CN115041676B - Preparation method of oil-dispersible nano gold particles - Google Patents
Preparation method of oil-dispersible nano gold particles Download PDFInfo
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- CN115041676B CN115041676B CN202210503496.9A CN202210503496A CN115041676B CN 115041676 B CN115041676 B CN 115041676B CN 202210503496 A CN202210503496 A CN 202210503496A CN 115041676 B CN115041676 B CN 115041676B
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Abstract
The invention discloses a preparation method of oil-dispersible gold nanoparticles, which comprises the steps of adopting tetrachloroauric acid and triisopropylsilane as raw materials, preparing ultrafine gold nanowires in a mixed solution of normal hexane and oleylamine by using a soft template method, centrifugally separating, transferring sediment into normal hexane, chloroform or toluene again, performing ultrasonic crushing, heating and stirring to obtain gold nanoparticles mainly mixed with ellipsoidal and rod-shaped particles with a certain size, and adding a proper amount of sorbitan dodecanoate and oleylamine to obtain stable gold nanoparticle sol. The gold nanoparticles prepared by the method have good stability in organic solvents, good plasmon effect and fluorescence enhancement effect, and can be used in the fields of solar energy and luminescence.
Description
Technical Field
The invention relates to a preparation method of oil-dispersible nano gold particles, and belongs to the technical field of nano materials.
Background
Gold, one of the inert metals for decorations and jewelry, is one of the social status and wealth symbols due to its stable properties and gorgeous surface gloss. However, when gold size reaches the nanoscale (1-100 nm), the larger specific surface area and the spatially confined effect of electrons make gold nanomaterials more pronounced optical, catalytic and electrical properties than bulk gold. Compared with other nano metal materials, the nano gold material has stable performance, good biocompatibility, easy coupling of surface biomolecules and unique electromagnetic, optical and electrical properties. Therefore, it is widely used in various fields such as solar cells, surface photocatalysis, biochemical detection, biological imaging, tumor diagnosis and treatment.
The nano-gold material generally comprises nano-particles, nano-films and the like. Among these, in particular, gold nanoparticles have a pronounced surface plasmon effect, which excites a strong local electric field. The plasmon effect is strongly focused by physics and material scientists, and is widely studied in the fields of photoelectric detection, photocatalysis and solar cells, and remarkable scientific research results are obtained. Such as:
(1) In the detection field, the plasmon effect of the gold nanoparticles can be used for cooperating with Surface Enhanced Raman Scattering (SERS), and can also be used for enhancing gold silicon Schottky junction near-infrared photoelectric detection and the like.
(2) In the field of photocatalysis, the noble metal nano structure can greatly improve the absorption efficiency of visible light by exciting a Surface Plasmon Resonance (SPR), directly drive the oxidation-reduction reaction of the surface and strengthen and promote the chemical reaction of the metal surface.
(3) In the field of energy, the surface plasmon technology can be utilized to improve the short-circuit current density of the semiconductor material and enhance the photoelectric conversion efficiency of the solar cell.
In addition, the study shows that the plasmon effect of ellipsoidal nano gold particles and rod-shaped nano gold particles with sharp angles is more obvious. However, depending on the method of preparation, the gold nanoparticles are typically water-dispersible, with less reports of oil-dispersible gold nanoparticles, which would limit the application of gold nanoparticles in these areas.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects existing in the prior art, and provides a preparation method of oil-dispersible nano gold particles, which combines a preparation method of nano materials from bottom to top and from bottom to top, adopts tetrachloroauric acid and triisopropylsilane as raw materials, prepares ultrafine gold nanowires in a mixed solution of normal hexane and oleylamine by using a soft template method, centrifugally separates and transfers precipitate into normal hexane, chloroform or toluene again, ultrasonically breaks, stirs at room temperature, obtains nano gold particles which are mainly mixed in an ellipsoidal shape and a rod shape, and then adds a proper amount of sorbitan dodecanoate and oleylamine to obtain stable nano gold particle sol. The gold nanoparticles prepared by the method have good stability in organic solvents, good plasmon effect and fluorescence enhancement effect, and can be used in the fields of solar energy and luminescence.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a process for preparing the oil-dispersing nano-gold particles includes such steps as preparing superfine gold nanoparticles by soft template method in the mixture of n-hexane and oleylamine, centrifugal separation, transferring the lower deposit to organic solvent, ultrasonic breaking, stirring at room temp.
