CN109380304B

CN109380304B - Oxide nano material for resisting plant rot disease, preparation method and application thereof

Info

Publication number: CN109380304B
Application number: CN201811430130.3A
Authority: CN
Inventors: 阮伟东; 张檬; 谢修鸿; 周铁莉; 王亚楠; 李倩文; 王皓雅; 赵冰; 王旭
Original assignee: Jilin University
Current assignee: Jilin University
Priority date: 2018-11-28
Filing date: 2018-11-28
Publication date: 2020-12-01
Anticipated expiration: 2038-11-28
Also published as: CN109380304A

Abstract

An oxide nano material for resisting plant rot, a preparation method and application thereof, belonging to the technical field of nano materials. The invention provides preparation and application of antimony doped tin oxide (ATO), indium doped tin oxide (ITO), aluminum doped zinc oxide (AZO), indium doped cadmium oxide (ICO) and other nano particles modified by mercaptopyridine as a novel antibacterial agent, wherein the nano particles generate near-infrared and intermediate-infrared plasmon resonance phenomena on the surfaces of the nano particles. The invention synthesizes and researches a novel inorganic antibacterial agent, which takes nano particles such as ATO, ITO, AZO, ICO and the like as main components, is modified by mercaptopyridine, is added with other auxiliary agents, and is prepared into the novel anti-rotten disease agent by utilizing the characteristic of a nano structure. The invention is based on a plasmon resonance mechanism and can realize long-term sterilization and disease resistance.

Description

Oxide nano material for resisting plant rot disease, preparation method and application thereof

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to a pyrithione-modified plant rot disease-resistant oxide nano material with plasmon resonance property in an infrared region, a preparation method and application thereof.

Background

The rot disease of plants is a common disease which troubles farmers. The rot disease is also called as rot disease and rotten skin disease, is a common disease which is easily generated by fruit and wood plants and is generated all over the world.

Rot is mainly caused by hundreds of fungi and bacteria carried by the soil and is characterized by disintegration and decay of plants. Decay may be hard, dry, spongy or watery, chyme or sticky. Root rot is caused by many fungi, which are rotten and covered with black linear bundles of mold layers. Wood decay is also caused by fungi, and the affected wood often discolors or stains, and the soft rot is fragile or powdery mildew. Rot diseases usually damage slowly, often over many years. Infection almost all occurs through the wound. The horseshoe-shaped and layer-shelf shaped fruiting bodies develop along the branches or form mushrooms at the base or wound of the trunk. In the early stage of the disease, the appearance is not easily recognized, and when the epidermis of the branches is opened, moist small dark brown to reddish brown spots or dry brown spots are visible, and sometimes, the area of the internal lesion is already large, but the lesion is still not easily recognized from the outside. The skin layer is easy to separate after pathological changes, the rotten skin layer is reddish brown, and the rotten skin layer has vinasse taste when being wet. In the later stage of the disease, the diseased part loses water and dries out, becomes dark brown and sinks, and produces dark brown speckles on the upper side, namely conidiophores of pathogenic bacteria, which become the source of the reoccurrence.

The rot disease mainly damages the branches of fruits, and saplings and seedlings can be invaded, but the disease is less. Because the early stage of the disease is difficult to be noticed, the prevention and treatment work is difficult to be done.

The existing method for preventing and treating the plant rot disease comprises the steps of spraying pesticides, resisting bacteria and sterilizing, reasonably controlling the planting distance, timely felling the diseased branches, consuming time and consuming materials and being incapable of radically treating the diseased branches. The use of antibacterial agents is one of the most effective ways to achieve control of plant rot. The antibacterial agent with antibacterial function and capable of stably existing in the solvent is added, and the antibacterial agent with antibacterial and bactericidal functions is prepared after certain processing, so that the antibacterial agent does not pollute the environment, and can keep the antibacterial and bactericidal effects for a long time.

