CN103008681B - The preparation method of monodispersed gold nano grain and assembly thereof - Google Patents
The preparation method of monodispersed gold nano grain and assembly thereof Download PDFInfo
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- CN103008681B CN103008681B CN201210531699.5A CN201210531699A CN103008681B CN 103008681 B CN103008681 B CN 103008681B CN 201210531699 A CN201210531699 A CN 201210531699A CN 103008681 B CN103008681 B CN 103008681B
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Abstract
The invention discloses the preparation method of a kind of monodispersed gold nano grain and assembly thereof, first adopt circumfluence method to prepare gold nano grain: by 82.4mgHAuCl
44H
2o and 5.5ml mass concentration is oleyl amine and the mixing of 50ml cyclohexane of 80%, at room temperature stir and lead to more than argon gas 30min, be rapidly heated after also keeping 10h at this temperature to 90 ° of C subsequently, be cooled to room temperature gradually, then ethanol is utilized to wash unreacted solvent and the accessory substance in reacting in solution off, centrifugally obtain gold nano grain, the gold nano grain obtained is dispersed in 2ml cyclohexane; Then mushy gold nano grain aggregate is prepared by the process of water-oil phase micro emulsion method and organic phase of slowly volatilizing.Technique is simple, with low cost, device simple, highly sensitive, can be applicable to the preparation of other function nano particle agglomeration.
Description
Technical field
The present invention relates to a kind of technology of preparing of noble metal nano particles, particularly relate 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 as aspects such as bioengineering, biochemistry, medicine transport, catalytic degradation, SERSs (SERS).Because SERS can realize detecting, so precious metal material is significant to organic trace detection quick, the hypersensitization of organic supramolecular.
In prior art, a lot of researchs focus on the self-assembled structures of noble metal nano particles, because can exist in this structure a large amount of " focus ", and usually show unique physicochemical characteristics as optical, electrical and photoelectric characteristic.As three-dimensional solid matter colloidal spheres (the Yuan Chao that silver nano-grain is assembled into, 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: first, prepares the Ag nano particle of oleic acid protection and is dispersed in apolar agent; Secondly, the Ag nano particle disperseed in oil phase and the surfactant solution in aqueous phase are mixed according to a certain volume and strong stirring, thus obtain homogeneous oil-water microemulsion; Then, this emulsion Keep agitation under 70 degree, to remove organic phase completely, is finally obtained the three-dimensional solid matter colloidal spheres of disperseing in aqueous phase.
In above-mentioned prior art, organic phase to remove speed too fast, the oil-water interface energy sharply increased, causes the nano particle in micro emulsion chamber to concentrate rapidly, nano particle is sharply reunited, finally obtains the higher and particle aggregate of the solid matter that void density is less of concentration class.
Summary of the invention
The object of this invention is to provide and a kind ofly the present invention relates to that a kind of technique is simple, with low cost, the preparation method of device simple, highly sensitive monodispersed gold nano grain and assembly thereof.
The object 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, comprising:
First circumfluence method is adopted to prepare gold nano grain: by 82.4mgHAuCl
44H
2o and 5.5ml mass concentration is oleyl amine and the mixing of 50ml cyclohexane of 80%, at room temperature stir and lead to more than argon gas 30min, be rapidly heated after also keeping 10h at this temperature to 90 ° of C subsequently, be cooled to room temperature gradually, then ethanol is utilized to wash unreacted solvent and the accessory substance in reacting in solution off, centrifugally obtain gold nano grain, the gold nano grain obtained is dispersed in 2ml cyclohexane;
Then mushy gold nano grain aggregate is prepared by the process of water-oil phase micro emulsion method and organic phase of slowly volatilizing.
As seen from the above technical solution provided by the invention, the monodispersed gold nano grain that the embodiment of the present invention provides and the preparation method of assembly thereof, first adopt circumfluence method to prepare gold nano grain: by 82.4mgHAuCl
44H
2o and 5.5ml mass concentration is oleyl amine and the mixing of 50ml cyclohexane of 80%, at room temperature stir and lead to more than argon gas 30min, be rapidly heated after also keeping 10h at this temperature to 90 ° of C subsequently, be cooled to room temperature gradually, then ethanol is utilized to wash unreacted solvent and the accessory substance in reacting in solution off, centrifugally obtain gold nano grain, the gold nano grain obtained is dispersed in 2ml cyclohexane; Then mushy gold nano grain aggregate is prepared by the process of water-oil phase micro emulsion method and organic phase of slowly volatilizing.By regulating and controlling the rate of volatilization of organic phase in oil-water microemulsion, thus 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, medical sample, and can be applicable to the preparation of other function nano particle agglomeration.
