CN102266946B - Method for preparing nano-golden particle - Google Patents
Method for preparing nano-golden particle Download PDFInfo
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- CN102266946B CN102266946B CN 201110212667 CN201110212667A CN102266946B CN 102266946 B CN102266946 B CN 102266946B CN 201110212667 CN201110212667 CN 201110212667 CN 201110212667 A CN201110212667 A CN 201110212667A CN 102266946 B CN102266946 B CN 102266946B
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Abstract
The invention provides a method for preparing a nano-golden particle and relates to a nano-golden material. The method has mild reaction condition and is easy to operate and the sizes of reaction products are controllable. The nano-golden particle is synthesized by adopting micelle solution self-assembled by polydimethylsiloxane-b-polymethyl-methacrylate-b-poly(heptafluorobutyl)methacrylate (PDMS-b-PMMA-b-PHFBMA) as a template; the micelle solution is formed in a mixed solvent consisting of tetrahydrofuran and ethyl acetate through PDMS-b-PMMA-b-PHFBMA; the micelle solution is used as the template for synthesizing the nano-golden particle; and the nano-golden particle is produced by adopting chloroauric acid tetrahydrate serving as a metal inorganic salt precursor and sodium borohydride serving as reducing agent. The method comprises the steps of: firstly, preparing the micelle solution of the PDMS-b-PMMA-b-PHFBMA; and secondly, synthesizing the nano-golden particle by adopting the micelle solution serving as the template.
Description
Technical field
The present invention relates to a kind of nm of gold material, especially relate to a kind of preparation method of nanogold particle.
Background technology
Because each block of block copolymer is different to the affinity of solvent, therefore in the solution of definite composition self assembly can occur, form nano level micellar structure, synthesize metal nanoparticle and these micellar structures can be used as soft template, product can be realized the premium properties of organic/inorganic composite material.
The poly-seven fluorine butyl methyl acrylate of dimethyl silicone polymer-b-polymethyl methacrylate-b-combine the premium properties of fluorine silicon materials, have good heat-resisting, weather-proof, anti-oxidant, radiation-resistant performance and can play an important role in the low-surface-energy material field.In addition, owing to 3 blocks that form this copolymer, their solubility parameters has than big difference, and therefore by the suitable solvent composition of regulation and control, they can realize self assembly in the mixed solvent of cosolvent and selective solvent composition.Again because nanometer technology is still very powerful and exceedingly arrogant in recent years, and just attracted the eyeball of large quantities of chemists with the development that polymer synthesizes metal nanoparticle as soft template.
Summary of the invention
The objective of the invention is to propose the preparation method of the nanogold particle that a kind of reaction condition is gentle, the product size is controlled and easy and simple to handle.
Described nanogold particle is that template is synthetic for the micellar solution that adopts the poly-seven fluorine butyl methyl acrylate self assemblies of dimethyl silicone polymer-b-polymethyl methacrylate-b-to form; Described dimethyl silicone polymer-b-polymethyl methacrylate-b-gathers seven fluorine butyl methyl acrylic acid (PDMS-b-PMMA-b-PHFBMA), and its chemical structural formula is as follows:
Wherein, x is the degree of polymerization of hydroxy-end capped dimethyl silicone polymer (PDMS-OH), and y is the degree of polymerization of polymethyl methacrylate (PMMA), z is-gather the degree of polymerization of seven fluorine butyl methyl acrylate (PHFBMA).
In the mixed solvent of oxolane and ethyl acetate composition, form micellar solution with PDMS-b-PMMA-b-PHFBMA, then utilize this micellar solution as the template of synthesis of nano gold grain, select four hydration gold chloride (HAuCl
4H
2O) as the metal inorganic salt presoma, sodium borohydride (NaBH
4) as reducing agent, and finally generate nanogold particle; Its reaction equation is as follows:
Wherein, HAuCl
44H
2O is four hydration gold chlorides, NaBH
4Be sodium borohydride, Au is nanogold particle, H
3BO
3Be boric acid, HCl is hydrochloric acid, and NaCl is sodium chloride, H
2O is water, and micellar solution is the micellar solution that PDMS-b-PMMA-b-PHFBMA forms in the mixed solvent of oxolane and ethyl acetate composition.
The preparation method of described nanogold particle may further comprise the steps:
1) micellar solution of preparation PDMS-b-PMMA-b-PHFBMA
Be 1 with PDMS-b-PMMA-b-PHFBMA, cosolvent by volume with selective solvent: (5～10): change in the airtight container sealing after mix (1.25～15) over to and place, get the micellar solution of PDMS-b-PMMA-b-PHFBMA;
In step 1) in, the time of described mixing can be 5～10min, and the temperature that described sealing is placed can be 20～35 ℃, and the time that sealing is placed can be 24～72h.