Currently, the main sterilization materials can be divided into inorganic sterilization materials and organic sterilization materials. Inorganic sterilization materials are relatively limited due to concerns about safety to the environment and human tissues, no toxic side effects, and biocompatibility. The inorganic sterilization material can be divided into metal ion type (silver, copper, zinc and the like) and oxide photocatalysis type (titanium dioxide, zinc oxide, magnesium oxide and the like), and after the inorganic sterilization material is prepared into a nano scale, the specific surface area is increased, so that the inorganic sterilization material can better adsorb microorganisms and has good antibacterial effect. The metal ion type inorganic sterilizing material is typically a nano-silver sterilizing material, and has the advantages that after thalli are inactivated, Ag ions are dissociated from the thalli, repeated sterilization is carried out, the effect is durable, and the long-acting effect is achieved. Has the disadvantages of easy operationDiscoloration and high cost. The antibacterial effect of Ag ions is greatly affected by light and heat, is unstable, and is easily reduced by long-term use, thereby lowering the antibacterial effect. Oxide photocatalytic type mainly made of TiO₂The antibacterial agent has the advantages of stable chemical property, wide antibacterial performance, acid and alkali resistance, no toxicity and rich raw material sources. The disadvantages are difficult sedimentation and difficult recovery. Representative organic bactericides include chitosan, flavonoids, antibiotics, quaternary ammonium (phosphonium) salts, and polymeric bactericides. Its advantages are high biocompatibility, low cost, no poison and high antibacterial performance. The disadvantages are poor water solubility, difficulty in using it as an additive, and the need for an acidic environment.

In order to overcome the defects of the prior antibacterial agent applied to the control of plant rot, the eye is focused on a novel inorganic antibacterial agent, so that the novel inorganic antibacterial agent has outstanding advantages in various aspects such as durability, broad-spectrum antibacterial property, light resistance and heat resistance.

The patent researches and develops a novel inorganic antibacterial agent, which comprises antimony doped tin oxide (ATO), indium doped tin oxide (ITO), aluminum doped zinc oxide (AZO), indium doped cadmium oxide (ICO) and other nano materials with infrared plasmon resonance characteristics, which are modified by mercaptopyridine, and the infrared plasmon resonance characteristics are utilized to effectively prevent and treat the plant rot.

The materials have the advantages of low raw material cost, easy production and processing, high antibacterial broad spectrum, light irradiation resistance, little light corrosion and the like. Experimental results show that the antibacterial material inhibits spore germination and hypha development by taking infrared plasmon resonance characteristics or combining mediation of mercaptopyridine molecules as an antibacterial mechanism. Currently, there is no commercial distribution and literature report on the market.

Disclosure of Invention

Aiming at the pathogenic bacteria and environmental requirements of plant rot, the invention provides preparation and application of a novel antibacterial agent which is prepared by taking antimony-doped tin oxide (ATO), indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped cadmium oxide (ICO) and other nano particles modified by mercaptopyridine as the nano particles, wherein the nano particles generate near-infrared and mid-infrared plasmon resonance phenomena on the surfaces of the nano particles. The invention synthesizes and researches a novel inorganic antibacterial agent, takes nano particles such as ATO, ITO, AZO, ICO and the like as main components, is modified by mercaptopyridine, is added with other auxiliary agents, utilizes the characteristics of a nano structure to prepare the novel anti-rot agent, and researches the inhibition effect on plant rot after the novel anti-rot agent is applied.

For most fungi, the primary mechanism of resistance is the destruction of cellular tissue to inhibit germ germination and hyphal development. The antibacterial mechanism of the antibacterial material is as follows: due to the special energy level structure of the nano material, infrared plasmon resonance phenomenon is generated on the surfaces of nano particles such as ATO, ITO, AZO, ICO and the like under the irradiation of sunlight, the conversion of infrared plasmon resonance energy is utilized, the conversion is mediated or directly converted through mercaptopyridine molecules, and the generated energy acts on proteins of fungal cells and spores thereof, so that the proteins, lipids and the like on the surfaces of the cells are activated, oxidized and even destroyed, the internal structure of the cells is further destroyed, and the germination and growth of hyphae are inhibited at the same time, thereby achieving the antibacterial effect. Meanwhile, the nano material has a large specific surface area, is more easily in large-area contact with germs, and is also beneficial to digestion.