Preferably, the organic solvent is selected from at least one of n-hexane, chloroform and toluene.
Preferably, the ultra-fine gold nanowires are encapsulated with oleylamine.
Preferably, the width of the superfine gold nanowire is 1.5-3nm, and the length is 1-20 mu m.
Preferably, the content of the gold nanoparticles in the organic solvent is 0.1-5mg/mL.
Preferably, the ultrasonic treatment is carried out for 10-30 minutes, stirred for 0.5-2.0 hours in a room temperature environment of 24-36 ℃, and then kept stand for 1-7 days, so as to obtain the nano-gold particle mixture mainly comprising ellipsoidal and rod-shaped nano-gold particles.
Preferably, the prepared nano gold particle sol contains 0.001-0.05mg/mL of sorbitan dodecanoate and 0.01-0.05mg/mL of oleylamine.
Preferably, the preparation method of the oil-dispersible nano gold particles comprises the following steps:
(1) Tetrachloroauric acid (HAuCl) 4 ·3H 2 O) dissolving in a mixture of n-hexane and oleylamine, magnetically stirring until the color becomes pale yellow, then adding triisopropylsilane, and keeping the solution undisturbed in a water bath kettle for a set time until the solution becomes dark red, wherein the superfine gold nanowires are synthesized, and the average width of the superfine gold nanowires is 1.0-3.0nm and the length of the superfine gold nanowires is 1-10nm for later use;
(2) Repeatedly centrifuging the superfine gold nanowire obtained in the step (1) for at least three times by using a mixed solvent of ethanol and n-hexane, thoroughly washing to remove the residual chemical substances on the upper layer, and re-dispersing the precipitate in n-hexane, chloroform or toluene to form sol;
(3) Carrying out ultrasonic treatment on the sol prepared in the step (2) for 5-30 minutes, heating and stirring for 0.5-2.0 hours, standing in an environment of 24-36 ℃ for 1-7 days; the gold colloid is fused under the room temperature environment to form a gold nanoparticle mixture material mainly comprising ellipsoidal and rod-shaped gold nanoparticles, and a proper amount of sorbitan dodecanoate and oleylamine are added to form stable sol; the surface of the prepared gold nanoparticle is coated by oleylamine, so that the gold nanoparticle is an oil-dispersible gold nanoparticle material.
Preferably, in the step (1), the ratio of the tetrachloroauric acid to the triisopropylsilane is 10mg:0.5mL.
Preferably, in the step (1), the ratio of the tetrachloroauric acid, the n-hexane and the oleylamine is 10mg:10mL:0.35mL.
Preferably, in said step (1), the solution is left undisturbed for at least 2 days in a water bath at 27.5-30 ℃.
Preferably, in the step (2), the volume ratio of ethanol to n-hexane is controlled to be 3:2, and the centrifugal speed is not lower than 11000 rpm.
Preferably, in the step (3), after the sol is sonicated for 25 to 30 minutes, the sol is heated and stirred for 1.0 to 2.0 hours and is kept stand in an environment of 28 to 36 ℃ for 3 to 7 days.
Preferably, in the step (3), the particle size of the gold nanoparticles is between 8 and 20 nm.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the oil-dispersible nano gold particles prepared by the method have the particle size of 8-20nm, are an ellipsoidal and rod-shaped mixture, are dispersed in an organic solvent, have a plasmon enhancement effect, and can be applied to solar cells and enhance fluorescence;
2. the invention relates to a preparation method of oil-dispersible nano gold particles, which combines a preparation method of nano materials from bottom to top and from bottom to top, and the prepared nano gold particles are ellipsoidal and rod-shaped mixtures, are dispersed in organic solvents such as normal hexane, chloroform or toluene, and can greatly expand the application range of the nano gold particles;
3. the gold nanoparticles prepared by the method have good stability in an organic solvent, good plasmon effect and fluorescence enhancement effect, and can be used in the fields of solar energy and luminescence.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
example 1
A process for preparing the oil-dispersing nano-gold particles includes such steps as preparing superfine gold nanoparticles by soft template method in the mixture of n-hexane and oleylamine, centrifugal separation, transferring the lower deposit to organic solvent, ultrasonic breaking, stirring at room temp.
