CN110563022B - Monodisperse AgO hollow porous microsphere and preparation method and application thereof - Google Patents

Monodisperse AgO hollow porous microsphere and preparation method and application thereof Download PDF

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CN110563022B
CN110563022B CN201910807130.9A CN201910807130A CN110563022B CN 110563022 B CN110563022 B CN 110563022B CN 201910807130 A CN201910807130 A CN 201910807130A CN 110563022 B CN110563022 B CN 110563022B
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沈文宁
葛延峰
王旭
冯拉俊
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Xian University of Technology
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    • C01P2004/30—Particle morphology extending in three dimensions
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    • C01P2006/12—Surface area

Abstract

The invention discloses a preparation method of monodisperse AgO hollow porous microspheres, which comprises the following steps: adding a sodium hydroxide solution and ammonia water into a silver nitrate solution, and then adjusting the pH value; adding fumed silica, and calculating the molar weight of silver ions adsorbed by the fumed silica; preparing a sodium chloride solution, reacting to obtain a solid, and dispersing the solid by using deionized water; are each independently of K2S2O8And (3) reacting the solution with a sodium hydroxide solution, and soaking, separating, cleaning and drying the solid after the reaction is finished to obtain the monodisperse AgO hollow porous microspheres. The invention has the beneficial effects that: the monodisperse AgO hollow porous microspheres prepared by the method are of a hollow porous structure and are in a monodisperse state, so that the specific surface area is high, the bactericidal activity of AgO is enhanced, the gas-phase silicon dioxide nanospheres are used as templates, the operation process and the preparation equipment are simple, the process is easy to amplify and produce, the process is environment-friendly, and the preparation cost is low.

Description

Monodisperse AgO hollow porous microsphere and preparation method and application thereof
Technical Field
The invention belongs to the technical field of AgO hollow microsphere preparation, and particularly relates to a monodisperse AgO hollow porous microsphere, a preparation method of the material and application of the material.
Background
The AgO material has high battery specific capacity, electromagnetic property, electrochemical activity, strong bacteriostatic, bactericidal and broad-spectrum antibacterial capabilities, has potential application values in the fields of batteries with high requirements on specific power and battery capacity, drinking water purification treatment and sterilization, and becomes a research hotspot.
The existing preparation method of AgO material mainly comprises an oxidation precipitation method, an electrochemical method, a chemical deposition method, a thermal evaporation method and the like. By adding different morphology control agents, nano-particles or submicron particles with one-dimensional or two-dimensional structures such as flakes, squares, spheres, rods and the like can be obtained. Although AgO particles with different shapes synthesized by the methods have strong sterilization effect under extremely low concentration, the powder particles have the defects of low specific surface area, easy agglomeration, difficult formation of monodisperse particles and the like. Studies have shown that the bactericidal activity of a material is closely related to its specific surface area. The higher the specific surface area of the material, the stronger the bactericidal activity. The material is made into a three-dimensional hollow porous structure, and the hollow porous structure has lower density, unique internal structure and internal and external surfaces, so that the specific surface area can be effectively improved, the contact chance of the material and bacteria can be increased, and the properties of the material such as bactericidal activity and the like can be improved.
