CN101497135B - Method for preparing spherical silver nano granule - Google Patents
Method for preparing spherical silver nano granule Download PDFInfo
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- CN101497135B CN101497135B CN2009100964858A CN200910096485A CN101497135B CN 101497135 B CN101497135 B CN 101497135B CN 2009100964858 A CN2009100964858 A CN 2009100964858A CN 200910096485 A CN200910096485 A CN 200910096485A CN 101497135 B CN101497135 B CN 101497135B
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Abstract
The invention discloses a method for preparing spherical silver nanoparticles, which comprises the following steps: evenly mixing a silver nitrate clearing solution, a reducer clearing solution and a stabilizing agent clearing solution of anhydrous low mass molecule alcohols; stirring the mixture at a temperature of between 70 and 80 DEG C and refluxing the product to obtain a silver nanoparticle colloidal solution; and vaporizing or removing the low mass molecule alcohols, and drying the remaining substance to obtain the spherical silver nanoparticles with the particle size not more than 15 nanometers. A reaction system of the invention has simple process, saves raw materials, reduces links and improves preparation efficiency; in the reaction system, the anhydrous low mass molecule alcohols are taken as solvent to replace the prior water solution to prepare the anhydrous spherical silver nanoparticles; therefore, the invention discloses a method for preparing the anhydrous spherical silver nanoparticles with good dispersibility and stability, which has the advantages of simple process, few varieties of used raw materials and high preparation efficiency.
Description
Technical field
The present invention relates to a kind of preparation method of silver nano-grain, be specifically related to a kind of preparation method of spherical silver nano particle.
Background technology
Silver is a kind of precious metal material, has excellent ductility, thermal conductivity and electric conductivity, and chemical property is stable, not with the reaction of oxygen G﹠W, not with hydrochloric acid, dilute sulfuric acid and highly basic reaction.Silver nano-grain is widely used in the conductive magneto-conductive material, high-performance electronic slurry, effective catalyst and antiseptic field.Wherein the High Performance Shielding application of paints is very extensive, has good market prospects, and annual requirement reaches 600 tons (about silver contents 30%); High-performance electronic slurry annual requirement reaches 200 tons (about silver contents 50%).Development High Performance Shielding material can promote the development of China in high-tech sectors such as information, electronics, Aero-Space, weaponrys widely, eliminates or the pollution of minimizing electromagenetic wave radiation.Simultaneously, because silver nano-grain has significant surface plasma body resonant vibration effect, make that going the silver nano-grain material also to have in fields such as solar cell, nonlinear optical material, biomedical detection widely uses.
At present, preparation silver nano-grain method, be in pure water, to synthesize silver nano-grain, utilize natrium citricum or glucose as reducing agent, as notification number is CN100420528C, the day for announcing is on September 24th, 2008, name is called the patent of invention that the pre-crystallization reducing process preparation of silver halide can disperse the method for silver nano-grain again, disclose and utilize glucose as reducing agent, with polyvinylpyrrolidone (PVP) is surfactant and stabilizing agent, also to have under PH conditioning agent and the halide salts condition, syntheticly in water obtain the silver nano-grain that particle diameter is 5～30 nanometers.The reaction system complexity of this patent of invention needs PH adjusting, the pre-crystallization of silver halide, and colloidal sol is also wanted the dialysis silver halide in the preparation, just can obtain the silver nano-grain that the grain diameter scope extensively contains moisture content again; Therefore its preparation method reaction system is complicated and need auxiliary material more, and what obtain is the silver nano-grain that contains moisture content, and has considerable silver nano-grain material just can use under the state of exclusion.Therefore, the preparation method who needs a kind of water-free silver nano-grain of development.
