CN111097922A - Nano silver particle and preparation method and application thereof - Google Patents
Nano silver particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nano silver particle and a preparation method and application thereof, wherein the preparation method of the nano silver particle comprises the steps of mixing a silver ammonia solution and a protective agent dispersion liquid, and then adding a reducing agent for mixing reaction to obtain the nano silver particle; the method for preparing the nano silver particles by one-step reaction has the advantages of simple reaction system, capability of controlling the particle size of the nano silver particles by using temperature regulation and capability of being used for batch production of the nano silver particles.
Description
Technical Field
The invention belongs to the field of metal nano materials, and relates to a nano silver particle, a preparation method and application thereof.
Background
Among various nano metals, the unusual optical, electrical and chemical properties of nano silver based on its particle size and structure are attracting wide attention of the scientific community, and its excellent properties open the door for corresponding technical applications. Over the last two decades, a great deal of research on the particle size and morphology control of nano silver has been reported.
Generally, the main preparation method of nano-silver comprises the step of carrying out the treatment on Ag in the presence of a protective agent+Chemical reduction, thermal degradation in organic solvents, chemical or optical reduction in reverse micelles, and the like. By using the methods, the nano silver which is spherical, octahedral, tetrahedral, hexagonal, cubic, linear, coaxial linear, flaky and banded can be prepared.
The chemical reduction method is a common method for preparing nano silver powder, silver salt is added into an organic or inorganic solvent, a proper amount of reducing agent is added into the solution to reduce silver ions into small crystal nuclei, the small crystal nuclei are aggregated to grow silver particles with a certain particle size, and a protective agent forms an organic matter layer on the surface to keep monodispersion among the particles and prevent further growth. However, due to the thickness of the protective agent and the size of the voids between the particles, the properties after sintering never exceed those of the bulk metal itself.
CN103769603A discloses a method for preparing nano-silver, which takes biological molecules as a template and utilizes AgNO3The solution provides silver ions, and silver nanoparticles with spherical morphology are regulated and synthesized.
CN106623971A discloses a method for synthesizing stable silver nanoparticles, which adopts a mixed solution of a reducing agent and silver nitrate to synthesize stable silver nanoparticles, and includes two steps of mixing a silver source and an organic amine solution to obtain a mixed solution and synthesizing the silver nanoparticles, wherein silver nitrate is used as the silver source, hydrazine hydrate or sodium borohydride is used as the reducing agent, and organic amine is used as a protective agent.
Therefore, the development of a preparation method of the nano-silver particles, which has the advantages of simple reaction system, small particle size of the prepared nano-silver particles, narrow particle size distribution range and suitability for batch preparation, is still significant.
Disclosure of Invention
The invention aims at providing a nano silver particle and a preparation method and application thereof, wherein the preparation method of the nano silver particle comprises the steps of mixing a silver ammonia solution and a protective agent dispersion solution, and then adding a reducing agent for mixing reaction to obtain the nano silver particle; the method for preparing the nano silver particles by one-step reaction has the advantages of simple reaction system, capability of controlling the particle size of the nano silver particles by using temperature regulation and capability of being used for batch production of the nano silver particles.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing nano silver particles, comprising the steps of:
(1) mixing the silver-ammonia solution and the protective agent dispersion liquid to obtain a mixed solution;
(2) adding a reducing agent dispersion liquid into the mixed solution obtained in the step (1) for reaction to obtain the nano silver particles;
wherein, the reducing agent in the reducing agent dispersion liquid in the step (2) comprises any one or a combination of at least two of ascorbic acid, glucose, citric acid, oxalic acid or formic acid, and the combination exemplarily comprises a combination of ascorbic acid and glucose, a combination of citric acid and oxalic acid or a combination of formic acid and glucose, and the like.
According to the method, the reducing agent dispersion liquid is added into the mixed solution of the silver-ammonia solution and the protective agent dispersion liquid for reaction, nano silver particles with small particle size and narrow particle size distribution are obtained through one-step reaction, the particle size of the obtained nano silver particles is distributed between 10nm and 120nm, the uniformity is high, and the agglomeration is not easy to occur. In addition, the shape and the particle size of the prepared product can be regulated and controlled by adjusting the reaction temperature in the preparation process, so that the controllability of the preparation process is improved.