At present, hollow porous structure materials with high specific surface area are successfully prepared by methods such as a template method, a solvothermal method, a self-assembly method and the like, and show higher activity; however, few reports have been made on hollow porous AgO bactericidal materials. The Chinese patent of invention of a hollow porous microsphere catalytic material and a preparation method and application thereof in degrading NO (publication No. CN108080000A, published Japanese 20180529) discloses a hollow porous microsphere catalytic material with larger specific surface area and a preparation method thereof, namely, cobalt nitrate, manganese nitrate, cerium nitrate, polyvinyl alcohol and ammonium bicarbonate are used as raw materials, and a soft template-hydrothermal method is adopted to prepare novel CeOx-(Co,Mn)3O4The hollow porous material can obtain excellent denitration performance, but the method takes polyvinyl alcohol as a template, but the reducibility of the polyvinyl alcohol in the AgO preparation process prevents AgO oxidation reaction from proceeding, and the polyvinyl alcohol cannot be used as the template of the AgO hollow porous material. Although the use of mesoporous SiO has been reported2Nanospheres and the like are used as hard templates, and hollow porous structures can be obtained by soaking and removing the templates, but mesoporous SiO2The cost is high, and the application of the AgO hollow porous material is not facilitated. T.Preuksaratawut is equal to the publication "fibre of silver ho", 2011 on Materials Chemistry and Physics Vol.130Low microspheres by sodium hydroxide in glycerol solution ", reported as Ag2SO4The preparation method of the spherical particles which are silver sources and templates, the mixed solution of sodium hydroxide and glycerol which is a reducing agent and ammonia water which is a template removing agent prepares the silver hollow microspheres, but the ammonia water can also dissolve AgO materials. Therefore, how to prepare the monodisperse AgO hollow porous microspheres, obtain larger specific surface area, and improve the AgO activity to promote the practical application of AgO is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a monodisperse AgO hollow porous microsphere, which solves the problems that the existing AgO material has low specific surface area and cannot be monodisperse.
The second purpose of the invention is to provide a preparation method of the monodisperse AgO hollow porous microspheres, which solves the problem that the monodisperse AgO hollow porous microspheres cannot be prepared.
The third purpose of the invention is to provide an application of the monodisperse AgO hollow porous microspheres in killing of staphylococcus aureus.
The first technical scheme adopted by the invention is that the mono-dispersed AgO hollow porous microspheres have the particle size of 600 nm-1 mu m and are hollow.
It is also characterized in that the method comprises the following steps,
the specific surface area of the monodisperse AgO hollow porous microspheres is 20.28-28.19 m2/g。
The second technical scheme adopted by the invention is that the preparation method of the monodisperse AgO hollow porous microspheres comprises the following steps:
step 1, dropwise adding a first sodium hydroxide solution into a silver nitrate solution to form a precipitate, adding ammonia water to dissolve the precipitate, and adjusting the pH value of the solution to 4-9 to obtain a silver-ammonia solution;
step 2, adding fumed silica into the silver ammonia solution, stirring, performing centrifugal separation to obtain fumed silica containing silver ions and a supernatant, dispersing the fumed silica containing the silver ions by using deionized water to obtain a first suspension, measuring the silver ion concentration of the supernatant, and calculating the molar quantity n of the silver ions adsorbed by the fumed silica;
step 3, preparing a sodium chloride solution containing n moles of sodium chloride by using deionized water, dropwise adding the sodium chloride solution into the first suspension under the stirring condition for reaction, separating to obtain a first solid after the reaction is finished, and cleaning the first solid by using deionized water to obtain AgCl/SiO2The composite material is then dispersed with deionized water2Obtaining a second suspension of the composite material;
step 4, respectively preparing K2S2O8Solution and a second sodium hydroxide solution, adding K2S2O8Placing the solution in a constant temperature environment, and stirring the solution to the K2S2O8And (3) dropwise adding the second suspension and a second sodium hydroxide solution in sequence to react, soaking the separated second solid in a third sodium hydroxide solution for 4-20 hours after the reaction is finished, and cleaning and drying the separated black powder to obtain the monodisperse AgO hollow porous microspheres.
It is also characterized in that the method comprises the following steps,
the specific steps in step 1 are as follows: the specific steps in step 1 are as follows: dropwise adding a first sodium hydroxide solution into a silver nitrate solution according to the molar ratio of silver nitrate to sodium hydroxide of 0.5-1.1 to form a precipitate, adding ammonia water to dissolve the precipitate, and then using HNO3The pH value of the solution is adjusted to obtain the silver ammonia solution.
And 2, adding fumed silica into the silver-ammonia solution and stirring for 1-2 hours, wherein the molar ratio of the fumed silica to the silver nitrate is 1.2-5.5.
