CN103624265A - Gold nanoparticles and preparation method thereof - Google Patents
Gold nanoparticles and preparation method thereof Download PDFInfo
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- CN103624265A CN103624265A CN201210298958.4A CN201210298958A CN103624265A CN 103624265 A CN103624265 A CN 103624265A CN 201210298958 A CN201210298958 A CN 201210298958A CN 103624265 A CN103624265 A CN 103624265A
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Abstract
The invention discloses gold nanoparticles and a preparation method thereof. The method comprises the steps of enabling chloroauric acid hydrated to make contact with a reducing agent on the condition that a solvent and a stabilizer exist, wherein the stabilizer is thiol-functionalized methoxypolyethylene glycol amine. The preparation method of the gold nanoparticles is easy to achieve, the sizes of the obtained gold nanoparticles are small and uniform, the gold nanoparticles are good in dispersity in the solution and wide in application prospect, and a new simple and direct way is provided for preparation of the gold nanoparticles.
Description
Technical field
The present invention relates to a kind of nanogold particle and preparation method thereof, particularly, relate to a kind of being uniformly dispersed, and the preparation method of the super undersized nanogold particle that can control the size of nanogold particle and the nanogold particle of preparing by the method.
Background technology
Nm of gold has unique physics and chemistry character, is greatly paid close attention in recent years and studies, and is widely used in optics, catalysis, biomedicine field.With regard to the preparation method of nm of gold, mostly adopt chemical reduction method.Thereby with reducing agent, the gold ion in tetra chlorauric acid solution is reduced to gold atom and forms nanogold particle.The reducing agent utilizing comprises inorganic reducing agent and organic reducing agent, and conventional inorganic reducing agent is the sodium borohydride that reproducibility is strong, and organic reducing agent has oxalic acid and hydroxyethyl piperazine second thiosulfonic acid (HEPES) cushioning liquid, and its reduction rate is fast, therefore more difficult control.Therefore, in redox reaction process, use stabilizing agent to control reaction speed, conventional stabilizing agent has polyvinylpyrrolidone, natrium citricum, alkylamine and mercaptan, uses particle diameter distribution and the stability of the resulting nanogold particle of these stabilizing agents to be not quite similar.Nanogold particle prepared by existing method needs further to improve in particle diameter and uniformity, and cannot control the size of resulting nanogold particle.
Summary of the invention
The object of the invention is to address the above problem, providing a kind of can control and also can make the preparation method of the nanogold particle that extra small size and particle size uniformity are good and the nanogold particle being prepared by the method the size of nanogold particle.
Reducing agent can be reduced into gold atom by the gold ion in tetra chlorauric acid, the gold atom obtaining mutually absorption formation gold atom bunch also further forms gold nano grain, the present inventor finds, the sulfydryl of methoxy poly (ethylene glycol) amine one end of sulfhydrylation can form Au-S key with the gold atom on gold grain surface, thereby stop the gold atom restoring further to form the gold nano grain of large-size and make the gold grain generating in solvent, there is good dispersiveness, playing the effect of stabilizing agent compares with other stabilizing agents, this stabilizing agent has better stabilization, the size of nanometer gold grain obtaining is less, homogeneous more, dispersiveness in solvent is better, in addition, the ratio of regulating stabilizer and tetra chlorauric acid obtains the monodispersity nano particle of different-grain diameter size within the specific limits, thereby completed the present invention.
To achieve these goals, the invention provides a kind of preparation method of nanogold particle, the method is included under the condition of solvent and stabilizing agent existence, tetra chlorauric acid is contacted to the methoxy poly (ethylene glycol) amine that described stabilizing agent is sulfhydrylation with reducing agent.
The present invention also provides the nanogold particle of preparing by method of the present invention.
The preparation method of nanogold particle of the present invention is simple, and the nano particle uniformity obtaining is very good, can also be prepared into super undersized nano particle, therefore, has a extensive future, for the preparation of nm of gold provides new simple and direct approach.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with the specific embodiment one below.In the accompanying drawings:
Fig. 1 a and 1b are the transmission electron microscope photo (enlargement ratio is respectively 71000 times and 450000 times) of the nanogold particle of embodiment 1 preparation;
Fig. 2 a and 2b are the transmission electron microscope photo (enlargement ratio is respectively 195000 times and 450000 times) of the nanogold particle of embodiment 2 preparations;
Fig. 3 a and 3b are the transmission electron microscope photo (enlargement ratio is respectively 145000 times and 400000 times) of the nanogold particle of embodiment 3 preparations;
Fig. 4 is that (enlargement ratio is 71000 times for the transmission electron microscope photo of nanogold particle of comparative example 1 preparation.）
The specific embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be appreciated that the specific embodiment described herein, only for description and interpretation the present invention, is not limited to the present invention.