The method adopts the reducing agents, and the reducing agents have mild reducing capability, and meanwhile, the reducing capability and the temperature have great relationship, so that the reaction can be carried out at a lower temperature, and the increase of the particle size of the nano silver particles caused by the accelerated Oswald curing of a high-temperature reaction is avoided; the method adopts the reducing agent and combines proper reaction temperature (0-60 ℃), can well control the formation speed and the growth speed of the nano-silver crystal nucleus, and obtains nano-silver particles with different sizes, uniform appearance and good dispersibility.
Preferably, the reducing agent in the reducing agent dispersion liquid in the step (2) is ascorbic acid.
The invention adopts the ascorbic acid as the reducing agent, has simple structure and proper reducing capability and is beneficial to the control of the appearance.
Preferably, the preparation method of the silver-ammonia solution in the step (1) includes dispersing silver nitrate in water to obtain a silver nitrate solution, and then adding ammonia water to obtain the silver-ammonia solution.
Preferably, the concentration of the aqueous ammonia is 15-20%, such as 16%, 17%, 18%, 19%, or the like.
Preferably, the silver nitrate solution contains 2-12% by mass of silver nitrate, such as 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or 11%, preferably 4-6%.
Preferably, the protecting agent in the protecting agent dispersion liquid in the step (1) comprises any one or a combination of at least two of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, oleic acid, polyethylene glycol, n-dodecyl mercaptan, polyacrylic acid or lauric acid; exemplary combinations include a combination of sodium dodecylbenzenesulfonate and polyvinylpyrrolidone, a combination of polyvinyl alcohol and oleic acid, a combination of polyethylene glycol and n-dodecylmercaptan, or a combination of polyacrylic acid and lauric acid, etc., preferably polyvinylpyrrolidone.
The invention adopts polyvinylpyrrolidone as a protective agent, has low cost and small residual amount after subsequent washing treatment.
Preferably, the mass percentage of the protecting agent in the protecting agent dispersion liquid in the step (1) is 2-10%, for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, etc.
Preferably, the ratio of the mass of the silver nitrate in the silver ammonia solution in the step (1) to the mass of the protective agent in the protective agent dispersion is 1 (0.25-4), for example, 1:0.3, 1:0.5, 1:0.7, 1:1, 1:1.1, 1:1.3, 1:1.5 or 1:1.8, etc., preferably 1 (0.5-2).
The ratio of the mass of the silver nitrate in the silver-ammonia solution to the mass of the protective agent in the protective agent dispersion liquid in the preparation process of the method is 1 (0.25-4), and the mass generates steric hindrance effect in the preparation process of the nano silver particles, so that the aggregation and growth of the silver particles are inhibited, and the nano silver particles with small particle size and narrow particle size distribution range are obtained. When the mass ratio is less than 1:4, the concentration of the protective agent is insufficient, the crystal face adsorption protection is insufficient, silver nanowires and nanorods are easy to generate, and when the mass ratio is more than 1:0.25, the influence of the continuous increase of the dosage of the protective agent on the particle size is not large, and the residual quantity after washing treatment is increased.
Preferably, the solvent of the protective agent dispersion liquid in the step (1) is water and/or ethanol; preferably water.
Preferably, the solvent of the reducing agent dispersion liquid in the step (2) is water and/or ethanol, and preferably water.
Preferably, the mass percentage content of the reducing agent in the reducing agent dispersion liquid is 10-20%, such as 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and the like.
The mass percentage of the reducing agent in the reducing agent dispersion liquid used in the invention is 10-20%, which is beneficial to controlling the nucleation process of silver particles in the reaction process and increasing the controllability of the preparation process, thereby being beneficial to obtaining nano silver particles with small particle size and narrow particle size distribution; when the mass percentage of the reducing agent in the reducing agent dispersion liquid is less than 10%, the reaction is insufficient, silver ions are not completely reduced, and when the mass percentage of the reducing agent in the reducing agent dispersion liquid is more than 20%, the silver ions are rapidly reduced into simple substances due to the excessive reducing agent, so that the nano particles are agglomerated.
Preferably, the ratio of the mass of silver nitrate in the silver ammonia solution in the step (1) to the mass of the reducing agent in the reducing agent dispersion liquid in the step (2) is 1 (0.1-0.3), for example, 1:0.15, 1:0.2, or 1: 0.25.