The doping degree of the nano particles, the mass fraction of the nano particles in the antibacterial agent and the acting time of pathogenic bacteria all have obvious influence on the antibacterial rate. The doping degree of nanoparticles is controlled by a synthesis method of nanoparticle powder such as antimony doped tin oxide (ATO), indium doped tin oxide (ITO), aluminum doped zinc oxide (AZO), indium doped cadmium oxide (ICO) and the like, the plant rot disease resistance effect is enhanced by adding mercaptopyridine modified nanoparticle powder, the obtained nanoparticle powder is dispersed into a specific organic solvent to prepare a nanoparticle antibacterial agent for resisting plant rot diseases, and other auxiliary components are added to improve the stability and the effect of the nanoparticle antibacterial agent in the environment.

The invention synthesizes antimony doped tin oxide (ATO), indium doped tin oxide (ITO), aluminum doped zinc oxide (AZO), indium doped cadmium oxide (ICO) and other nano particles with small grain diameter and modified by mercaptopyridine by a simple method, and further disperses in a specific solvent and adds in an auxiliary agent to prepare the antibacterial agent.

The method comprises two steps of preparing nano particles and preparing an antibacterial agent respectively; the method comprises the following specific steps:

firstly, preparing nano particles (taking the preparation of ATO nano particles as an example, the preparation of other nano particles only needs to change the raw materials of metal elements)

The method 1 adopts a hydrothermal synthesis method and comprises the following steps:

(1) mixing a soluble tin source and a soluble antimony source with the total mole number of 0.1 mol according to different proportions (the soluble tin source and the soluble antimony source are not zero, the soluble antimony source is antimony potassium tartrate, antimony chloride, antimony nitrate and the like, further, the molar doping amount of the antimony source is 5-25%) and adding the mixture into 0.8-1.2L of deionized water, adding 1mol/L of sodium hydroxide solution to adjust the pH value to 9.8-10.2, and uniformly mixing;

(2) heating the uniformly mixed transparent solution obtained in the step (1) to 180-220 ℃ for 20-30 h to obtain black precipitate;

(3) cooling the reaction liquid obtained in the step (2) to room temperature, centrifuging, washing the obtained precipitate with ethanol for 3-5 times, and vacuum-drying at 50-80 ℃ for 40-60 h to obtain ATO nano-powder with different doping ratios, wherein the particle diameter is 10-20 nm;

(4) mixing the ATO nano powder obtained in the step (3) with 10^-3Mixing the 4-MPY solution of M, and centrifuging to obtain ATO nano powder modified by mercaptopyridine; 0.8-1.2L and 10 g of ATO powder^-34-MPY solution of M;

method 2, combustion synthesis, the steps are as follows:

(1) adding 0.1 mol of soluble tin source and 0.08-0.1L of nitric acid and 0.08-0.1L of citric acid and 0.08-0.1L of soluble antimony source and 0.08-0.1L of citric acid into 0.8-1.2L of deionized water according to different proportions (the soluble tin source and the soluble antimony source are not zero, the soluble antimony source is antimony potassium tartrate, antimony chloride, antimony nitrate and the like, and the mol doping amount of the antimony source is 5-25%) and uniformly mixing to obtain a uniformly mixed solution;

(2) adding an ammonia water solution with the mass fraction of 25% into the uniformly mixed solution obtained in the step (1), and adjusting the pH value to be 6.8-7.2;

(3) heating the solution obtained in the step (2) at 80-120 ℃ for drying to obtain a white colloid;

(4) putting the white colloid obtained in the step (3) in an oven for heat treatment at 260-360 ℃ for 10-15 h, and then calcining at 500-700 ℃ for 10-15 h to obtain ATO nano-powder with different doping ratios, wherein the particle diameter is 10-20 nm;

(5) mixing the ATO nano powder obtained in the step (4) with 10^-3Mixing the 4-MPY solution of M, and centrifuging to obtain ATO nano powder modified by mercaptopyridine; 0.8-1.2L and 10 g of ATO powder^-34-MPY solution of M;

the ATO nano powder obtained by the

methods

1 and 2 can be used for preparing antibacterial agents.