2) take the micellar solution of PDMS-b-PMMA-b-PHFBMA as template synthesis of nano gold grain
(1) with four hydration gold chlorides and step 1) micellar solution of PDMS-b-PMMA-b-PHFBMA of preparation mixes, and wiring solution-forming A is with sodium borohydride and water mixing wiring solution-forming B;
In step (1), described four hydration gold chloride and steps 1) volume ratio of the micellar solution of the PDMS-b-PMMA-b-PHFBMA of preparation can be 1: (10～20), and described mixing can be rocked mixing 5～10min in 20～35 ℃ in brown airtight container; The volume ratio of described sodium borohydride and water can be 1: (1.5～5), described mixing can be rocked in 20～35 ℃ and be mixed 5～10min.
(2) solution B is transferred in the solution A, after the stirring, with mixed solution be transferred to leave standstill in the container after, obtaining the upper strata is light red, lower floor is two layers of colourless solution;
In step (2), described solution B is transferred in the solution A, can under nitrogen protection, solution B be transferred in the solution A, being preferably in temperature is to use magnetic agitation under 30 ℃ in the container of brown sealing, the time of described magnetic agitation can be 30min, and the volume ratio of best described solution B and solution A can be 1: (1～5); Describedly mixed solution is transferred to the time of leaving standstill in the container can be 15min.
(3) directly adopt extracting process that two layers of solution that step (2) obtains are separated, migrate out upper solution, namely obtain the mother liquor of nano-golden particle-containing;
(4) mother liquor of nano-golden particle-containing is centrifugal, filter, get solid particle and be nanogold particle.
The micellar solution that the present invention proposes the poly-seven fluorine butyl methyl acrylate of a kind of Non-amphiphilic block copolymer-dimethyl silicone polymer that adopts all blocks all to be insoluble in water-b-polymethyl methacrylate-b-is the preparation method of template synthesis of nano gold grain, four hydration gold chlorides are as the presoma of nm of gold, sodium borohydride is as reducing agent, with micellar solution as microreactor, crystallization and the growth of restriction gold, and become nanogold particle.
Compare with existing nanogold particle preparation method, the present invention has following outstanding advantages:
1) reaction condition of the present invention is gentle, and the product size is controlled, and is easy and simple to handle.
2) soft template of the present invention's employing is fluorosilicic block copolymer, and it is a Non-amphiphilic block copolymer, and its concentrates the premium properties of fluorine silicon, is easy to form micella in the mixed solvent of cosolvent and selective solvent composition.
3) the present invention has realized the unification of organic-inorganic nano material, and resulting nanoparticle size dispersiveness is fine, and particle diameter is controlled.In this system, play the fluorosilicic block copolymer of soft template effect, the base-material that it can be used as low surface energy anti-fouling paint uses, and gold nano grain is with its unique electrical and optical properties, good stability, small size and skin effect and unique bioaffinity, make it show potential using value in fields such as biochemical immunity, photoelectricity, catalysis, pigment, the combination of the two is so that they have more tempting application prospect in fields such as nano-latexes.
The nanogold particle that the present invention obtains characterizes by transmission electron microscope (TEM).Adopt the 200kV high-resolution-ration transmission electric-lens of Jeol Ltd., model JEM-2100 has the copper mesh of carbon film to immerse gently in the sample on the surface, with filter paper unnecessary solution is on every side blotted, and at room temperature places 24h and allows solvent evaporates.The particle diameter that records is between 8～14nm.
Description of drawings
Fig. 1 is the transmission electron microscope picture of the prepared gold nano grain of the embodiment of the invention 1.In Fig. 1, scale is 10nm.
The specific embodiment
The invention will be further elaborated in connection with accompanying drawing for following examples.
Embodiment 1
(1). the micellar solution of preparation PDMS-b-PMMA-b-PHFBMA
With PDMS-b-PMMA-b-PHFBMA, cosolvent and selective solvent by being to rock at 1: 5: 1.25 to mix to change in the airtight container sealing behind the 8min over to and behind 25 ℃ of lower 30h of placement, be prepared into micellar solution by volume.