Preferably, the reducing agent dispersion liquid in the step (2) is added dropwise.
Preferably, the reaction in step (2) is carried out at a temperature of 0 to 60 ℃, e.g., 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃ or 50 ℃, etc.
According to the method, the temperature for reaction by adding the reducing agent dispersion liquid is 0-60 ℃, silver ions in the silver ammonia solution can be reduced at a lower temperature, the reaction condition is mild, and the nano silver particles with small particle size and high appearance uniformity can be obtained. When the temperature is lower than 0 ℃, the solvent is easy to solidify; when the temperature is higher than 60 ℃, the reducing capability of the reducing agent is strengthened, and the irregular movement of the nano particles is increased, so that the nano particles are agglomerated, and the particle size is increased.
Preferably, the reaction in step (2) is carried out for a time of 0.5 to 6h, such as 1h, 2h, 3h, 4h or 5h, etc.
Preferably, the addition of the reducing agent dispersion in step (2) is accompanied by stirring.
Preferably, the rotation speed of the stirring is 600-2000rpm, such as 700rpm, 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1600rpm, 1700rpm, 1800rpm, 1900rpm, and the like.
Preferably, the reaction in the step (2) is finished, and the product is subjected to solid-liquid separation, washing and drying.
Preferably, the method of solid-liquid separation comprises any one of filtration, sedimentation, evaporation or centrifugation or a combination of at least two thereof, the combination illustratively comprising a combination of filtration and sedimentation, a combination of sedimentation and evaporation or a combination of centrifugation and sedimentation, and the like, preferably filtration.
Preferably, the detergent for washing comprises ethanol and water.
Preferably, the washing is accompanied by ultrasound.
Preferably, the drying method includes any one of vacuum drying, natural drying, heat drying or forced air drying.
Preferably, the drying is vacuum drying.
Preferably, the temperature of the vacuum drying is 20-50 ℃, such as 25 ℃, 30 ℃, 35 ℃, 40 ℃ or 45 ℃ and the like.
Preferably, the drying time is 12-24h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h or 23h, etc.
As a preferable technical scheme of the present invention, the preparation method of the nano silver particles comprises the following steps:
(a) dispersing silver nitrate in water to obtain a silver nitrate solution with the mass percentage of 2-12%, and then adding ammonia water to obtain a silver ammonia solution; dispersing a protective agent in a first solvent to obtain a protective agent dispersion liquid, and dispersing a reducing agent in a second solvent to obtain a reducing agent dispersion liquid; the first solvent and the second solvent are respectively and independently selected from ethanol and/or water;
(b) mixing the silver-ammonia solution and the protective agent dispersion liquid in the step (a) in a container to obtain a mixed solution, and then placing the mixed solution in a constant-temperature water bath at the temperature of 0-60 ℃; the mass ratio of the silver nitrate in the silver ammonia solution to the protective agent in the protective agent dispersion liquid is 1 (0.25-4);
(c) and (3) dropwise adding the reducing agent dispersion liquid in the step (a) into the mixed solution in the step (b) at the stirring speed of 600 plus 2000rpm, reacting for 0.5-6h, and then carrying out solid-liquid separation, washing and drying to obtain the nano silver particles.
The raw materials adopted in the preparation process of the method are basically nontoxic and pollution-free, the method is environment-friendly, the reaction process is carried out under mild conditions, no special pressure or temperature requirement is required, the equipment requirement is low, and the process equipment and energy consumption cost are reduced.
In a second aspect, the present invention provides a method for controlling the particle size of nano-silver particles, the method comprising using the method according to the first aspect.
Preferably, the method comprises adjusting the temperature at which the reaction is carried out in step (2).
Preferably, the reaction is carried out at a temperature of 0 to 60 ℃, e.g., 5 ℃, 10 ℃, 20 ℃, 30 ℃ or 40 ℃, etc.
According to the method, the reducing agent dispersion liquid is added into the mixed solution of the silver ammonia solution and the protective agent dispersion liquid, then the reaction is carried out, the nano silver particles are obtained, the shape and the particle size of the product nano silver particles can be effectively adjusted by adjusting the reaction temperature in the preparation process, and the controllability of the preparation process of the nano silver particles is improved.