Preparation of antibacterial agent

The methyl esterified vegetable oil is used as a solvent, and the synthesis method comprises the following steps: mixing 230-250 g of vegetable oil (including cottonseed oil, rape oil and palm oil) and 4.8-5.2L of sodium hydroxide methanol solution (the mass fraction of sodium hydroxide is 10%), and keeping the mixture at the temperature of 30-50 ℃ for 0.5-1 h to obtain methyl esterified vegetable oil; mixing the obtained methyl esterified vegetable oil, 0.3-0.5 g of diethyl aminoethyl hexanoate (DA-6, a product of Mediterranean chemical Co., Ltd. in Zhengzhou), 0.5-0.7 g of dispersing agent (alkyl naphthalene sulfonate, including alkyl naphthalene sulfonic acid sodium salt and alkyl naphthalene sulfonic acid ammonium salt), 0.5-0.7 g of adhesive (improving the washing resistance to rainwater and the lasting effect, mineral oil, gelatin, polyvinyl alcohol and the like), 0.4-0.6 g of defoaming agent (a common coating additive for inhibiting the generation of foam, a Foamex 3062 defoaming agent with the height of Texaco) and 12-15 g of ATO nano powder modified by mercaptopyridine prepared in the step (one) to obtain a mixed solution; dispersing at low speed for 2-5 h to obtain the ATO nano antibacterial agent.

In the invention, antimony doped tin oxide (ATO) plasmon resonance nano material modified by mercaptopyridine is adopted as the application of the agent for resisting plant rot, and the innovative significance is as follows: (1) developing a novel inorganic antibacterial material for plant rot, and based on a plasmon resonance mechanism and surface modification molecule mediation, the plasmon resonance energy generated by the nanoparticles under the irradiation of sunlight destroys the synthesis and the action of fungal protein, destroys the fungal structure, and inhibits the germination and hypha development of fungi, thereby sterilizing and resisting diseases; (2) based on a plasmon resonance mechanism, long-term sterilization and disease resistance can be realized; (3) low raw material cost, easy preparation, small harm to the environment and contribution to mass production and technical popularization.

Drawings

FIG. 1: the onset of fruit tree rot is shown in the following schematic diagrams (a) and (b).

FIG. 2: powder X-ray diffraction (XRD) pattern of ATO nanoparticles. Wherein, the ATO nano-particles are prepared by a hydrothermal method and a combustion method, and the molar doping ratio of antimony is 5%, 10%, 15%, 20% and 25% respectively.

FIG. 3: comparison of antibacterial effectiveness of the agent (a) prepared from ATO nanoparticles without mercaptopyridine modification and the agent (b) prepared from ATO nanoparticles with mercaptopyridine modification (survival of germs in the culture medium after two ATO nanoparticle antibacterial agents are used; germs are apple tree canker germs, obtained from the onset of apple tree canker, cultured at room temperature of 25 ℃ and tested). The results show that: the ATO nano-particle modified by the mercaptopyridine has higher antibacterial rate which can reach 99 percent.

FIG. 4: the relation graph of the mass fraction of the ATO nano particles in the antibacterial agent and the antibacterial rate. The results show that: along with the continuous increase of the mass fraction of the ATO nano particles in the antibacterial agent, the antibacterial rate of the ATO nano particle antibacterial agent is rapidly increased and then gradually stabilized, and the antibacterial rate of the ATO nano particle antibacterial agent and the mass fraction of the ATO nano particle antibacterial agent in the agent are not in a linear relation; when the mass fraction of the ATO nano particles in the antibacterial agent reaches 10%, the ATO nano particle antibacterial agent shows good antibacterial property.

FIG. 5: the relationship graph of the acting time of the ATO nano-particle antibacterial agent and the bacterial colony and the antibacterial rate. The results show that: with the increase of the action time, the antibacterial rate of the ATO nano-particle antibacterial agent is obviously improved and reaches saturation after 12 hours.

