CN103008681A - Preparation method for monodisperse gold nanoparticle and assembly thereof - Google Patents
Preparation method for monodisperse gold nanoparticle and assembly thereof Download PDFInfo
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- CN103008681A CN103008681A CN2012105316995A CN201210531699A CN103008681A CN 103008681 A CN103008681 A CN 103008681A CN 2012105316995 A CN2012105316995 A CN 2012105316995A CN 201210531699 A CN201210531699 A CN 201210531699A CN 103008681 A CN103008681 A CN 103008681A
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Abstract
The invention discloses a preparation method for a monodisperse gold nanoparticle and an assembly thereof. The preparation method comprises the following steps of: firstly, preparing the monodisperse gold nanoparticle with a reflux method: mixing 82.4mg of HAuCl4.4H2O, 5.5ml of oleylamine with the mass concentration of 80% and 50ml of cyclohexane, stirring and introducing argon in for more than 30 minutes at the room temperature, then quickly raising temperature to 90DEG C, keeping for 10 hours at the temperature, gradually cooling to the room temperature, then, washing away solvent which does not react in the solution and byproducts in the reaction by ethanol, and carrying out centrifugation to obtain the gold nanoparticle; dispersing the obtained gold nanoparticle into 2ml of cyclohexane; and then, preparing a porous gold nanoparticle aggregate with an oil-water two-phase micro-emulsion method in a process of slowly volatilizing an organic phase. The preparation method has the advantages of simple technology, low cost, simple equipment and high sensitivity and can be applied to the preparation of other functional nanoparticle aggregates.
Description
Technical field
The present invention relates to a kind of technology of preparing of noble metal nano particles, relate in particular to the preparation method of a kind of monodispersed gold nano grain and assembly thereof.
Background technology
Precious metal material (Au, Ag, Cu) is a kind of multifunctional material and is widely used in numerous areas such as aspects such as bioengineering, biochemistry, medicine transport, catalytic degradation, SERSs (SERS).Because SERS can realize quick, the hypersensitization of organic supramolecular are detected, so precious metal material is significant to organic trace detection.
In the prior art, a lot of researchs focus on the self-assembled structures of noble metal nano particles, because can have a large amount of " focus " in this structure, and usually show unique physicochemical characteristics such as light, electricity and photoelectric characteristic.Three-dimensional solid matter colloidal spheres (the Yuan Chao that is assembled into such as silver nano-grain, etal, Single clusters of self-assembled silvernanoparticles for surface-enhanced Raman scattering sensing of a dithiocarbamatefungicide, J.Mater.Chem., 2011,21,16264 – 16270), its techniqueflow is: at first, the Ag nano particle of preparation oleic acid protection also is dispersed in the nonpolar reagent; Secondly, Ag nano particle and the surfactant solution of aqueous phase that disperses in the oil phase mixed also strong stirring according to a certain volume, thereby obtain the oil-water microemulsion of homogeneous; Then, this emulsion is continued to stir to remove organic phase fully under 70 degree, finally obtain the three-dimensional solid matter colloidal spheres that aqueous phase disperses.
In the above-mentioned prior art, organic phase to remove speed too fast, the oil-water interface energy that sharply increases causes the nano particle the micro emulsion chamber in to concentrate rapidly, so that nano particle sharply reunites, finally obtain the particle aggregate of the higher and solid matter that void density is less of concentration class.
Summary of the invention
The purpose of this invention is to provide a kind ofly the present invention relates to that a kind of technique is simple, with low cost, device simple, highly sensitive monodispersed gold nano grain and the preparation method of assembly thereof.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of monodispersed gold nano grain of the present invention and assembly thereof comprises:
At first adopt circumfluence method to prepare gold nano grain: with 82.4mgHAuCl
44H
2O and 5.5ml mass concentration are that 80% oleyl amine and 50ml cyclohexane mix, at room temperature stir and more than the logical argon gas 30min, be rapidly heated subsequently to 90 ° of C and after keeping 10h under this temperature, be cooled to gradually room temperature, then utilize ethanol to wash accessory substance in unreacted solvent in the solution and the reaction off, the centrifugal gold nano grain that obtains is dispersed to the gold nano grain that obtains in the 2ml cyclohexane;
Then prepare mushy gold nano grain aggregate by the process of profit two-phase micro emulsion method and slow volatilization organic phase.