According to the preparation method of nanogold particle of the present invention, the method is included under the condition of solvent and stabilizing agent existence, tetra chlorauric acid is contacted to the methoxy poly (ethylene glycol) amine that described stabilizing agent is sulfhydrylation with reducing agent.
According to the preparation method of the nanogold particle of invention, the methoxy poly (ethylene glycol) amine of described stabilizing agent sulfhydrylation can be commercially available, also can prepare by means commonly known in the art, preferably, the methoxy poly (ethylene glycol) amine of the described stabilizing agent sulfhydrylation using in the present invention is and is commercially available from Beijing Xi Kai Creative Technology Ltd., for example, the product of article No. SK6-1 and article No. SK6-1-05.
According to the preparation method of the nanogold particle of invention, preferably, the weight average molecular weight of the methoxy poly (ethylene glycol) amine of described stabilizing agent sulfhydrylation is 1000-10000; More preferably, the weight average molecular weight of the methoxy poly (ethylene glycol) amine of described sulfhydrylation is 2000-5000.
According to the preparation method of the nanogold particle of invention, under preferable case, the methoxy poly (ethylene glycol) amine of described tetra chlorauric acid, sulfhydrylation and the mol ratio of reducing agent are 1:0.1-2:5-40; More preferably, the methoxy poly (ethylene glycol) amine of described tetra chlorauric acid, sulfhydrylation and the mol ratio of reducing agent are 1:0.3-1.3:10-20.
According to the preparation method of the nanogold particle of invention, for described reducing agent, have no particular limits, can use the conventional various reducing agents in this area, described reducing agent can be that inorganic reducing agent can be also organic reducing agent, described inorganic reducing agent is selected from sodium borohydride and/or potassium borohydride, described organic reducing agent is selected from oxalic acid and/or hydroxyethyl piperazine second thiosulfonic acid (HEPES), conventionally hydroxyethyl piperazine second thiosulfonic acid is to use with the form of cushioning liquid, the compound method of hydroxyethyl piperazine second thiosulfonic acid is method well known in the art, for example: the HEPES of 19.15g is dissolved in 400ml distilled water, the NaOH aqueous solution adjusting pH that adds 0.5-1M is 6.8-8.2, then with distilled water, be settled to 500ml, in 4 ℃ of preservations.The present invention preferably uses sodium borohydride.
According to the present invention, described solvent can dissolve tetra chlorauric acid, stabilizing agent and reducing agent, and preferably, described solvent is water.
According to the preparation method of nanogold particle of invention, for the method for described contact, have no particular limits, described contact method can be to mix, described mixing can under agitation be carried out, further preferred, under 1300-1700rpm, stirs; Contact conditions for tetra chlorauric acid and reducing agent has no particular limits, it can be the conventional condition in this area, preferably, the condition of described contact comprises: Contact Temperature is 0-45 ℃, more preferably, Contact Temperature is 25-40 ℃, and the time of contact only guarantees gold ion fully to reduce, preferably, be 0.5-24 hour time of contact; 2-10 hour more preferably.
According to the preparation method of the nanogold particle of invention, addition sequence for described tetra chlorauric acid, reducing agent and stabilizing agent has no particular limits, under preferable case, stabilizing agent is joined in the aqueous solution of tetra chlorauric acid, and drip described reducing agent in the mixture that contains tetra chlorauric acid and stabilizing agent.
According to the preparation method of the nanogold particle of invention, in order to make tetra chlorauric acid, reducing agent and stabilizing agent contact fully and react better, according to a specific embodiment of the present invention, preferably, by tetra chlorauric acid, the methoxy poly (ethylene glycol) amine of reducing agent and sulfhydrylation is configured to respectively the form of the aqueous solution and uses, for tetra chlorauric acid, the concentration of the aqueous solution of the methoxy poly (ethylene glycol) amine of reducing agent and sulfhydrylation has no particular limits, as long as preferably make described tetra chlorauric acid, the methoxy poly (ethylene glycol) amine of sulfhydrylation and the mol ratio of reducing agent are 1-10:1:1-15, preferably, the concentration of the described tetra chlorauric acid aqueous solution is 1-5g/100ml, and the concentration of the aqueous solution of reducing agent is 1-5g/100ml, and the concentration of the methoxy poly (ethylene glycol) amine aqueous solution of described sulfhydrylation is 1-5g/100ml.
The average grain diameter of the nanogold particle of preparing according to method of the present invention is 1-10nm; Preferably, the average grain diameter of described nanogold particle is 1-5nm.