FIG. 6: the infrared absorption spectrum (a) of ATO nano particles with different doping ratios and the 12-hour antibacterial rate curve (b) of the antibacterial agent are shown. The results show that: in the graph (a), the ATO nano particles with the 5% mol doping ratio have poor surface plasmon resonance (LSPR) property, the generated resonance energy is low, the antibacterial rate of the antibacterial agent taking the ATO nano particles as the raw material is low, as shown in the graph (b), the mol doping ratio reaches 10%, the nano particles have excellent LSPR property, the antibacterial rate of the antibacterial agent is also improved, the mol doping ratio is continuously increased, and both the LSPR property and the antibacterial rate are maintained.

Detailed description of the preferred embodiments

The invention is further illustrated by the following examples, which are not intended to be limiting.

Example 1

An infrared plasmon resonance nano material for resisting plant rot disease and its application, relating to the application of ATO nano-particle antibacterial agent and its preparation method, comprising the preparation of ATO nano-particle and the preparation of antibacterial agent. The method comprises the following specific steps:

preparing ATO nano particles:

(1) accurately weighing 0.095mol of sodium stannate and 0.005mol of antimony potassium tartrate by using a balance, adding the sodium stannate and the antimony potassium tartrate into 1L of deionized water, uniformly mixing, and adding 1mol/L of sodium hydroxide solution to adjust the pH value to 10;

(2) heating the mixed solution at 200 ℃ for 24h to obtain black precipitate;

(3) cooling the system to room temperature, washing the precipitate obtained after centrifugation with ethanol for 4 times, putting the precipitate into a vacuum drying oven, and drying the precipitate for 50 hours at the temperature of 60 ℃ to obtain 13g of ATO nano powder doped with 5 mol% of antimony;

(4) 13g, 13L and 10L of the obtained ATO nano powder^-3And mixing the M4-MPY solution, shaking for 12h, centrifuging, washing and drying to obtain 13g of ATO nano powder modified by mercaptopyridine.

(II) preparing an antibacterial agent:

250g of vegetable oil (cottonseed oil) and 5L of sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%) were mixed and maintained at 40 ℃ for 1 hour to obtain methyl esterified vegetable oil. Mixing the obtained methyl esterified vegetable oil, diethyl aminoethyl hexanoate (DA-6, diethyl aminoethyl hexanoate, produced by Zhengzhou union chemical products Co., Ltd.) 0.3g, dispersant (sodium dodecyl naphthalene sulfonate) 0.5g, adhesive (mineral oil) 0.5g, defoaming agent (a common coating additive for inhibiting foam generation, Foamex 3062 defoaming agent with Texaco height) 0.4g and ATO nano powder 13g prepared in the step (I) to obtain the antibacterial agent.

The characterization of the ATO nano-particle antibacterial agent comprises the characterization of optical characteristics, crystal structure and antibacterial property, and specifically comprises the following steps:

the powder X-ray diffraction (XRD) pattern of the ATO nanoparticles is shown in fig. 2. Wherein, the ATO nano-particles are prepared by a hydrothermal method and a combustion method, and the molar doping ratio of antimony is 5%, 10%, 15%, 20% and 25% respectively.

A comparison graph of antibacterial effect of the agent caused by ATO nanoparticles without mercaptopyridine modification and the agent made by ATO nanoparticles with mercaptopyridine modification (survival of germs in the culture medium after the ATO nanoparticle antibacterial agent is used, the germs are apple tree canker germs, which are obtained from the onset of apple tree canker, and are cultured and tested at 25 ℃ room temperature) is shown in FIG. 3. The results show that: the ATO nano-particle modified by the mercaptopyridine has higher antibacterial rate which can reach 99 percent.

Fig. 4 shows a graph of the relationship between the mass fraction of ATO nanoparticles in the antibacterial agent and the antibacterial ratio. The results show that: along with the continuous increase of the mass fraction of the ATO nano particles in the antibacterial agent, the antibacterial rate of the ATO nano particle antibacterial agent is rapidly increased and then gradually stabilized, and the antibacterial rate of the ATO nano particle antibacterial agent and the mass fraction of the ATO nano particle antibacterial agent in the agent are not in a linear relation; when the mass fraction of the ATO nano particles in the antibacterial agent reaches 10%, the ATO nano particle antibacterial agent shows good antibacterial property.

