CN103496666A - Method for phase transferring and three-dimensional assembling of precious metal nano-particles - Google Patents
Method for phase transferring and three-dimensional assembling of precious metal nano-particles Download PDFInfo
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Abstract
The invention discloses a method for phase transferring and three-dimensional assembling of precious metal nano-particles. The method comprises the following steps that after centrifugation is carried out on the aqueous solutions of the precious metal nano-particles, the aqueous solutions of 2 (diethyl aminoethyl acyl methyl ethyl) octadecylamine are added to sediments acquired through the centrifugation for ultrasonication, obtained dispersion liquid and the organic solutions of the 2 (diethyl aminoethyl acyl methyl ethyl) octadecylamine are mixed and vibrated, standing is carried out, and the precious metal nano-particles are transferred from a water phase to an oil phase. Centrifugation is carried out on the precious metal nano-particles transferred to the oil phase for the first time, the organic solutions of the 2 (diethyl aminoethyl acyl methyl ethyl) octadecylamine are added to the sediments acquired through the centrifugation for the ultrasonication, then obtained dispersion liquid and the organic solutions of silicon dioxide balls decorated by sulfydryl are mixed and stirred, centrifugation is carried out for the second time, obtained sediments are the precious metal nano-particles after the three-dimensional assembling, and the three-dimensional assembling of the precious metal nano-particles is achieved. The method is simple in operation, balance time for the phase transferring is short, and repeatability and controllability are better.
Description
Technical field
The present invention relates to a kind of method that noble metal nano particles carries out phase transfer and three-dimensional assembling.
Background technology
In recent years, the numerous application studies of optics, electricity and the magnetic property that noble metal nano particles is peculiar in material science have caused people's great interest.The research work of early stage regulation and control nano material physical property is devoted to control the dielectric constant of composition, size, pattern and the medium of nano particle.In view of the significance of controllability in functional material of the coupling between particle in the assembly of nano particle and surface plasma body resonant vibration intensity, the assembling of nano particle becomes the focus of a research already.In numerous assemble methods, the spherical colloid particle of take is a typical example as silica as the 3D supported assembles.Yet, because most adopts the silica spheres that surface is water miscible amino head, it can only remove by weak electrostatic force the adsorbing metal nano particle, therefore, the attach amount of metal nanoparticle on silica spheres is difficult to control, and effectively assembling can't realize.Silica spheres as amido modified as people such as ChungangWang attaches the probe that nanometer gold bar is usingd as immunoassays.(Wang, C.; Chen, Y.; Wang, T.; Ma, Z.; Su, Z.Monodispersed Gold Nanorod-Embedded Silica Particles as Novel Raman Labels for Biosensing.Advanced Functional Materials 2008,18 (2), 355-361) the silica spheres as sulfydryl modification for hydrophobic function group, it attaches metal nanoparticle by strong chemical bond, yet, because the nano particle of major applications is water-soluble, dimension, the application of hydrophobic silica ball is subject to great restriction.As the people such as Sarah L.Westcott utilize the silica spheres of sulfydryl modification to remove the nanogold particle of attach～3nm, its amount of attaching is very little; (Westcott, Sarah L.; Oldenburg, Steven J.; Lee, T.Randall; Halas, Naomi J.Formation and Adsorption of Clusters of Gold Nanoparticles onto Functionalized Silica Nanoparticle Surfaces, Langmuir 1998,14 (19), 5396-5401.) people such as Zhenda Lu multiple nano particle that difference is formed effectively attaches on the silica spheres of sulfydryl modification, obtained the assembly of several functions.(Lu, Zhenda; Gao, Chuanbo; Zhang, Qiao; Chi, Miaofang; Howe, Jane Y.; Yin, Yadong.Direct Assembly of Hydrophobic Nanoparticles to Multifunctional Structures, Nano Letters (2011), 11 (8), 3404-3412) in addition, the above-mentioned method of mentioning only demonstrates and attaches preferably effect the granule below 10nm, has therefore greatly limited its range of application.
