CN1358596A - Method for preparing silver-golden core-shell nano granule 2D collector - Google Patents

Method for preparing silver-golden core-shell nano granule 2D collector Download PDF

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CN1358596A
CN1358596A CN01140157A CN01140157A CN1358596A CN 1358596 A CN1358596 A CN 1358596A CN 01140157 A CN01140157 A CN 01140157A CN 01140157 A CN01140157 A CN 01140157A CN 1358596 A CN1358596 A CN 1358596A
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fractal
preparation
core
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silver
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CN1143817C (en
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金永东
董绍俊
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

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  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The present invention belongs to a preparation method of silver-gold core-shell nano particle two-D meso-observation fractal aggregate. Said method is mainly characterized by that it is based on the diffusion limited aggregation (DLA) of silver-gold core-shell nano particle whose surface has prickle structure in the boundary surface of water and air. Said method uses the different silver nano particles whose grain diameter range is 15-75 nm as core-forming particles, and uses HAuCl4/NH2OH system as core-forming reagent in the course of heating solution. Said method not only is simple in operation, good in reproductivity, but also its fractal structure and size can be finely regulated by means of controlling concentration of reaction solution and reaction time.

Description

The preparation method of Yin-Jin nuclear-core/shell nanoparticles 2-dimensional mesoscopic fractal aggregate
Technical field: the preparation method who the invention belongs to Yin-Jin nuclear-core/shell nanoparticles 2-dimensional mesoscopic fractal aggregate.
Background technology: light, electricity, the magnetic characteristic of the integral body that the brilliant assembly in order of particle dispersed nano is had more and more become the hot subject of people's research.Controlling these nanocrystalline spaces arranges and usually causes producing some chemistry, machinery, light, electrical property and be different from single nanocrystalline new material fully.Recently, the metal nanoparticle fractal aggregate has caused that people pay close attention to greatly, because ubiquitous local dynamic exciting characteristic is all being played the part of important role (D.P.Tsai in these fractal aggregates in many physical processes, J.Kovacs, et al.Phys.Rev.Lett.1994,72,4149-4152 and references therein).Especially, the resonance dipole intrinsic mode of local can make many optical effects be strengthened significantly, and for example Raman scattering strengthens, or the like.Preliminary result of study shows that the nanocrystalline fractal aggregate of this metalloid will have some significant application prospects, especially aspect the nanocomposite optical in future.Yet, because preparation two-dimensional metallic nano particle fractal aggregate truly is quite difficult, to compare with a large amount of theoretical works, the experimental work of this respect is quite rare.In these researchs of report, the preparation of metal nanoparticle fractal aggregate is by add adsorbent in solution, as 2, and 3-benzodiazine, pyridine or gelatin and obtain.Say that strictly these aggregations are three-dimensional in solution, collapse into two-dimensional structure in the sample drying process.In addition, when characterizing, solution example drips to be let alone also to be accompanied by in the dry process other gathering and takes place on copper mesh, makes fractal aggregate organization definition complexity.
Summary of the invention: the preparation method who the purpose of this invention is to provide the Yin-Jin nuclear-core/shell nanoparticles 2-dimensional mesoscopic fractal aggregate on a kind of real two-dimensional sense.This method mainly based on the Yin-Jin nuclear-core/shell nanoparticles (galactic nucleus, golden shell) of surface band barbed structure assemble in the diffusion limited at water and air interface (diffusion-limited aggregation, DLA).This legal system is equipped with Yin-Jin nuclear-core/shell nanoparticles 2-dimensional mesoscopic fractal aggregate, not only simple to operate, quick, favorable reproducibility, and fractal structure can be able to meticulous adjusting by the concentration and the reaction time of control reaction solution.
Among the present invention we used the particle diameter scope at the Nano silver grains of the different sizes of 10-75nm as becoming nuclear particle, in solution with HAuCl 4/ NH 2The OH system is for becoming shell reagent.By the heating reaction solution, generate the Yin-Jin nuclear-core/shell nanoparticles of surface band barbed structure gradually.The nuclear of compound particle/shell size can realize by the silver in the regulation system/golden ratio.Control heat time heating time can make Yin-Jin nuclear-core/shell nanoparticles come-up of surface band barbed structure, and in the quick random walk in water and air interface, is assembled (DLA) definition and is formed size and see fractal aggregate Jie of millimeter between extremely centimetre by diffusion limited.And in the fractal aggregate between the adjacent particles the further deposition because of gold be adhesive into a firm integral body.The control reaction gathering time, the size that can regulate fractal aggregate effectively.In addition, the concentration that changes over shell reagent can be regulated fractal fine structure effectively.
The present invention is earlier with the different silver sols of the synthetic particle diameter scope of natrium citricum reducing process at 10-75nm.Control AgNO 3Reaction density at 0.2mM and AgNO 3With the mol ratio of natrium citricum 1: 0.5-2 makes the different silver sols of particle diameter scope at 10-75nm.Get the freshly prepd silver sol of 5ml, the rare one-tenth of water 10ml, the under agitation rapid 0.02M NH that adds freshly prepd 0.10ml 20.1% (w/v) HAuCl of OH and 0.10-1.0ml 4Be mixed into shell reagent.The heating reaction solution keeps boiling 3-10min to boiling, and after stopping to heat, naturally cools to room temperature.Behind ebuillition of heated 3-7min, as seen some tiny stains appear in naked eyes at the water and air interface greatly, and these pore ramps present dendritic fractal pattern.Control subsequently heat time heating time is at 2-3min, the size that can control the fractal aggregation body structure millimeter to centimetre between, accompanying drawing 1 is that multiplication factor is 40 times a optical microscope image.Sample can move on the appropriate carriers with transfer method and study, as moves to and can be directly used in transmission electron microscope pattern observation on the copper mesh.