And 3, dropwise adding the sodium chloride solution into the first suspension under the stirring condition to react for 10-30 min, separating to obtain a first solid after the reaction is finished, and washing the first solid with deionized water for not less than 3 times.
K in step 42S2O8K in solution2S2O8Is 3n and the molar amount of sodium hydroxide in the second sodium hydroxide solution is 7 n.
Step 4 is to add K2S2O8Solution deviceKeeping the temperature at 55-65 ℃ and stirring the mixture to K2S2O8And (3) dropwise adding the second suspension and the second sodium hydroxide solution into the solution in sequence to react for 60-140 min, and soaking the separated second solid in a third sodium hydroxide solution for 4-20 h after the reaction is finished.
And 4, cleaning the black powder obtained by separation, and drying at 50-70 ℃ for 0.5-3 h.
The third technical scheme adopted by the invention is that the application of the monodisperse AgO hollow porous microspheres in killing of staphylococcus aureus.
The invention has the beneficial effects that: the method adopts the gas-phase silicon dioxide nanospheres as templates, has the characteristics of low price, chemical stability, oxidation resistance, acid insolubility, strong alkali solubilization and the like, silver ions directly wrap the surfaces of the silicon dioxide nanospheres through the strong electrostatic attraction of silver-ammonia complex ions to obtain a core-shell structure, ammonia is removed through NaCl, and then oxidation reaction is directly carried out, so that AgO generated by reaction can be uniformly wrapped on the surfaces of the silicon dioxide to form a porous structure, the silicon dioxide core is dissolved by utilizing sodium hydroxide to obtain a hollow structure, the specific surface area of the AgO is increased, and the bactericidal activity of the AgO is enhanced; the method has the advantages of simple operation process and preparation equipment, easy scale-up production, environment-friendly process and low preparation cost.
Drawings
FIG. 1 is an SEM topography of a monodisperse AgO hollow porous microsphere prepared by the preparation method of the monodisperse AgO hollow porous microsphere of the invention;
FIG. 2 is an XRD spectrum of a monodisperse AgO hollow porous microsphere prepared by the preparation method of the monodisperse AgO hollow porous microsphere of the invention;
FIG. 3 is a surface distribution energy spectrum of Ag element of the monodisperse AgO hollow porous microspheres prepared by the preparation method of the monodisperse AgO hollow porous microspheres;
FIG. 4 is an O element surface distribution energy spectrum of the monodisperse AgO hollow porous microsphere prepared by the preparation method of the monodisperse AgO hollow porous microsphere.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The monodisperse AgO hollow porous microsphere has the particle size of 600 nm-1 mu m, the AgO microsphere has a hollow porous structure, and the specific surface area of the AgO hollow porous microsphere is 20.28-28.19 m2/g。
The invention relates to a preparation method of monodisperse AgO hollow porous microspheres, which is implemented according to the following steps:
step 1, preparing 100mL of 0.185-0.245 mol/L silver nitrate solution, then dropwise adding 4.5-7 mL of 5mol/L first sodium hydroxide solution into the silver nitrate solution to form a precipitate, adding 5mol/L ammonia water into the precipitate to dissolve the precipitate, and using HNO (HNO) to dissolve the precipitate3Adjusting the pH value of the solution to 4-9 to obtain a silver-ammonia solution;
step 2, adding 2-6 g of fumed silica into the silver ammonia solution, stirring for 1-2 hours, then performing centrifugal separation to obtain the silver ion-containing fumed silica and a supernatant, and re-dispersing the silver ion-containing fumed silica with 50mL of deionized water to obtain a first suspension; measuring the silver ion concentration of the supernatant by adopting an atomic absorption spectrophotometer, and calculating to obtain the molar quantity n of the silver ions absorbed by the fumed silica;
the silver-ammonia complex ions are adsorbed on the surface of the silicon dioxide nanospheres to form a core-shell structure through the strong electrostatic adsorption effect of the silver-ammonia complex ions.