Recently, a lot of scholars are devoted to water miscible nano particle is transferred to oil phase to obtaining oil-soluble nano particle from water, then these methods adopt poisonous solvent as ionic liquid and lauryl mercaptan, in addition, it is main nano particle that these methods can only shift the following spherical particle of 18nm, and its equilibration time is also very long.As the people such as Matthias Karg successfully transfer in oil phase by the water-soluble nano gold grain below 18nm with the alkylamine of amphipathic different chain length to some extent; (Karg, Matthias; Schelero, Natascha; Oppel, Claudia; Gradzielski, Michael; Hellweg, Thomas; Von Klitzing, Regine.Versatile Phase Transfer of Gold Nanoparticles from Aqueous Media to Different Organic Media, Chemistry – A European Journal (2011), 17 (16), 4648-4654.) people such as Guor-Tzo Wei be take ionic liquid and nanogold particle is transferred to oil phase from water as medium.(Wei, Guor-Tzo; Yang, Zusing; Lee, Chia-Ying; Yang, Hsiao-Yen; Wang, C.R.Chris.Aqueous-Organic Phase Transfer of Gold Nanoparticles and Gold Nanorods Using an Ionic Liquid, Journal of the American Chemical Society (2004), 126 (16), 5036-5037.) therefore, be necessary to develop a kind of eurytopic, economic, phase transfer method easily.
Summary of the invention
The purpose of this invention is to provide a kind of method of nanogold particle being carried out to phase transfer and three-dimensional assembling.
The invention provides a kind of two (amino-ethyl acyl Methylethyl) octadecylamine noble metal nano particles is being transferred to the application in oil phase by water.
The present invention also provides a kind of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out the application in three-dimensional assembling at noble metal nano particles.
In above-mentioned application, described noble metal is selected from least one in gold, platinum and silver;
In described water, solvent is water;
In described oil phase, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The particle diameter of described noble metal nano particles is 2-500nm;
The apparent pattern of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The length of described nanometer gold bar is 25-500nm, and diameter is 5-30nm;
The diameter of described nanometer golden flower is 30-100nm;
The diameter of described nano gold spherical is 2-40nm.
The method of oil phase that noble metal nano particles is transferred to by water provided by the invention, comprise the steps:
After the aqueous solution of noble metal nano particles is centrifugal, in centrifugal gained precipitation, add the aqueous solution of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out ultrasonic, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed to after vibration, standing, complete the transfer to oil phase by water of described noble metal nano particles;
Perhaps,
In the aqueous solution of noble metal nano particles, add the aqueous solution of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out ultrasonic dispersion, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed to after vibration, standing, complete the transfer to oil phase by water of described noble metal nano particles.
In said method, described noble metal is selected from least one in gold, platinum and silver;
The apparent pattern of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The particle diameter of described noble metal nano particles is 2-500nm;
In the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene.
In described centrifugation step, centrifugal force is 400-10000g;
When described noble metal nano particles is nanometer gold bar, centrifugal force is specially 8000g;
When described noble metal nano particles is nanometer golden flower, centrifugal force is specially 7000g;
Centrifugal number of times is 2-5 time, is specially 3 times;
Each centrifugal time is 7-20 minute, is specially 10 minutes;
The concentration of the aqueous solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.1-3mM, is specially 1mM;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described ultrasonic step, power is 200-800W, is specially 600W;
Time is 20-60 second, is specially 30 seconds;
The mass percentage concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.8-2.5%, is specially 1%;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described vibrating step, the time is 20 seconds to 3 minutes, is specially 30 seconds;
In described standing step, the time is 20 seconds to 5 minutes, is specially 1 minute.
Noble metal nano particles provided by the invention carries out the method for three-dimensional assembling, comprises the steps:
1) according to aforementioned method provided by the invention, described noble metal nano particles is transferred to oil phase by water;
2) noble metal nano particles that the step 1) gained is transferred to oil phase carries out centrifugal for the first time, in centrifugal gained precipitation, add the organic solution of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out ultrasonic, the gained dispersion liquid is stirred again with after the organic solution of the silica spheres of sulfydryl modification is mixed, carry out centrifugal for the second time, the gained precipitation is the described noble metal nano particles after three-dimensional assembling, completes the three-dimensional assembling of described noble metal nano particles.