In a third aspect, the present invention provides the nano silver particles prepared by the method of the first aspect, wherein the nano silver particles have a particle size of 10-120nm, such as 15nm, 20nm, 25nm, 30nm, 35nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 105nm, 110nm or 115nm, etc.
Preferably, the nano silver particles are of a cubic crystal structure.
In a fourth aspect, the invention provides a use of the nano silver particles according to the third aspect, wherein the nano silver particles are used in flexible printing conductive ink, solder in the field of semiconductor packaging or medical nano antibacterial material.
The preparation method of the nano-silver particles has the advantages of simple operation, low equipment cost, narrow particle size distribution and the like, can be used for preparing the nano-silver particles in batches, and can be applied to the fields of flexible printing conductive ink, solder in the field of semiconductor packaging and the like; the method utilizes the fact that when the particle diameter of the metal nanoparticles is less than 100nm, the melting point of the metal nanoparticles is sharply reduced along with the reduction of the size, so that the sintered material can have the properties close to those of bulk metal, such as electric conductivity, thermal conductivity, hardness and the like, by reducing the particle diameter of the nanoparticles to reduce the sintering temperature.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method of the nano silver particles adopts a liquid phase chemical reduction method, the reducing agent dispersion liquid is added into the mixed solution of the silver ammonia solution and the protective agent dispersion liquid, and then the nano silver particles are obtained through reaction, the nano silver particles with small particle size and narrow particle size distribution range are obtained through one-step reaction in the preparation process, the particle size of the obtained nano silver particles is 10-120nm, and the product has high uniformity and is not easy to agglomerate;
(2) the preparation method of the nano-silver particles has the advantages that the raw materials are cheap, the particle size of the prepared nano-silver particles can be effectively adjusted by adjusting the reaction temperature, and the method is suitable for preparing the nano-silver particles in batches;
(3) the method simplifies the types of reactants, reduces byproducts, simplifies the post-treatment process, ensures that the reaction is easier to control, and effectively reduces the cost of raw materials and the process.
Drawings
FIG. 1 is a scanning electron microscope image of nano-silver particles prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of nano-silver particles prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the nano-silver particles prepared in example 2 of the present invention;
FIG. 4 is a scanning electron microscope image of the nano-silver particles prepared in example 3 of the present invention;
FIG. 5 is a scanning electron microscope image of the nano-silver particles prepared in example 4 of the present invention;
fig. 6 is a scanning electron microscope image of the nano silver particles prepared in example 5 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 10g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 10%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 1g of polyvinylpyrrolidone into 12g of water to obtain polyvinylpyrrolidone dispersion liquid with the mass fraction of 8.3%; 0.2g of ascorbic acid was dispersed in 1g of water to obtain an ascorbic acid solution with a mass fraction of 20%
(b) Mixing the silver ammonia solution obtained in the step (a) and the polyvinylpyrrolidone dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 0 ℃;
(c) slowly dripping the prepared ascorbic acid solution under the condition of mechanical stirring at 1000r/min, reacting for 6 hours, carrying out solid-liquid separation, washing and drying for 24 hours to obtain the nano silver particles.
The scanning electron microscope image of the nano silver particles prepared in this example is shown in fig. 1, and as can be seen from fig. 1, the prepared nano silver particles have high uniformity and good dispersibility.
The X-ray diffraction curve of the nano-silver particles prepared in this example is shown in fig. 2, and it can be seen from fig. 2 that the nano-silver particles prepared in this example have a cubic crystal structure.
Example 2
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 10g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 10%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 1g of polyvinylpyrrolidone into 12g of water to obtain polyvinylpyrrolidone dispersion liquid with the mass fraction of 8.3%; 0.2g of formic acid was dispersed in 2g of water to give a 10% by weight formic acid solution
(b) Mixing the silver ammonia solution obtained in the step (a) and the polyvinylpyrrolidone dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 20 ℃;
(c) slowly dripping the prepared formic acid solution under the condition of mechanical stirring at 1000r/min, reacting for 6 hours, carrying out solid-liquid separation, washing and drying for 24 hours to obtain the nano silver particles.
The scanning electron microscope image of the nano silver particles prepared in this example is shown in fig. 3, and as can be seen from fig. 3, the prepared nano silver particles have high uniformity and good dispersibility.