Step 3, weighing n moles of sodium chloride, preparing a sodium chloride solution by using 50mL of deionized water, dropwise adding the sodium chloride solution into the first suspension under the stirring condition, reacting for 10-30 min, centrifuging, and cleaning the product of the obtained first solid by using the deionized water for not less than 3 times to obtain AgCl/SiO2The composite material is finally dispersed with 50mL of deionized water2Forming a second suspension of the composite material; formation of AgCl/SiO after Ammonia removal by NaCl2A composite material;
step 4, preparing 100mL of K respectively2S2O8A solution and a second sodium hydroxide solution, wherein K2S2O8K in solution2S2O8Has a molar weight of 3n and a molar weight of sodium hydroxide in the second sodium hydroxide solution of 7n, andK2S2O8and (3) placing the solution at a constant temperature of 55-65 ℃, dropwise adding a second suspension under a stirring condition, dropwise adding a second sodium hydroxide solution after dropwise adding the second suspension, reacting for 60-140 min after dropwise adding, centrifugally separating to obtain a second solid after the reaction is finished, soaking the second solid in a third sodium hydroxide solution of 2mol/L for 4-20 h, separating to obtain black powder, cleaning the black powder, and finally drying at 50-70 ℃ for 0.5-3 h to obtain the monodisperse AgO hollow porous microspheres.
By K2S2O8And (3) carrying out oxidation reaction, so that AgO generated by the reaction can be uniformly coated on the surface of the silicon dioxide and has a porous structure, and dissolving a silicon dioxide core by using a sodium hydroxide solution to obtain a hollow structure.
Application of monodisperse AgO hollow porous microspheres in killing staphylococcus aureus.
Example 1
Step 1, preparing 100mL of 0.185mol/L silver nitrate solution, then dropwise adding 4.5mL of 5mol/L first sodium hydroxide solution into the silver nitrate solution to form a precipitate, adding 5mol/L ammonia water into the precipitate to dissolve the precipitate, and then using HNO (HNO) to dissolve the precipitate3Adjusting the pH value of the solution to 4 to obtain a silver-ammonia solution;
step 2, adding 2g of fumed silica into the silver ammonia solution, rapidly stirring for 1h, then carrying out centrifugal separation to obtain the silver ion-containing fumed silica and a supernatant, and re-dispersing the silver ion-containing fumed silica with 50mL of deionized water to obtain a first suspension; measuring the silver ion concentration of the supernatant by atomic absorption spectrophotometer to obtain the molar quantity n (Ag) of silver ions adsorbed by the fumed silica+ Adsorption) 0.0185 mol;
step 3, weighing 0.0185mol of sodium chloride, preparing a sodium chloride solution with the concentration of 0.37mol/L by using 50mL of deionized water, dropwise adding the sodium chloride solution into the first suspension liquid under the stirring condition, reacting for 10min, centrifuging, and cleaning the product of the obtained first solid by using the deionized water for 3 times to obtain AgCl/SiO2The composite material is finally dispersed with 50mL of deionized water2Forming a second suspension of the composite material; (ii) a
Step 4, respectively preparing 100mL of K with the concentration of 0.555mol/L2S2O8The solution and a second sodium hydroxide solution with the concentration of 1.295mol/L are added2S2O8And (3) placing the solution in a constant temperature of 55 ℃, dropwise adding a second suspension under the stirring condition, dropwise adding a second sodium hydroxide solution, reacting for 60min after dropwise adding, centrifugally separating to obtain a second solid after the reaction is finished, soaking the second solid in a 2mol/L third sodium hydroxide solution for 4h, separating to obtain black powder, cleaning the black powder, and finally drying at the temperature of 70 ℃ for 0.5h to obtain the monodisperse AgO hollow porous microspheres.
