CN109128211B - Method for preparing micro-nano silver particles in aqueous solution system - Google Patents
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Abstract
The invention relates to a method for preparing micro-nano silver particles in an aqueous solution system, which comprises the following steps: and mixing the silver salt aqueous solution with the complexing agent aqueous solution to prepare a silver complex precursor solution, then dropwise mixing the silver complex precursor solution with the reducing agent aqueous solution at the same time, and carrying out one-step reduction reaction to obtain the micro-nano silver particles. The method is carried out in water solution at normal temperature and pressure, without using high molecular polymer as protective agent and dispersing agent and hydrazine hydrate as reducing agent, reducing silver complex precursor. The preparation method is simple, the residue of high molecular polymer on the surface of the silver powder is avoided, and the prepared flower-shaped micro-nano silver particles are regular in morphology, uniform in particle size distribution, good in dispersity, controllable in size and high in yield.
Description
Technical Field
The invention discloses a method for preparing micro-nano silver particles in an aqueous solution system, and belongs to the field of preparation of micro-nano material silver.
Background
The silver micro-nano material has unique physical and chemical properties and has wide application prospects in the fields of electricity, catalysis, magnetism, SERS spectrum and the like. The properties of the micro-nano silver material are closely related to factors such as properties, sizes, structures and the like. In recent years, nanoparticles and nanomaterials have become one of the hot spots of research in the field of material science. The research and development of micro-nano silver in China started in the early 60 s, and the eight and ninety years enter a rapid development stage, in the period, the government investment is large, a plurality of units participate in the research of silver powder preparation technology, and a plurality of series of silver powder are produced, so that the domestic blank is filled. In China, a lot of silver powder manufacturers are available, and the silver powder is of complete variety and good quality. Compared with developed countries in the world, the silver powder produced in China at present is not very complete in variety and series, and has certain gap in performance with foreign countries. In order to meet various practical requirements, many research institutes and research groups also successfully synthesize silver materials with micro-nano structures of different shapes, sizes and structures by using various methods. The shape control is an effective way for regulating and controlling the physical and chemical properties of the metal nano structure, so the shape-controllable preparation of the silver is still a focus of the current research.
Both theoretical calculations and experimental results indicate that the surface plasmon resonance and surface enhanced raman scattering properties of silver nanoparticles are highly dependent on their morphology. The flower-like silver powder with the micro-nano structure is formed by nano sheets or rods and other nano appearances, the surface has certain roughness, sharp edges and corners at the micron level and the like, a thermal field can be provided on the surface of a single particle, and the flower-like silver powder is an excellent substrate with a surface Raman scattering effect; the conductive filler is used in the printing paste ink, the flower-like spherical silver sheet is in surface contact with the sheet, the silver content in unit area is obviously improved, and the defect that the sheet silver powder is easy to migrate in a humid environment is overcome; the ultraviolet curing conductive ink has good diffuse reflection effect on ultraviolet irradiation in the photocuring process, and when the ultraviolet curing conductive ink is applied to photocuring conductive ink, the ultraviolet curing technology and the conductive ink technology are combined to form good printing precision, high-speed printability, adhesion, and good conductivity and stability.
The flower-like silver prepared at present is complex in structure and generally assembled by nano flakes and the like, and cannot be prepared by a physical method due to the complex structure, and can be prepared by a chemical reduction method only under the control of specific conditions. The reducing agent is mainly ascorbic acid, ferrous sulfate, amino acid, catechol, hydrogen peroxide, glycol, polyvinylpyrrolidone and the like. For example, PVP is used as a protective agent and a reducing agent to reduce silver nitrate at 100 ℃ to prepare flower-shaped silver nanoparticles (see: He et al, gold, 2013, 34 (1)); polyvinylpyrrolidone is used as a reducing agent, and the flower-like silver powder can be reduced and prepared at the temperature of more than 80 ℃ (see: Anhua chapter, non-ferrous metals, 4 th year 2017, 52-57). Therefore, the system using the polyvinylpyrrolidone as the reducing agent and the dispersing agent is required to be heated in a water bath to a certain temperature to prepare the flower-shaped silver powder, and the polyvinylpyrrolidone is difficult to be completely treated in the post-treatment process.
