CN103231067B - A kind of preparation method of nano-metal particle - Google Patents
A kind of preparation method of nano-metal particle Download PDFInfo
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- CN103231067B CN103231067B CN201310139136.6A CN201310139136A CN103231067B CN 103231067 B CN103231067 B CN 103231067B CN 201310139136 A CN201310139136 A CN 201310139136A CN 103231067 B CN103231067 B CN 103231067B
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Abstract
The invention provides a kind of preparation method of nano-metal particle, comprise the following steps: adopt spontaneous combustion method to prepare the hybrid particles of metal and carbon as presoma, and presoma is added in ethanol, ultrasonic presoma suspension; Presoma hanging drop is added to carrying of transmission electron microscope online, leave standstill and ethanol is volatilized; Net will be carried be placed in transmission electron microscope and utilize electron beam irradiation, obtain nano-metal particle.This preparation method's technique is simple, easy to operate, preparation efficiency is high, the parameter such as position, yardstick, pattern of metallic particles accurately can be controlled by the way controlling beam current density, at electron microscope situ ground growing nano scale metal particles, the nano-metal particle degree of crystallinity of preparation is high, pattern enriches.
Description
Technical field
The invention belongs to material science, particularly a kind of preparation method of nano-metal particle.
Background technology
Nano-metal particle size is little, percentage by volume shared by surface is large, because surface atom lacks pining down of adjacent atom, surface atom key state is different from granule interior with electronic state, have many dangling bonds, surface atom coordination is incomplete, there is unsaturated linkage, there is unsaturation, easily combine with other atom and form dynamic stabilization system; Therefore metallic particles particle diameter is once enter nano level yardstick, and its specific area increases sharply, and surface-active is strengthened, and can carry out chemical reaction at a lower temperature, show high chemical catalysis efficiency.Metal nanoparticle is as catalyst material, progressively be applied to the aspects such as hydrogenation, oxidation, reduction and electrochemical reaction, be mainly used in the fields such as purifying vehicle exhaust catalysis, ammoxidation catalysis, petroleum cracking catalysis, high power-fuel cell at present, and will have broad application prospects.
Metal nanoparticle also possesses unique optical property simultaneously, and its surface plasma body resonant vibration character is also one of study hotspot in recent years.The size and dimension of the frequency that metal nanoparticle surface plasma absorbs and width and metallic particles has substantial connection, also relevant with the dielectric constant of surrounding medium with the dielectric constant of metal itself.By controlling the size of metal nanoparticle, pattern and structure, its surface plasma body resonant vibration peak position adjustable, it is made to can be applicable to the aspects such as biologic single molecular detection, biomarker, biology sensor, molecular image, going deep into its application and will constantly expand simultaneously along with research.
Because the reality and potentiality application potential of nano-metal particle is very large, although the influence factor more complicated of nano metal shape controlled synthesis, but through nanosecond science and technology worker persistent exploration and study assiduously, metal nano particle shape controlled synthesis method achieves impressive progress.The current correlation technique preparing nano metal material mainly liquid phase method, comprises template, solution phase chemical reduction, microwave auxiliary liquid phase reduction and water (solvent) heat, microemulsion method, chemical reduction method, photoreduction met hod and microwave method etc.Such as: Zhang etc. utilize butanedioic acid (ethylhexyl) sodium sulfonate (Sodiumdioctylsulfosuccinate, AOT) make surfactant, cyclohexane makees continuous phase solvent, and silver nitrate does the predecessor of silver, form water in oil microemulsion system, prepare silver nano-grain.First Brendan etc. prepare the mixed aqueous solution obtaining PVP, natrium citricum, silver nitrate and L-arginine, then sodium borohydride solution is added, stir until system becomes glassy yellow from lark, after metal chloride light irradiation, prepared decahedron silver nano-grain.Zhu etc. utilize microwave method to prepare silver nano-grain in the ammonia spirit of silver, without the need to adding other reducing agent and protective agent, just obtain monodispersed silver nano-grain through tens minutes.Zhou etc. at ambient temperature, in PVP aqueous phase system, utilize NaOH to make initator, adopt wet chemistry method to prepare monodisperse gold particle fast.Shao etc. utilize asparatate to make reducing agent, and gold chloride does the predecessor of gold, and having prepared is cut triangle or a hexagonal gold-nano-piece in a large number.