The described step 2 of said method), for the first time in centrifugation step, centrifugal force is 400-5000g;
When described noble metal nano particles is nanometer gold bar and nanometer golden flower, centrifugal force is specially 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is specially 4000g;
Centrifugal number of times is 2-5 time, is specially 2 times;
Each centrifugal time is 3-15 minute, is specially 5 minutes;
In the organic solution of described two (the amino-ethyl acyl Methylethyl) organic solutions of octadecylamine and the silica spheres of sulfydryl modification, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.01-2mM, is specially 0.05mM;
Volumetric usage is identical with the volume that described noble metal nano particles is transferred to oil phase gained solution;
The silica spheres of described sulfydryl modification is rigging, and its diameter is 100-400nm, is specially 200nm;
In the organic solution of the silica spheres of described sulfydryl modification, in the silica spheres of sulfydryl modification and described organic solution, the amount ratio of organic solvent is 14mg:2mL;
The volume ratio that the organic solution of the silica spheres of described sulfydryl modification and noble metal nano particles are transferred to oil phase gained solution is 5-50 μ L:4mL, is specially 15 μ L:4mL;
In described ultrasonic step, power is 200-800W, is specially 600W;
Time is 20-60 second, is specially 20 seconds;
In described whipping step, rotating speed is 300-1200rpm, is specially 600rpm;
Time is 0.5-8 hour, is specially 3 hours;
In described centrifugation step for the second time, centrifugal force is 400-5000g;
When described noble metal nano particles is nanometer gold bar and nanometer golden flower, centrifugal force is specially 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is specially 4000g;
Centrifugal number of times is 2-5 time, is specially 2 times;
Each centrifugal time is 2-10 minute, is specially 3 minutes.
The surfactant molecule C of the present invention application " branch " shape, amphipathic, polyamino head
18n
3(two (amino-ethyl acyl Methylethyl) octadecylamine), as protective agent, makes nanogold particle forward the oil phase by the protection of individual layer surfactant at large-area oil-water interfaces place to from the water of the protection of the hydrophily protective agent by double-layer surface-active agent or individual layer under vibration condition.
The method of three-dimensional assembling provided by the invention, silica spheres by sulfydryl modification is template, silica spheres stirring reaction in oil phase by the dewatering nano gold grain after phase transfer and sulfydryl modification, generation by strong S-Au key, make large nano particle also can firmly be adsorbed on the silica spheres of sulfydryl modification, form the 3D assembly of the nanogold particle of different morphologies, and its adsorption density is reported much larger than current document.
The present invention compares with the existing method that nanogold particle is carried out to phase transfer and 3D assembling, has following advantage:
For phase transfer: the existing environmental friendliness more of reporting of raw material; Operating process is simple, and the phase transfer equilibration time is short; The reaction needed raw material is cheap and easy to get, has reduced to produce to rise this; The size of the nanogold particle shifted is greater than the size that current document is reported, has enlarged its range of application; Can shift different morphologies as spherical, bar-shaped, flower-shaped nanogold particle; Reproducible.
For 3D, assemble: easy and simple to handle, one-step method can realize the nanogold particle direct-assembling of large-sized different morphologies on the silica spheres of spherical template-sulfydryl modification; Better control: can regulate the nanometer assembly that nanogold particle attaching on the silica spheres of sulfydryl modification measures different structure by the ratio of regulating the two.
The accompanying drawing explanation
Fig. 1 is the photo before and after the nanogold particle phase transfer in embodiment 1,2,3.
Fig. 2 (a) is the stereoscan photograph of nanometer gold bar before phase transfer in embodiment 1, and Fig. 2 (b) is the stereoscan photograph of nanometer gold bar after phase transfer in embodiment 1, can find out, nanometer gold bar its pattern before and after phase transfer does not change substantially.
Fig. 2 (c) is the stereoscan photograph of nanometer golden flower before phase transfer in embodiment 2, and Fig. 2 (d) is the stereoscan photograph of nanometer golden flower after phase transfer in embodiment 2, can find out, nanometer golden flower its pattern before and after phase transfer does not change substantially.
Fig. 2 (e) is the stereoscan photograph of nano gold spherical before phase transfer in embodiment 3, and Fig. 2 (f) is the stereoscan photograph of nano gold spherical after phase transfer in embodiment 2, can find out, nano gold spherical its pattern before and after phase transfer does not change substantially.
Fig. 3 (a) is the electromicroscopic photograph of nanometer gold bar 3D assembling on the silica spheres of sulfydryl modification in embodiment 4.
Fig. 3 (b) is the electromicroscopic photograph of nanometer golden flower 3D assembling on the silica spheres of sulfydryl modification in embodiment 5.
Fig. 3 (c) is the electromicroscopic photograph of nano gold spherical 3D assembling on the silica spheres of sulfydryl modification in embodiment 6.
All scales in Fig. 2 are 1 μ m.
