CN1493421A - Preparation method of one-dimensional nano silver material - Google Patents

Preparation method of one-dimensional nano silver material Download PDF

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Publication number
CN1493421A
CN1493421A CNA021461813A CN02146181A CN1493421A CN 1493421 A CN1493421 A CN 1493421A CN A021461813 A CNA021461813 A CN A021461813A CN 02146181 A CN02146181 A CN 02146181A CN 1493421 A CN1493421 A CN 1493421A
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gelatin
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CN1196554C (en
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唐芳琼
任湘菱
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention belongs to the technical field of preparation and application of metal photoelectric functional nano materials, and particularly relates to a preparation method of a one-dimensional nano silver material. Preparing a one-dimensional nano silver material by using the coacervation characteristic of gelatin and a metal salt reduction method, wherein the diameter of the obtained one-dimensional nano silver material is 10-300 nm; the length is 200 to 3000 nm. The method of the invention has the advantages of low energy consumption, high product purity and good dispersibility, and the sizes of the nano-wires and the nano-rods can be controlled by means of reaction conditions.

Description

The preparation method of 1-dimention nano ag material
Technical field
The invention belongs to the preparation and the applied technical field of metal photoelectric functional nano material, particularly relate to the preparation method of 1-dimention nano ag material.
Background technology
Silver has favorable conductive, heat conduction and reflecting properties in metal, and good chemical stability and ductility, thereby has extensive use in electronic industry.And nano silver particles is because surfactivity and surface energy are very high, and has special propertys such as antistatic, diamagnetic, sterilization, catalysis, can be widely used in fields such as catalystic material, antistatic material, anti-biotic material, low temperature thermally conductive material and photon crystal material.
The unidimensional nano material is meant and is nanoscale that on two-dimensional direction length is more much bigger than the yardstick on the above-mentioned two-dimensional direction, even is the novel nano-material of maroscopic quantity.Aspect ratio (ratio of length and diameter) is little is nanometer rod, and aspect ratio is big is called nano thread.Semi-conductor and metal nanometer line are commonly referred to quantum wire.
In recent years, the preparation research of monodimension nanometer material has been obtained remarkable progress.Be the synthetic method of some nano threads and nanometer rod below:
(1) carbon nanotube template.Because carbon nanotube is the one-dimensional material with hollow structure, available it do template and prepare the new class one-dimensional material, this is the advanced subject of present international research.For example utilize the capillarity of carbon nanotube some element can be inserted in the pipe, make the have special property One-dimensional Quantum line of (as magnetic, supraconductivity).See also article " carbon nanotube prepares nanostructure and nano combined metal oxide as removable template " (the Ajayan P.M. of nineteen ninety-five " nature " magazine 564-567 page or leaf, StephanO., Redlich Ph., Colllex C., Carbon nanotubes as removable templates for metaloxide nanocomposites and nanostructures, Nature, 1995,375:564-567).In recent years, successfully having adopted carbon nanotube is nano thread and the nanometer rod that template has been synthesized multiple carbide and nitride.
(2) Gu crystalline gas-growth method.Gu (Vapor-Solid, VS) method has prepared the MgO nano thread that aligns in the crystal gas-growth of usefulness such as Harvard University poplars in 1997 modification.
(3) select electrodip process to prepare the magneticmetal nano wire, usefulness selection electrodip processes such as Fasol had prepared magnetic permalloy nano wire in 1997.
(4) Gu laser ablation and crystalline gas-liquid-growth method IV family semiconductor nanowires combines the technology of growth Si and Ge nano wire with crystalline gas-liquid-(VLS) method Gu Morales of Harvard University in 1998 and Lieber have reported with laser ablation.
(5) Gu combining with crystalline gas-liquid-growth method, the organometallics vapour phase epitaxy generates III-V compound semiconductor nano wire.HIT has reported with organometallics vapor phase epitaxial growth method (MOVPE) Gu combine growth GaAs and InAs nano wire with crystalline gas-liquid-(VLS) growth method.