The research of Chen et al shows that silver powder with micro-nano structure with high surface roughness and the particle size of about 0.5 micron is prepared by reducing silver nitrate with hydrogen peroxide under the assistance of ultrasound, and the silver powder can be used as a substrate through the verification experiment of detecting trace chemicals through Raman scattering (see: CHEN H J, Journal of physical chemistry C, 2009, 113 (44): 19258-. The Wangxiangyu researches the preparation of micro-nano silver powder with rough surface by using polymer stabilizers such as polyacrylamide and polyvinylpyrrolidone and a small molecule surfactant citric acid in a academic paper, wherein the reducing agents are ascorbic acid and hydroquinone. And the SERS activity of the silver powder is researched, and the result shows that the micro-nano silver powder with the rough surface can obtain a Raman absorption peak with obvious enhancement effect, and trace detection of rhodamine B is realized (see: Wangxiangyu, preparation of the micro-nano silver powder with the rough surface and research on the SERS activity thereof, academic thesis of Huadong university of science and technology, 2013).
In the report of preparing flower-like silver powder at room temperature, ascorbic acid is used as a reducing agent. For example, silver nitrate and ascorbic acid are used as raw materials, and react for 2h at room temperature with the aid of citric acid and polyvinylpyrrolidone to synthesize the silver flower-like ball (see: Wuhuije et al, materials guide, 5 months 2014, volume 28, album 23). Flower-like silver particles of 500nm-2 μm were synthesized by ascorbic acid reduction of silver nitrate with the aid of polyvinylpyrrolidone by adjusting the concentration of silver nitrate (see: H, y. liang, advanced Materials,2009,21(45): 4614-. Flower-like silver nanoparticles were prepared by reducing silver nitrate with ascorbic acid under conditions containing polyvinylpyrrolidone and trisodium citrate (see X.S. Shen et al, Physical Chemistry Chemical Physics,2009,11(34): 7450-7454.). A method for preparing a flower-like silver micro-nano structure composed of nanosheets by using ascorbic acid to reduce silver nitrate in a system with the pH value adjusted by nitric acid and trisodium citrate, wherein the pH value is adjusted by using concentrated nitric acid, and the flower-like silver micro-nano structure with good appearance and the diameter of about 1.5 mu m can be obtained only when the pH value of a solution is about 3.5. Experimental results show that the flower-like silver micro-nano structure has strong activity as a substrate for surface enhanced Raman scattering (see Zhang Bo et al, Proc. in higher school chemistry, 2010, 8, 1491-1495).
The preparation method using other reducing agents, for example, Chinese patent document CN103273082A uses ferrous sulfate as a reducing agent to prepare flower-like spherical silver powder with a particle size of 0.5-3 μm. The Chinese patent document CN106424752A uses two reducing agents with different reducibility to fully react at-10 to 80 ℃ to obtain the flower-shaped silver powder. The prepared silver powder is applied to the conductive ink, so that the conductivity of the conductive ink can be improved, and the printability and the printing precision of the conductive ink are better. The Chinese patent document CN107127355A uses amino acid as a reducing agent, firstly uses a pH value regulator to regulate the pH value to 4-6, and needs to react for 5-10h under the condition of heating at 30-80 ℃ to reduce silver ammonia solution to obtain flower-shaped silver microspheres.
In addition, chinese patent document CN101875130A discloses a method for preparing and separating nano silver particles. Firstly, AgNO is prepared3Adding a certain amount of surfactant into the mixed aqueous solution of the complexing agent, adjusting the pH value of the system, stirring to completely dissolve the added surfactant, dropwise adding a reducing agent into the solution under vigorous stirring, controlling the reaction temperature at room temperature, and after the dropwise adding of the reducing agent is finished, continuing stirring until the reaction is finished to obtain nano-silver sol; adjusting pH of the nano silver sol to be slightly acidic or neutral (pH 2-7) by using a pH value regulator, separating out a solid, washing the solid by using an organic solvent, separating again to obtain wet nano silver particles, and drying in vacuum to obtain the nano silver particles. Most complexing agents used in the method are not easy to generate sheet subunits and grow into flower-shaped silver particles, so that nano silver sol is prepared under the regulation of a surfactant and acidity and alkalinity, and then the nano silver particles are obtained.