As seen from the above technical solution provided by the invention, the monodispersed gold nano grain that the embodiment of the invention provides and the preparation method of assembly thereof at first adopt circumfluence method to prepare gold nano grain: with 82.4mgHAuCl
44H
2O and 5.5ml mass concentration are that 80% oleyl amine and 50ml cyclohexane mix, at room temperature stir and more than the logical argon gas 30min, be rapidly heated subsequently to 90 ° of C and after keeping 10h under this temperature, be cooled to gradually room temperature, then utilize ethanol to wash accessory substance in unreacted solvent in the solution and the reaction off, the centrifugal gold nano grain that obtains is dispersed to the gold nano grain that obtains in the 2ml cyclohexane; Then prepare mushy gold nano grain aggregate by the process of profit two-phase micro emulsion method and slow volatilization organic phase.By regulating and control the rate of volatilization of organic phase in oil-water microemulsion, thereby obtain the colloidal spheres of different concentration class, the method technique is simple, with low cost, device simple, highly sensitive, be expected to realize the trace detection to organic pollution in environmental sample, food, the medical sample, and can be applicable to the preparation of other function nano cluster of grains aggressiveness.
Description of drawings
Fig. 1 a and Fig. 1 b are transmission electron micrograph and the corresponding size distribution plot of the gold nano grain of embodiment of the invention preparation;
Fig. 2 a to 2d is that the aqueous solution of gold nano grain and SDS in the embodiment of the invention obtains the gold nano grain aggregation of volatilization preparation under mixed emulsion and the different conditions by the stirring and emulsifying mode, and wherein: figure a and figure b are the gold nano grain aggregate of the low concentration class that obtains of room temperature volatilization; Figure c and figure d are the gold nano grain aggregate of the high concentration class that volatilization obtains under 70 ° of C.
Fig. 3 is the SERS spectrogram that the gold nano grain aggregate of embodiment of the invention preparation of the present invention detects the trace R6G aqueous solution, and among the figure: (1)-(3) obtain the SERS spectrogram that R6G is surveyed in the nanoparticle agglomerates health check-up for volatilization under the room temperature, and detection limit is about 10
-10M; (4)-(5) be that volatilization obtains the SERS spectrogram that aggregates of nanoparticles detects R6G under 70 ° of C, detection limit is about 10
-8M.
The specific embodiment
The below will be described in further detail the embodiment of the invention.
The preparation method of monodispersed gold nano grain of the present invention and assembly thereof, its better specific embodiment comprises:
At first adopt circumfluence method to prepare gold nano grain: with 82.4mgHAuCl
44H
2O and 5.5ml mass concentration are that 80% oleyl amine and 50ml cyclohexane mix, at room temperature stir and more than the logical argon gas 30min, be rapidly heated subsequently to 90 ° of C and after keeping 10h under this temperature, be cooled to gradually room temperature, then utilize ethanol to wash accessory substance in unreacted solvent in the solution and the reaction off, the centrifugal gold nano grain that obtains is dispersed to the gold nano grain that obtains in the 2ml cyclohexane;
Then prepare mushy gold nano grain aggregate by the process of profit two-phase micro emulsion method and slow volatilization organic phase.
The preparation of described gold nano grain aggregate comprises step:
At first prepare the aqueous solution of surfactant, and mix with the cyclohexane solution of gold nano grain, obtain the oil-in-water emulsions of homogeneous by strong stirring or ultrasonic mode;
Then, organic phase is removed in volatilization under different temperatures, thereby obtains the aggregate of the nano particle of different concentration class.
Described surfactant is softex kw or lauryl sodium sulfate.
The preparation method of monodispersed gold nano grain of the present invention and assembly thereof is for the preparation of the spherical assembly of gold nano grain.By regulating and control the rate of volatilization of organic phase in oil-water microemulsion, thereby obtain the colloidal spheres of different concentration class.With the lower colloidal spheres of concentration class as SERS (SERS) substrate, realized to rhodamine (R6G) fast, trace detection.The method technique is simple, with low cost, device simple, highly sensitive, is expected to realize the trace detection to organic pollution in environmental sample, food, the medical sample, and can be applicable to the preparation of other function nano cluster of grains aggressiveness.
The present invention slowly removes by means of organic phase, obtains the spherical particles clustered body that concentration class is lower, contain a large amount of spaces and hole, and has very strong SERS activity, can be used as the SERS substrate to detect trace organic substance.