In this embodiment, a method for preparing oil-dispersible gold nanoparticles includes the following steps:
(1) 10mg of HAuCl 4 ·3H 2 O was dissolved in a mixture of 10mL n-hexane and 0.35mL oleylamine; magnetically stirring for 20min until the color becomes pale yellow, then adding about 0.5mL triisopropylsilane, and keeping the solution undisturbed in a water bath at 27.5 ℃ for 2 days until the solution becomes dark red to obtain a colloid for later use;
(2) Passing the gold nanowires in the step (1) through a metal wire having a volume ratio of 3:2, repeatedly centrifuging the ethanol/n-hexane mixed solvent for three times to thoroughly wash and remove the residual chemical substances on the upper layer, and re-dispersing the precipitate in 10mL of n-hexane to form sol for later use at an offline rotating speed of 11000 r/min;
(3) After ultrasonic treatment of the sol in the step (2) for 30 minutes, heating and stirring for 2.0 hours, and standing in an environment of 30 ℃ for 7 days; the gold colloid is fused under the room temperature environment to form nano gold particles mainly mixed with ellipsoidal shapes and rods, and then 0.01g of sorbitan dodecanoate and 0.3mL of oleylamine are added to form stable sol; the surface of the prepared nano gold particles is coated by oleylamine, so that the nano gold particles are oil-dispersible.
Test analysis:
the oil-dispersible gold nanoparticles prepared by the method of this example have an average particle size of 20nm, are a mixture of ellipsoidal and rod-like shapes, have colloidal stability, and are dispersed in an organic solvent of n-hexane.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a method for preparing oil-dispersible gold nanoparticles includes the following steps:
(1) 10mg of HAuCl 4 ·3H 2 O was dissolved in 10ml of n-hexane and 0.35ml of oilIn a mixture of amines; magnetically stirring for 20min until the color becomes pale yellow, then adding about 0.5mL triisopropylsilane, and keeping the solution undisturbed in a water bath at 30 ℃ for 2 days until the solution becomes dark red to obtain a colloid for later use;
(2) Passing the gold nanowires in step (1) through a metal wire having a volume ratio of 3:2, repeatedly centrifuging the ethanol/n-hexane mixed solvent for three times to thoroughly wash and remove the residual chemical substances on the upper layer, and re-dispersing the precipitate in 10mL of chloroform to form sol at an offline rotation speed of 11000 r/min;
(3) After ultrasonic treatment of the sol in the step (2) for 25 minutes, heating and stirring for 1.0 hour, standing in an environment of 28 ℃ for 3 days; the gold colloid is fused under the room temperature environment to form nano gold particles which have certain size and are mainly mixed with rods in an ellipsoidal shape, and then 0.01g of sorbitan dodecanoate and 0.3mL of oleylamine are added to form stable sol; the surface of the prepared nano gold particles is coated by oleylamine, so that the nano gold particles are oil-dispersible.
Test analysis:
the oil-dispersible gold nanoparticles prepared by the method of this example have an average particle size of 12nm, are a mixture of ellipsoidal and rod-like shapes, have colloidal stability, and are dispersed in chloroform organic solvent.
Example III
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a method for preparing oil-dispersible gold nanoparticles includes the following steps:
(1) 10mg of HAuCl 4 ·3H 2 O was dissolved in a mixture of 10ml n-hexane and 0.35ml oleylamine; magnetically stirring for 20min until the color becomes pale yellow, then adding about 0.5mL triisopropylsilane, and keeping the solution undisturbed in a water bath kettle at 27.5 ℃ for 2 days until the solution becomes dark red, wherein the superfine gold nanowire is synthesized, and the average width is 2nm, and the length is several micrometers to tens micrometers under a transmission electron microscope, so that the superfine gold nanowire is ready for use;
(2) Passing the gold nanowires in the step (1) through a metal wire having a volume ratio of 3:2, repeatedly centrifuging the ethanol/n-hexane mixed solvent for three times to thoroughly wash and remove the residual chemical substances on the upper layer, and re-dispersing the precipitate in 10mL of toluene to form sol for later use at an offline rotating speed of 11000 r/min;
(3) After ultrasonic treatment of the sol in the step (2) for 30 minutes, heating and stirring for 2.0 hours, standing in an environment at 36 ℃ for 3 days; the gold colloid is fused under the room temperature environment to form nano gold particles which have certain size and are mainly mixed with rods in an ellipsoidal shape, and then 0.01g of sorbitan dodecanoate and 0.3mL of oleylamine are added to form stable sol; the surface of the prepared nano gold particles is coated by oleylamine, so that the nano gold particles are oil-dispersible.