(2) take the micellar solution of PDMS-b-PMMA-b-PHFBMA as template synthesis of nano gold grain
1) be in brown airtight container in 30 ℃ to rock at 1: 15 to mix 8min, wiring solution-forming A by volume with the micellar solution of the PDMS-b-PMMA-b-PHFBMA of four hydration gold chlorides and above-mentioned steps (1) preparation; Sodium borohydride and deionized water 1: 3 by volume rocked in 25 ℃ mix 8min wiring solution-forming B;
2) under high pure nitrogen protection, the solution B of 1 part of volume is transferred in the solution A of 3 parts of volumes, and the control temperature is after using magnetic agitation 30min under 30 ℃ in the container of brown sealing, mixed solution in the brown airtight container is transferred in the unlimited vial, to leave standstill and obtain the upper strata behind the 15min be light red to mixed solution in the vial, and lower floor is two layers of colourless solution;
3) directly adopting extracting process with step 2) two layers of solution obtaining separate, and migrate out upper solution, namely obtain the mother liquor of nano-golden particle-containing;
4) mother liquor of nano-golden particle-containing is carried out centrifugal under normal pressure, filter, the solid particle that obtains is Average Particle Diameters at the nanogold particle of 8nm, and figure is referring to Fig. 1 for its Electronic Speculum.
Embodiment 2
Compare with embodiment 1, except the volume ratio with PDMS-b-PMMA-b-PHFBMA, cosolvent and selective solvent changes into 1: 10: 1.25, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 8nm.
Embodiment 3
Compare with embodiment 1, except with PDMS-b-PMMA-b-PHFBMA, cosolvent and selective solvent by volume ratio change into 1: 5: 15, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 9nm.
Embodiment 4
Compare with embodiment 1, the sealing laying temperature changes into 35 ℃ in PDMS-b-PMMA-b-PHFBMA, cosolvent and selective solvent mixed solution being changed over to the molten device of sealing, and other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 8nm.
Embodiment 5
Compare with embodiment 1, except the volume ratio with the micellar solution of four hydration gold chlorides in the step (2) and step (1) preparation changes into 1: 10, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 10nm.
Embodiment 6
Compare with embodiment 1, except the volume ratio with the micellar solution of four hydration gold chlorides in the step (2) and step (1) preparation changes into 1: 20, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 9nm.
Embodiment 7
Compare with embodiment 1, except the mixed solution laying temperature in brown airtight container with the micellar solution of four hydration gold chlorides in the step (2) and step (1) preparation changes into 20 ℃, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 12nm.
Embodiment 8
Compare with embodiment 1, except the volume ratio with the sodium borohydride in the step (2) and deionized water changes into 1: 1.5, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 10nm.
Embodiment 9
Compare with embodiment 1, except the volume ratio with the sodium borohydride in the step (2) and deionized water changes into 1: 5, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 13nm.
Compare with embodiment 1, except the laying temperature with the mixed solution of the sodium borohydride in the step (2) and deionized water changes into 20 ℃, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 14nm.
Embodiment 11
Compare with embodiment 1, except the laying temperature with the mixed solution of the sodium borohydride in the step (2) and deionized water changes into 35 ℃, other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 12nm.
Embodiment 12
Compare with embodiment 1, except " solution B of 1 part of volume changes in the solution A of 3 parts of volumes " in the step (2) changed into " solution B of 1 part of volume changes in the solution A of 1 part of volume ", other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 10nm.
Embodiment 13
Compare with embodiment 1, except " solution B of 1 part of volume changes in the solution A of 3 parts of volumes " in the step (2) changed into " solution B of 1 part of volume changes in the solution A of 5 parts of volumes ", other is identical with embodiment 1.Obtain Average Particle Diameters at the nanogold particle of 14nm.
Claims (8)
1. the preparation method of a nanogold particle is characterized in that described nanogold particle is that template is synthetic for the micellar solution that adopts the poly-seven fluorine butyl methyl acrylate self assemblies of dimethyl silicone polymer-b-polymethyl methacrylate-b-to form; Poly-seven its chemical structural formulas of fluorine butyl methyl acrylate of described dimethyl silicone polymer-b-polymethyl methacrylate-b-are as follows:
Wherein, x is the degree of polymerization of hydroxy-end capped dimethyl silicone polymer, and y is the degree of polymerization of polymethyl methacrylate, z is-gather the degree of polymerization of seven fluorine butyl methyl acrylate;
In the mixed solvent of oxolane and ethyl acetate composition, form micellar solution with the poly-seven fluorine butyl methyl acrylate of dimethyl silicone polymer-b-polymethyl methacrylate-b-, then utilize this micellar solution as the template of synthesis of nano gold grain, select four hydration gold chlorides as the metal inorganic salt presoma, sodium borohydride is as reducing agent, and finally generates nanogold particle; Its reaction equation is as follows:
Wherein, HAuCl
44H
2O is four hydration gold chlorides, NaBH
4Be sodium borohydride, Au is nanogold particle, H
3BO
3Be boric acid, HCl is hydrochloric acid, and NaCl is sodium chloride, H
2O is water, and micellar solution is the micellar solution that the poly-seven fluorine butyl methyl acrylate of dimethyl silicone polymer-b-polymethyl methacrylate-b-form in the mixed solvent of oxolane and ethyl acetate composition.