In the prior art, the preparation of micro-nano silver particles mostly adopts high molecular polymers such as polyvinylpyrrolidone or polyacrylamide and the like as surface protective agents and dispersing agents, reducing agents are ascorbic acid, ferrous sulfate, amino acid, catechol, hydrogen peroxide, glycol, polyvinylpyrrolidone and the like, and some processes need heating or high-temperature hydrothermal reaction; some reaction processes need to use acid and alkali to adjust the pH value, or use two reducing agents to carry out reduction reaction step by step, and other complicated processes. And the flower-shaped micro-nano silver particles with clean surfaces are prepared by reducing at normal temperature by using hydrazine hydrate as a reducing agent without using high molecular polymers as a surface protective agent and a dispersing agent, which is not reported. The invention is therefore proposed.
Disclosure of Invention
Aiming at the defects of the prior art, the method for preparing the micro-nano silver particles in the aqueous solution system is used for preparing a large amount of flower-shaped quasi-spherical micro-nano silver powder with clean surfaces by only adopting hydrazine hydrate to reduce a silver complex precursor without using a high-molecular polymer in the aqueous solution system at normal temperature.
The technical scheme of the invention is as follows:
the method for preparing the micro-nano silver particles in the aqueous solution system comprises the following steps:
and mixing the silver salt aqueous solution with the complexing agent aqueous solution to prepare a silver complex precursor solution, then dropwise mixing the silver complex precursor solution with the reducing agent aqueous solution at the same time, and carrying out one-step reduction reaction to obtain the micro-nano silver particles.
According to the present invention, preferably, the silver salt is silver nitrate, silver acetate, silver sulfate;
the concentration of the silver salt aqueous solution is preferably 0.01 to 8g/mL, more preferably 0.05 to 1 g/mL.
According to the invention, preferably, the complexing agent is citric acid, trisodium citrate, ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate;
preferably, the concentration of the aqueous complexing agent solution is 0.02-0.2 g/mL.
According to the invention, the molar ratio of complexing agent to silver salt is preferably from 0.1 to 10, more preferably from 0.2 to 5.
According to the present invention, preferably, the reducing agent is hydrazine hydrate; preferably, the concentration of the aqueous reducing agent solution is 1% to 30%, more preferably 2% to 10%.
According to the present invention, it is preferable that the complex precursor solution and the aqueous solution of the reducing agent are simultaneously added dropwise to water during the dropwise mixing to perform a mixing reaction.
According to the invention, the feeding time of the dropwise adding and mixing is preferably 5-60min, and more preferably 10-30 min;
according to the present invention, the time of the reduction reaction is preferably 10 to 300min, and more preferably 30 to 120 min.
According to the invention, after the reduction reaction is finished, a uniform brownish black solution is obtained, and the flower-shaped micro-nano silver particles are obtained after washing for two or three times and freeze drying.
The grain size of the micro-nano silver particles obtained by the invention is between 200nm and 2000 nm.
Under the conditions of normal temperature and normal pressure, the invention reduces the complex precursor of silver by only using hydrazine hydrate as a reducing agent without using high molecular polymers as a protective agent and a dispersing agent, and prepares the flower-shaped spheroidal micro-nano particles with clean surfaces. Firstly, mixing a silver nitrate aqueous solution with a complexing agent aqueous solution to prepare a silver complex precursor, then simultaneously dropwise adding the silver complex precursor and a reducing agent hydrazine hydrate at normal temperature, and carrying out mixing reaction to generate uniformly dispersed flower-shaped micro-nano silver particles with uniform size and clean surfaces. The complexing agent and silver nitrate are firstly adopted to prepare a silver complex precursor, which is beneficial to the reaction to generate flower-shaped micro-nano silver flaky subunits, and can also slow down the oxidation-reduction reaction rate and prevent particle agglomeration. The hydrazine hydrate has the advantages that the hydrazine hydrate is an alkaline solution, the silver precursor solution is reduced in an alkaline environment, self-assembly of flower-shaped structures is easy to form under the condition that no high-molecular polymer is used for surface protection, and the cold welding effect is avoided, so that flower-shaped micro-nano silver particles with uniform appearance and size can be prepared. The complex precursor of silver and the reducing agent are simultaneously dripped and mixed to react, and the dripping mode is different from the mode of dripping the silver source into the reducing agent solution and the mode of dripping the reducing agent into the silver source solution, so that the side effect caused by overhigh local concentration due to overhigh local silver source or overhigh local reducing agent is avoided, and the growth mode of the silver nanocrystal is better controlled.