Test analysis:
the oil-dispersible gold nanoparticles prepared by the method of the embodiment have an average particle size of 8nm, are an ellipsoidal and rod-shaped mixture, have colloidal stability, and can be dispersed in toluene organic solvent.
The preparation method of the oil-dispersible gold nanoparticles adopts tetrachloroauric acid and triisopropylsilane as raw materials, comprises the steps of preparing ultrafine gold nanowires in a mixed solution of normal hexane and oleylamine by a soft template method, centrifugally separating, transferring precipitates into normal hexane, chloroform or toluene again, ultrasonically crushing, heating and stirring to obtain nano gold particles mainly mixed with ellipsoidal shapes and rods with certain size, and adding a proper amount of laurate sorbate and oleylamine to obtain stable nano gold particle sol. The gold nanoparticles prepared by the method disclosed by the embodiment of the invention have good stability in an organic solvent, good plasmon effect and fluorescence enhancement effect, and can be used in the fields of solar energy and luminescence.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various changes, modifications, substitutions, combinations or simplifications can be made according to the spirit and principles of the technical solution of the present invention, and the present invention is not limited to the above embodiments, but is limited to the protection scope of the present invention as long as the technical principles and the inventive concept of the present invention are not deviated.
Claims (7)
1. A preparation method of oil-dispersible gold nanoparticles is characterized by comprising the following steps: adopting tetrachloro-acid and triisopropyl silane as raw materials, preparing ultrafine gold nanowires in a mixed solution of normal hexane and oleylamine by using a soft template method, then centrifugally separating, transferring a lower precipitate into an organic solvent again, ultrasonically crushing, stirring at room temperature to obtain a nano gold particle mixture mainly comprising ellipsoidal and rod-shaped nano gold particles, and then adding sorbitan dodecanoate and oleylamine to obtain nano gold particle sol for storage; the ultrasonic treatment is carried out for 10 to 30 minutes, stirring is carried out for 0.5 to 2.0 hours in a room temperature environment of 24 to 36 ℃, then standing is carried out for 1 to 7 days, and a nano gold particle mixture mainly comprising ellipsoidal and rod-shaped nano gold particles is obtained; the width of the superfine gold nanowire is 1.5-3nm, and the length is 1-20 mu m.
2. The method for producing oil-dispersible nano-gold particles according to claim 1, wherein: the organic solvent is at least one selected from normal hexane, chloroform and toluene.
3. The method for producing oil-dispersible nano-gold particles according to claim 1, wherein: the superfine gold nanowires are coated with oleylamine.
4. The method for producing oil-dispersible nano-gold particles according to claim 1, wherein: the content of the nano gold particles in the organic solvent is 0.1-5mg/mL.
5. The method for producing oil-dispersible nano-gold particles according to claim 1, wherein: the prepared nano gold particle sol contains 0.001-0.05mg/mL of sorbitan dodecanoate and 0.01-0.05mg/mL of oleylamine.
6. The method for producing oil-dispersible nano-gold particles according to claim 1, wherein: the volume ratio of ethanol to n-hexane is controlled to be 3:2, and the centrifugal rotating speed is not lower than 11000 r/min.
7. The method for producing oil-dispersible nano-gold particles according to claim 1, wherein: the ratio of the tetrachloroauric acid to the triisopropylsilane is 10mg:0.5 And (3) mL.
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| US8455048B1 (en) * | 2010-03-18 | 2013-06-04 | Sandia Corporation | Method for making nanomaterials |
| CN105345023B (en) * | 2015-10-30 | 2018-01-19 | 溧阳市立方贵金属材料有限公司 | The preparation method of the super fine silver powder of good dispersion |
| CN106735164B (en) * | 2016-12-08 | 2019-01-25 | 国家纳米科学中心 | The low-dimensional method of nano wire |
| CN110125431B (en) * | 2019-04-04 | 2022-05-31 | 华南师范大学 | Method for preparing gold nanospheres based on Rayleigh instability |
| CN109894622A (en) * | 2019-04-11 | 2019-06-18 | 国家纳米科学中心 | It is a kind of by nano wire be converted into quantum dot method and quantum dot obtained |
| CN110227815B (en) * | 2019-06-11 | 2021-04-27 | 东南大学 | Preparation method of water-dispersible gold nanowire |
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