Example 3
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 10g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 10%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 1g of polyvinylpyrrolidone into 12g of water to obtain polyvinylpyrrolidone dispersion liquid with the mass fraction of 8.3%; 0.2g of formic acid was dispersed in 2g of water to give a 10% by weight formic acid solution
(b) Mixing the silver ammonia solution obtained in the step (a) and the polyvinylpyrrolidone dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 40 ℃;
(c) slowly dripping the prepared formic acid solution under the condition of mechanical stirring at 1000r/min, reacting for 6 hours, carrying out solid-liquid separation, washing and drying for 24 hours to obtain the nano silver particles.
The scanning electron microscope image of the nano silver particles prepared in this example is shown in fig. 4, and as can be seen from fig. 4, the prepared nano silver particles have high uniformity and good dispersibility.
As can be seen from comparison of examples 2 and 3, the temperature for the reaction in step (c) is adjusted during the preparation of the silver nanoparticles, so that the particle size of the prepared silver nanoparticles can be effectively adjusted, and the silver nanoparticles with narrow particle size distribution range and high uniformity can be obtained within the temperature range.
Example 4
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 20g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 5%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 1g of oleic acid in 16g of absolute ethyl alcohol to obtain oleic acid dispersion liquid with the mass fraction of 6.25%; dispersing 0.2g of ascorbic acid in 1g of water to obtain an ascorbic acid solution with the mass fraction of 20%;
(b) mixing the silver ammonia solution obtained in the step (a) and the oleic acid dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 0 ℃;
(c) slowly dripping the prepared ascorbic acid solution into the reactor under the condition of mechanical stirring at 1200r/min, reacting for 6 hours, carrying out solid-liquid separation, washing and drying for 18 hours to obtain the nano-silver particles.
As shown in fig. 5, a scanning electron microscope image of the nano silver particles prepared in this embodiment is shown in fig. 5, and it can be seen from fig. 5 that the prepared nano silver particles have high uniformity and good dispersibility.
Example 5
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 20g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 5%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 1g of oleic acid in 16g of absolute ethyl alcohol to obtain oleic acid dispersion liquid with the mass fraction of 6.25%; 0.2g of ascorbic acid was dispersed in 1g of water to obtain an ascorbic acid solution with a mass fraction of 20%
(b) Mixing the silver ammonia solution obtained in the step (a) and the oleic acid dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 10 ℃;
(c) slowly dripping the prepared ascorbic acid solution into the reactor under the condition of mechanical stirring at 1200r/min, reacting for 6 hours, carrying out solid-liquid separation, washing and drying for 18 hours to obtain the nano-silver particles.
As shown in fig. 6, a scanning electron microscope image of the nano silver particles prepared in this embodiment is shown in fig. 6, and it can be seen from fig. 6 that the prepared nano silver particles have high uniformity and good dispersibility.
As can be seen from comparison of examples 4 and 5, the temperature for the reaction in step (c) is adjusted during the preparation of the silver nanoparticles, so that the particle size of the prepared silver nanoparticles can be effectively adjusted, and the silver nanoparticles having a narrow particle size distribution range and high uniformity can be obtained within the above temperature range.
Example 6
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 50g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 2%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 0.25g of n-dodecyl mercaptan in 10g of water to obtain an n-dodecyl mercaptan dispersion liquid with the mass fraction of 2%; dispersing 0.1g of citric acid in 1g of water to obtain a citric acid solution with the mass fraction of 10%;
(b) mixing the silver ammonia solution obtained in the step (a) and n-dodecyl mercaptan dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 60 ℃;
(c) slowly dripping the prepared citric acid solution under the condition of mechanical stirring at 600r/min, reacting for 1h, carrying out solid-liquid separation, washing and drying for 12h to obtain the nano-silver particles.
Example 7
The preparation method of the nano silver particles comprises the following steps:
(a) dispersing 1g of silver nitrate in 10g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 10%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 4g of polyvinyl alcohol in 50g of water to obtain a polyvinyl alcohol dispersion liquid with the mass fraction of 8%; dispersing 0.1g of glucose in 1g of water to obtain a glucose solution with the mass fraction of 10%;
(b) mixing the silver ammonia solution obtained in the step (a) and the polyvinyl alcohol dispersion liquid in a three-neck flask, and placing the mixture in a constant-temperature water bath at 40 ℃;
(c) slowly dripping the prepared glucose solution under the condition of mechanical stirring at 1000r/min, reacting for 4 hours, carrying out solid-liquid separation, washing and drying for 24 hours to obtain the nano-silver particles.