The content of AgO in the monodisperse AgO hollow porous microspheres prepared in the example is 72.81%, and the specific surface area is 20.28m2/g。
Fig. 1 is an SEM picture of the AgO hollow porous microsphere prepared in this example, and it can be seen from the figure that the prepared AgO material is in the form of a monodisperse hollow porous microsphere with uniform particles, and the particle size of the microsphere is 600nm to 1 μm.
The concentration of the AgO hollow porous microspheres prepared in the example is 5mg/L, and the colony count is 1.4 multiplied by 107Staphylococcus aureus at CFU/mL was exposed for 5min, and the number of surviving colonies was 10.7 CFU/mL.
Example 2
Step 1, preparing 100mL of 0.200mol/L silver nitrate solution, then dropwise adding 5mL of 5mol/L first sodium hydroxide solution into the silver nitrate solution to form a precipitate, adding 5mol/L ammonia water into the precipitate to dissolve the precipitate, and then using HNO (HNO) to dissolve the precipitate3Adjusting the pH value of the solution to 4 to obtain a silver-ammonia solution;
step 2, adding 3g of fumed silica into the silver ammonia solution, rapidly stirring for 1.5h, then performing centrifugal separation to obtain the silver ion-containing fumed silica and a supernatant, and re-dispersing the silver ion-containing fumed silica by using 50mL of deionized water to obtain a first suspension; measuring the silver ion concentration of the supernatant by atomic absorption spectrophotometer to obtain the molar quantity n (Ag) of silver ions adsorbed by the fumed silica+ Adsorption) Is 0.02mol；
Step 3, weighing 0.02mol of sodium chloride, preparing a sodium chloride solution with the concentration of 0.4mol/L by using 50mL of deionized water, dropwise adding the sodium chloride solution into the first suspension liquid under the stirring condition, reacting for 10min, centrifuging, and cleaning the product of the obtained first solid by using the deionized water for 4 times to obtain AgCl/SiO2The composite material is finally dispersed with 50mL of deionized water2Forming a second suspension of the composite material;
step 4, respectively preparing 100mL of K with the concentration of 0.60mol/L2S2O8The solution and a second sodium hydroxide solution with the concentration of 1.20mol/L are added2S2O8And (3) placing the solution in a constant temperature of 60 ℃, dropwise adding a second suspension under the stirring condition, dropwise adding a second sodium hydroxide solution, reacting for 80min after dropwise adding, centrifugally separating to obtain a second solid after the reaction is finished, soaking the second solid in a 2mol/L third sodium hydroxide solution for 8h, separating to obtain black powder, cleaning the black powder, and finally drying at 65 ℃ for 1.0h to obtain the monodisperse AgO hollow porous microspheres.
The content of AgO in the monodisperse AgO hollow porous microspheres prepared in the example is 81.83%, and the specific surface area is 21.25m2/g。
The concentration of the AgO hollow porous microspheres prepared in the example is 5mg/L, and the colony count is 1.4 multiplied by 107Staphylococcus aureus at CFU/mL was exposed for 5min, and the number of surviving colonies was 8.7 CFU/mL.
