CN104128617B - The preparation method of a kind of spherical gold nano grain and application - Google Patents
The preparation method of a kind of spherical gold nano grain and application Download PDFInfo
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- CN104128617B CN104128617B CN201410399970.3A CN201410399970A CN104128617B CN 104128617 B CN104128617 B CN 104128617B CN 201410399970 A CN201410399970 A CN 201410399970A CN 104128617 B CN104128617 B CN 104128617B
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Abstract
The invention discloses preparation method and the application of a kind of spherical gold nano grain.It is prepared for the uniform gold nanoparticle of a kind of high concentration, high stability.This gold nano grain has Raman steady in a long-term, efficient and strengthens activity, can use as the surface enhancement Raman spectroscopy substrate material of a kind of commercialization.This preparation method has simple to operate, mild condition, reproducible and low cost and other advantages.
Description
Technical field
The present invention relates to nano material synthesis field, be specifically related in a kind of one-step synthesis spherical gold nano of high concentration high stability
The method of grain.
Background technology
Surface enhanced raman spectroscopy is the spectral technique of a kind of quick detection material surface molecule structure, and it is mainly characterized by can be fast
Speed obtains the finger print information of trace materials in complex system, has the advantage such as high sensitivity and high accuracy.Surface-enhanced Raman light
Spectral technology not only plays an important role in the scientific research such as electrochemistry and bio-imaging, is also being widely used in environment measuring, food
Quick detection in the practical field such as product safety, medicine, explosive and drugs.
Gold nano grain is presently the most one of surface-enhanced Raman spectrum active substrate material widely, although people's success
Synthesize the gold nano grain of various pattern and size, and can be as the Jenner of commercialization surface enhancement Raman spectroscopy substrate material
Rice grain is the most few.This is because, the surface enhancement Raman spectroscopy substrate material of commercialization both needs have higher Raman and strengthens alive
Property is required to again stable preservation.Having higher Raman and strengthen the gold nano grain surface of activity typically relatively totally, surface can be relatively
Height, long-term preserve during easily reunite and lose Raman and strengthen activity, as citrate protection Au nano-particle [Frens,
G.Nature:Phys.Sci.1973,241,20-22.】；And stable gold nano grain surface typically contains strong protective agent, these
Strong protective agent absorption seriously hinders the test substance enrichment at substrate material surface at substrate material surface, causes base material difficult
Strengthen with the Raman signal to test substance, such as Au nano-particle [the Yin Yadong et of iodide ion protection
al.Nanoscale,2012,4,2875-2878】.It addition, the gold nano grain production concentration obtained by existing synthetic method is general
All over relatively low, need when application further to be centrifuged concentrating, so can cause reunion and the loss of gold nano grain, to cost
All make a big impact with performance.
Therefore, it is necessary to exploitation new method prepares high concentration, the stability best buyization gold that have active with Raman enhancing
Nano-particle.
Summary of the invention
It is an object of the invention to provide preparation method and the application of a kind of spherical gold nano grain.Utilize alkylamine and polyethylene pyrrole
Reproducibility that pyrrolidone is suitable and protective effect, a step obtains high concentration, high stability, high Raman strengthen the gold nano of activity
Grain, solves gold nano grain production concentration low, and stability and Raman strengthen the problem that activity is difficult to have concurrently.
Described method is as follows:
(1) in water, the presoma of gold, polyvinylpyrrolidone, alkylamine are added, presoma matter in water of described gold
Amount fraction range is 0.005-5wt%；Polyvinylpyrrolidone mass fraction scope in water is 0.05-50wt%；
Alkylamine mass fraction scope in water is 0.005-5wt%, stirring；
(2) reacting certain time at a certain temperature, described temperature is 20-200 DEG C, the response time be 10 minutes-72 little
Time.
Wherein, the presoma of gold includes gold chloride or acetic acid gold；
Wherein, alkylamine includes that molecular formula meets RNH2(R=CnH2n+1, 0≤n≤16) material, preferably have ammonia, first
Amine, ethamine, n-butylamine, cetylamine etc.；
Wherein, presoma mass fraction in water of gold is more preferably 0.05～1wt%；Polyvinylpyrrolidone is mass fraction in water
Scope is 0.5～5wt%；Alkylamine mass fraction scope in water is 0.05～1wt%.
Wherein, temperature more preferably scope is 20～50 DEG C, and response time more preferably scope is 20 minutes～2 hours.
Main advantages of the present invention are: the gold nano grain (such as Fig. 1 and Fig. 3) that (1) the method prepares has steadily in the long term
High Raman strengthen activity (such as Fig. 4)；(2) the gold nano grain surface that the method prepares has layer of polyethylene ketopyrrolidine to make
For shell (such as Fig. 2) so that gold nano grain is highly stable, it is not necessary to harsh preservation condition, it is simple to outside during on-the-spot fast inspection
Go out to carry；(3) the gold nano grain surface applications that the ultra-thin polyvinylpyrrolidone that the method prepares wraps up as shell is on surface
The coupling distance between gold nano grain can be controlled time in Raman enhanced spectrum, obtain optimal Raman enhancing signal；(4) the party
The gold nano grain that method prepares has the feature of high concentration, than reduction of sodium citrate obtain gold nano grain production concentration improve
20 times, can directly use, be greatly saved in product concentration process the reunion and loss caused；(5) the method technique letter
Single, reproducible, it is simple to amplify and produce.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 gained gold nano grain, and size of nanometer gold grain is uniform.