FIG. 5 shows the relationship between the antibacterial rate of the ATO nanoparticle antibacterial agent and the action time of the agent with the germs. The results show that: with the increase of the action time, the antibacterial rate of the ATO nano particle antibacterial agent is obviously improved and reaches saturation after 12 hours.

The infrared absorption spectrum of ATO nano particles with different doping ratios and the 12-hour antibacterial rate of the antibacterial agent thereof are shown in FIG. 6. The results show that: the undoped ATO nanoparticles in the graph (a) have no infrared absorption and no antibacterial property, the surface plasmon resonance (LSPR) property of the ATO nanoparticles with the 5% molar doping ratio is poor, the generated resonance energy is low, the antibacterial rate of the antibacterial agent using the ATO nanoparticles as the raw material is low, as shown in the graph (b), the molar doping ratio reaches 10%, the nanoparticles have excellent LSPR property, the antibacterial rate of the antibacterial agent is also improved, the molar doping ratio is continuously increased, and both the LSPR property and the antibacterial rate are maintained.

Example 2

preparing ATO nano particles:

(1) adding 0.1L of nitric acid and 0.1L of citric acid into 1L of deionized water, uniformly mixing, weighing 0.090mol of tin nitrate and 0.010mol of antimony citrate by using a balance, and adding into the mixed solution to obtain a uniformly mixed solution;

(2) adding ammonia water solution with the volume ratio of 1:1 into the uniformly mixed solution, and adjusting the pH value to 7;

(3) drying the solution with the adjusted pH value at 100 ℃ for 12 hours to obtain white colloid;

(4) putting the white colloid in an oven for heat treatment at 300 ℃ for 12h, and then calcining at 600 ℃ for 12h to obtain 13g of 10 mol% antimony doped ATO nano powder;

(5) 13g and 13L 10 of the obtained ATO nano powder^-3And mixing the M4-MPY solution, shaking for 12h, and centrifugally washing to obtain 13g of ATO nano powder modified by mercaptopyridine.

(II) preparing an antibacterial agent:

250g of vegetable oil (cottonseed oil) and 5L of sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%) were mixed and maintained at 40 ℃ for 1 hour to obtain methyl esterified vegetable oil. Mixing the obtained methyl esterified vegetable oil, diethyl aminoethyl hexanoate (DA-6, diethyl aminoethyl hexanoate, available from union chemical products Co., Ltd. in Zhengzhou province) 0.3g, dispersant (alkyl naphthalene sulfonate) 0.5g, adhesive (mineral oil) 0.5g, defoaming agent (a common coating additive for inhibiting foam generation, Foamex 3062 defoaming agent with Texaco) 0.4g and ATO nano powder 13g prepared in the step (I) to obtain the antibacterial agent.

The characterization of the ATO nanoparticle antimicrobial agent sample was the same as that of example 1.

Example 3

preparing ATO nano particles:

(1) accurately weighing 0.085mol of sodium stannate and 0.015mol of antimony potassium tartrate by using a balance, adding the weighed materials into 1L of deionized water, uniformly mixing, adding 1mol/L of sodium hydroxide solution, and adjusting the pH value to 10;

(2) heating the mixed solution at 200 ℃ for 24h to obtain black precipitate;

(3) cooling the system to room temperature, washing the precipitate obtained after centrifugation with ethanol for 4 times, putting the precipitate into a vacuum drying oven, and drying the precipitate for 50 hours at the temperature of 60 ℃ to obtain 12g of ATO nano powder doped with 15 mol% of antimony;

(4) mixing the obtained ATO nanopowder 12g with 12L, 10^-3And mixing the M4-MPY solution, shaking for 12h, centrifuging, washing and drying to obtain 12g of ATO nano powder modified by mercaptopyridine.

