CN101811193B - Method for preparing silver nano sheet self-assembling material - Google Patents
Method for preparing silver nano sheet self-assembling material Download PDFInfo
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- CN101811193B CN101811193B CN2010101410749A CN201010141074A CN101811193B CN 101811193 B CN101811193 B CN 101811193B CN 2010101410749 A CN2010101410749 A CN 2010101410749A CN 201010141074 A CN201010141074 A CN 201010141074A CN 101811193 B CN101811193 B CN 101811193B
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Abstract
The invention discloses a method for preparing a silver nano sheet self-assembling material. The method prepares a silver nano sheet self-assembling body in methyl methacrylate reverse micelle solution of different carboxylic acids by taking AgNO3 and NaBH4 as raw materials. The silver nano sheet can realize different curling degrees by changing the used carboxylic acid, and is self-assembled by fine silver nano granules. The diameter distribution of the silver nano granules is narrow, and is controllable in the different carboxylic acids. The sheet silver nano granule self-assembling body can be used as an effective Raman surface enhancing substrate to improve the detection limit of some special substances in Raman spectrum. The silver has high electric conductivity, and the silver nano material with a two-dimensional structure can form silver nano wires after treatment, so the silver nano material can be used as a high-performance conductive component for preparing a conductive coating. Because of controllability of topography, the silver nano sheet has great application potential and development prospect in the preparation field of electronic devices.
Description
Technical field
The present invention relates to the nano material preparation technical field, specifically relate to a kind of preparation method of silver nano sheet self-assembling material.
Background technology
Silver nano material is in a lot of fields, as: fields such as effective catalyst, optics, electronic component, biological detection show very big application potential, have bright development prospect.The silver nano material of one peacekeeping two dimension is owing to the uniqueness of its pattern gets more and more people's extensive concerning.Traditional silver nano material, as nano wire, nanotube etc. owing to be subjected to the restriction of existing synthesis condition often on pattern, to lack further controllability, so limited to it at electronic component, the scope of application in fields such as optics.For the Yin Nami self-assembly, owing to formed by the mutual self assembly of secondary structure, so pattern and configuration all have sizable adjustability, has good development space and application prospect.
Yin Nami self-assembly with controllable appearance occupies very consequence in the silver nano material preparation field.Therefore efficient, the controlled preparation of Nano silver piece self-assembly just has very important significance.The Nano silver piece self-assembly that this patent synthesized is to be formed by the nano particle self assembly of average diameter in the 4-10nm scope, and nanometer sheet can curl into the nanometer blank pipe under certain condition.Self-assembling nanoparticles is small-sized, and the distance between the particle generally also is controlled at about 1nm.This self-assembly structure will provide that pattern is controlled for Raman spectrum detects, repeatability by force, the surface strengthens substrate efficiently.And having the people to report to utilize this silver-colored nanometer self-assembly to prepare the method for nano silver wire by sintering, this is just for providing this silver nano material the scheme of feasibility as the conductive filler in the coating.Because the controllability of pattern, this Nano silver piece also has very big application potential and development prospect in the preparation field of electronic device.[concrete document is seen: Liu J.H., C.Y.Tsai, et al., Nanotechnology, 2009,20,035301-035310; Du J., Han B., Liu Z., Liu Y.and Kang D.J.Crystal Growth ﹠amp; Design, 2007,7,900-904; He Y., Wu X., Lu G.and Shi G.Materials Chemistry and Physics, 2006,98,178-182; WangY., Xu H., et al., Advanced Materials 2009,21,1-16; Kyle J.M.Bishop, ChristopherE.Wilmer, et al., Small 2009,5,1600-1630; Lu, Y., G.Liu, et al.Nano Letters 2005,5,5-10; Zhang J., Li X., et al., J.Phys.Chem.B 2005,109 (25) 12544-12548.]
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of silver nano sheet self-assembling material is provided.
The preparation method of this silver nano sheet self-assembling material comprises the steps:
1) be that the silver nitrate aqueous solution of 0.2M～2M joins in the carboxylic acid that molar concentration is 0.02M～0.3M/methyl methacrylate solution with molar concentration, wherein the ratio of the mole of carboxylic acid is 20～80 in water in the silver nitrate aqueous solution and carboxylic acid/methyl methacrylate solution, stirs the reversed micelle solution that forms silver nitrate;
2) be that the sodium borohydride aqueous solution of 0.2M～2M joins in the carboxylic acid that molar concentration is 0.02M～0.3M/methyl methacrylate solution with molar concentration, wherein the ratio of the mole of carboxylic acid is 20～80 in water in the sodium borohydride aqueous solution and carboxylic acid/methyl methacrylate solution, stirs the reversed micelle solution that forms sodium borohydride;
3) the reversed micelle solution of isopyknic silver nitrate and the reversed micelle solution of sodium borohydride are slowly mixed, under stirring condition, react 0.5～4h;
4) with reactant liquor centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the controlled Nano silver piece self-assembly of crimpness with alcohol extract, dispersion.