Fig. 2 is the transmission electron microscope picture of embodiment 1 gained gold nano grain, it can be seen that gold nano grain surface have one layer ultra-thin poly-
Vinylpyrrolidone is as protection shell.
Fig. 3 is the X-ray powder diffraction figure of embodiment 1 gained gold nano grain.
Fig. 4 is the Raman spectrogram that embodiment 10 preserves that 1mM pyridine solution is detected by different time gold nano grain.1013
cm-1And 1038cm-1It is the characteristic peak of pyridine, it can be seen that 1mM pyridine solution is had stronger by gold nano grain
Raman strengthens activity, and during preserving 12 months, the Raman enhancing signal of pyridine almost without decay, is not had by gold nano grain yet
Occur miscellaneous peak, show that it has Raman-enhancing energy steady in a long-term.
Detailed description of the invention
The invention will be further described to combine accompanying drawing below by example
Embodiment 1
(1) in politef reactor, it is sequentially added into water, gold chloride, polyvinylpyrrolidone, methylamine water solution (30wt%),
Stirring is to obtaining settled solution.Wherein gold chloride mass fraction in water is 0.05wt%, and polyvinylpyrrolidone exists
Mass fraction in water is 10wt%, and methylamine mass fraction in water is 1wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall, obtain the named A of product.
Result is shown in Fig. 1, Fig. 2 and Fig. 3.
Embodiment 2
(1) in politef reactor, it is sequentially added into water, acetic acid gold, polyvinylpyrrolidone, methylamine water solution (30wt%),
Stirring is to obtaining settled solution.Wherein gold chloride mass fraction in water is 0.05wt%, and polyvinylpyrrolidone exists
Mass fraction in water is 10wt%, and methylamine mass fraction in water is 1wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall.
Embodiment 3
(1) in politef reactor, it is sequentially added into water, gold chloride, polyvinylpyrrolidone, methylamine water solution (30wt%),
Stirring is to obtaining settled solution.Wherein gold chloride mass fraction in water is 0.005wt%, and polyvinylpyrrolidone exists
Mass fraction in water is 0.05wt%, and methylamine mass fraction in water is 0.005wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall.
Embodiment 4
(1) in politef reactor, it is sequentially added into water, gold chloride, polyvinylpyrrolidone, methylamine water solution (30wt%),
Stirring is to obtaining settled solution.Wherein gold chloride mass fraction in water is 5wt%, and polyvinylpyrrolidone is at water
In mass fraction be 50wt%, methylamine mass fraction in water is 5wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall
Embodiment 5
(1) in politef reactor, it is sequentially added into water, gold chloride, polyvinylpyrrolidone, methylamine water solution (30wt%),
Stirring is to obtaining settled solution.Wherein acetic acid gold mass fraction in water is 5wt%, and polyvinylpyrrolidone is at water
In mass fraction be 50wt%, methylamine mass fraction in water is 5wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 20 DEG C of baking ovens.
Stopped reaction after (3) 72 hours, Temperature fall
Embodiment 6
(1) in politef reactor, it is sequentially added into water, gold chloride, polyvinylpyrrolidone, methylamine water solution (30wt%),
Stirring is to obtaining settled solution.Wherein acetic acid gold mass fraction in water is 5wt%, and polyvinylpyrrolidone is at water
In mass fraction be 50wt%, methylamine mass fraction in water is 5wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 200 DEG C of baking ovens.
Stopped reaction after (3) 10 minutes, Temperature fall.
Embodiment 7
(1) in politef reactor, it is sequentially added into water, gold chloride, polyvinylpyrrolidone, concentrated ammonia solution (25wt%),
Stirring is to obtaining settled solution.Wherein gold chloride mass fraction in water is 0.05wt%, and polyvinylpyrrolidone exists
Mass fraction in water is 10wt%, and ammonia mass fraction in water is 1wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall.
Embodiment 8
(1) being sequentially added into water, gold chloride, polyvinylpyrrolidone, n-butylamine in politef reactor, stirring is to obtaining
Settled solution.Wherein gold chloride mass fraction in water is 0.05wt%, polyvinylpyrrolidone quality in water
Mark is 10wt%, and n-butylamine mass fraction in water is 0.05wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall.
Embodiment 9
(1) being sequentially added into water, gold chloride, polyvinylpyrrolidone, cetylamine in politef reactor, stirring is to obtaining
Settled solution.Wherein gold chloride mass fraction in water is 0.05wt%, polyvinylpyrrolidone quality in water
Mark is 10wt%, and cetylamine mass fraction in water is 0.05wt%.