Example 8
This example is different from example 1 in that ascorbic acid in example 1 was replaced with oxalic acid of equal mass, and other conditions were exactly the same as in example 1.
Example 9
This example is different from example 1 in that ascorbic acid in example 1 was replaced with glucose of equal mass, and other conditions were completely the same as in example 1.
Comparative example 1
The preparation method of the nano silver particles in the comparative example comprises the following steps:
(a) dispersing 1g of silver nitrate in 10g of ultrapure water to obtain a silver nitrate solution with the mass fraction of 10%, and dropwise adding ammonia water to prepare a silver ammonia solution; dispersing 1g of polyvinylpyrrolidone into 12g of polyethylene glycol 400 to obtain polyvinylpyrrolidone dispersion liquid with the mass fraction of 8.3%;
(b) mixing the silver-ammonia solution obtained in the step (a) with the polyvinylpyrrolidone dispersion liquid, placing the mixture in a reaction kettle at the temperature of 60 ℃, stirring and mixing the mixture at the rotating speed of 500rpm for reaction for 3 hours, then carrying out solid-liquid separation, washing and vacuum drying for 6 hours to obtain the nano silver particles.
Comparative example 2
The present comparative example differs from example 1 in that no ammonia water was added in step (a), i.e., silver nitrate was used instead of the silver ammonia solution in step (b), and the other conditions were exactly the same as in example 1.
Comparative example 3
This comparative example is different from example 1 in that the reducing agent in step (a) is replaced by sodium borohydride from ascorbic acid or the like, and other conditions are exactly the same as those in example 1.
The results of the particle size test on the nano silver particles prepared in examples 1 to 9 and comparative examples 1 to 3 are shown in table 1;
TABLE 1
As can be seen from the table above, the nano silver particles prepared by the method of the invention have small particle size and narrow particle size distribution range, and the yield of the silver nano particles in the preparation process is high and is all more than 87%;
comparing examples 1, 8 and 9 with comparative example 3, it can be seen that the particle size distribution range of the nano-silver particles prepared by using the reducing agent of the present invention is significantly smaller than that of the nano-silver particles prepared by using sodium borohydride as the reducing agent; the widths of the particle size distribution ranges of the nano-silver particles prepared in examples 1, 8 and 9 are all less than or equal to 40nm, while the width of the particle size distribution range of the nano-silver particles prepared in comparative example 3 is 70 nm; and the yields of the preparation processes in examples 1, 8 and 9 are obviously better than those in comparative example 1;
as can be seen from the comparison of example 1 and comparative example 1, the method of the present invention can prepare nano silver particles at a lower temperature, the conditions of the preparation process are mild, the particle size distribution range of the product is narrow, and the yield is high.
Comparing example 1 with comparative example 2, it can be seen that the method of the present invention uses silver ammonia solution as silver source, and the nano silver particles prepared by the method have smaller particle size, narrow particle size distribution range and high yield.
As can be seen from the comparison of examples 2-3 and 4-5, respectively, the method of the present invention can effectively adjust the particle size distribution of the prepared nano silver particles by adjusting the reaction temperature during the preparation process.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing nano silver particles, which is characterized by comprising the following steps:
(1) mixing the silver-ammonia solution and the protective agent dispersion liquid to obtain a mixed solution;
(2) adding a reducing agent dispersion liquid into the mixed solution obtained in the step (1) for reaction to obtain the nano silver particles;
wherein, the reducing agent in the reducing agent dispersion liquid in the step (2) comprises any one or the combination of at least two of ascorbic acid, glucose, citric acid, oxalic acid or formic acid.
2. The method of claim 1, wherein the reducing agent in the reducing agent dispersion of step (2) is ascorbic acid;
preferably, the preparation method of the silver-ammonia solution in the step (1) includes dispersing silver nitrate in water to obtain a silver nitrate solution, and then adding ammonia water to obtain a silver-ammonia solution;
preferably, the mass percentage of the silver nitrate in the silver nitrate solution is 2-12%, preferably 4-6%.
