CN1810422A - Prepn process of nanometer silver sol - Google Patents
Prepn process of nanometer silver sol Download PDFInfo
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- CN1810422A CN1810422A CN 200610024151 CN200610024151A CN1810422A CN 1810422 A CN1810422 A CN 1810422A CN 200610024151 CN200610024151 CN 200610024151 CN 200610024151 A CN200610024151 A CN 200610024151A CN 1810422 A CN1810422 A CN 1810422A
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Abstract
The preparation process of nanometer silver gel with high stability features that one kind of high-valent small molecule and silver nitrate solution are complexed, pH regulated and with reductant solution at room temperature to produce nanometer silver gel. The process has simple technological process, low cost, high gel purity, high gel stability, small granularity and homogeneous grain size distribution among other advantages. Altering the technological conditions can produce nanometer silver gel of different grain sizes within 3-50 nm, and the nanometer silver gel may be used widely in electronic, catalytic, medicine, paint, fabric and other fields.
Description
Technical field
The present invention relates to a kind of preparation method of nano silver colloidal sol, belong to field of fine chemical.
Technical background
Nano Silver is a kind of emerging functional material, is widely used in industries such as superconduction, chemical industry, medical science, optics, electronics, electrical equipment.Nano-Ag particles and polyvinyl butyral resin are made complex enzyme membrane matrix fixing glucose oxidase, make up glucose biological sensor, can increase substantially oxidasic catalytic activity, significantly improve the response sensitivity of glucose oxidase (GOD) electrode; Nano Silver can be used as the matrix of SERS; In chemical fibre, add a small amount of Nano Silver, can give its very strong sterilizing ability; Nano-silver powder has high electric conductivity, can be used as conductive silver paste and battery electrode material in the integrated circuit; Nano Silver also can be used as multiple catalyst for reaction.In view of above wide applications, the preparation of Nano Silver has crucial meaning, also becomes the focus of field of nanometer material technology research.
The preparation method of Nano Silver mainly contains reducing agent method, luminescence method, ultrasonic method, electrolysis etc.Relatively the method for the Nano Silver of extensive use preparation is the reducing agent method at present, promptly utilizes reducing agents such as sodium borohydride, ascorbic acid that silver nitrate is reduced to Nano Silver.Although this method is simple to operate and with low cost, because reaction is difficult to control, the colloidal sol instability, thereby be difficult to large-scale industrial production.At present both at home and abroad the researcher is just attempting to improve the stability of the silver sol of reducing agent method preparation by adding protectant method, and the protective agent of having reported has silicon polymer, polyacrylic acid etc.But this family macromolecule protective agent chain is longer, will significantly increase the diameter of elargol grain; The existence of the thicker macromolecule clad in surface also can produce harmful effect to the surface-enhanced Raman character of Ag, electric conductivity etc.; In addition, silver sol broad particle distribution, unstable product quality.
Summary of the invention
For overcoming above shortcoming, the invention provides a kind of preparation method of nano silver colloidal sol, described method is to adopt a kind of high price small-molecule substance as protective agent, has obtained nano silver colloidal sol highly stable, high concentration by the reducing agent method.Utilize of the absorption of the little molecule protective agent of high price, significantly increase the silver surface quantity of electric charge, improve the electrostatic repulsion of elargol intergranular, thereby colloidal sol has high stability on the silver sol surface.The characteristics that this method is outstanding are that technology is simple, and the silver sol granularity of preparation is very even, stable in properties.Product can satisfy the quality requirement of many numerous areas such as chemical industry, medical science, optics, electronics to the silver sol product.
Preparation method's detailed process provided by the invention is: at first be dissolved in the silver nitrate solid particle in the deionized water and add the little molecule protective agent of a kind of high price and evenly be mixed and made into mixed solution; after regulating the pH value; the powerful stirring down is added dropwise to reductant solution rapidly in the above-mentioned mixed solution, at room temperature reacts to generate nano silver colloidal sol in 15 minutes ~ 1 hour.
Now details are as follows with each relevant process:
(1) selection of liquor argenti nitratis ophthalmicus concentration: silver nitrate is dissolved in that to be made into concentration in the deionized water be 10
-6～10
-1The liquor argenti nitratis ophthalmicus of mol/L.