But the preparation method of existing nano-metal particle is all the problems such as the method that have employed chemistry prepares nano-metal particle in aqueous, and due to the limitation of method, the metallic particles of synthesis has problems, as not good in dispersiveness, surface reagent absorption.
The people such as Yang (ANGEWANDTE CHEMIE-INTERNATIONAL EDITION48(2009) 8529-8531) disclose a kind of method utilizing spontaneous combustion method to prepare metal mixed composition granule.The method utilizes slaine, oxidant and complexing agent fuel to form colloidal sol in a solvent in the scope of pH1-10; Then by heating or solvent removed by evaporation, form gel, and in gel, preserve complexing agent fuel and oxidant; Gel is put in the reactor as the presoma that spontaneous combustion is reacted, flowing non-oxidizing gas protection under or light in vacuum; The gaseous product that burning generates, taken away by the non-oxidizing gas of flowing, product is metal and carbon composite.In this patent, make the metal prepared in this way and carbon composite be presoma exactly, adopt the way of electron beam irradiation, prepare nano-scale metal particles.
Summary of the invention
Goal of the invention: the object of this invention is to provide a kind of accurately can control metal nanoparticle size, pattern, position the preparation method of nano-metal particle.
Technical scheme: the preparation method of a kind of nano-metal particle provided by the invention, comprises the following steps:
(1) dispersion of presoma: adopt spontaneous combustion method to prepare the hybrid particles of metal and carbon as presoma, and presoma is added in ethanol, ultrasonic presoma suspension;
(2) preparation of predose sample: presoma hanging drop is added to carrying of transmission electron microscope online, leave standstill and ethanol is volatilized;
(3) preparation of nano-metal particle: net will be carried and be placed in transmission electron microscope and utilize electron beam irradiation, and obtain nano-metal particle.
In step (1), the amount ratio of described presoma and ethanol is 1g:(10-100) ml.
In step (1), ultrasonic time is 5-15min.
In step (3), the vacuum of transmission electron microscope is 1 × 10
-5more than Pa, filament brightness is 1 × 10
4-5 × 10
6a/m
2.
Beneficial effect: preparation method's technique of metal nanoparticle provided by the invention is simple, easy to operate, preparation efficiency is high, the parameter such as position, yardstick, pattern of metallic particles accurately can be controlled by the way controlling beam current density, at electron microscope situ ground growing nano scale metal particles, the nano-metal particle degree of crystallinity of preparation is high, pattern enriches.
The method effectively can solve the problem such as reunion, SURFACTANT ADSORPTION adopting the method for growing nano particle in the aqueous solution to cause, and technique is simple, controllability good; The metal nanoparticle using the method to prepare, has very strong potential use in single-molecule detection.
The present invention adopts the way of electron beam irradiation to prepare nano-metal particle, relates to this way before making the present invention without any document and patent, and the preparation for nano-metal particle provides a new thinking.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the silver of predose and the aggregate of carbon;
Fig. 2 is the nano-Ag particles TEM photo grown after electron beam irradiation, and left figure is close-up view, and right figure is enlarged drawing;
Fig. 3 is the electron diffraction pattern of nano-Ag particles, (111), (200), (220) of four main diffraction maximum difference corresponding A g, (311) face;
Fig. 4 is the characteristic X-ray power spectrum of nano-Ag particles; The signal of Cu and Mo carries net from transmission electron microscope, and the signal of Cr and Fe is from the specimen holder of transmission electron microscope, and the signal of Ag is from metallic particles;
Fig. 5 is the nano copper particle TEM photo grown after electron beam irradiation, and left figure is close-up view, and right figure is enlarged drawing;
Fig. 6 is the electron diffraction pattern of Cu nano particle, (111), (200), (220) of four corresponding Cu of main diffraction maximum difference, (311) face.