(6) solution-liquid phase-solid state growth legal system is equipped with III-V family semiconductor nanowires, the Buhro of Washington, DC university etc. adopt solution-liquid phase-solid phase (SLS) method, and (165~203 ℃) have synthesized III-V compound semiconductor (InP, InAs, GaP, GaAs) nano wire at low temperatures.
(7) prepare silicon nanowires with the high-temperature laser method of evaporation.1998, Yu of Peking University roc etc. were adopted the synthetic Si nano wire of the method for excimer pulsed laser evaporation.
(8) simple physical evaporation preparation silicon nanowires.1998, Yu of Peking University roc etc. were successfully synthesized silicon nanowires with the simple physical method of evaporation.
(9) the synthetic GaN nano crystal silk of High Temperature Gas phase reaction.
(10) nanoscale drop epitaxial method synthesizing silicon carbide nano wire.
Utilize that nano thread or nanometer rod and other materials are compound can prepare diversified nano complex, these artificial superstructure systems have good physical property.For example: nano thread is put in the organic polymer (PCM-1), and the electricity of this system is led and can be improved two orders of magnitude.This has just opened up new situation for the application of nano material.
The preparation method of existing monodimension nanometer material mainly is the preparation semiconductor material, and will use large-scale instrument mostly, at high temperature carry out, and complex process, cost is very high, is unfavorable for scale operation.
Summary of the invention
The object of the present invention is to provide the method for the controlled 1-dimention nano ag material of a kind of preparation size at low temperatures.Adopt present method to boost productivity, reduce production costs, the 1-dimention nano silver diameter of preparing is 10~300nm, and length is 200~3000nm.
The objective of the invention is to be achieved through the following technical solutions:
Utilize the cohesion characteristic of gelatin, prepare the 1-dimention nano ag material with the metal-salt reduction method.
The step of concrete grammar is as follows:
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 0.001~10 grams per liter, is preferably 0.01~10 grams per liter.
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 0.001~10 mol in the complex solution, is preferably 0.01~10 mol; The concentration of ammonia is 0.002~20 mol, is preferably 0.02~20 mol, this complex solution is joined in the gelatin solution of step (1), obtains mixing solutions, and the volume ratio of gelatin solution and complex solution is 1: 0.1~1: 5.
(3). organic acid and reductive agent are added in the mixing solutions that step (2) obtains, and making the organic acid concentration of mixing in the solution of back is 0.005~5 mol, is preferably 0.005~1 mol; The concentration of reductive agent is 0.1 * 10 -6~1 * 10 -2Mol is preferably 0.1 * 10 -5~1 * 10 -3Mol continues under the room temperature to stir 0.5~4 hour, obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material, and diameter is 10~300nm, is preferably 20~260nm; Length is 200~3000nm, is preferably 300~2000nm.
Described organic acid comprises citric acid, lactic acid or acetic acid etc.
Described reductive agent comprises organic amine, polyol, hydrazine hydrate, sodium borohydride, Resorcinol, formaldehyde or they two or more mixture arbitrarily.
Described organic amine is methane amide, Ursol D, 4-amino-N-ethyl-N-(Beta-methyl sulphonamide ethyl) meta-aminotoluene list water vitriol, trolamine or their any mixture.
Described polyol is Virahol, ethylene glycol or their any mixture.
Purposes of the present invention: end-use of the present invention is extensive, is high functional conductive, heat conduction and catalytic material, is widely used in fields such as catalystic material, battery electrode material, nanoelectronic circuits, transmitter, nanometer robot and low temperature thermally conductive material.
Adopt 1-dimention nano ag material that method of the present invention obtains shown in accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3.
Method of the present invention not only energy consumption is low, the product purity height, and good dispersity, and the size of nano wire and nanometer rod can be controlled by reaction conditions.
The present invention mainly utilizes the coacervation of gelatin.The coacervation of gelatin is under room temperature or subambient condition, and gelatin molecule produces to be assembled, and forms aggregate.The concentration that changes gelatin can be controlled the degree of cohesion.In addition, add special ion can promote cohesion in gelatin solution generation, as organic hydrochlorate.Utilize this phenomenon, nanometer silver has been assembled rice, form one-dimensional material by the cohesion of gelatin.And by controlling the cohesion degree of gelatin, the size of control 1-dimention nano ag material.It is simple that the present invention prepares the method for 1-dimention nano ag material, is easy to apply.
