same as embodiment 1.
Embodiment 6
A kind of infrared plasmon resonance nano material anti-plant decay disease effect and application, about through mercaptopyridine
The preparation side of the nano materials such as the indium doping tin oxide (ITO) of modification, aluminium-doped zinc oxide (AZO), indium doping cadmium oxide (ICO)
Method and its application in terms of anti-plant decay disease, the system comprising nanoparticles such as ITO, AZO, ICO for being modified through mercaptopyridine
Standby, antimicrobial agent preparation.It is specific as follows:
(1) preparation of the nanoparticles such as ITO, AZO, ICO:
The preparation method is the same as that of Example 1~and 5, only change the metallic element raw material and its proportion of investment, other operations in experiment
It is identical: to prepare ITO and use the soluble indium source (indium acetate, inidum chloride, indium nitrate etc.) of corresponding mol ratio and soluble tin source (tin
Sour sodium, tin acetate, nitric acid tin etc.) it is used as raw material;Prepare soluble silicon source (aluminium acetate, chlorination that AZO uses corresponding mol ratio
Aluminium, aluminum nitrate etc.) and soluble Zn source (zinc nitrate, zinc acetate, zinc chloride etc.) be used as raw material;It prepares ICO and uses corresponding mole
The soluble indium source (indium acetate, inidum chloride, indium nitrate, indium oxide etc.) of ratio and soluble cadmium source (cadmium acetate, caddy, nitric acid
Cadmium etc.) it is used as raw material.
(2) preparation of antimicrobial agent:
The preparation method is the same as that of Example 1~and 5, raw material and concrete operations do not change.Only change in antimicrobial agent preparation process
Nano-powder type is respectively ITO, AZO, the ICO for the different ratio modified through mercaptopyridine, and other raw materials and concrete operations are equal
Do not change.
Table 1: mole doping through mercaptopyridine modification is than being that the nanoparticles such as 5~25% ATO, ITO, AZO, ICO are anti-
Bacterium medicament it is close, in infrared mean transmissivity and be directed to the antibiotic rate data of crop rot disease
The property representation of corresponding nanoparticle antimicrobial agent is embodied in table 1.Show: this kind of material have based on it is close,
In infrared plasmon resonance characteristic sterilizing antibacterial action, its antibiotic rate sick for plant decay reaches as high as 99%.
Claims (7)
1. a kind of preparation method of the nano material of anti-plant decay disease, its step are as follows:
(1) the soluble tin source that total mole number is 0.1 mole is mixed to join 0.8~1.2L deionized water with soluble antimony source
In, 1mol/L sodium hydroxide solution is added and adjusts pH 9.8~10.2, is uniformly mixed;
(2) clear solution uniformly mixed obtained by step (1) is warming up to 20~30h of heating at 180~220 DEG C, obtains black
Precipitating;
(3) reaction solution that step (2) obtains is cooled to room temperature, centrifuged pellet with ethanol washing 3~5 times, 50~
It is dried in vacuo 40~60h at 80 DEG C, obtains ATO nano-powder;
(4) the ATO nano-powder and 10 for obtaining step (3)-3The 4-MPY solution of M mixes, and obtains repairing through mercaptopyridine after centrifugation
The ATO nano-powder of decorations;The ATO powder of 1g uses 0.8~1.2L, 10-3The 4-MPY solution of M.
2. a kind of preparation method of the nano material of anti-plant decay disease, its step are as follows:
(1) the soluble tin source by total mole number for 0.1 mole and soluble antimony source, 0.08~0.1L nitric acid, 0.08~0.1L
Citric acid is added in 0.8~1.2L deionized water, is uniformly mixed, is obtained uniformly mixed solution;
(2) ammonia spirit of mass fraction 25% is added into the obtained uniformly mixed solution of step (1), adjusts pH and exists
6.8~7.2;
(3) solution that step (2) obtains is calorified and is dried at 80~120 DEG C, obtain white colloidal;
(4) white colloidal that step (3) obtains is put into 260~360 DEG C of 10~15h of heat treatment in an oven, then 500~
10~15 are calcined at 700 DEG C, obtain ATO nano-powder;
(5) the ATO nano-powder and 10 for obtaining step (4)-3The 4-MPY solution of M mixes, and obtains repairing through mercaptopyridine after centrifugation
The ATO nano-powder of decorations;The ATO powder of 1g uses 0.8~1.2L, 10-3The 4-MPY solution of M.
3. a kind of nano material of anti-plant decay disease, it is characterised in that: be prepared by method of any of claims 1 or 2
It arrives.
4. nano material the answering in the antimicrobial agent for preparing anti-plant decay disease of anti-plant decay disease as claimed in claim 3
With.
5. the nano material of anti-plant decay disease as claimed in claim 4 is in the antimicrobial agent for preparing anti-plant decay disease
Using, it is characterised in that: by 230~250g vegetable oil and 4.8~5.2L, the sodium hydroxide that sodium hydroxide mass fraction is 10%
Methanol solution mixing, 0.5~1h is kept at 30~50 DEG C, obtains methylated vegetable oil;By obtained methylated vegetable oil, amine
Fresh 0.3~0.5g of ester, 0.5~0.7g of dispersing agent, 0.5~0.7g of sticker, 0.4~0.6g of defoaming agent and claim 4 institute
12~the 15g of nano material for the anti-plant decay disease stated is mixed, and obtains mixed solution;After low speed disperses 2~5h, ATO is obtained
Nano-antibacterial medicament.
6. the nano material of anti-plant decay disease as claimed in claim 5 is in the antimicrobial agent for preparing anti-plant decay disease
Using, it is characterised in that: vegetable oil is cottonseed oil, rape oil or big palm oil;Diethyl aminoethyl hexanoate is diethylamino ethanol caproate DA-6;
Dispersing agent is alkylnaphthalene sulfonate;Sticker is mineral oil, gelatin or polyvinyl alcohol;Defoaming agent is the Foamex of Degussa Digao
3062 defoaming agents.
7. a kind of nano material of anti-plant decay disease, it is characterised in that: the indium doping to modify through mercaptopyridine aoxidizes sijna
Rice flour body, aluminum-doped zinc oxide nanometer powder or indium doping cadmium oxide nano-powder.
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