The invention has the beneficial effects that:
the method is carried out in water solution at normal temperature and pressure, without using high molecular polymer as protective agent and dispersing agent and hydrazine hydrate as reducing agent, reducing silver complex precursor. The preparation method is simple, the residue of high molecular polymer on the surface of the silver powder is avoided, and the prepared flower-shaped micro-nano silver particles are regular in morphology, uniform in particle size distribution, good in dispersity, controllable in size and high in yield. By adopting the method, the diameter of the flower-like spherical nano silver particles prepared by synthesis can be controlled between 200nm and 2000nm by using different complexing agents, adjusting the dosage of the raw materials, controlling the reaction temperature, the adding speed of the raw materials and other reaction conditions.
Drawings
FIG. 1 is a scanning electron microscope image with low magnification of the flower-like spherical nano silver particles prepared in example 1.
FIG. 2 is a high magnification scanning electron microscope image of the flower-like spherical nano silver particles prepared in example 2.
FIG. 3 is a scanning electron microscope image with low magnification of the flower-like spherical nano silver particles prepared in example 3.
FIG. 4 is a high magnification scanning electron microscope image of the flower-like spherical nano silver particles prepared in example 4.
FIG. 5 is a high magnification scanning electron micrograph of the sample prepared in comparative example 1.
FIG. 6 is a high magnification scanning electron micrograph of the sample prepared in comparative example 2.
FIG. 7 is a scanning electron micrograph at low magnification of a sample obtained in comparative example 3.
FIG. 8 is a high magnification scanning electron micrograph of the sample prepared in comparative example 4.
The specific implementation mode is as follows:
the present invention will be further described with reference to the following examples, but is not limited thereto, in conjunction with the accompanying drawings.
In the embodiment, after the reduction reaction is finished, a uniform brownish black solution is obtained, and flower-shaped nano silver particles are obtained after treatment. The processing steps are as follows: washing with water for 3 times, settling, removing supernatant, and freeze drying to obtain flower-shaped micro-nano silver particles.
Example 1
Weighing trisodium citrate, dissolving the trisodium citrate in deionized water, and preparing an aqueous solution of the trisodium citrate with the concentration of 0.11 g/mL. Dissolving silver nitrate in deionized water to prepare a silver nitrate water solution with the concentration of 0.5 g/mL. And (3) mixing 40mL of trisodium citrate aqueous solution with 10mL of silver nitrate aqueous solution, and stirring for 30min to obtain a uniform silver complex solution which is a silver precursor solution. Adding hydrazine hydrate into deionized water to prepare a hydrazine hydrate reducing agent solution with the concentration of 6%. Then dripping 50mL of reducing agent solution and 50mL of silver precursor solution into 200mL of water by using a metering pump for mixing reaction, wherein the charging time is 15min, continuously stirring and reacting for 60min at the temperature of 10 ℃ under the stirring of 600 revolutions per minute to obtain uniform brownish black solution, and performing post-treatment to obtain silver particles, wherein the silver particles are flower-shaped micro-nano particles, are good in dispersity, uniform in particle size distribution and 550nm in average particle size, as shown in figure 1.
Example 2
Weighing trisodium citrate, dissolving the trisodium citrate in deionized water, and preparing an aqueous solution of the trisodium citrate with the concentration of 0.16 g/mL. Dissolving silver nitrate in deionized water to prepare a silver nitrate water solution with the concentration of 0.1 g/mL. And (3) mixing 50mL of trisodium citrate aqueous solution with 50mL of silver nitrate aqueous solution, and stirring for 30min to obtain a uniform silver complex solution which is a silver precursor solution. Adding hydrazine hydrate into deionized water to prepare a hydrazine hydrate reducing agent solution with the concentration of 4%. Then dropping 100mL of reducing agent solution and 100mL of silver precursor solution into 100mL of water by using a metering pump for mixing reaction, wherein the feeding time is 25min, continuously stirring and reacting for 60min at the temperature of 20 ℃ under the stirring of 600 revolutions per minute to obtain uniform brownish black solution, and performing post-treatment to obtain silver particles, wherein the silver particles are flower-shaped micro-nano particles, as shown in figure 2, and have good dispersibility, uniform particle size distribution and 750nm average particle size.