All scales in Fig. 3 are 2 μ m.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
In the present invention, the method that nanometer gold bar and original solution thereof can provide according to following document prepares and obtains: Sau, Tapan K.; Murphy, Catherine J.Seeded High Yield Synthesis of Short Au Nanorods in Aqueous Solution, Langmuir (2004), 20 (15), 6414-6420:
Be specially:
(1) first prepare gold seeds: the 10mM NaBH that will just prepare
4(0.6mL) add 0.1M CTAB(7.5mL) and 0.01M HAuCl
4(0.25mL) in mixed aqueous solution, vigorous stirring 2min, then by it in 25 ℃ of standing 2h.
(2) growth of rod: by 0.10M CTAB(4.75mL), 0.01M HAuCl
43H
2o(0.200mL), 0.01M AgNO
3(0.030mL) join successively in flask, it stirred and evenly mixed, then by 0.10M AA(0.032mL) add in mixed solution, last, seed solution (0.01mL) is added in above-mentioned mixed solution, after stirring 10s, in 25 ℃ of standing 12h, obtain.
The length of gained nanometer gold bar is 25-500nm, and diameter is 5-30nm;
Nanometer golden flower can prepare by the following method and obtain:
1) the gold seeds solution (the gold seeds solution concentration is 0.24mM) that is 20nm by the particle diameter of 50 μ L natrium citricum protections joins 4mL by C18N3 and HAuCl
4in the mixed aqueous solution formed, wherein, the concentration of C18N3 is 0.6mM, HAuCl
4concentration be 0.25mM, then in this mixed solution, add the ascorbic acid AA of 10 μ L0.1M, this mixed solution of light shaking, the then standing reduction reaction 12h that carries out of room temperature;
2) step 1) is reacted to complete mixed solution centrifugal 5min under 5000rpm, draw supernatant liquor, precipitation is disperseed again with ultra-pure water, this process repeats 3 times, finally the gold nano grain obtained is dispersed in the 1mL ultra-pure water, drip on the copper mesh of silicon chip and carbon film covering, drying at room temperature, obtain nanometer golden flower again.Whole course of reaction is carried out (20-25 ℃) in room temperature.
Gained nanometer golden flower is scanned and the transmission electron microscope sign, known, the surperficial branch density of gained nanometer golden flower is high, and particle diameter is 100nm, and the mode of appearance of surperficial branch is the feeler type, and the particle diameter of core is 20nm, and surperficial branch is mono-crystalline structures; And this nanometer golden flower has better monodispersity, and rough surface.
The method that nano gold spherical can provide according to following document prepares and obtains: Ji, Xiaohui; Song, Xiangning; Li, Jun; Bai, Yubai; Yang, Wensheng; Peng, Xiaogang.Size Control of Gold Nanocrystals in Citrate Reduction:The Third Role of Citrate, Journal of the American Chemical Society (2007), 129 (45), 13939-13948;
The diameter of gained nano gold spherical is 2-40nm.
The method that the silica spheres of sulfydryl modification can provide according to following document prepares and obtains: Kim, J.-H.; Kim, J.-S.; Choi, H.; Lee, S.-M.; Jun, B.-H.; Yu, K.-N.; Kuk, E.; Kim, Y.-K.; Jeong, D.H.; Cho, M.-H.; Lee, Y.-S.Nanoparticle Probes with Surface Enhanced Raman Spectroscopic Tags for Cellular Cancer Targeting, Analytical Chemistry (2006), 78 (19), 6967-6973.
Be specially:
Tetraethoxysilane (1.8mL) is dropwise added under stirring condition in the mixed solution of ammoniacal liquor (3mL) and absolute ethyl alcohol (40mL), this mixed solution is stirred to 24h under 25 ℃ of conditions.By mixed solution centrifuge washing 3 times under 5000g, the condition of 8min/ time, place 3h and make its drying in 40 ℃ of baking ovens, be the silica spheres of gained.Take the 0.2g silica spheres and be dissolved in 3mL ethanol, to it, add successively 50 μ L MPTMS and 50 μ L ammoniacal liquor, this mixed solution is stirred to 12h under 25 ℃ of conditions.By this mixture centrifuge washing 3 times under 5000g, the condition of 8min/ time, place 3h and make its drying in 60 ℃ of baking ovens, be the silica spheres of sulfydryl modification;
The silica bulb diameter of gained sulfydryl modification is 200nm;
Surfactant amphiphile, amphiphilic molecule two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) the method preparation that can provide according to following document and obtaining: Wang, W.; Lu, W.S.; Jiang, L.Influence of pH on the Aggregation Morphology of a Novel Surfactant with Single Hydrocarbon Chain and Multi-Amine Headgroups, J.Phys.Chem.B (2008), 112,1409-1413.