Example 3
Step 1, preparing 100mL of 0.215mol/L silver nitrate solution, then dropwise adding 5.5mL of 5mol/L first sodium hydroxide solution into the silver nitrate solution to form a precipitate, adding 5mol/L ammonia water into the precipitate to dissolve the precipitate, and then using HNO (HNO) to dissolve the precipitate3Adjusting the pH value of the solution to 6 to obtain a silver-ammonia solution;
step 2, adding 4g of fumed silica into the silver ammonia solution, rapidly stirring for 1.5h, then carrying out centrifugal separation to obtain the silver ion-containing fumed silica and a supernatant, and re-dispersing the silver ion-containing fumed silica by using 50mL of deionized water to obtain a first suspension; using atomic absorption spectroscopyThe silver ion concentration of the supernatant is measured, and the molar quantity n (Ag) of the silver ions adsorbed by the fumed silica is calculated+ Adsorption) 0.0215 mol;
step 3, weighing 0.0215mol of sodium chloride, preparing a sodium chloride solution with the concentration of 0.43mol/L by using 50mL of deionized water, dropwise adding the sodium chloride solution into the first suspension under the stirring condition, reacting for 20min, centrifuging, and cleaning the product of the obtained first solid by using the deionized water for 3 times to obtain AgCl/SiO2The composite material is finally dispersed with 50mL of deionized water2Forming a second suspension of the composite material;
step 4, respectively preparing 100mL of K with the concentration of 0.645mol/L2S2O8The solution and a second sodium hydroxide solution with the concentration of 1.505mol/L are added2S2O8And (3) placing the solution in a constant temperature of 60 ℃, dropwise adding a second suspension under the stirring condition, dropwise adding a second sodium hydroxide solution, reacting for 80min after dropwise adding, centrifugally separating to obtain a second solid after the reaction is finished, soaking the second solid in a 2mol/L third sodium hydroxide solution for 12h, separating to obtain black powder, cleaning the black powder, and finally drying at the final temperature of 60 ℃ for 1.5h to obtain the monodisperse AgO hollow porous microspheres.
The content of AgO in the monodisperse AgO hollow porous microspheres prepared in the example is 85.29%, and the specific surface area is 23.54m2/g。
The concentration of the AgO hollow porous microspheres prepared in the example is 5mg/L, and the colony count is 1.4 multiplied by 107Staphylococcus aureus at CFU/mL was exposed for 5min, and the number of surviving colonies was 6 CFU/mL.
Example 4
Step 1, preparing 100mL of 0.23mol/L silver nitrate solution, then dropwise adding 6mL of 5mol/L first sodium hydroxide solution into the silver nitrate solution to form a precipitate, adding 5mol/L ammonia water into the precipitate to dissolve the precipitate, and then using HNO (HNO) to dissolve the precipitate3Adjusting the pH value of the solution to 9 to obtain a silver-ammonia solution;
step 2, adding 5g of fumed silica into the silver ammonia solution, quickly stirring for 1.5h, and then centrifugally separating to obtain a silver ion-containing fumed silicaSilicon oxide and supernatant, redispersing the above fumed silica containing silver ions with 50mL of deionized water to obtain a first suspension; measuring the silver ion concentration of the supernatant by atomic absorption spectrophotometer to obtain the molar quantity n (Ag) of silver ions adsorbed by the fumed silica+ Adsorption) 0.023 mol;
step 3, weighing 0.023mol of sodium chloride, preparing a sodium chloride solution with the concentration of 0.46mol/L by using 50mL of deionized water, dropwise adding the sodium chloride solution into the first suspension liquid under the condition of stirring, reacting for 25min, centrifuging, and cleaning the product of the obtained first solid by using the deionized water for 4 times to obtain AgCl/SiO2The composite material is finally dispersed with 50mL of deionized water2Forming a second suspension of the composite material;
step 4, respectively preparing 100mL of K with the concentration of 0.69mol/L2S2O8The solution and a second sodium hydroxide solution with the concentration of 1.61mol/L are added2S2O8And (3) placing the solution in a constant temperature of 60 ℃, dropwise adding a second suspension under the stirring condition, dropwise adding a second sodium hydroxide solution, reacting for 80min after dropwise adding, centrifugally separating to obtain a second solid after the reaction is finished, soaking the second solid in a 2mol/L third sodium hydroxide solution for 16h, separating to obtain black powder, cleaning the black powder, and finally drying at 55 ℃ for 2h to obtain the monodisperse AgO hollow porous microspheres.
The content of AgO in the monodisperse AgO hollow porous microspheres prepared in the example is 99.51%, and the specific surface area of the monodisperse AgO hollow porous microspheres is 28.19m2/g。
Referring to fig. 2, an XRD spectrum of the monodisperse AgO hollow porous microsphere prepared in this example uses a Cu target, a tube voltage is 40kV, a current is 30mA, a scanning speed is 10 °/min, a scanning angle range is 10 ° to 90 °, XRD data obtained by the test is compared with a JCPDF standard card, and it is found that the obtained product has only one crystal structure, is monoclinic AgO, and does not see SiO2This indicates that sodium hydroxide has reacted with SiO2The nuclei are removed.