Detailed description of the invention
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, concrete material proportion, process conditions and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The preparation of embodiment 1. nano-Ag particles
Get the mixture that 1g adopts the metal A g for preparing of auto-combustion method and carbon, be placed in 10ml alcoholic solution, sonic oscillation 10min.
Take out a little solution with dropper, drop in transmission electron microscope special carry online, leave standstill 15 minutes natural air dryings in atmosphere.After air-dry, carry just there will be a large amount of metal A g and the aggregate of carbon on the net, aggregate pattern is as shown in Figure 1.As can be seen from Figure 1, aggregate is very loose, has a large amount of cavities to exist.
Transmission electron microscope is put into, when vacuum reaches above 1 × 10 carrying net
-5during more than Pa, open filament, adjust its brightness and arrive 1 × 10
4a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Ag can be obtained around aggregate.Product morphology is shown in Fig. 2 TEM photo, and the electron diffraction pattern of product grain is shown in Fig. 3, and the power spectrum of product grain is shown in Fig. 4.As can be seen from Figure 2, have a large amount of particles to exist in product, the size of particle is in a few to tens of nanometers, and the pattern of particle is triangle sheet, bar-shaped or random shape.From electronic diffraction collection of illustrative plates and the power spectrum of product grain, above-mentioned metallic particles is nano-Ag particles.
The preparation of embodiment 2. nano copper particle
Get the mixture that 1g adopts the Ni metal prepared of auto-combustion method and carbon, be placed in 10ml alcoholic solution, sonic oscillation 10min.
Take out a little solution with dropper, drop in transmission electron microscope special carry online, leave standstill 15 minutes natural air dryings in atmosphere.After air-dry, just there will be a large amount of metal A g and the aggregate of carbon on the net carrying, its aggregate is very loose, has the existence of a large amount of cavity.
Transmission electron microscope is put into, when vacuum reaches above 1 × 10 carrying net
-5during more than Pa, open filament, adjust its brightness and arrive 1 × 10
6a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Ag can be obtained around aggregate.Product morphology is shown in Fig. 5 TEM photo, and the electron diffraction pattern of product grain is shown in Fig. 6.As can be seen from Figure 5, have a large amount of particles to exist in product, the size of particle is in a few to tens of nanometers, and the pattern of particle is triangle sheet, bar-shaped or random shape.From the electronic diffraction collection of illustrative plates of product grain, above-mentioned metallic particles is nano copper particle.
The preparation of embodiment 3.Pt nano-metal particle
Take out the mixture of Pt metal that a little employing auto-combustion method prepares and carbon, be placed in 100ml alcoholic solution, sonic oscillation 5 minutes.
Take out a little solution with dropper, drop in special the carrying on the net of transmission electron microscope, put 15 minutes natural air dryings in atmosphere.
This micro-grid film is put into transmission electron microscope, when vacuum reaches 1 × 10
-5during more than Pa, open filament, adjust its brightness and arrive 4 × 10
5a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Pt can be obtained around aggregate.
The preparation of embodiment 4.Pd nano-metal particle
Take out the mixture of Pt metal that a little employing auto-combustion method prepares and carbon, be placed in 50ml alcoholic solution, sonic oscillation 15 minutes.
Take out a little solution with dropper, drop in special the carrying on the net of transmission electron microscope, put 15 minutes natural air dryings in atmosphere.
This micro-grid film is put into transmission electron microscope, when vacuum reaches 1 × 10
-5during more than Pa, open filament, adjust its brightness and arrive 1 × 10
5a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Pd can be obtained around aggregate.
The preparation of embodiment 5.Au nano-metal particle
Take out the mixture of Pt metal that a little employing auto-combustion method prepares and carbon, be placed in 30ml alcoholic solution, sonic oscillation 12 minutes.
Take out a little solution with dropper, drop in special the carrying on the net of transmission electron microscope, put 15 minutes natural air dryings in atmosphere.
This micro-grid film is put into transmission electron microscope, when vacuum reaches 1 × 10
-5during more than Pa, open filament, adjust its brightness and arrive 2 × 10
5a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Au can be obtained around aggregate.