Embodiment 1, utilize surfactant two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) by the nanometer gold bar phase transfer
Be centrifuge washing three times under 8000g, the condition of 10min/ time by nanometer gold bar original solution (4mL) in centrifugal force, to go out unnecessary CTAB in preparation process, in centrifugal product, add the C that 4mL concentration is 1mM
18n
3the aqueous solution, by its ultrasonic 30s under the condition of 600W.By solution obtained above and 1%C
18n
3chloroformic solution mix, vibration 30s, standing 1 minute, complete phase transfer, the chloroform that nanometer gold bar is transferred to lower floor from the water on upper strata mutually, as shown in Fig. 1 (a).
Nanometer gold bar at the pattern in water and oil phase respectively as Fig. 2 (a), 2(b) as shown in, can see that its pattern does not almost become before and after the phase transfer.
Embodiment 2, utilize surfactant two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) by nanometer golden flower phase transfer
According to the step of embodiment 1, only the nanometer gold bar in embodiment 1 is replaced with to nanometer golden flower, centrifugal force replaces with 7000g, completes the phase transfer of nanometer golden flower.
As shown in Fig. 1 (b).Nanometer golden flower at the pattern in water and oil phase respectively as Fig. 2 (c), 2(d) as shown in, can see that its pattern does not almost become before and after the phase transfer.
Embodiment 3, utilize surfactant two (amino-ethyl acyl Methylethyl) octadecylamine (C
18n
3) by the nano gold spherical phase transfer
By nano gold spherical original solution (4mL), with mass percentage concentration, be 1%C
18n
3chloroformic solution mix, vibration 30s, standing 1 minute, complete phase transfer, the chloroform that nano gold spherical is transferred to lower floor from the water on upper strata mutually, as shown in Fig. 1 (c).
Nano gold spherical at the pattern in water and oil phase respectively as Fig. 2 (e), 2(f) as shown in, can see that its pattern does not almost become before and after the phase transfer.
Embodiment 4, nanometer gold bar be take to the silica spheres of sulfydryl modification as template, carry out the 3D assembling, step is as follows:
The chloroformic solution of the nanometer gold bar that phase transfer is obtained (4mL), with centrifuge washing twice under 3000g, the condition of 5min/ time, adds 0.05mM C to centrifugal product
18n
3chloroformic solution (2mL), by its ultrasonic 20s under the condition of 600W.Add the chloroformic solution (15 μ L) of the silica spheres of sulfydryl modification to gained solution, under the condition with 600r/min, stir 3h.By this mixture, with centrifuge washing twice under 3000g, the condition of 3min/ time, the centrifugal product of gained is the 3D assembly of nanometer gold bar, as shown in Fig. 3 (a).
Wherein, the chloroformic solution of the silica spheres of sulfydryl modification is the silica spheres of the sulfydryl modification of 14mg to be joined in the 2mL chloroform to dissolve disperse to obtain.
Embodiment 5, nanometer golden flower be take to the silica spheres of sulfydryl modification as template, carry out the 3D assembling, step is as follows:
The chloroformic solution of the nanometer golden flower that phase transfer is obtained (4mL), with centrifuge washing twice under 3000g, the condition of 5min/ time, adds 0.05mM C to centrifugal product
18n
3chloroformic solution (2mL), by its ultrasonic 20s under the condition of 600W.Add the chloroformic solution (15 μ L) of the silica spheres of sulfydryl modification to gained solution, under the condition with 600r/min, stir 3h.By this mixture, with centrifuge washing twice under 3000g, the condition of 3min/ time, the centrifugal product of gained is the 3D assembly of nanometer golden flower, and nanometer golden flower successfully attaches on the silica spheres of sulfydryl modification, as shown in Figure 3 (b).
Embodiment 6, nano gold spherical be take to the silica spheres of sulfydryl modification as template, carry out the 3D assembling, step is as follows:
The chloroformic solution of the nano gold spherical that phase transfer is obtained (4mL), with centrifuge washing twice under 4000g, the condition of 5min/ time, adds 0.05mM C to centrifugal product
18n
3chloroformic solution (2mL), by its ultrasonic 20s under the condition of 600W.Add the chloroformic solution (15 μ L) of the silica spheres of sulfydryl modification to gained solution, under the condition with 600r/min, stir 3h.By this mixture, with centrifuge washing twice under 4000g, the condition of 3min/ time, the centrifugal product of gained is the 3D assembly of nano gold spherical, and as shown in Figure 3 (b), nano gold spherical attaches to high-density on the silica spheres of sulfydryl modification.