Fig. 3 is an element surface distribution energy spectrum of the AgO hollow porous microsphere Ag prepared in this example, and fig. 4 is an element surface distribution energy spectrum of the AgO hollow porous microsphere O prepared in this example.
The concentration of the AgO hollow porous microspheres prepared in the example is 5mg/L, and the colony count is 1.4 multiplied by 107Staphylococcus aureus at CFU/mL was exposed for 5min, and the number of surviving colonies was 5.34 CFU/mL.
Example 5
Step 1, preparing 100mL of 0.245mol/L silver nitrate solution, then dropwise adding 7mL of 5mol/L first sodium hydroxide solution into the silver nitrate solution to form a precipitate, adding 5mol/L ammonia water into the precipitate to dissolve the precipitate, and then using HNO (HNO) to dissolve the precipitate3Adjusting the pH value of the solution to 9 to obtain a silver-ammonia solution;
step 2, adding 6g of fumed silica into the silver ammonia solution, rapidly stirring for 1.5h, then performing centrifugal separation to obtain the silver ion-containing fumed silica and a supernatant, and re-dispersing the silver ion-containing fumed silica by using 50mL of deionized water to obtain a first suspension; measuring the silver ion concentration of the supernatant by atomic absorption spectrophotometer to obtain the molar quantity n (Ag) of silver ions adsorbed by the fumed silica+ Adsorption) 0.0245 mol;
step 3, weighing 0.0245mol of sodium chloride, preparing a sodium chloride solution with the concentration of 0.49mol/L by using 50mL of deionized water, dropwise adding the sodium chloride solution into the first suspension under the stirring condition, reacting for 30min, centrifuging, and cleaning the product of the obtained first solid by using the deionized water for 3 times to obtain AgCl/SiO2The composite material is finally dispersed with 50mL of deionized water2Forming a second suspension of the composite material;
step 4, respectively preparing 100mL of K with the concentration of 0.735mol/L2S2O8The solution and a second sodium hydroxide solution with the concentration of 1.715mol/L are added2S2O8Placing the solution in a constant temperature of 65 ℃, dropwise adding the second suspension under the condition of stirring, dropwise adding the second sodium hydroxide solution, reacting for 140min after dropwise adding, centrifugally separating to obtain a second solid after the reaction is finished, soaking the second solid in a third sodium hydroxide solution of 2mol/L for 20h, separating to obtain black powder, and adding a second sodium hydroxide solution of 2mol/L into the black powderAnd cleaning the powder, and finally drying the powder at the temperature of 50 ℃ for 3h to obtain the monodisperse AgO hollow porous microspheres.
The content of AgO in the monodisperse AgO hollow porous microspheres prepared in the example is 82.87%, and the specific surface area of the monodisperse AgO hollow porous microspheres is 20.38m2/g。
The concentration of the AgO hollow porous microspheres prepared in the example is 5mg/L, and the colony count is 1.4 multiplied by 107Staphylococcus aureus at CFU/mL was exposed for 5min, and the number of surviving colonies was 8 CFU/mL.
The monodisperse AgO hollow porous microspheres prepared by the method have monoclinic crystal structures and hollow porous structures, the AgO content of the monodisperse AgO hollow porous microspheres can reach 99.51%, and the specific surface area is 20.28-28.19 m2(ii)/g; and with K2S2O8AgNO oxide3The specific surface area of the prepared AgO particles with the particle size of about 100nm and the square shape is only 7.02m2The specific surface area of the AgO hollow porous microspheres prepared by the method is far larger than that of AgO particles with the square shapes.