(2) the protectant selection of the little molecule of high price: the little molecule protective agent of high price is a kind of pentabasic acid, 2-phosphonic acids butane-1,2,4-tricarboxylic acids (PBTCA).Protective agent should be controlled at a certain amount of, adds very fewly, is not enough to form protective layer on elargol grain surface, and silver will be reunited; Add too much, colloidal sol intermediate ion intensity is too high, and colloidal sol is also reunited easily, and the PBTCA molal quantity should be 1～4 times of silver nitrate, and the concentration of PBTCA solution is 10
-6～0.4mol/L.
(3) adjusting of mixed solution pH value: in the mixed solution of silver nitrate and PBTCA, add NaOH and regulate between its pH value to 6～9, to guarantee the most of or all disassociations of anionic protective agent PBTCA, for the silver sol that generates improves enough electrostatic repulsions.The powerful stirring in the course of reaction, to avoid the reunion sedimentation of Ag micelle, powerful speed of agitator is 1000～4000 rev/mins.
(4) selection of reducing agent: reducing agent comprises sodium borohydride or citric acid, and the mol ratio of reducing agent and silver nitrate is 2: 1～10: 1.
Prepare nano silver colloidal sol by method provided by the invention, not only stability is high, can keep keeping in 3 months stable under the room temperature, and can change technological parameter, the particle diameter of silver sol that makes preparation is between 3 ~ 50nm, and particle diameter is evenly distributed, and silver sol is circular nano particle.(seeing embodiment for details); Its three be under the room temperature reaction to generate the Nano silver solution time only be 15 minutes～1 hour.
Description of drawings
Fig. 1 is silver sol preparation flow figure of the present invention.
Fig. 2 is the transmission electron microscope photo (A) and the silver granuel footpath distribution map (B) of silver sol prepared among the embodiment 1, and silver sol is rounded particle, and average grain diameter is 3.6nm, and standard deviation is 0.8nm.
Fig. 3 is the ultraviolet-visible spectrum of silver sol prepared among the embodiment 1, and the absworption peak of 394nm is corresponding to the surface plasma vibration peak of silver among the figure.
Fig. 4 is the transmission electron microscope photo (A) and the silver granuel footpath distribution map (B) of silver sol prepared among the embodiment 2, and silver sol is a circular granular, and average grain diameter is 5.9nm, and standard deviation is 1.5nm.
The specific embodiment
Further specify innovative point of the present invention below in conjunction with example, and limit the present invention by no means.
Embodiment 1
Dissolve in 1 liter of deionized water of silver nitrate adding with 0.2 mM, and add 0.6 mM 2-phosphonic acids butane-1,2, the 4-tricarboxylic acids stirs, and with NaOH solution its pH value is transferred to 8.8, makes A liquid; The sodium borohydride of 1.2 mMs is dissolved in 4 ml deionized water, makes B liquid; B liquid is added dropwise to rapidly in the A liquid, made nano silver colloidal sol in 15 minutes with powerful stirring of per minute 2000 rotational speed rates.Fig. 2 is the transmission electron microscope photo and the silver granuel footpath distribution map of silver sol prepared in the present embodiment 1, and silver sol is circular nano particle, and average grain diameter is 3.6nm, and standard deviation is 0.8nm, and particle diameter is evenly distributed.Fig. 3 is the ultraviolet-visible spectrum of gained silver sol, and wherein the absworption peak at 394nm place is the surface plasma vibration peak of Nano Silver micelle.This colloidal sol can at room temperature be placed and keep stable more than 3 months.
Embodiment 2
Dissolve in 1 liter of deionized water of silver nitrate adding with 0.2 mM, and add 0.6 mM 2-phosphonic acids butane-1,2, the 4-tricarboxylic acids stirs, and with NaOH solution its pH value is transferred to 6.5, makes A liquid; The sodium borohydride of 1.2 mMs is dissolved in 4 ml deionized water, makes B liquid; B liquid is added dropwise to rapidly in the A liquid, stirred 15 minutes, make nano silver colloidal sol so that per minute 3000 rotational speed rates are powerful.Fig. 4 is the TEM photo and the silver granuel footpath distribution map of gained silver sol, and silver sol is circular nano particle, and average grain diameter is 5.9nm, and standard deviation is 1.5nm, and particle diameter is evenly distributed.Place under this colloidal sol room temperature and can in 3 months, keep stable.
Embodiment 3
To dissolve in 1 liter of deionized water of silver nitrate adding of 0.01 mole, and add 0.02 mole of 2-phosphonic acids butane-1,2, the 4-tricarboxylic acids stirs, and with NaOH solution its pH value is transferred to 8.8, makes A liquid; 0.1 mole sodium borohydride is dissolved in 300 ml deionized water, makes B liquid; B liquid is added dropwise to rapidly in the A liquid, stirred 1 hour, make particle diameter between 4～20 nanometers and the uniform nano silver colloidal sol of particle diameter so that per minute 2000 rotational speed rates are powerful.Place under this colloidal sol room temperature and can in 3 months, keep stable.