Accompanying drawing explanation
Fig. 1 a and Fig. 1 b is the transmission electron micrograph of gold nano grain prepared by the embodiment of the present invention and corresponding size distribution plot;
Fig. 2 a to 2d is that the aqueous solution of gold nano grain and SDS in the embodiment of the present invention obtains mixed emulsion by stirring and emulsifying mode and the gold nano grain aggregation prepared that volatilizees under different condition, wherein: figure a and figure b is that room temperature is volatilized the gold nano grain aggregate of the low concentration class obtained; Figure c and figure d is the gold nano grain aggregate of the high concentration class obtained of volatilizing under 70 ° of C.
Fig. 3 is the SERS spectrogram of the gold nano grain aggregate detection trace R6G aqueous solution prepared by the embodiment of the present invention of the present invention, in figure: (1)-(3) obtain for volatilizing under room temperature the SERS spectrogram that R6G is surveyed in nanoparticle agglomerates health check-up, and detection limit is about 10
-10m; (4)-(5) are that under 70 ° of C, volatilization obtains the SERS spectrogram that aggregates of nanoparticles detects R6G, and detection limit is about 10
-8m.
Detailed description of the invention
To be described in further detail the embodiment of the present invention below.
The preparation method of monodispersed gold nano grain of the present invention and assembly thereof, its preferably detailed description of the invention comprise:
First circumfluence method is adopted to prepare gold nano grain: by 82.4mgHAuCl
44H
2o and 5.5ml mass concentration is oleyl amine and the mixing of 50ml cyclohexane of 80%, at room temperature stir and lead to more than argon gas 30min, be rapidly heated after also keeping 10h at this temperature to 90 ° of C subsequently, be cooled to room temperature gradually, then ethanol is utilized to wash unreacted solvent and the accessory substance in reacting in solution off, centrifugally obtain gold nano grain, the gold nano grain obtained is dispersed in 2ml cyclohexane;
Then mushy gold nano grain aggregate is prepared by the process of water-oil phase micro emulsion method and organic phase of slowly volatilizing.
The preparation of described gold nano grain aggregate comprises step:
First prepare the aqueous solution of surfactant, and mix with the cyclohexane solution of gold nano grain, obtain homogeneous oil-in-water emulsions by strong stirring or ultrasonic mode;
Then, organic phase is removed in volatilization at different temperatures, thus 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, for the preparation of the spherical assembly of gold nano grain.By regulating and controlling the rate of volatilization of organic phase in oil-water microemulsion, thus obtain the colloidal spheres of different concentration class.By the lower colloidal spheres of concentration class as SERS (SERS) substrate, achieve quick, the trace detection to rhodamine (R6G).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, medical sample, and can be applicable to the preparation of other function nano particle agglomeration.
The present invention's slowly removing by means of organic phase, obtains that concentration class is lower, spherical particles clustered body containing a large amount of space and hole, and it is active to have very strong SERS, can be used as SERS substrate to detect trace organic substance.
Specific embodiment:
First prepare the gold nano grain of oleyl amine protection, then prepare mushy gold nano grain aggregate by the process of water-oil phase micro emulsion method and organic phase of slowly volatilizing.The concrete operation step of this preparation method is as follows:
The preparation of gold nano grain:
Circumfluence method prepares gold nano grain (size is about 10.7nm): by 82.4mg (0.2mmol) HAuCl
44H
2pour in 100ml three-neck flask after O, 5.5ml (14mmol) oleyl amine (tech.80%, ACROS) and the mixing of 50ml cyclohexane.This system at room temperature stirred and leads to the about 30min of argon gas thoroughly to get rid of the air in reaction system, be rapidly heated subsequently to 90 ° of C and keep 10h at this temperature.After stopping reaction, system is cooled to room temperature gradually, utilizes ethanol to wash accessory substance in unreacted solvent in solution and reaction off, centrifugally obtains end product and is dispersed in 2ml cyclohexane.