The present invention prepares Yin-Jin nuclear-core/shell nanoparticles 2-dimensional mesoscopic fractal aggregate, and not only easy and simple to handle, favorable reproducibility the more important thing is that its fractal structure is defined by DLA, and structure are firm, and can be finely tuned by changing reaction condition.Accompanying drawing 2 is sem images of bar=100nm, the formation path that high-visible nano particle diffusion limited is assembled.In addition, prepared its component units of nano particle fractal aggregate is the Yin-Jin nucleocapsid structure with band prickle, is expected to exist some new function and applications.Accompanying drawing 3 is sem images of bar=100nm, the Yin of high-visible band prickle-Jin nucleocapsid structure.What deserves to be mentioned is that this method can prepare large-area nano particle 2-dimensional mesoscopic fractal aggregate, for experiment basis has been established in the application of future on the nano photoelectric device after improving.
The specific embodiment:
Embodiment 1: get the silver sol of 5ml particle diameter based on 15nm, the rare one-tenth of water 10ml, the under agitation rapid 0.02M NH that adds freshly prepd 0.10ml 20.1% (w/v) HAuCl of OH and 0.10ml 4Be mixed into shell reagent.The heating reaction solution keeps boiling 6min to boiling, and after stopping to heat, naturally cools to room temperature.Behind ebuillition of heated 3min, as seen some tiny stains appear in naked eyes at the water and air interface greatly, and these pore ramps present dendritic fractal pattern.The size of fractal aggregation body structure millimeter to centimetre between.Sample is transferred to and is directly used in the observation of transmission electron microscope pattern on the copper mesh, is the network structure of fractal definition, and wherein nano particle becomes the less intensive dendroid pattern in space by the barbed structure adhesion.
Embodiment 2: get the silver sol of 5ml particle diameter based on 50nm, the rare one-tenth of water 10ml, the under agitation rapid 0.02M NH that adds freshly prepd 0.10ml 2OH and 0.1% (w/v) HAuCl of 0.10 4Be mixed into shell reagent.The heating reaction solution keeps boiling 10min to boiling, and after stopping to heat, naturally cools to room temperature.Behind ebuillition of heated 7min, as seen some tiny stains appear in naked eyes at the water and air interface greatly, and these pore ramps present dendritic fractal pattern.The size of fractal aggregation body structure millimeter to centimetre between.Sample is transferred to and is directly used in the observation of transmission electron microscope pattern on the copper mesh, is the network structure of fractal definition, and wherein nano particle becomes the less dendroid pattern of branch by the barbed structure adhesion.Accompanying drawing 4 is sem images of bar=100nm, the dendroid fractal pattern of high-visible nanometer particle congery.
Embodiment 3: get the silver sol of 5ml particle diameter based on 50nm, the rare one-tenth of water 10ml, the under agitation rapid 0.02M NH that adds freshly prepd 0.10ml 20.1% (w/v) HAuCl of OH and 0.25ml 4Be mixed into shell reagent.The heating reaction solution keeps boiling 8min to boiling, and after stopping to heat, naturally cools to room temperature.Behind ebuillition of heated 6min, as seen some tiny stains appear in naked eyes at the water and air interface greatly, and these pore ramps present dendritic fractal pattern.The size of fractal aggregation body structure millimeter to centimetre between.Sample is transferred to and is directly used in the observation of transmission electron microscope pattern on the copper mesh, is the network structure of fractal definition, and wherein nano particle becomes the more dendroid pattern of branch by the barbed structure adhesion.Accompanying drawing 5 is sem images of bar=500nm, the dendroid fractal pattern of high-visible nanometer particle congery.
Embodiment 4: get the silver sol of 5ml particle diameter based on 50nm, the rare one-tenth of water 10ml, the under agitation rapid 0.02M NH that adds freshly prepd 0.10ml 20.1% (w/v) HAuCl of OH and 1.0ml 4Be mixed into shell reagent.The heating reaction solution keeps boiling 6min to boiling, and after stopping to heat, naturally cools to room temperature.Behind ebuillition of heated 3min, as seen some tiny stains appear in naked eyes at the water and air interface greatly, and these pore ramps present dendritic fractal pattern.The size of fractal aggregation body structure millimeter to centimetre between.Sample is transferred to and is directly used in the observation of transmission electron microscope pattern on the copper mesh, is the network structure of fractal definition, and wherein nano particle becomes the less intensive dendroid pattern in space by the barbed structure adhesion.Accompanying drawing 6 is sem images of bar=500nm, the dendroid fractal pattern of high-visible nanometer particle congery.
Embodiment 5: get the silver sol of 5ml particle diameter based on 75nm, the rare one-tenth of water 10ml, the under agitation rapid 0.02M NH that adds freshly prepd 0.10ml 20.1% (w/v) HAuCl of OH and 0.50ml 4Be mixed into shell reagent.The heating reaction solution keeps boiling 8min to boiling, and after stopping to heat, naturally cools to room temperature.Behind ebuillition of heated 6min, as seen some tiny stains appear in naked eyes at the water and air interface greatly, and these pore ramps present dendritic fractal pattern.The size of fractal aggregation body structure millimeter to centimetre between.Sample is transferred to and is directly used in the observation of transmission electron microscope pattern on the copper mesh, is the network structure of fractal definition, and wherein nano particle becomes the more dendroid pattern of branch by the barbed structure adhesion.