Summary of the invention
Technical problem to be solved by this invention provides the less and preparation method of the higher spherical silver nano particle of preparation efficiency of simple, the raw materials used kind of a kind of technology, and the spherical silver nano particle that obtains is not moisture, and its particle diameter is not more than 15 nanometers.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: a kind of preparation method of spherical silver nano particle comprises the steps:
1) preparation of liquor argenti nitratis ophthalmicus: silver nitrate is dissolved in the anhydrous low mass molecule alcohol, is stirred to silver nitrate and dissolves fully, the silver nitrate settled solution that obtains concentration and be 0.05～0.3g/L is stand-by;
2) preparation of reductant solution: will contain-NH
2Group and-reducing agent of OH group is dissolved in the anhydrous low mass molecule alcohol, is stirred to the reducing agent material and dissolves fully, obtaining concentration is that 2～6g/L reducing agent settled solution is stand-by;
3) preparation of stabiliser solution: polyvinylpyrrolidone powder art is dissolved in the anhydrous low mass molecule alcohol, is stirred to polyvinylpyrrolidone and dissolves fully, the stabilizing agent settled solution that obtains concentration and be 0.1～0.9g/L is stand-by;
4) preparation of silver nano-grain: with silver nitrate, reducing agent and the stabilizing agent settled solution of above-mentioned steps 1, above-mentioned steps 2 and above-mentioned steps 3, by volume 3～5: evenly mix at 1: 1, also ceaselessly stir, reflux with water-bath or oil bath heating then, make the temperature of solution rise to 70～80 ℃, become kermesinus to solution colour, stop heating, stir and naturally cool to room temperature, promptly obtain silver nano-grain colloidal solution;
5) collection of silver nano-grain: remove most of anhydrous low mass molecule alcohol in the above-mentioned steps 4 gained colloidal solution with rotary evaporator evaporation or with supercentrifuge, obtain silver-colored nano-colloid concentrate, drying nano colloid concentrate obtains the spherical silver nano particle that particle diameter is not more than 15 nanometers.
Described anhydrous low mass molecule alcohol is an absolute ethyl alcohol.
Described anhydrous low mass molecule alcohol is an absolute methanol.
Described containing-NH
2Group and-reducing agent of OH group is a hydramine.
Compared with prior art, the invention has the advantages that silver nitrate settled solution, reducing agent settled solution and stabilizing agent settled solution with anhydrous low mass molecule alcohol evenly mix, acquisition silver nano-grain colloidal solution stirs under 70～80 ℃ of temperature conditions, refluxes, through evaporating or removing low mass molecule alcohol, drying obtains the spherical silver nano particle that particle diameter is not more than 15 nanometers; The present invention needn't need the PH conditioning agent, also needn't need with halide salts as generating the pre-crystallization of intermediate silver halide, reduced raw material type, and saved with infiltration and gone the halide ion process, therefore the technology of reaction system is simpler, also saved raw material, reduced link, improved preparation efficiency, and make solvent in reaction system with anhydrous low mass molecule alcohol and substitute present aqueous solvent, what obtain is water-free spherical silver nano particle, and the particle diameter of this spherical silver nano particle is not more than 15 nanometers, and this spherical silver nanoparticulate dispersed is better with stable; Can be widely used in the conductive magneto-conductive material, the high-performance electronic slurry, effective catalyst and antiseptic field are particularly useful for the applicable neck of ability city under the state of exclusion.Therefore the present invention is the few and preparation method of the higher water-free spherical silver nano particle of preparation efficiency of simple, the raw materials used kind of a kind of technology.
Description of drawings
Fig. 1 is the TEM picture of spherical silver nano particle;
Fig. 2 is the absorption spectrum of silver nano-grain colloidal solution.
The specific embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment
A kind of preparation method of spherical silver nano particle is silver-colored source with analytically pure silver nitrate, and the 0.06g silver nitrate is dissolved in the 160ml absolute ethyl alcohol, and it is stand-by to be stirred to the solution clarification; Contain-NH analyzing pure about 0.17g
2Group and-the triethanolamine reducing agent of OH group is dissolved in the 40ml absolute ethyl alcohol and to be stirred to the solution clarification stand-by; Being dissolved in the PVP of about 0.024g in the 40ml absolute ethyl alcohol and being stirred to solution clarifies stand-by; Above three solution are poured into to the triangular flask of 250ml mix and stir, again triangular flask being put into the water-bath heating follows stirring and refluxes, make solution temperature reach 70～80 ℃, become transparent kermesinus up to solution, stop heating then, be cooled to room temperature, promptly obtain silver nano-grain colloidal solution, tangible surface plasma body resonant vibration (SPR) absworption peak has appearred in this colloidal solution at the 415nm place as shown in Figure 2, and colloidal solution is highly stable, can place for a long time.Adopt rotary evaporator evaporation absolute ethyl alcohol to obtain silver nano-grain glue concentrated solution, obtain dispersiveness spherical silver nano particle preferably as shown in Figure 1 after the drying, the mean size of the silver nano-grain that makes after measured is about 10nm.
Absolute ethyl alcohol can be used replacements such as absolute methanol, propyl alcohol in the foregoing description; Rotary evaporator also can substitute with supercentrifuge.Triethanolamine also can substitute with other hydramine in the foregoing description.