The experimental technique using in the present invention if no special instructions, is conventional method; The material using, reagent etc., if no special instructions, all can obtain from commercial channels.Sulfhydrylation methoxy poly (ethylene glycol) amine is purchased from Beijing Xi Kai Creative Technology Ltd., comprises that article No. SK6-1(weight average molecular weight is 2000), article No. SK6-1-05(weight average molecular weight is 5000).
The Tecnai G220S-TWIN that the transmission electron microscope using in the present invention is FEI Co..
Below in conjunction with embodiment, describe the preparation method of nanogold particle of the present invention in detail.
Embodiment 1
The present embodiment is for illustrating the preparation of nanogold particle provided by the invention.
(1), at 25 ℃, the tetra chlorauric acid solution that is 1g/100ml by the concentration of 1mL joins in 5mL tri-distilled water and stirs 10min;
(2) the methoxy poly (ethylene glycol) amine of the sulfhydrylation that is 2.5g/100ml by 2.5mL concentration (weight average molecular weight the is 2000) aqueous solution joins in the solution that step (1) obtains, and stirs 20min;
(3) sodium borohydride aqueous solution that is 2g/100ml by 1mL concentration is slowly added drop-wise in the solution that step (2) obtains, 2h is stirred with the speed of 1700rpm in dropping limit, limit, obtain dark solution, be nanogold particle solution, pass through transmission electron microscope observing, as shown in Fig. 1 a and Fig. 1 b, the particle diameter of resulting nanogold particle is distributed as 1 ± 0.6nm.
Embodiment 2
The present embodiment is for illustrating the preparation of nanogold particle provided by the invention.
(1), at 30 ℃, the tetra chlorauric acid aqueous solution that is 1g/100ml by the concentration of 1mL joins in 7mL tri-distilled water and stirs 10min;
(2) the methoxy poly (ethylene glycol) amine of the sulfhydrylation that is 2g/100ml by 2mL concentration (weight average molecular weight the is 2000) aqueous solution joins in the solution that step (1) obtains, and stirs 20min;
(3) sodium borohydride aqueous solution that is 1.5g/100ml by 1mL concentration is slowly added drop-wise in the solution that step (2) obtains, 5h is stirred with the speed of 1500rpm in dropping limit, limit, obtain dark solution, be nanogold particle solution, pass through transmission electron microscope observing, as shown in Figure 2 a and 2 b, the particle diameter of resulting nanogold particle is distributed as 3.2 ± 0.7nm.
Embodiment 3
The present embodiment is for illustrating the preparation of nanogold particle provided by the invention.
(1), at 40 ℃, by the concentration of 1mL, be that 1g/100ml tetra chlorauric acid solution joins in 8mL tri-distilled water and stirs 10min;
(2) by 2mL concentration, be that methoxy poly (ethylene glycol) amine (weight average molecular weight the is 5000) aqueous solution of 2g/100ml sulfhydrylation joins in the solution that step (1) obtains, stir 10min;
(3) by 1mL concentration, be 1g/100ml sodium borohydride aqueous solution be slowly added drop-wise to that step (2) obtains in, 10h is stirred with the speed of 1300rpm in dropping limit, limit, obtain dark solution, be nanogold particle solution, pass through transmission electron microscope observing, as shown in Figure 3 a and Figure 3 b shows, the particle diameter of resulting nanogold particle is distributed as 4.6 ± 1.5nm.
Comparative example 1
The tetra chlorauric acid solution that is 1g/100ml by 2mL concentration and 192mL tri-distilled water mix and blend, be heated to boiling, then adding wherein 6mL concentration is the sodium citrate solution of 1g/100mL, rapid stirring, after 3min, solution colour starts to occur a series of variations, finally becomes orange red, after 30min, stop heating, continue to stir 2h, be cooled to room temperature (25 ℃), by the particle diameter of the resulting nanogold particle of transmission electron microscope observing, be distributed as 12.8 ± 2.5nm
By Figure of description, can know that the nanogold particle (embodiment 1-3) of preparing by method of the present invention is of a size of 1-5nm, and the nanogold particle of preparing by the method for prior art is of a size of 13nm, the nanogold particle size of preparing by method of the present invention is significantly less than the size of the nanogold particle of preparing by the method for prior art, and uniformity is very good, and simple according to the preparation method of nanogold particle of the present invention.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.It should be noted that in addition, each concrete technical characterictic described in the above-mentioned specific embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible combinations.In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for nanogold particle, is characterized in that, the method is included under the condition of solvent and stabilizing agent existence, tetra chlorauric acid is contacted to the methoxy poly (ethylene glycol) amine that described stabilizing agent is sulfhydrylation with reducing agent.