Claims (3)

1, the preparation method of a kind of Yin-Jin nuclear-core/shell nanoparticles 2-dimensional mesoscopic fractal aggregate, its step is as follows:
With the different silver sols of the synthetic particle diameter of natrium citricum reducing process;
Preparation NH 2OH and HAuCl 4Be mixed into shell reagent;
Silver sol under agitation adds the one-tenth shell reagent of preparation rapidly;
The heating reaction solution is to boiling, and maintenance boiling 3-10min, naturally cools to room temperature;
AgNO in the described natrium citricum reducing process 3Reaction density be 0.2mM;
AgNO in the described natrium citricum reducing process 3With the mol ratio of natrium citricum 1: 0.5-2;
NH in the described one-tenth shell reagent 2The concentration of OH is 0.02M, and addition is 0.10ml; HAuCl 4Concentration be 0.1% (w/v), addition is 0.10-1.0ml.
2, preparation method as claimed in claim 1 is characterized in that, the particle diameter scope of described silver sol is 10-75nm, and synthetic bimetallic compound particle is the Yin-Jin nuclear-core/shell nanoparticles of surface band barbed structure.
3, preparation method as claimed in claim 1 is characterized in that, described heating reaction solution is when seething with excitement, and silver sol is assembled (DLA) in the diffusion limited at water and air interface, and fractal aggregate is of a size of millimeter to Centimeter Level.
CNB011401575A 2001-11-28 2001-11-28 Method for preparing silver-golden core-shell nano granule 2D collector Expired - Fee Related CN1143817C (en)