Example 3
Disodium ethylene diamine tetraacetate is weighed and dissolved in deionized water to prepare disodium ethylene diamine tetraacetate water solution with the concentration of 0.06 g/mL. Dissolving silver nitrate in deionized water to prepare a silver nitrate water solution with the concentration of 0.1 g/mL. And mixing 60mL of ethylene diamine tetraacetic acid disodium aqueous solution with 50mL of silver nitrate aqueous solution, and stirring for 30min to obtain a uniform silver complex solution which is a silver precursor solution. Adding hydrazine hydrate into deionized water to prepare a hydrazine hydrate reducing agent solution with the concentration of 5 percent. Then, dripping 110mL of reducing agent solution and 110mL of silver precursor solution into 80mL of water by using a metering pump for mixing reaction, wherein the adding time is 30min, then continuously stirring and reacting for 60min at the temperature of 15 ℃ under the stirring of 600 r/min, and finishing the reaction. And then washing for 2 times for three times, and performing post-treatment to obtain silver particles, which are flower-shaped micro-nano particles as shown in figure 3, and have good dispersibility, uniform particle size distribution and average particle size of 900 nm.
Example 4
Weighing citric acid and dissolving in deionized water to obtain 0.18g/mL citric acid aqueous solution. Dissolving silver nitrate in deionized water to obtain a silver nitrate water solution with the concentration of 0.14 g/mL. And (3) mixing 35mL of citric acid aqueous solution with 35mL of silver nitrate aqueous solution, and stirring for 30min to obtain a uniform silver complex solution which is a silver precursor solution. Adding hydrazine hydrate into deionized water to obtain hydrazine hydrate reducing agent solution with the concentration of 5%. And then dripping 70mL of reducing agent solution and 70mL of silver precursor solution into 160mL of water by using a metering pump for mixing reaction, wherein the charging time is 20min, continuously stirring and reacting for 60min at the temperature of 20 ℃ under the stirring of 600 revolutions per minute to obtain uniform brownish black solution, and performing post-treatment to obtain silver particles, wherein the silver particles are flower-shaped micro-nano particles, are good in dispersity, uniform in particle size distribution and 1.3 mu m in average particle size, as shown in figure 4.
Comparative example 1
The synthesis of this comparative example is otherwise the same as example 2, except that the addition time:
and dropwise adding 100mL of reducing agent solution and 100mL of silver precursor solution into 100mL of water by using a metering pump for mixing reaction for 30s, and then continuously stirring and reacting for 60min at the temperature of 20 ℃ and under the stirring of 600 rpm to obtain a brownish black solution, wherein the SEM result of the product is shown in figure 5, and unsmooth particles are obtained.
Comparative example 2
The synthesis of this comparative example is otherwise the same as example 2, except that the addition time:
dropping 100mL of reducing agent solution and 100mL of silver precursor solution into 100mL of water by using a metering pump for mixing reaction, wherein the adding time is 120min, then continuously stirring and reacting for 60min at the temperature of 20 ℃ under the stirring of 600 revolutions per minute to obtain a brownish black solution, and the SEM result of the product is shown in figure 6, and the obtained product is in a large petal-shaped appearance instead of a flower shape, and the sphericity of the micro-nano silver is poor.
Comparative example 3
The synthesis of this comparative example is otherwise the same as example 2, except that the reducing agent:
weighing trisodium citrate, dissolving the trisodium citrate in deionized water, and preparing an aqueous solution of the trisodium citrate with the concentration of 0.16 g/mL. Dissolving silver nitrate in deionized water to prepare a silver nitrate water solution with the concentration of 0.1 g/mL. And (3) mixing 50mL of trisodium citrate aqueous solution with 50mL of silver nitrate aqueous solution, and stirring for 30min to obtain a uniform silver complex solution which is a silver precursor solution. Ascorbic acid was added to deionized water to make up a 0.14g/mL solution of ascorbic acid reducing agent. Then dropping 100mL of reducing agent solution and 100mL of silver precursor solution into 100mL of water by using a metering pump for mixing reaction, wherein the feeding time is 25min, then continuously stirring and reacting for 60min at the temperature of 20 ℃ under the stirring of 600 r/min to obtain a brownish black solution, and performing post-treatment to obtain silver particles, as shown in FIG. 7, the flower-shaped silver particles are few, and mainly some particles with irregular shapes.