The preparation of gold nano grain aggregate:
(1) prepare 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) homogeneous oil-in-water emulsions is obtained by strong stirring or ultrasonic mode; (3) under different temperatures, organic phase is removed in volatilization, thus obtains the aggregate of the nano particle of different concentration class.Such as: join in the aqueous solution of SDS (1.25mM) of 5mL by the cyclohexane solution (~ 0.1M) of 0.5ml Au nano particle, then at room temperature strong stirring (1500rpm) 1 hour, obtains homogeneous oil-water microemulsion.This emulsion is at room temperature stirred the sufficiently long time with organic phase of slowly volatilizing, finally prepare the lower and nanoparticle agglomerates body that gap densities is larger of particle aggregation degree and detect substrate as SERS.This substrate tentatively can detect 10
-6m(mole), 10
-8m, 10
-10the R6G aqueous solution of M, and the higher aggregate of the concentration class that 70 degree of lower volatilization organic phases obtain can only detect 10
-6m, 10
-8the R6G aqueous solution (see accompanying drawing 3) of M.
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change 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. a preparation method for monodispersed gold nano grain and assembly thereof, is characterized in that, comprising:
First circumfluence method is adopted to prepare gold nano grain: by 82.4mgHAuCl
44H
2o and 5.5ml mass concentration is oleyl amine and the mixing of 50ml cyclohexane of 80%, at room temperature stir and lead to more than argon gas 30min, be rapidly heated after also keeping 10h at this temperature to 90 DEG C subsequently, be cooled to room temperature gradually, then ethanol is utilized to wash unreacted solvent and the accessory substance in reacting in solution off, centrifugally obtain gold nano grain, the gold nano grain obtained is dispersed in 2ml cyclohexane;
Then mushy gold nano grain aggregate is prepared by the process of water-oil phase micro emulsion method and at room temperature stirring slow volatilization organic phase.
2. the preparation method of monodispersed gold nano grain according to claim 1 and assembly thereof, is characterized in that, in the preparation process of described gold nano grain aggregate:
First prepare the aqueous solution of surfactant, and mix with the cyclohexane solution of gold nano grain, obtain homogeneous oil-in-water emulsions by strong stirring or ultrasonic mode.
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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| CN104550936B (en) * | 2014-12-31 | 2017-05-31 | 中国科学院合肥物质科学研究院 | Colloid material of nano particle assembling and preparation method 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368198A (en) * | 2008-09-24 | 2009-02-18 | 江南大学 | Preparation method for self-assembly material of nano golden and Lambda DNA chain connection |
| CN101992302A (en) * | 2009-08-21 | 2011-03-30 | 中国科学院大连化学物理研究所 | Method for preparing high-dispersion precious metal and alloy nanoparticles thereof |
| CN102416468A (en) * | 2011-11-21 | 2012-04-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano metal leaf and preparation method thereof |
| CN102553594A (en) * | 2010-12-21 | 2012-07-11 | 冯刚 | Preparation method for metallic nano cluster catalyst |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323022B (en) * | 2008-07-11 | 2011-04-06 | 中山大学 | Method for preparing gold magnetic core-shell nano-particle |
| CN101830445B (en) * | 2009-12-15 | 2014-12-10 | 河南大学 | Novel method for synthetizing inorganic nanocrystal by taking acetylacetone as raw material |
| CN101811192B (en) * | 2010-03-09 | 2011-11-09 | 上海师范大学 | Water-soluble monodisperse iron-nickel magnetic nanoparticles and application thereof |
| KR101335616B1 (en) * | 2011-02-17 | 2013-12-02 | 이화여자대학교 산학협력단 | PRODUCING METHOD OF Au NANOPARTICLE PATTERN HAVING LOCALIZED SURFACE PLASMON RESONANCE COUPLING PROPERTY, AND Au NANOPARTICLE PATTERN BY THE SAME |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101368198A (en) * | 2008-09-24 | 2009-02-18 | 江南大学 | Preparation method for self-assembly material of nano golden and Lambda DNA chain connection |
| CN101992302A (en) * | 2009-08-21 | 2011-03-30 | 中国科学院大连化学物理研究所 | Method for preparing high-dispersion precious metal and alloy nanoparticles thereof |
| CN102553594A (en) * | 2010-12-21 | 2012-07-11 | 冯刚 | Preparation method for metallic nano cluster catalyst |
| CN102416468A (en) * | 2011-11-21 | 2012-04-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano metal leaf and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《single clusters of self assembled silver nanoparticles for surface-enhanced Raman scattering sensing of a dithiocarbamate fungicide》;Chao Yuan 等;《J.Mater.Chem.》;20110914;第21卷;16264-16270 * |
| 《Synthesis of Organo-Silan Functionalized Nanocrystal Micelles and Their Self-Assembly》;Hongyou Fan 等;《J.AM.CHEM.SOC.》;20050917;第127卷(第40期);13746-13747 * |
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