Embodiment 4
To dissolve in 1 liter of deionized water of silver nitrate adding of 0.1 mole, and add 0.3 mole of 2-phosphonic acids butane-1,2, the 4-tricarboxylic acids stirs, and with NaOH solution its pH value is transferred to 8.8, makes A liquid; 0.3 mole sodium borohydride is dissolved in 1 liter of deionized water, makes B liquid; B liquid is added dropwise to rapidly in the A liquid, stirred 1 hour, make particle diameter between 5～30 nanometers and the uniform nano silver colloidal sol of particle diameter so that per minute 4000 rotational speed rates are powerful.Place under this colloidal sol room temperature and can in 3 months, keep stable.
Embodiment 5
To dissolve in 1 liter of deionized water of 0.1 equimolar silver nitrate adding, and add 0.4 mole of 2-phosphonic acids butane-1,2, the 4-tricarboxylic acids stirs, and with NaOH solution its pH value is transferred to 8.8, makes A liquid; 0.6 mole citric acid is dissolved in 1 liter of deionized water, makes B liquid; B liquid is added dropwise to rapidly in the A liquid, stirred 1 hour, make particle diameter between 10～50 nanometers and the uniform nano silver colloidal sol of particle diameter so that per minute 2000 rotational speed rates are powerful.Place under this colloidal sol room temperature and can in 3 months, keep stable.
Claims (7)
1. the preparation method of a nano silver colloidal sol, it is characterized in that, at first be dissolved in silver nitrate in the deionized water and add the little molecule protective agent of a kind of high price and evenly be mixed and made into mixed solution, after regulating pH value to 6～9, the powerful stirring down is added dropwise to reductant solution in the above-mentioned mixed solution, and reaction at room temperature generates nano silver colloidal sol;
The little molecule protective agent of described high price is a 2-phosphonic acids butane-1,2, the 4-tricarboxylic acids, and its molal quantity is 1～4 times of silver nitrate in the mixed solution;
Described reducing agent is sodium borohydride or citric acid, and the mol ratio of reducing agent and silver nitrate is 2: 1～10: 1.
2. by the preparation method of the described nano silver colloidal sol of claim 1, it is characterized in that described silver nitrate is dissolved in that to be made into concentration in the deionized water be 10
-6～10
-1Mol/L, 2-phosphonic acids butane-1,2, the tricarboxylic concentration of 4-is 10
-6～0.4mol/L.
3. by the preparation method of the described nano silver colloidal sol of claim 1, it is characterized in that it is by at silver nitrate and 2-phosphonic acids butane-1,2 that pH value is regulated, add NaOH enforcement in the 4-tricarboxylic acids mixed solution.
4. by the preparation method of the described nano silver colloidal sol of claim 1, it is characterized in that the powerful speed that stirs is that per minute 1000～4000 changes.
5. the preparation method of nano silver colloidal sol according to claim 1 is characterized in that the reaction generation nano silver colloidal sol time is 15 minutes～1 hour under the room temperature.
6. according to the preparation method of any described nano silver colloidal sol in the claim 1,2,3,4 and 5, the particle diameter that it is characterized in that prepared silver sol is between 3～50nm, and particle diameter is evenly distributed.
7. nano silver colloidal sol according to claim 6 is characterized in that silver sol is circular nano particle.