The reaction system using ascorbic acid as a reducing agent is acidic, the pH value is about 3, and the reaction system is different from an alkaline reaction system using hydrazine hydrate as a reducing agent, and the pH value is 8-9. Different acid-base systems need to be adjusted under proper conditions to prepare the target morphology.
Comparative example 4
The synthesis of this comparative example is otherwise the same as example 2, except that PVP is added to the system:
weighing trisodium citrate, dissolving the trisodium citrate in deionized water, and preparing an aqueous solution of the trisodium citrate with the concentration of 0.16 g/mL. Dissolving silver nitrate in deionized water to prepare a silver nitrate water solution with the concentration of 0.1 g/mL. And (3) mixing 50mL of trisodium citrate aqueous solution with 50mL of silver nitrate aqueous solution, and stirring for 30min to obtain a uniform silver complex solution which is a silver precursor solution. Adding hydrazine hydrate into deionized water to prepare a hydrazine hydrate reducing agent solution with the concentration of 4%. Then, 100mL of reducing agent solution and 100mL of silver precursor solution are dripped into 100mL of water containing 5.2% of PVP by mass fraction by using a metering pump for mixing reaction, the charging time is 25min, then the mixture is continuously stirred and reacts for 60min at the temperature of 20 ℃ under the stirring of 600 r/min to obtain a brownish black solution, silver particles are obtained after post-treatment, and the obtained accumulation body is in a sheet shape and a particle shape as shown in figure 8. Although the addition of PVP can play a role in dispersion, the presence of PVP can induce isotropic growth, so that more particles are grown.
Claims (11)
1. The method for preparing flower-shaped micro-nano silver particles in an aqueous solution system comprises the following steps:
mixing a silver salt aqueous solution and a complexing agent aqueous solution to prepare a silver complex precursor solution, then dropwise mixing the silver complex precursor solution and a reducing agent aqueous solution at the same time, and carrying out one-step reduction reaction to obtain flower-shaped micro-nano silver particles;
the concentration of the silver salt aqueous solution is 0.01-8g/mL, the reducing agent is hydrazine hydrate, the concentration of the reducing agent aqueous solution is 1% -30%, the feeding time of dropwise adding and mixing is 5-60min, and the time of reduction reaction is 10-300 min.
2. The method for preparing flower-like micro-nano silver particles in an aqueous system according to claim 1, wherein the silver salt is silver nitrate, silver acetate or silver sulfate.
3. The method for preparing flower-like micro-nano silver particles in the aqueous system according to claim 1, wherein the concentration of the silver salt aqueous solution is 0.05-1 g/mL.
4. The method for preparing flower-like micro-nano silver particles in an aqueous system according to claim 1, wherein the complexing agent is citric acid, trisodium citrate, ethylenediaminetetraacetic acid or disodium ethylenediaminetetraacetate.
5. The method for preparing flower-shaped micro-nano silver particles in an aqueous system according to claim 1, wherein the concentration of the complexing agent in the aqueous system is 0.02-0.2 g/mL.
6. The method for preparing flower-shaped micro-nano silver particles in an aqueous system according to claim 1, wherein the molar ratio of the complexing agent to the silver salt is 0.1-10: 1.
7. the method for preparing flower-like micro-nano silver particles in an aqueous system according to claim 1, wherein the molar ratio of the complexing agent to the silver salt is 0.2-5: 1.
8. The method for preparing flower-shaped micro-nano silver particles in an aqueous solution system according to claim 1, wherein the concentration of the aqueous solution of the reducing agent is 2% -10%.
9. The method for preparing flower-shaped micro-nano silver particles in an aqueous solution system according to claim 1, wherein the complex precursor solution and the aqueous solution of the reducing agent are simultaneously added dropwise into water for mixing reaction during the dropwise addition mixing process.
10. The method for preparing flower-shaped micro-nano silver particles in an aqueous system according to claim 1, wherein the adding time of the dropwise adding mixing is 10-30 min.
11. The method for preparing flower-shaped micro-nano silver particles in an aqueous solution system according to claim 1, wherein the time of the reduction reaction is 30-120 min.
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| CN115502408A (en) * | 2022-09-21 | 2022-12-23 | 四川工程职业技术学院 | Preparation method of flower-like silver powder |
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