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WO2008025751A1 (en) * 2006-08-30 2008-03-06 Umicore Ag & Co. Kg Core/shell-type catalyst particles comprising metal or ceramic core materials and methods for their preparation
CN101927345A (en) * 2010-09-23 2010-12-29 湖南科技大学 Method for preparing core-shell gold nanoparticles and detecting concentration of silver ions
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US8058204B2 (en) 2008-10-24 2011-11-15 GM Global Technology Operations LLC Method for generating a shell of noble metal overlaid on a core of non-noble metal, and catalysts made thereby
US8288308B2 (en) 2006-08-30 2012-10-16 Umicore Ag & Co. Kg Core/shell-type catalyst particles and methods for their preparation
CN104148667A (en) * 2014-08-14 2014-11-19 青岛大学 Method for preparing fractal aggregate with gas sensitivity and reversibility of metal nanoparticles
CN102076447B (en) * 2008-06-30 2014-12-17 同和电子科技有限公司 Metal microparticle containing composition and process for production of the same
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US8691717B2 (en) 2006-08-30 2014-04-08 Umicore Ag & Co. Kg Core/shell-type catalyst particles and methods for their preparation
WO2008025750A1 (en) * 2006-08-30 2008-03-06 Umicore Ag & Co. Kg Core/shell-type catalyst particles and methods for their preparation
CN101522345A (en) * 2006-08-30 2009-09-02 尤米科尔股份公司及两合公司 Core/shell-type catalyst particles comprising metal or ceramic core materials and methods for their preparation
JP2010501345A (en) * 2006-08-30 2010-01-21 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト Core / shell type catalyst particles containing metal or ceramic core material and method for producing the same
JP2010501344A (en) * 2006-08-30 2010-01-21 ユミコア・アクチエンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト Core / shell type catalyst particles and method for producing them
WO2008025751A1 (en) * 2006-08-30 2008-03-06 Umicore Ag & Co. Kg Core/shell-type catalyst particles comprising metal or ceramic core materials and methods for their preparation
US8227372B2 (en) 2006-08-30 2012-07-24 Umicore Ag & Co. Kg Core / shell-type catalyst particles comprising metal or ceramic core materials and methods for their preparation
US8288308B2 (en) 2006-08-30 2012-10-16 Umicore Ag & Co. Kg Core/shell-type catalyst particles and methods for their preparation
US8304362B2 (en) 2006-08-30 2012-11-06 Umicore Ag & Co. Kg Core/shell-type catalyst particles and methods for their preparation
CN102076447B (en) * 2008-06-30 2014-12-17 同和电子科技有限公司 Metal microparticle containing composition and process for production of the same
US8058204B2 (en) 2008-10-24 2011-11-15 GM Global Technology Operations LLC Method for generating a shell of noble metal overlaid on a core of non-noble metal, and catalysts made thereby
CN101927345A (en) * 2010-09-23 2010-12-29 湖南科技大学 Method for preparing core-shell gold nanoparticles and detecting concentration of silver ions
CN102071209B (en) * 2010-12-06 2013-03-27 王深明 Nanometer gene transfer material
CN102071209A (en) * 2010-12-06 2011-05-25 王深明 Nanometer gene transfer material
CN105307798A (en) * 2013-06-07 2016-02-03 Lg化学株式会社 Metal nanoparticles
CN105307798B (en) * 2013-06-07 2018-07-03 Lg化学株式会社 Metal nanoparticle
CN104148667A (en) * 2014-08-14 2014-11-19 青岛大学 Method for preparing fractal aggregate with gas sensitivity and reversibility of metal nanoparticles
CN104148667B (en) * 2014-08-14 2016-04-20 青岛大学 The preparation method of the reversible fractal aggregate of a kind of vapor sensitivity metal nanoparticle
CN110227816A (en) * 2019-07-15 2019-09-13 福州大学 A kind of gold and silver nano flower particle and its preparation method and application with core-shell structure
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CN111299570A (en) * 2020-03-20 2020-06-19 中国科学院合肥物质科学研究院 LSPR (localized surface plasmon resonance) adjustable gold @ silver core-shell nanostar and preparation method thereof

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