The beneficial effect that the present invention compared with prior art has is:
1, utilizes different surfactant carboxylic acids to prepare the Nano silver piece of assembling particle diameter stable and controllable first, have a good application prospect.
2, raw material is easy to get, and process is simple, the reaction efficiency height.
3, process of the test stability is high, and is repeatable strong.
4, the Nano silver grain particle size distribution range is very narrow, and stability is high, and interparticle distance is also relatively stable.
5, experiment need not under the sonic oscillation condition pre-dispersedly, can directly mix stirring reaction.
In a word, experimentation of the present invention is simple, and raw material is easy to get, and reaction condition gentleness and combined coefficient are higher relatively.Synthetic silver nano material structure and pattern are controlled, detect at nano electron device, Raman molecular, and the field of electrically-conducting paint has bigger application potential and development space.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 1, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 3nm;
Fig. 2 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 2, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 3nm;
Fig. 3 is SEM (SEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 2;
Fig. 4 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 3, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 3nm;
Fig. 5 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 4, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 8nm;
Fig. 6 is SEM (SEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 4;
Fig. 7 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 5, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 8nm;
Fig. 8 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 6, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 8nm;
Fig. 9 is transmission electron microscope (TEM) picture of the synthetic curling Nano silver piece self-assembly of the embodiment of the invention 7, and picture upper right corner illustration is its high power transmission electron micrograph, and the average diameter of self-assembled nanometer particle is about 8nm.
The specific embodiment
The invention will be further described to enumerate several specific embodiments below.
Embodiment 1:
The AgNO that in the beaker that fills the stearic MMA solution of 5ml 0.04M, adds 72 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, fill the NaBH that adds 72 μ l 0.2M in the beaker of the stearic MMA solution of 5ml 0.04M at another
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=20 of stearic mole in water in the material solution and stearic acid/methyl methacrylate solution.Fig. 1 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.
Embodiment 2:
The AgNO that in the beaker that fills the stearic MMA solution of 5ml 0.04M, adds 144 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, fill the NaBH that adds 144 μ l 0.2M in the beaker of the stearic MMA solution of 5ml 0.04M at another
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=40 of stearic mole in water in the material solution and stearic acid/methyl methacrylate solution.Fig. 2 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.Fig. 3 is the scanning electron microscope diagram (SEM) of the synthetic curling Nano silver piece self-assembly of present embodiment
Embodiment 3:
The AgNO that in the beaker that fills the stearic MMA solution of 5ml 0.04M, adds 216 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, fill the NaBH that adds 216 μ l 0.2M in the beaker of the stearic MMA solution of 5ml 0.04M at another
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=60 of stearic mole in water in the material solution and stearic acid/methyl methacrylate solution.Fig. 4 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.
Embodiment 4:
The AgNO that in the beaker that fills the sad MMA solution of 5ml 0.04M, adds 144 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, the NaBH that in another fills the beaker of sad MMA solution of 5ml 0.04M, adds 144 μ l 0.2M
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=40 of sad mole in water in the material solution and the sad/methyl methacrylate solution.Fig. 5 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.Fig. 6 is the scanning electron microscope diagram (SEM) of the synthetic curling Nano silver piece self-assembly of present embodiment.
Embodiment 5:
The AgNO that in the beaker that fills the sad MMA solution of 5ml 0.08M, adds 144 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, the NaBH that in another fills the beaker of sad MMA solution of 5ml 0.08M, adds 144 μ l 0.2M
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=20 of sad mole in water in the material solution and the sad/methyl methacrylate solution.Fig. 7 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.
Embodiment 6:
The AgNO that in the beaker that fills the sad MMA solution of 5ml 0.02M, adds 144 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, the NaBH that in another fills the beaker of sad MMA solution of 5ml 0.02M, adds 144 μ l 0.2M
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=80 of sad mole in water in the material solution and the sad/methyl methacrylate solution.Fig. 8 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.