(II) preparing an antibacterial agent:

250g of vegetable oil (cottonseed oil) and 5L of sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%) were mixed and maintained at 40 ℃ for 1 hour to obtain methyl esterified vegetable oil. Mixing the obtained methyl esterified vegetable oil, diethyl aminoethyl hexanoate (DA-6, diethyl aminoethyl hexanoate, available from union chemical products Co., Ltd. in Zhengzhou province) 0.3g, dispersant (alkyl naphthalene sulfonate) 0.5g, adhesive (mineral oil) 0.5g, defoaming agent (a common coating additive for inhibiting foam generation, Foamex 3062 defoaming agent with Texaco) 0.4g and ATO nano powder 12g prepared in the step (I) to obtain the antibacterial agent.

Example 4

preparing ATO nano particles:

(1) adding 0.1L of nitric acid and 0.1L of citric acid into 1L of deionized water, uniformly mixing, and adding 0.080mol of tin nitrate and 0.020mol of antimony citrate into the mixed solution by balance to obtain a uniformly mixed solution;

(4) placing the white colloid in an oven for heat treatment at 300 ℃ for 12h, and then calcining at 600 ℃ for 12h to obtain 14g of antimony-doped ATO nano powder with the mol percent of 20;

(5) 14g and 14L 10 of the obtained ATO nano powder^-3And mixing the M4-MPY solution, shaking for 12h, and centrifugally washing to obtain 14g of ATO nano powder modified by mercaptopyridine.

(II) preparing an antibacterial agent:

250g of vegetable oil (cottonseed oil) and 5L of sodium hydroxide-methanol mixed solution (sodium hydroxide mass fraction is 10%) were mixed and maintained at 40 ℃ for 1 hour to obtain methyl esterified vegetable oil. Mixing the obtained methyl esterified vegetable oil, diethyl aminoethyl hexanoate (DA-6, diethyl aminoethyl hexanoate, available from Union chemical products, Zhengzhou province) 0.3g, dispersant (alkyl naphthalene sulfonate) 0.5g, adhesive (mineral oil) 0.5g, defoaming agent (a common coating additive for inhibiting foam generation, Foamex 3062 defoaming agent with Texaco height) 0.4g and ATO nano powder 14g prepared in the step (I) to obtain the antibacterial agent.

Example 5

preparing ATO nano particles:

(1) accurately weighing 0.075mol of sodium stannate and 0.025mol of antimony potassium tartrate by using a balance, adding the weighed materials into 1L of deionized water, uniformly mixing, adding 1mol/L of sodium hydroxide solution, and adjusting the pH value to 10;

(2) heating the mixed solution at 200 ℃ for 24h to obtain black precipitate;

(3) cooling the system to room temperature, washing the precipitate obtained after centrifugation with ethanol for 4 times, putting the precipitate into a vacuum drying oven, and drying the precipitate for 50 hours at the temperature of 60 ℃ to obtain 12g of 25 mol% antimony-doped ATO nano powder;

(II) preparing an antibacterial agent:

Example 6

An infrared plasmon resonance nano material for resisting plant rot disease and its application, relates to a preparation method of indium-doped tin oxide (ITO), aluminum-doped zinc oxide (AZO), indium-doped cadmium oxide (ICO) and other nano materials modified by mercaptopyridine and its application in resisting plant rot disease, and comprises the preparation of nanoparticles of ITO, AZO, ICO and the like modified by mercaptopyridine and the preparation of antibacterial agents. The method comprises the following specific steps:

preparing ITO, AZO, ICO and other nano particles:

the preparation method is the same as that of the embodiments 1-5, only the metal element raw materials and the proportion thereof are changed in the experiment, and the other operations are the same: preparing ITO by using soluble indium sources (indium acetate, indium chloride, indium nitrate and the like) and soluble tin sources (sodium stannate, tin acetate, tin nitrate and the like) as raw materials in corresponding molar ratios; the preparation of AZO uses soluble aluminum sources (aluminum acetate, aluminum chloride, aluminum nitrate, etc.) and soluble zinc sources (zinc nitrate, zinc acetate, zinc chloride, etc.) in corresponding molar ratios as raw materials; the preparation of ICO uses soluble indium sources (indium acetate, indium chloride, indium nitrate, indium oxide, etc.) and soluble cadmium sources (cadmium acetate, cadmium chloride, cadmium nitrate, etc.) in corresponding molar ratios as starting materials.