The preparation of embodiment 6.Bi nano-metal particle
Take out the mixture of Pt metal that a little employing auto-combustion method prepares and carbon, be placed in 70ml alcoholic solution, sonic oscillation 8 minutes.
Take out a little solution with dropper, drop in special the carrying on the net of transmission electron microscope, put 15 minutes natural air dryings in atmosphere.
This micro-grid film is put into transmission electron microscope, when vacuum reaches 1 × 10
-5during more than Pa, open filament, adjust its brightness and arrive 1 × 10
4a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Bi can be obtained around aggregate.
The preparation of embodiment 7:Ni nano-metal particle
Take out the mixture of W metal that a little employing auto-combustion method prepares and carbon, be placed in 50ml alcoholic solution, sonic oscillation 10 minutes.
Take out a little solution with dropper, drop in special the carrying on the net of transmission electron microscope, put 15 minutes natural air dryings in atmosphere.
This micro-grid film is put into transmission electron microscope, when vacuum reaches 1 × 10
-5during more than Pa, open filament, adjust its brightness and arrive 1 × 10
6a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Ni can be obtained around aggregate.
The preparation of embodiment 8.Co nano-metal particle
Take out the mixture of Pt metal that a little employing auto-combustion method prepares and carbon, be placed in 40ml alcoholic solution, sonic oscillation 14 minutes.
Take out a little solution with dropper, drop in special the carrying on the net of transmission electron microscope, put 15 minutes natural air dryings in atmosphere.
This micro-grid film is put into transmission electron microscope, when vacuum reaches 1 × 10
-5during more than Pa, open filament, adjust its brightness and arrive 8 × 10
5a/m
2, under aggregate is exposed to electron beam, in a few second, the nano-scale particle of a large amount of Co can be obtained around aggregate.
Claims (2)
1. a preparation method for nano-metal particle, is characterized in that: comprise the following steps:
(1) adopt spontaneous combustion method to prepare the hybrid particles of metal and carbon as presoma, and presoma is added in ethanol, ultrasonic presoma suspension; The amount ratio of presoma and ethanol is 1g:(10-100) ml;
(2) presoma hanging drop is added to carrying of transmission electron microscope online, leave standstill and ethanol is volatilized;
(3) net will be carried be placed in transmission electron microscope and utilize electron beam irradiation, obtain nano-metal particle; Wherein, the vacuum of transmission electron microscope is 1 × 10
-5more than Pa, filament brightness is 1 × 10
4-5 × 10
6a/m
2.
2. the preparation method of a kind of nano-metal particle according to claim 1, is characterized in that: in step (1), and ultrasonic time is 5-15min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0735001A2 (en) * | 1995-02-09 | 1996-10-02 | Research Development Corporation Of Japan | Ultrafine particles and production method thereof |
| CN1557588A (en) * | 2004-01-13 | 2004-12-29 | 上海大学 | Method for manufacturing nano-silver |
| CN101543894A (en) * | 2009-03-19 | 2009-09-30 | 南京大学 | Method for preparing metal and alloy material with sol-gel self-combustion method |
| CN101817086A (en) * | 2010-04-14 | 2010-09-01 | 中国科学院生态环境研究中心 | Novel process for converting silver-containing scarp to nano-silver |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000192113A (en) * | 1998-12-28 | 2000-07-11 | Japan Science & Technology Corp | Manufacture of metallic superfine particle, and metallic superfine particle aggregate to which the manufacture is applied |
| JP4631095B2 (en) * | 2005-05-23 | 2011-02-16 | 学校法人慶應義塾 | Method for producing metal nanoparticles |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0735001A2 (en) * | 1995-02-09 | 1996-10-02 | Research Development Corporation Of Japan | Ultrafine particles and production method thereof |
| CN1557588A (en) * | 2004-01-13 | 2004-12-29 | 上海大学 | Method for manufacturing nano-silver |
| CN101543894A (en) * | 2009-03-19 | 2009-09-30 | 南京大学 | Method for preparing metal and alloy material with sol-gel self-combustion method |
| CN101817086A (en) * | 2010-04-14 | 2010-09-01 | 中国科学院生态环境研究中心 | Novel process for converting silver-containing scarp to nano-silver |
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