What method of the present invention was significantly different with preparation method in the past is, in the present invention, the preparation of 1-dimention nano ag material is to carry out at low temperatures, and without large-scale instrument, thereby cost is very low, is fit to scale operation.
Description of drawings
Fig. 1. the 1-dimention nano ag material electromicroscopic photograph of embodiments of the invention 1;
Fig. 2. the 1-dimention nano ag material electromicroscopic photograph of embodiments of the invention 2;
Fig. 3. the 1-dimention nano ag material electromicroscopic photograph of embodiments of the invention 3.
Specific embodiments
Embodiment 1
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 0.05 grams per liter.
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 0.4 mol in the complex solution; The concentration of ammonia is 0.8 mol, this complex solution is joined in the gelatin solution of step (1), and the volume ratio of gelatin solution and complex solution is 1: 1.
(3). lactic acid and hydrazine hydrate are added in the mixing solutions that step (2) obtains, and making the concentration of lactic acid of mixing in the solution of back is 0.1 mol; The concentration of hydrazine hydrate is 3.5 * 10 -5Mol continues under the room temperature to stir 1 hour, obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material, and diameter is 70nm; Length is 1200nm.See accompanying drawing 1.
Embodiment 2
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 0.1 grams per liter.
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 0.03 mol in the complex solution; The concentration of ammonia is 0.06 mol, this complex solution is joined in the gelatin solution of step poly-(1), and the volume ratio of gelatin solution and complex solution is 1: 5.
(3). acetic acid and formaldehyde are added in the mixing solutions that step (2) obtains, and making the concentration of mixing the acetic acid in the solution of back is 0.08 mol; The concentration of formaldehyde is 2.5 * 10 -4Mol continues under the room temperature to stir 2 hours, obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material, and diameter is 30nm; Length is 436nm.See accompanying drawing 2.
Embodiment 3
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 0.8 grams per liter.
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 3.5 mol in the complex solution; The concentration of ammonia is 7.0 mol, this complex solution is joined in the gelatin solution of step (1), and the volume ratio of gelatin solution and complex solution is 1: 0.5.
(3). lactic acid and methane amide are added in the mixing solutions that step (2) obtains, and making the concentration of lactic acid of mixing in the solution of back is 0.7 mol; The concentration of methane amide is 0.6 * 10 -4Mol continues under the room temperature to stir 2.5 hours, obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material, and diameter is 180nm; Length is 667nm.See accompanying drawing 3.
Embodiment 4
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 2 grams per liters.
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 0.7 mol in the complex solution; The concentration of ammonia is 1.4 mol, this complex solution is joined in the gelatin solution of step (1), and the volume ratio of gelatin solution and complex solution is 1: 1.5.
(3). citric acid and Resorcinol are added in the mixing solutions that step (2) obtains, and making the concentration of mixing the citric acid in the solution of back is 0.03 mol; The concentration of Resorcinol is 7.4 * 10 -5Mol continues under the room temperature to stir 4 hours, obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material, and diameter is 90nm; Length is 850nm.
Embodiment 5
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 0.35 grams per liter.
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 1.2 mol in the complex solution; The concentration of ammonia is 2.4 mol, this complex solution is joined in the gelatin solution of step (1), and the volume ratio of gelatin solution and complex solution is 1: 0.7.
(3). acetic acid and Ursol D are added in the mixing solutions that step (2) obtains, and making the concentration of mixing the acetic acid in the solution of back is 0.56 mol; The concentration of Ursol D is 0.4 * 10 -3Mol continues under the room temperature to stir 0.5 hour, obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material, and diameter is 62nm; Length is 1800nm.