Specific embodiment:
Then the gold nano grain that at first prepares the oleyl amine protection prepares mushy gold nano grain aggregate by the process of profit two-phase micro emulsion method and slow volatilization organic phase.This preparation method's concrete operation step is as follows:
The preparation of gold nano grain:
Circumfluence method prepares gold nano grain (size is about 10.7nm): with 82.4mg (0.2mmol) HAuCl
44H
2O, 5.5ml (14mmol) oleyl amine (tech.80%, ACROS) and 50ml cyclohexane are poured in the 100ml three-neck flask after mixing.This system at room temperature stirred and the about 30min of logical argon gas with the air in the thorough eliminating reaction system, be rapidly heated subsequently to 90 ° of C and under this temperature, keep 10h.Stop to react rear system and be cooled to gradually room temperature, utilize ethanol to wash accessory substance in unreacted solvent in the solution and the reaction off, centrifugally obtain end product and be dispersed in the 2ml cyclohexane.
The preparation of gold nano grain aggregate:
(1) prepares the aqueous solution of certain density surfactant (softex kw (CTAB) or lauryl sodium sulfate (SDS)), and mix according to a certain volume with the cyclohexane solution of gold nano grain; (2) obtain the oil-in-water emulsions of homogeneous by strong stirring or ultrasonic mode; (3) organic phase is removed in volatilization under the different temperatures, thereby obtains the aggregate of the nano particle of different concentration class.For example: with the cyclohexane solution of 0.5ml Au nano particle (～0.1M) join in the aqueous solution of SDS (1.25mM) of 5mL, strong stirring (1500rpm) 1 hour at room temperature then obtains the oil-water microemulsion of homogeneous.This emulsion is at room temperature stirred the sufficiently long time with slow volatilization organic phase, finally prepare the particle aggregation degree is lower and a gap density is larger nanoparticle agglomerates body and detect substrate as SERS.This substrate tentatively can detect 10
-6The M(mole), 10
-8M, 10
-10The R6G aqueous solution of M, and the higher aggregate of concentration class that the lower volatilization organic phase of 70 degree obtains can only detect 10
-6M, 10
-8The R6G aqueous solution of M (seeing accompanying drawing 3).
The above; only for the better specific embodiment of the present invention, but protection scope of the present invention is not limited to this, anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (3)
1. the preparation method of a monodispersed gold nano grain and assembly thereof is characterized in that, comprising:
At first adopt circumfluence method to prepare gold nano grain: with 82.4mgHAuCl
44H
2O and 5.5ml mass concentration are that 80% oleyl amine and 50ml cyclohexane mix, at room temperature stir and more than the logical argon gas 30min, be rapidly heated subsequently to 90 ° of C and after keeping 10h under this temperature, be cooled to gradually room temperature, then utilize ethanol to wash accessory substance in unreacted solvent in the solution and the reaction off, the centrifugal gold nano grain that obtains is dispersed to the gold nano grain that obtains in the 2ml cyclohexane;
Then prepare mushy gold nano grain aggregate by the process of profit two-phase micro emulsion method and slow volatilization organic phase.
2. the preparation method of monodispersed gold nano grain according to claim 1 and assembly thereof is characterized in that, the preparation of described gold nano grain aggregate comprises step:
At first prepare the aqueous solution of surfactant, and mix with the cyclohexane solution of gold nano grain, obtain the oil-in-water emulsions of homogeneous by strong stirring or ultrasonic mode;
Then, organic phase is removed in volatilization under different temperatures, thereby obtains the aggregate of the nano particle of different concentration class.
3. the preparation method of monodispersed gold nano grain according to claim 2 and assembly thereof is characterized in that, described surfactant is softex kw or lauryl sodium sulfate.
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Cited By (3)
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| CN104550936A (en) * | 2014-12-31 | 2015-04-29 | 中国科学院合肥物质科学研究院 | Colloid material composed of nano-particles and preparation method thereof |
| CN113770371A (en) * | 2021-09-10 | 2021-12-10 | 厦门大学 | Preparation method of high-yield small-particle-size silver nanoparticles |
| CN113828790A (en) * | 2021-08-25 | 2021-12-24 | 海南大学 | Preparation method of gold and core-shell nanocrystal thereof |
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Cited By (5)
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| CN113828790A (en) * | 2021-08-25 | 2021-12-24 | 海南大学 | Preparation method of gold and core-shell nanocrystal thereof |
| CN113828790B (en) * | 2021-08-25 | 2024-05-14 | 海南大学 | Gold and preparation method of core-shell nanocrystalline thereof |
| CN113770371A (en) * | 2021-09-10 | 2021-12-10 | 厦门大学 | Preparation method of high-yield small-particle-size silver nanoparticles |
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