2. the preparation method of a kind of nanogold particle as claimed in claim 1 is characterized in that may further comprise the steps:
1) micellar solution of the poly-seven fluorine butyl methyl acrylate of preparation dimethyl silicone polymer-b-polymethyl methacrylate-b-
Be 1 with the poly-seven fluorine butyl methyl acrylate of dimethyl silicone polymer-b-polymethyl methacrylate-b-, oxolane by volume with ethyl acetate: (5～10): change sealing placement in the airtight container after mix (1.25～15) over to, get the micellar solution that dimethyl silicone polymer-b-polymethyl methacrylate-b-gathers seven fluorine butyl methyl acrylate;
2) gather the micellar solution of seven fluorine butyl methyl acrylate as template synthesis of nano gold grain take dimethyl silicone polymer-b-polymethyl methacrylate-b-
The micellar solution of the dimethyl silicone polymer of (1) four hydration gold chlorides and step 1) being prepared-poly-seven fluorine butyl methyl acrylate of b-polymethyl methacrylate-b-is mixed, and wiring solution-forming A is with sodium borohydride and water mixing wiring solution-forming B;
(2) solution B is transferred in the solution A, after the stirring, with mixed solution be transferred to leave standstill in the container after, obtaining the upper strata is light red, lower floor is two layers of colourless solution;
(3) directly adopt extracting process that two layers of solution that step (2) obtains are separated, migrate out upper solution, namely obtain the mother liquor of nano-golden particle-containing;
(4) mother liquor of nano-golden particle-containing is centrifugal, filter, get solid particle and be nanogold particle.
3. the preparation method of a kind of nanogold particle as claimed in claim 2 is characterized in that in step 1), and the time of described mixing is 5～10min, and the temperature that described sealing is placed is 20～35 ℃, and the time that sealing is placed is 24～72h.
4. the preparation method of a kind of nanogold particle as claimed in claim 2, it is characterized in that in step 2) part (1) in, the volume ratio of the micellar solution of the dimethyl silicone polymer of described four hydration gold chlorides and step 1) preparation-poly-seven fluorine butyl methyl acrylate of b-polymethyl methacrylate-b-is 1: (10～20).
5. the preparation method of a kind of nanogold particle as claimed in claim 2 is characterized in that in step 2) part (1) in, described mixing is to rock in 20～35 ℃ to mix 5～10min in brown airtight container.
6. the preparation method of a kind of nanogold particle as claimed in claim 2 is characterized in that in step 2) part (1) in, the volume ratio of described sodium borohydride and water is 1: (1.5～5) describedly are mixed in 20～35 ℃ and rock and mix 5～10min.
7. the preparation method of a kind of nanogold particle as claimed in claim 2 is characterized in that in step 2) part (2) in, described solution B is transferred in the solution A, be under nitrogen protection, solution B to be transferred in the solution A; The volume ratio of described solution B and solution A is 1: (1～5); It is described that mixed solution is transferred to the time of leaving standstill in the container is 15min.
8. the preparation method of a kind of nanogold particle as claimed in claim 7; it is characterized in that describedly under nitrogen protection, solution B being transferred in the solution A; be to be to use magnetic agitation under 30 ℃ in the container of brown sealing in temperature, the time of described magnetic agitation is 30min.
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| CN104275494B (en) * | 2013-07-08 | 2016-08-24 | 江南大学 | A kind of nanometer gold colloid of new structure and preparation method thereof |
| CN104439272B (en) * | 2014-11-04 | 2016-05-18 | 天津大学 | A kind of wetting removal and template combine and prepare the method for ordered arrangement gold grain |
| CN111687428B (en) * | 2020-05-13 | 2021-11-19 | 华南理工大学 | Amphiphilic polymer mediated gold nanoparticle controllable assembly and preparation and application thereof |
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| CN1260025C (en) * | 2003-07-15 | 2006-06-21 | 武汉大学 | Preparation method of nano-gold particle |
| CN1302849C (en) * | 2004-12-02 | 2007-03-07 | 黄德欢 | Method for preparing supported nano gold powder |
| US7524354B2 (en) * | 2005-07-07 | 2009-04-28 | Research Foundation Of State University Of New York | Controlled synthesis of highly monodispersed gold nanoparticles |
| CN1876290A (en) * | 2006-06-23 | 2006-12-13 | 浙江大学 | Aqueous phase synthesis method for preparing nanometer gold grains |
| CN100563881C (en) * | 2008-01-23 | 2009-12-02 | 厦门大学 | A kind of method of polyacrylic acid hydro-thermal synthesis of nano gold |
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