3. The method of claim 1 or 2, wherein the protecting agent in the protecting agent dispersion of step (1) comprises any one or a combination of at least two of sodium dodecylbenzene sulfonate, polyvinylpyrrolidone, polyvinyl alcohol, oleic acid, polyethylene glycol, n-dodecyl mercaptan, polyacrylic acid, or lauric acid; preferably polyvinylpyrrolidone;
preferably, the mass percentage of the protective agent in the protective agent dispersion liquid in the step (1) is 2-10%;
preferably, the ratio of the mass of the silver nitrate in the silver ammonia solution in the step (1) to the mass of the protective agent in the protective agent dispersion liquid is 1 (0.25-4), preferably 1 (0.5-2).
4. The process according to any one of claims 1 to 3, wherein the solvent of the protective agent dispersion of step (1) is water and/or ethanol; preferably water;
preferably, the solvent of the reducing agent dispersion liquid in the step (2) is water and/or ethanol, preferably water;
preferably, the mass percentage content of the reducing agent in the reducing agent dispersion liquid is 10-20%.
5. The method of any one of claims 1 to 4, wherein the ratio of the mass of silver nitrate in the silver ammonia solution of step (1) to the mass of reducing agent in the reducing agent dispersion of step (2) is 1 (0.1 to 0.3);
preferably, the reducing agent dispersion liquid in the step (2) is added dropwise;
preferably, the temperature for carrying out the reaction in step (2) is 0-60 ℃, preferably 0-10 ℃;
preferably, the reaction time in the step (2) is 0.5-6 h;
preferably, the reducing agent dispersion liquid is added in the step (2) with stirring;
preferably, the rotation speed of the stirring is 600-2000 rpm.
6. The method of any one of claims 1 to 5, wherein the reaction of step (2) is finished and the method further comprises the steps of carrying out solid-liquid separation, washing and drying on the product;
preferably, the method of solid-liquid separation comprises any one or a combination of at least two of filtration, sedimentation, evaporation or centrifugation, preferably filtration;
preferably, the detergent for washing comprises ethanol and water;
preferably, the washing is accompanied by ultrasound;
preferably, the drying method includes any one of vacuum drying, natural drying, heating drying or forced air drying;
preferably, the drying is vacuum drying;
preferably, the temperature of the vacuum drying is 20-50 ℃;
preferably, the drying time is 12-24 h.
7. The method according to any one of claims 1 to 6, characterized in that it comprises the steps of:
(a) dispersing silver nitrate in water to obtain a silver nitrate solution with the mass percentage of 2-12%, and then adding ammonia water to obtain a silver ammonia solution; dispersing a protective agent in a first solvent to obtain a protective agent dispersion liquid, and dispersing a reducing agent in a second solvent to obtain a reducing agent dispersion liquid; the first solvent and the second solvent are respectively and independently selected from ethanol and/or water;
(b) mixing the silver-ammonia solution and the protective agent dispersion liquid in the step (a) in a container to obtain a mixed solution, and then placing the mixed solution in a constant-temperature water bath at the temperature of 0-60 ℃; the mass ratio of the silver nitrate in the silver ammonia solution to the protective agent in the protective agent dispersion liquid is 1 (0.25-4);
(c) and (3) dropwise adding the reducing agent dispersion liquid in the step (a) into the mixed solution in the step (b) at the stirring speed of 600 plus 2000rpm, reacting for 0.5-6h, and then carrying out solid-liquid separation, washing and drying to obtain the nano silver particles.
8. A method for regulating the particle size of nano silver particles, which comprises using the method according to any one of claims 1 to 7;
preferably, the method comprises adjusting the temperature at which the reaction is carried out in step (2);
preferably, the temperature at which the reaction is carried out is from 0 to 60 ℃.
9. The nano-silver particles produced by the method according to any one of claims 1 to 7, wherein the nano-silver particles have a particle size of 10 to 120 nm;
preferably, the nano silver particles are of a cubic crystal structure.
10. Use of the nano silver particles according to claim 9 in flexible printing of conductive inks, solders in the field of semiconductor packaging or medical nano antibacterial materials.
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