Claims (4)
1. the preparation method of a spherical silver nano particle is characterized in that comprising the steps:
1) preparation of liquor argenti nitratis ophthalmicus: silver nitrate is dissolved in the anhydrous low mass molecule alcohol, is stirred to silver nitrate and dissolves fully, the silver nitrate settled solution that obtains concentration and be 0.05～0.3g/L is stand-by;
2) preparation of reductant solution: will contain-NH
2Group and-reducing agent of OH group is dissolved in the anhydrous low mass molecule alcohol, is stirred to the reducing agent material and dissolves fully, obtaining concentration is that 2～6g/L reducing agent settled solution is stand-by;
3) preparation of stabiliser solution: polyvinylpyrrolidonepowder powder is dissolved in the anhydrous low mass molecule alcohol, is stirred to polyvinylpyrrolidone and dissolves fully, the stabilizing agent settled solution that obtains concentration and be 0.1～0.9g/L is stand-by;
4) preparation of silver nano-grain: with silver nitrate, reducing agent and the stabilizing agent settled solution of above-mentioned steps 1, above-mentioned steps 2 and above-mentioned steps 3, by volume 3～5: evenly mix at 1: 1, also ceaselessly stir, reflux with water-bath or oil bath heating then, make the temperature of solution rise to 70～80 ℃, become kermesinus to solution colour, stop heating, stir and naturally cool to room temperature, promptly obtain silver nano-grain colloidal solution;
5) collection of silver nano-grain: remove most of anhydrous low mass molecule alcohol in the above-mentioned steps 4 gained colloidal solution with rotary evaporator evaporation or with supercentrifuge, obtain silver-colored nano-colloid concentrate, drying nano colloid concentrate obtains the spherical silver nano particle that particle diameter is not more than 15 nanometers.
2. the preparation method of a kind of spherical silver nano particle as claimed in claim 1 is characterized in that described anhydrous low mass molecule alcohol is an absolute ethyl alcohol.
3. the preparation method of a kind of spherical silver nano particle as claimed in claim 1 is characterized in that described anhydrous low mass molecule alcohol is an absolute methanol.
4. the preparation method of a kind of spherical silver nano particle as claimed in claim 1 is characterized in that described containing-NH
2Group and-reducing agent of OH group is a hydramine.
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| CN109079154B (en) * | 2018-09-07 | 2022-03-01 | 长春永固科技有限公司 | Nano silver and synthetic method thereof |
| CN109202061B (en) * | 2018-09-29 | 2020-08-18 | 华南理工大学 | Silver nanosphere and preparation method and application thereof |
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| CN115138857B (en) * | 2022-07-21 | 2023-12-22 | 四川省伊洁士医疗科技有限公司 | Nano silver particles, preparation method and application thereof |
| CN116987436A (en) * | 2023-09-14 | 2023-11-03 | 东北大学 | Modified WPU coating, preparation method thereof and application thereof in antibacterial aspect |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN1247297C (en) * | 2001-04-30 | 2006-03-29 | 学校法人浦项工科大学校 | Colloid solution of metal nanoparticles, metal-polymer nanocompositions and method for preparation thereof |
| CN1263573C (en) * | 2003-09-28 | 2006-07-12 | 中国印钞造币总公司 | Method for preparing nano silver powder |
| CN101214555A (en) * | 2008-01-16 | 2008-07-09 | 武汉理工大学 | Method for preparing spherical nano silver powder |
| CN100463748C (en) * | 2006-12-27 | 2009-02-25 | 沈阳工业大学 | Chemical preparation method of Ag nanoparticle |
| CN101384388A (en) * | 2006-03-10 | 2009-03-11 | 三井金属矿业株式会社 | Process for production of ultrafine silver particles and ultrafine silver particles produced by the process |
-
2009
- 2009-03-12 CN CN2009100964858A patent/CN101497135B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN1247297C (en) * | 2001-04-30 | 2006-03-29 | 学校法人浦项工科大学校 | Colloid solution of metal nanoparticles, metal-polymer nanocompositions and method for preparation thereof |
| CN1263573C (en) * | 2003-09-28 | 2006-07-12 | 中国印钞造币总公司 | Method for preparing nano silver powder |
| CN101384388A (en) * | 2006-03-10 | 2009-03-11 | 三井金属矿业株式会社 | Process for production of ultrafine silver particles and ultrafine silver particles produced by the process |
| CN100463748C (en) * | 2006-12-27 | 2009-02-25 | 沈阳工业大学 | Chemical preparation method of Ag nanoparticle |
| CN101214555A (en) * | 2008-01-16 | 2008-07-09 | 武汉理工大学 | Method for preparing spherical nano silver powder |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2006-225760A 2006.08.31 |
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