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| CN 200610024151 CN1810422A (en) | 2006-02-24 | 2006-02-24 | Prepn process of nanometer silver sol |
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| CN 200610024151 CN1810422A (en) | 2006-02-24 | 2006-02-24 | Prepn process of nanometer silver sol |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008075933A1 (en) | 2006-12-20 | 2008-06-26 | Servicios Industriales Peñoles, S.A. De C.V. | Process for manufacture of nanometric, monodisperse and stable metallic silver and product obtained therefrom |
| CN101811193A (en) * | 2010-04-06 | 2010-08-25 | 浙江大学 | Method for preparing silver nano sheet self-assembling material |
| CN101885072A (en) * | 2010-07-01 | 2010-11-17 | 苏州永拓环境科技有限公司 | Preparation method of nano-silver sol |
| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN101710497B (en) * | 2009-12-08 | 2011-04-20 | 华中科技大学 | Nano-silver conductive slurry |
| CN101585088B (en) * | 2008-05-21 | 2011-07-27 | 任晓艳 | Method for preparing nano-silver thread |
| CN101731272B (en) * | 2009-12-24 | 2012-07-25 | 中国人民解放军军事医学科学院基础医学研究所 | Method for preparing antibacterial nanometer silver colloid |
| CN102901722A (en) * | 2012-09-29 | 2013-01-30 | 浙江理工大学 | Method for rapidly detecting thiabendazole residue in liquid beverage |
| CN101622090B (en) * | 2007-02-27 | 2013-03-13 | 三菱麻铁里亚尔株式会社 | Dispersion solution of metal nanoparticle, method for production thereof, and method for synthesis of metal nanoparticle |
| CN102120265B (en) * | 2010-01-07 | 2013-04-10 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| CN103586461A (en) * | 2013-11-16 | 2014-02-19 | 华中科技大学 | Nano-silver sol and preparation and purification method thereof |
| CN103726406A (en) * | 2014-01-09 | 2014-04-16 | 福建农林大学 | Cationic nano-silver multifunctional papermaking aid and preparation method thereof |
| CN109954886A (en) * | 2019-03-07 | 2019-07-02 | 四川农业大学 | A kind of preparation method and purposes of collagen nano silver material |
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2006
- 2006-02-24 CN CN 200610024151 patent/CN1810422A/en active Pending
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9371572B2 (en) | 2006-12-20 | 2016-06-21 | Servicios Administrativos Penoles S.A. De C.V. | Process for manufacture of nanometric, monodisperse, stable metallic silver and a product obtained therefrom |
| CN101610865B (en) * | 2006-12-20 | 2015-04-01 | 派诺尔斯管理服务公司 | Process for manufacture of nanometric, monodisperse and stable metallic silver and product obtained therefrom |
| WO2008075933A1 (en) | 2006-12-20 | 2008-06-26 | Servicios Industriales Peñoles, S.A. De C.V. | Process for manufacture of nanometric, monodisperse and stable metallic silver and product obtained therefrom |
| CN101622090B (en) * | 2007-02-27 | 2013-03-13 | 三菱麻铁里亚尔株式会社 | Dispersion solution of metal nanoparticle, method for production thereof, and method for synthesis of metal nanoparticle |
| CN101585088B (en) * | 2008-05-21 | 2011-07-27 | 任晓艳 | Method for preparing nano-silver thread |
| CN101926363B (en) * | 2009-06-23 | 2013-01-30 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN101926363A (en) * | 2009-06-23 | 2010-12-29 | 上海六立纳米材料科技有限公司 | Method for preparing liquid antibacterial agent containing complex silver |
| CN101710497B (en) * | 2009-12-08 | 2011-04-20 | 华中科技大学 | Nano-silver conductive slurry |
| CN101731272B (en) * | 2009-12-24 | 2012-07-25 | 中国人民解放军军事医学科学院基础医学研究所 | Method for preparing antibacterial nanometer silver colloid |
| CN102120265B (en) * | 2010-01-07 | 2013-04-10 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| CN101811193B (en) * | 2010-04-06 | 2011-08-24 | 浙江大学 | Method for preparing silver nano sheet self-assembling material |
| CN101811193A (en) * | 2010-04-06 | 2010-08-25 | 浙江大学 | Method for preparing silver nano sheet self-assembling material |
| CN101885072A (en) * | 2010-07-01 | 2010-11-17 | 苏州永拓环境科技有限公司 | Preparation method of nano-silver sol |
| CN102901722A (en) * | 2012-09-29 | 2013-01-30 | 浙江理工大学 | Method for rapidly detecting thiabendazole residue in liquid beverage |
| CN103586461A (en) * | 2013-11-16 | 2014-02-19 | 华中科技大学 | Nano-silver sol and preparation and purification method thereof |
| CN103586461B (en) * | 2013-11-16 | 2016-01-20 | 华中科技大学 | A kind of nano silver colloidal sol and preparation and purification method thereof |
| CN103726406A (en) * | 2014-01-09 | 2014-04-16 | 福建农林大学 | Cationic nano-silver multifunctional papermaking aid and preparation method thereof |
| CN109954886A (en) * | 2019-03-07 | 2019-07-02 | 四川农业大学 | A kind of preparation method and purposes of collagen nano silver material |
| CN109954886B (en) * | 2019-03-07 | 2022-08-26 | 四川农业大学 | Preparation method and application of collagen nano-silver material |
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