Claims (8)
1. two (amino-ethyl acyl Methylethyl) octadecylamine is being transferred to the application in oil phase by noble metal nano particles by water.
2. two (amino-ethyl acyl Methylethyl) octadecylamine carries out the application in three-dimensional assembling at noble metal nano particles.
3. application according to claim 1 and 2 is characterized in that: described noble metal is selected from least one in gold, platinum and silver;
In described water, solvent is water;
In described oil phase, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The particle diameter of described noble metal nano particles is 2-500nm;
The apparent pattern of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The length of described nanometer gold bar is 25-500nm, and diameter is 5-30nm;
The diameter of described nanometer golden flower is 30-100nm;
The diameter of described nano gold spherical is 2-40nm.
4. one kind is transferred to noble metal nano particles the method for oil phase by water, comprises the steps:
After the aqueous solution of noble metal nano particles is centrifugal, in centrifugal gained precipitation, add the aqueous solution of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out ultrasonic, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed to after vibration, standing, complete the transfer to oil phase by water of described noble metal nano particles;
Perhaps,
In the aqueous solution of noble metal nano particles, add the aqueous solution of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out ultrasonic dispersion, the organic solution of gained dispersion liquid and two (amino-ethyl acyl Methylethyl) octadecylamine is mixed to after vibration, standing, complete the transfer to oil phase by water of described noble metal nano particles.
5. method according to claim 4, it is characterized in that: described noble metal is selected from least one in gold, platinum and silver;
The apparent pattern of described noble metal nano particles is nanometer gold bar, nanometer golden flower, nano gold spherical, nanometer star or nanometer sheet;
The particle diameter of described noble metal nano particles is 2-500nm;
In the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene.
6. according to the described method of claim 4 or 5, it is characterized in that: in described centrifugation step, centrifugal force is 400-10000g;
When described noble metal nano particles is nanometer gold bar, centrifugal force is specially 8000g;
When described noble metal nano particles is nanometer golden flower, centrifugal force is specially 7000g;
Centrifugal number of times is 2-5 time, is specially 3 times;
Each centrifugal time is 7-20 minute, is specially 10 minutes;
The concentration of the aqueous solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.1-3mM, is specially 1mM;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described ultrasonic step, power is 200-800W, is specially 600W;
Time is 20-60 second, is specially 30 seconds;
The mass percentage concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.8-2.5%, is specially 1%;
Volumetric usage is identical with the volume of the aqueous solution of described noble metal nano particles;
In described vibrating step, the time is 20 seconds to 3 minutes, is specially 30 seconds;
In described standing step, the time is 20 seconds to 5 minutes, is specially 1 minute.
7. the method that noble metal nano particles carries out three-dimensional assembling, comprise the steps:
1) according to the arbitrary described method of claim 4-6, described noble metal nano particles is transferred to oil phase by water;
2) noble metal nano particles that the step 1) gained is transferred to oil phase carries out centrifugal for the first time, in centrifugal gained precipitation, add the organic solution of two (amino-ethyl acyl Methylethyl) octadecylamine to carry out ultrasonic, the gained dispersion liquid is stirred again with after the organic solution of the silica spheres of sulfydryl modification is mixed, carry out centrifugal for the second time, the gained precipitation is the described noble metal nano particles after three-dimensional assembling, completes the three-dimensional assembling of described noble metal nano particles.