(II) preparing an antibacterial agent:

the preparation method is the same as that of the examples 1-5, and raw materials and specific operations are not changed. In the process of preparing the antibacterial agent, only the types of the nano powder are changed into ITO, AZO and ICO which are modified by mercaptopyridine and have different proportions, and other raw materials and specific operation are not changed.

Table 1: average transmittance of near-infrared and intermediate-infrared of nano-particle antibacterial agents such as ATO, ITO, AZO, ICO and the like with molar doping ratio of 5-25% modified by mercaptopyridine and antibacterial rate data aiming at crop rot

Characterization of the properties of the corresponding nanoparticle antimicrobial agents is presented in table 1. Shows that: the material has the sterilization and antibacterial effects based on near-infrared and mid-infrared plasmon resonance characteristics, and the antibacterial rate of the material on plant rot can reach 99 percent at most.

Claims

1. An ATO nano antibacterial agent is characterized in that: mixing 230-250 g of vegetable oil and 4.8-5.2L of sodium hydroxide methanol solution with the mass fraction of 10%, and keeping the mixture at the temperature of 30-50 ℃ for 0.5-1 h to obtain methyl esterified vegetable oil; mixing the obtained methyl esterified vegetable oil, 0.3-0.5 g of diethyl aminoethyl hexanoate, 0.5-0.7 g of dispersing agent, 0.5-0.7 g of adhesive, 0.4-0.6 g of defoaming agent and 12-15 g of plant rot disease resistant nano material to obtain a mixed solution; dispersing at low speed for 2-5 h to obtain an ATO nano antibacterial agent;

the nano material for resisting plant rot is prepared by the following steps,

(1) mixing a soluble tin source and a soluble antimony source with the total mole number of 0.1 mol, adding the mixture into 0.8-1.2L of deionized water, adding 1mol/L of sodium hydroxide solution, adjusting the pH value to 9.8-10.2, and uniformly mixing;

(3) cooling the reaction liquid obtained in the step (2) to room temperature, centrifuging, washing the obtained precipitate with ethanol for 3-5 times, and vacuum-drying at 50-80 ℃ for 40-60 h to obtain ATO nano powder;

(4) mixing the ATO nano powder obtained in the step (3) with 10^-3Mixing the 4-MPY solution of M, and centrifuging to obtain ATO nano powder modified by mercaptopyridine; 0.8-1.2L 10 of ATO powder 1g is used^-3The M4-MPY solution or the nano material for resisting the plant rot disease is prepared by the following steps,

(1) adding a soluble tin source and a soluble antimony source with the total mole number of 0.1 mol, 0.08-0.1L of nitric acid and 0.08-0.1L of citric acid into 0.8-1.2L of deionized water, and uniformly mixing to obtain a uniformly mixed solution;

(4) putting the white colloid obtained in the step (3) in an oven for heat treatment at 260-360 ℃ for 10-15 h, and then calcining at 500-700 ℃ for 10-15 h to obtain ATO nano powder;

(5) mixing the ATO nano powder obtained in the step (4) with 10^-3Mixing the 4-MPY solution of M, and centrifuging to obtain ATO nano powder modified by mercaptopyridine; 0.8-1.2L 10 of ATO powder 1g is used^-3M in 4-MPY.

2. The ATO nanoantibiotic agent of claim 1, wherein: the vegetable oil is cotton seed oil, rape oil or palm oil; the diethyl aminoethyl hexanoate is diethyl aminoethyl hexanoate DA-6; the dispersant is alkyl naphthalene sulfonate; the adhesive is mineral oil, gelatin or polyvinyl alcohol; the antifoaming agent is a Foamex 3062 antifoaming agent with a height of degusside.