Embodiment 7:
The AgNO that in the beaker that fills the sad MMA solution of 5ml 0.6M, adds 1080 μ l 0.2M
3The aqueous solution, stirring at room forms the reversed micelle solution A.In addition, the NaBH that in another fills the beaker of sad MMA solution of 5ml 0.6M, adds 1080 μ l 0.2M
4The aqueous solution, stirring at room forms the reversed micelle solution B.Then, under magnetic agitation, join reversed micelle B in the reversed micelle A liquid lentamente and react 1h.With the centrifugation under the rotating speed of 2500～5000rpm of gained reactant liquor, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the Nano silver piece self-assembly that curls with alcohol extract, dispersion.The ratio w=20 of sad mole in water in the material solution and the sad/methyl methacrylate solution.Fig. 9 is the transmission electron microscope figure (TEM) of the synthetic curling Nano silver piece self-assembly of present embodiment, and upper right corner illustration is its high power transmission electron microscope figure.
Claims (2)
1. the preparation method of a silver nano sheet self-assembling material is characterized in that comprising the steps:
1) be that the silver nitrate aqueous solution of 0.2M～2M joins in the carboxylic acid that molar concentration is 0.02M～0.3M/methyl methacrylate solution with molar concentration, wherein the ratio of the mole of carboxylic acid is 20～80 in water in the silver nitrate aqueous solution and carboxylic acid/methyl methacrylate solution, stirs the reversed micelle solution that forms silver nitrate;
2) be that the sodium borohydride aqueous solution of 0.2M～2M joins in the carboxylic acid that molar concentration is 0.02M～0.3M/methyl methacrylate solution with molar concentration, wherein the span of the ratio of the mole of carboxylic acid is 20～80 in water in the sodium borohydride aqueous solution and carboxylic acid/methyl methacrylate solution, stirs the reversed micelle solution that forms sodium borohydride;
3) the reversed micelle solution of isopyknic silver nitrate and the reversed micelle solution of sodium borohydride are slowly mixed, under stirring condition, react 0.5～4h;
4) with reactant liquor centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, spend deionised water, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 1～3 time is again with ethanol washing, centrifugation under the rotating speed of 2500～5000rpm, remove supernatant liquor, repeated washing 2～3 times, sediment obtains the controlled Nano silver piece self-assembly of crimpness with alcohol extract, dispersion.
2. the preparation method of a kind of silver nano sheet self-assembling material according to claim 1, it is characterized in that: described carboxylic acid is a stearic acid or sad.
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| CN108788180A (en) * | 2018-07-06 | 2018-11-13 | 山东大学 | A kind of optical property is controllable and the preparation method of the Ag aggregates of nanoparticles of the reversible assembling of pH response dynamics |
| CN112156793B (en) * | 2020-10-19 | 2023-03-24 | 西安工程大学 | Silver nanowire-ReS 2 Functional composite material and preparation method thereof |
| CN114839177B (en) * | 2022-04-25 | 2023-10-10 | 哈尔滨医科大学 | Method for detecting effective components of Chinese herbal medicine without labels based on surface-enhanced Raman spectroscopy technology and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147841A (en) * | 1990-11-23 | 1992-09-15 | The United States Of America As Represented By The United States Department Of Energy | Method for the preparation of metal colloids in inverse micelles and product preferred by the method |
| CN1583332A (en) * | 2004-06-08 | 2005-02-23 | 陈丽琼 | Nanometer silver sol and preparing method thereof |
| CN1810422A (en) * | 2006-02-24 | 2006-08-02 | 中国科学院上海硅酸盐研究所 | Prepn process of nanometer silver sol |
| US7241814B2 (en) * | 2001-11-09 | 2007-07-10 | Japan Science And Technology Agency | Preparation of metallic nanoparticles with shell-crosslinked micelle as mold |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147841A (en) * | 1990-11-23 | 1992-09-15 | The United States Of America As Represented By The United States Department Of Energy | Method for the preparation of metal colloids in inverse micelles and product preferred by the method |
| US7241814B2 (en) * | 2001-11-09 | 2007-07-10 | Japan Science And Technology Agency | Preparation of metallic nanoparticles with shell-crosslinked micelle as mold |
| CN1583332A (en) * | 2004-06-08 | 2005-02-23 | 陈丽琼 | Nanometer silver sol and preparing method thereof |
| CN1810422A (en) * | 2006-02-24 | 2006-08-02 | 中国科学院上海硅酸盐研究所 | Prepn process of nanometer silver sol |
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