8. method according to claim 7 is characterized in that: described step 2) for the first time in centrifugation step, centrifugal force is 400-5000g;
When described noble metal nano particles is nanometer gold bar and nanometer golden flower, centrifugal force is specially 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is specially 4000g;
Centrifugal number of times is 2-5 time, is specially 2 times;
Each centrifugal time is 3-15 minute, is specially 5 minutes;
In the organic solution of described two (the amino-ethyl acyl Methylethyl) organic solutions of octadecylamine and the silica spheres of sulfydryl modification, solvent is chloroform, carrene, toluene, acetone, DMF or chlorobenzene;
The concentration of the organic solution of described two (amino-ethyl acyl Methylethyl) octadecylamine is 0.01-2mM, is specially 0.05mM;
Volumetric usage is identical with the volume that described noble metal nano particles is transferred to oil phase gained solution;
The diameter of the silica spheres of described sulfydryl modification is 100-400nm, is specially 200nm;
In the organic solution of the silica spheres of described sulfydryl modification, in the silica spheres of sulfydryl modification and described organic solution, the amount ratio of organic solvent is 14mg:2mL;
The volume ratio that the organic solution of the silica spheres of described sulfydryl modification and noble metal nano particles are transferred to oil phase gained solution is 5-50 μ L:4mL, is specially 15 μ L:4mL;
In described ultrasonic step, power is 200-800W, is specially 600W;
Time is 20-60 second, is specially 20 seconds;
In described whipping step, rotating speed is 300-1200rpm, is specially 600rpm;
Time is 0.5-8 hour, is specially 3 hours;
In described centrifugation step for the second time, centrifugal force is 400-5000g;
When described noble metal nano particles is nanometer gold bar and nanometer golden flower, centrifugal force is specially 3000g;
When described noble metal nano particles is nano gold spherical, centrifugal force is specially 4000g;
Centrifugal number of times is 2-5 time, is specially 2 times;
Each centrifugal time is 2-10 minute, is specially 3 minutes.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410341852.7A CN104129753B (en) | 2013-09-09 | 2013-09-09 | Noble metal nano particles carries out the method for three-dimensional assembling |
| CN201310406513.8A CN103496666B (en) | 2013-09-09 | 2013-09-09 | Method for phase transferring and three-dimensional assembling of precious metal nano-particles |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105602544A (en) * | 2015-12-24 | 2016-05-25 | 北京北达聚邦科技有限公司 | Preparation method for converting aqueous phase quantum dots into oil phase quantum dots |
| CN106270498A (en) * | 2016-08-24 | 2017-01-04 | 浙江大学 | A kind of method that noble metal nano particles is carried out phase transfer |
| CN111283183A (en) * | 2018-12-06 | 2020-06-16 | 财团法人工业技术研究院 | Modified metal nanosheet and conductive paste comprising same |
| CN113500200A (en) * | 2021-06-24 | 2021-10-15 | 北京航空航天大学 | Surface modification method for gold nanorod water-phase-oil-phase conversion by using seed growth method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106935871B (en) * | 2015-12-31 | 2019-07-09 | 中国科学院化学研究所 | A kind of mesoporous PtAu nano material of hollow ball-shape and the preparation method and application thereof |
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| CN101003728A (en) * | 2006-12-22 | 2007-07-25 | 华中师范大学 | Water-soluble quantum point under condition of phase transition, and preparation method |
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| CN102051687B (en) * | 2009-11-03 | 2012-07-25 | 中国科学院化学研究所 | Method for preparing gold crystals by adopting surface active agent molecule C18N3 |
| CN102233434B (en) * | 2011-06-16 | 2013-03-27 | 中国科学院化学研究所 | Method for preparing nano/micron gold hierarchical structure material |
| CN102728831B (en) * | 2012-06-19 | 2015-04-29 | 中国科学院化学研究所 | Method for dispersing, purifying and/or assembling nano gold rods |
| CN103273080B (en) * | 2013-05-30 | 2015-08-12 | 中国科学院化学研究所 | A kind of nanometer golden flower and preparation method thereof and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105602544A (en) * | 2015-12-24 | 2016-05-25 | 北京北达聚邦科技有限公司 | Preparation method for converting aqueous phase quantum dots into oil phase quantum dots |
| CN106270498A (en) * | 2016-08-24 | 2017-01-04 | 浙江大学 | A kind of method that noble metal nano particles is carried out phase transfer |
| CN106270498B (en) * | 2016-08-24 | 2018-09-18 | 浙江大学 | A method of phase transfer is carried out to noble metal nano particles |
| CN111283183A (en) * | 2018-12-06 | 2020-06-16 | 财团法人工业技术研究院 | Modified metal nanosheet and conductive paste comprising same |
| CN113500200A (en) * | 2021-06-24 | 2021-10-15 | 北京航空航天大学 | Surface modification method for gold nanorod water-phase-oil-phase conversion by using seed growth method |
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| CN103496666B (en) | 2015-04-29 |
| CN104129753B (en) | 2015-09-16 |
| CN104129753A (en) | 2014-11-05 |
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