2. method according to claim 1, wherein, the weight average molecular weight of the methoxy poly (ethylene glycol) amine of described sulfhydrylation is 1000-10000.
3. method according to claim 2, wherein, the weight average molecular weight of the methoxy poly (ethylene glycol) amine of described sulfhydrylation is 2000-5000.
4. according to the method described in any one in claim 1-3, wherein, the methoxy poly (ethylene glycol) amine of described tetra chlorauric acid, sulfhydrylation and the mol ratio of reducing agent are 1:0.1-2:5-40.
5. method according to claim 4, wherein, the methoxy poly (ethylene glycol) amine of described tetra chlorauric acid, sulfhydrylation and the mol ratio of reducing agent are 1:0.3-1.3:10-20.
6. method according to claim 4, wherein, described reducing agent is inorganic reducing agent or organic reducing agent, and described inorganic reducing agent is sodium borohydride and/or potassium borohydride, and described organic reducing agent is oxalic acid and/or hydroxyethyl piperazine second thiosulfonic acid.
7. method according to claim 1, wherein, described solvent is water.
8. method according to claim 1, wherein, the condition of described contact comprises: Contact Temperature is 0-45 ℃, be 0.5-24 hour time of contact; Preferably, Contact Temperature is 25-40 ℃, and be 2-10 hour time of contact.
9. the nanogold particle of preparing according to the method described in any one in claim 1-8.
10. nanogold particle according to claim 9, wherein, the average grain diameter of described nanogold particle is 1-10nm.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920889A (en) * | 2014-04-03 | 2014-07-16 | 东南大学 | Application of thiol-polyethylene glycol in preparation of water-soluble gold nano-clusters |
| CN105925963A (en) * | 2016-05-23 | 2016-09-07 | 厦门大学 | Method for preparing gold substrate through self-assembly of dry mediate gold nanoparticles and application of method |
| CN106176807A (en) * | 2016-07-20 | 2016-12-07 | 国家纳米科学中心 | A kind of industrialized preparing process of nanometer gold antibacterial |
| CN108693162A (en) * | 2018-05-21 | 2018-10-23 | 浙江理工大学 | A kind of Au@mSiO2Nano flower SERS substrates and preparation method thereof |
| CN111468741A (en) * | 2020-06-04 | 2020-07-31 | 中国农业大学 | Preparation method of ultra-uniform spherical gold nanoparticles with different particle sizes |
| CN112304998A (en) * | 2020-08-20 | 2021-02-02 | 成都理工大学 | Shale pore structure fluid flow channel tracer, preparation method and tracing method |
| CN113732279A (en) * | 2021-08-03 | 2021-12-03 | 北京化工大学 | Preparation method of nano-gold particles used as electron microscope developer and obtained nano-gold particles |
| CN114177198A (en) * | 2021-10-29 | 2022-03-15 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial agent and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920889A (en) * | 2014-04-03 | 2014-07-16 | 东南大学 | Application of thiol-polyethylene glycol in preparation of water-soluble gold nano-clusters |
| CN103920889B (en) * | 2014-04-03 | 2016-06-29 | 东南大学 | A kind of gold nanoclusters preparation method based on mercapto-polyglycol |
| CN105925963A (en) * | 2016-05-23 | 2016-09-07 | 厦门大学 | Method for preparing gold substrate through self-assembly of dry mediate gold nanoparticles and application of method |
| CN105925963B (en) * | 2016-05-23 | 2018-04-06 | 厦门大学 | A kind of dry mediation gold nano grain self assembly prepares the method and its application of gold substrate |
| CN106176807A (en) * | 2016-07-20 | 2016-12-07 | 国家纳米科学中心 | A kind of industrialized preparing process of nanometer gold antibacterial |
| CN108693162A (en) * | 2018-05-21 | 2018-10-23 | 浙江理工大学 | A kind of Au@mSiO2Nano flower SERS substrates and preparation method thereof |
| CN111468741A (en) * | 2020-06-04 | 2020-07-31 | 中国农业大学 | Preparation method of ultra-uniform spherical gold nanoparticles with different particle sizes |
| CN112304998A (en) * | 2020-08-20 | 2021-02-02 | 成都理工大学 | Shale pore structure fluid flow channel tracer, preparation method and tracing method |
| CN113732279A (en) * | 2021-08-03 | 2021-12-03 | 北京化工大学 | Preparation method of nano-gold particles used as electron microscope developer and obtained nano-gold particles |
| CN113732279B (en) * | 2021-08-03 | 2024-02-06 | 北京化工大学 | Preparation method of nano gold particles serving as electron microscope developer and obtained nano gold particles |
| CN114177198A (en) * | 2021-10-29 | 2022-03-15 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial agent and preparation method and application thereof |
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