(2) politef reactor is loaded in rustless steel outer lining, seal, be placed in 140 DEG C of baking ovens.
Stopped reaction after (3) 8 hours, Temperature fall.
Embodiment 10
(1) A is obtained according to embodiment 1 step (1)-(3)
(2) A is joined in 200mL water, centrifugal 1 time (rotating speed 10000rpm, centrifugation time 3min), outwell supernatant molten
Liquid, adds 1mL water, ultrasonic disperse, is stored in vial, the named B of product.
(3) 200 μ L water are taken in liquid-like QC
(4) 10 μ L B are added in liquid-like QC；
(5) use Raman spectrometer detection, obtain gold nano grain blank in aqueous and strengthen Raman spectrogram.Detector bar
Part is as follows: DeltaNu company of U.S. Inspector Portable Raman spectrometer, optical maser wavelength 785nm, laser merit
Rate 60mW, sweep time 1s, scanning times 1 time.
(6) 200 μ L pyridine solution (1mM) are taken in liquid-like QC
(7) 10 μ L B are added in liquid-like QC；
(8) use Raman spectrometer detection, obtain the gold nano grain enhancing Raman spectrum to 1mM pyridine solution of fresh preparation
Figure.Testing conditions is with the present embodiment step (5).
(9) B in the present embodiment step (2) is preserved for a long time, detect according to the present embodiment step (3)-(8), respectively
Being 1 month to the holding time, 3 months, the gold nano grain of 6 months and 12 months was to 1mM pyridine solution
Strengthen Raman spectrogram.
Result is shown in Fig. 4
Embodiment 11
(1) B is obtained according to step (1)-(2) in embodiment 10；
(2) take 10uL B to drip on silicon chip, naturally dry；
(3) on silicon chip, 10uL pyridine solution (1mM) is dripped；
Use the detection of Raman spectrogrph, the gold nano grain enhancing Raman spectrogram to 1mM pyridine solution.Testing conditions is same
Embodiment 10 step (5).
Claims (6)
1. the preparation method of a spherical gold nano grain, it is characterised in that described method includes the following:
1) in water, the presoma of gold, polyvinylpyrrolidone, alkylamine are added, the forerunner of described gold
Body mass fraction scope in water is 0.005-5wt%；Polyvinylpyrrolidone is mass fraction scope in water
For 0.05-50wt%；Alkylamine mass fraction scope in water is 0.005-5wt%, stirring；Wherein, institute
The alkylamine stated includes that molecular formula meets RNH2, wherein, R=CnH2n+1, the material of 0 < n≤16；
2) reacting certain time at a certain temperature, described temperature is 20-200 DEG C, and the response time is
10 minutes-72 hours.
The preparation method of a kind of spherical gold nano grain the most as claimed in claim 1, it is characterised in that described
The presoma of gold includes gold chloride or acetic acid gold.
The preparation method of a kind of spherical gold nano grain the most as claimed in claim 1, it is characterised in that described
Presoma mass fraction scope in water of gold is 0.05-1wt%；Polyvinylpyrrolidone quality in water is divided
Number scope is 0.5-5wt%；Alkylamine mass fraction scope in water is 0.05-1wt%.
The preparation method of a kind of spherical gold nano grain the most as claimed in claim 1, it is characterised in that described
Temperature is 20-50 DEG C, and the response time is 20 minutes-2 hours.
5. a gold nano grain, it is characterised in that it is to be obtained by the method for any one of Claims 1-4
Arrive.
6. the gold nano grain of claim 5 is as the purposes of surface enhancement Raman spectroscopy substrate material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101144183A (en) * | 2007-07-19 | 2008-03-19 | 中国科学院长春应用化学研究所 | Method for preparing gold micron crystal with surface enhanced Raman active branched surface |
| CN101357402A (en) * | 2008-09-17 | 2009-02-04 | 厦门大学 | Synthetic method of decahedron nano metal |
| CN102019432A (en) * | 2010-10-15 | 2011-04-20 | 安徽师范大学 | Preparation method of metal icosahedral nanoparticles |
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| US8129199B2 (en) * | 2004-12-13 | 2012-03-06 | University of South Caroliina | Surface enhanced Raman spectroscopy using shaped gold nanoparticles |
| US20130045877A1 (en) * | 2011-08-19 | 2013-02-21 | Agency For Science, Technology And Research | Methods to form substrates for optical sensing by surface enhanced raman spectroscopy (sers) and substrates formed by the methods |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101144183A (en) * | 2007-07-19 | 2008-03-19 | 中国科学院长春应用化学研究所 | Method for preparing gold micron crystal with surface enhanced Raman active branched surface |
| CN101357402A (en) * | 2008-09-17 | 2009-02-04 | 厦门大学 | Synthetic method of decahedron nano metal |
| CN102019432A (en) * | 2010-10-15 | 2011-04-20 | 安徽师范大学 | Preparation method of metal icosahedral nanoparticles |
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