The monodisperse AgO hollow porous microspheres prepared by the method have the concentration of 5mg/L and the colony count of 1.4 multiplied by 107The number of surviving colonies of the CFU/mL staphylococcus aureus after 5min action is 5.34-10.7 CFU/mL, and the number of surviving colonies of the AgO powder with the square shape under the same condition is 1130CFU/mL, so that the killing effect of the AgO hollow porous microspheres prepared by the method on the staphylococcus aureus is far higher than that of AgO particles with the square shape.

Claims (7)

1. A preparation method of monodisperse AgO hollow porous microspheres is characterized by comprising the following steps:
step 1, dropwise adding a first sodium hydroxide solution into a silver nitrate solution to form a precipitate, adding ammonia water to dissolve the precipitate, and adjusting the pH value of the solution to 4-9 to obtain a silver-ammonia solution;
step 2, adding fumed silica into the silver ammonia solution, stirring, performing centrifugal separation to obtain fumed silica containing silver ions and a supernatant, dispersing the fumed silica containing the silver ions by using deionized water to obtain a first suspension, measuring the silver ion concentration of the supernatant, and calculating the molar quantity n of the silver ions adsorbed by the fumed silica;
step 3, preparing a sodium chloride solution containing n moles of sodium chloride by using deionized water, dropwise adding the sodium chloride solution into the first suspension under the stirring condition for reaction, separating to obtain a first solid after the reaction is finished, and cleaning the first solid by using deionized water to obtain AgCl/SiO2The composite material is then dispersed with deionized water2Obtaining a second suspension of the composite material;
step 4, respectively preparing K2S2O8Solution and a second sodium hydroxide solution, adding K2S2O8Placing the solution in a constant temperature environment, and stirring the solution to the K2S2O8And (3) dropwise adding the second suspension and a second sodium hydroxide solution in sequence to react, soaking the separated second solid in a third sodium hydroxide solution for 4-20 hours after the reaction is finished, and cleaning and drying the separated black powder to obtain the monodisperse AgO hollow porous microspheres.
2. The preparation method of the monodisperse AgO hollow porous microsphere as claimed in claim 1, wherein the specific steps in step 1 are as follows:
the specific steps in step 1 are as follows: dropwise adding a first sodium hydroxide solution into a silver nitrate solution according to the molar ratio of silver nitrate to sodium hydroxide of 0.5-1.1 to form a precipitate, adding ammonia water to dissolve the precipitate, and then using HNO3Adjusting the pH value of the solution to prepare silver ammonia solution.
3. The preparation method of the monodisperse AgO hollow porous microsphere as claimed in claim 1, wherein in step 2, fumed silica is added into the silver ammonia solution and stirred for 1-2 h, wherein the molar ratio of fumed silica to silver nitrate is 1.2-5.5.
4. The preparation method of the monodisperse AgO hollow porous microsphere as claimed in claim 1, wherein in step 3, sodium chloride solution is dropwise added into the first suspension under stirring to react for 10-30 min, after the reaction is finished, a first solid is obtained by separation, and the first solid is washed with deionized water for not less than 3 times.
5. The preparation method of monodisperse AgO hollow porous microspheres according to claim 1, wherein K is in step 42S2O8K in solution2S2O8Is 3n and the molar amount of sodium hydroxide in the second sodium hydroxide solution is 7 n.
6. The preparation method of monodisperse AgO hollow porous microspheres as claimed in claim 1, wherein K is added in step 42S2O8The solution is placed at a constant temperature of 55-65 ℃ and is stirred to K2S2O8And (3) dropwise adding the second suspension and the second sodium hydroxide solution into the solution in sequence to react for 60-140 min, and soaking the separated second solid in a third sodium hydroxide solution for 4-20 h after the reaction is finished.
7. The preparation method of the monodisperse AgO hollow porous microsphere as claimed in claim 1, wherein the black powder obtained by separation in step 4 is dried at 50-70 ℃ for 0.5-3 h after being cleaned.
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