Claims (9)

1. the preparation method of a 1-dimention nano ag material, it is characterized in that: the step of this method is as follows:
(1). the preparation aqueous gelatin solution, the concentration of gelatin is 0.001~10 grams per liter;
(2). the preparation silver nitrate aqueous solution, add ammoniacal liquor and make it become complex solution, the concentration of Silver Nitrate is 0.001~10 mol in the complex solution; The concentration of ammonia is 0.002~20 mol, this complex solution is joined in the gelatin solution of step (1), obtains mixing solutions, and the volume ratio of gelatin solution and complex solution is 1: 0.1~1: 5;
(3). organic acid and reductive agent are added in the mixing solutions that step (2) obtains, and making the organic acid concentration of mixing in the solution of back is 0.005~5 mol; The concentration of reductive agent is 0.1 * 10 -6~1 * 10 -2Mol continues under the room temperature to stir, and obtains white suspension, and centrifugation again obtains white precipitate, after the gained precipitation drying, obtains the 1-dimention nano ag material.
2. the method for claim 1 is characterized in that: the concentration of gelatin is 0.01~10 grams per liter in the described step (1).
3. the method for claim 1, it is characterized in that: the concentration of Silver Nitrate is 0.01~10 mol in described step (2) complex solution, and the concentration of ammonia is 0.02~20 mol.
4. the method for claim 1, it is characterized in that: described step (3) organic acid concentration is 0.005~1 mol; The concentration of reductive agent is 0.1 * 10 -5~1 * 10 -3Mol.
5. as claim 1 or 4 described methods, it is characterized in that: described organic acid comprises citric acid, lactic acid or acetic acid.
6. as claim 1 or 4 described methods, it is characterized in that: described reductive agent comprises organic amine, polyol, hydrazine hydrate, sodium borohydride, Resorcinol, formaldehyde or they two or more mixture arbitrarily.
7. method as claimed in claim 6 is characterized in that: described organic amine is methane amide, Ursol D, 4-amino-N-ethyl-N-(Beta-methyl sulphonamide ethyl) meta-aminotoluene list water vitriol, trolamine or their any mixture.
8. method as claimed in claim 6 is characterized in that: described polyol is Virahol, ethylene glycol or their any mixture.
9. the method for claim 1, it is characterized in that: the diameter of described 1-dimention nano ag material is 10~300nm; Length is 200~3000nm.
CN 02146181 2002-11-01 2002-11-01 Preparation method of one-dimensional nano silver material Expired - Fee Related CN1196554C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101073830B (en) * 2007-06-15 2010-05-19 东华大学 Gelatin-silver nano-material production method
CN101804458A (en) * 2009-02-12 2010-08-18 施乐公司 Through organic amine stabilized silver nanoparticles and preparation method thereof
CN101161728B (en) * 2007-09-21 2010-11-17 东华大学 Gelatin-Ag nano compound having bacteriostasis efficacy and preparation method thereof
CN102019432A (en) * 2010-10-15 2011-04-20 安徽师范大学 Preparation method of metal icosahedral nanoparticles
CN1795141B (en) * 2003-05-13 2012-02-01 新留康郎 Method for preparation of metal nano-rod and use thereof
CN102365127A (en) * 2009-03-24 2012-02-29 巴斯夫欧洲公司 Preparation of shaped metal particles and their uses
CN102327284B (en) * 2009-08-11 2012-09-19 聊城大学 Liquid-phase synthesis method of silver-chitosan and/or chitosan derivative nanocomposite
CN103273078A (en) * 2013-05-12 2013-09-04 山东理工大学 Preparation method of anisotropy silver nanorod

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1795141B (en) * 2003-05-13 2012-02-01 新留康郎 Method for preparation of metal nano-rod and use thereof
CN101073830B (en) * 2007-06-15 2010-05-19 东华大学 Gelatin-silver nano-material production method
CN101161728B (en) * 2007-09-21 2010-11-17 东华大学 Gelatin-Ag nano compound having bacteriostasis efficacy and preparation method thereof
CN101804458A (en) * 2009-02-12 2010-08-18 施乐公司 Through organic amine stabilized silver nanoparticles and preparation method thereof
CN102365127A (en) * 2009-03-24 2012-02-29 巴斯夫欧洲公司 Preparation of shaped metal particles and their uses
CN102365127B (en) * 2009-03-24 2017-10-03 巴斯夫欧洲公司 Preparation of shaped metal particles and application thereof
CN102327284B (en) * 2009-08-11 2012-09-19 聊城大学 Liquid-phase synthesis method of silver-chitosan and/or chitosan derivative nanocomposite
CN102019432A (en) * 2010-10-15 2011-04-20 安徽师范大学 Preparation method of metal icosahedral nanoparticles
CN103273078A (en) * 2013-05-12 2013-09-04 山东理工大学 Preparation method of anisotropy silver nanorod

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