CN103341635A - Method using laser to generate hydrated electrons to prepare gold nanometer particles - Google Patents
Method using laser to generate hydrated electrons to prepare gold nanometer particles Download PDFInfo
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- CN103341635A CN103341635A CN2013102597972A CN201310259797A CN103341635A CN 103341635 A CN103341635 A CN 103341635A CN 2013102597972 A CN2013102597972 A CN 2013102597972A CN 201310259797 A CN201310259797 A CN 201310259797A CN 103341635 A CN103341635 A CN 103341635A
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Abstract
The invention discloses a method using laser to generate hydrated electrons to prepare gold nanometer particles. The method comprises the following steps of placing a surface active agent and small organic molecules into water to be ultrasonically dissolved to be prepared into water-surface active agent-organic molecule solution, dissolving chloroauric acid crystal into water to be prepared into chloroauric acid solution, forming a mixed solution through the water-surface active agent-organic molecule solution and the chloroauric acid solution in proportion, adding the mixed solution into a flow sample tank, focusing pulse laser to irradiate the mixed solution to generate the hydrated electrons to restore the chloroauric acid for 5-10min, and preparing the gold nanometer particles. The particle size of the gold nanometer particles can be changed by changing laser energy or changing the proportion of the mixed solution.
Description
Technical field
The present invention relates to materials science field, especially a kind of method for preparing nanogold particle by laser generation aqueous electron.
Background technology
Nm of gold, the nano particle that namely refers to gold, its diameter is at 1-100nm, nm of gold has application widely with its good stable, small-size effect, skin effect, optical effect and unique biological compatibility in fields such as Industrial Catalysis, biological medicine, bioanalysis chemistry, food security fast detecting.
The method for preparing at present nanogold particle mainly contains physics method and chemical method.In the physical method, modal is vacuum vapour deposition, soft landing method, laser ablation method etc.The physical method principle is simple, and products obtained therefrom impurity is few, quality is high, its shortcoming be to instrument and equipment have relatively high expectations, the producing cost costliness, the size and dimension of the nanogold particle that makes is wayward.Chemical method mainly contains water chemical reduction method, microemulsion method, phase transfer method etc., the I of the nanogold particle of chemical method preparation reaches several nanometers, control easily, shortcoming is that the nanogold particle that obtains is difficult for transfer and assembles, comprises easily impurity, easily assemble, and need to add more dispersant, stabilizing agent and reducing agent, bigger to environmental hazard.
Chinese invention patent application " a kind of method (application number: 201210499205.X that utilizes the laser preparation of nano metallic particles; Publication number: CN102962466A) "; this method is shone the metallic film that is deposited on the transparency carrier with laser in the inert gas cabin, metallic film is subjected to thermal evaporation to become the gas nano-metal particle; by the inert fluid cooling, finish the preparation of nano-metal particle.This method can accurately be controlled nanoparticle size, avoids small nano particle to reunite, but also has certain defective, as installs complexity, and process is loaded down with trivial details, length consuming time.
Summary of the invention
In view of above-mentioned background, the object of the invention is to provide a kind of preparation method of new nanogold particle, and this method is simple to operate, and is environmentally friendly, and prepared nanogold particle shifts easily at aqueous phase.Prepared nanogold particle particle size range is bigger, even particle size distribution.
In order to achieve the above object, the technical solution adopted in the present invention specifically comprises the steps:
Step 1. is put into water with surfactant, organic molecule, carry out ultrasonic dissolution after, be mixed with water-surfactant-organic molecule solution;
Among the above-mentioned preparation method, the concentration of described surfactant in water is higher than critical micelle concentration, can form micella.Surfactant is anion surfactant, and its hydrophobic grouping is in the inner formation of micella apolar regions, and hydrophilic radical contacts the formation hydrophilic region with water.
Among the above-mentioned preparation method, described organic molecule is dissolved in micella inside.Pulse laser excites water and organic molecule, and moment ionization goes out a large amount of free electrons.The free electron that produces from water is very fast compound with cation, has just disappeared.And at the inner free electron that produces of micella in a short period of time (about 10
-15S) transfer to aqueous phase from micella inside.This part electronics can not be compound with cation under the obstruction of the micellar structure of surfactant, can have the long period (about 10 at aqueous phase
-7-10
-5S).This part electronics is unnecessary at aqueous phase, and very fast formation aqueous electron can be used as the strong reductant of aqueous phase.
Among the above-mentioned preparation method, the ionization in water of described gold chloride goes out hydrogen ion (H
+) and tetrachloro alloy ion (AuCl
4 -), with aqueous electron as the equation of strong reductant reduction gold chloride be:
Among the above-mentioned preparation method, described pulse laser is femtosecond or ps pulsed laser and ns pulsed laser device.By changing the ratio of laser energy size or change mixed solution, can change the productive rate of aqueous electron, thereby prepare the nanogold particle of different size.
Advantage of the present invention and beneficial effect are:
1. the present invention utilizes pulse laser to excite water-surfactant-organic molecule solution to generate aqueous electron, the aqueous electron productive rate can reach 10%, the life-span of aqueous electron can reach for 200 nanoseconds to several milliseconds, high aqueous electron productive rate and long electron lifetime make metallic compound be easy to be reduced, and the aqueous electron that is attached on the nanogold particle is mutually exclusive, can stop the gathering of nm of gold to be grown up effectively, thereby form the nanogold particle that particle diameter is evenly distributed.Prepared nanogold particle particle size range is bigger, even particle size distribution.
2. the aqueous electron reducing process of the present invention's employing produces the method for nanogold particle, and is simple to operate, utilizes pulse laser and common chemical reagent just can realize.
3. the aqueous electron reducing process of the present invention's employing produces the method for nanogold particle, and employed chemical reagent comprises surfactant and organic molecule, and is environmentally friendly, can not pollute.
4. the aqueous electron reducing process of the present invention's employing produces the method for nanogold particle, and prepared nanogold particle shifts easily at aqueous phase.
The present invention not only can be used for the preparation of nm of gold, also can be used for the preparation of materials such as Nano Silver, nanometer copper, only gold chloride need be changed into corresponding silver or mantoquita or acid.
Description of drawings
Fig. 1 is a kind of schematic diagram for preparing the method for nanogold particle by laser generation aqueous electron;
Fig. 2 is the uv-visible absorption spectra figure of the nanogold particle of embodiment 1 preparation;
Fig. 3 is the electron microscope picture of the nanogold particle of embodiment 1 preparation;
In the accompanying drawing, 1. pulse laser, 2. surfactant, 3. organic molecule, 4. tetrachloro alloy ion, 5. water.
The specific embodiment
The present invention is described in detail below in conjunction with drawings and Examples.
As shown in Figure 1 a kind of generates the method that aqueous electron prepares nanogold particle by laser, and it comprises pulse laser 1, surfactant 2, organic molecule 3, tetrachloro alloy ion 4 and water 5.Described pulse laser 1 is femtosecond or ps pulsed laser and ns pulsed laser device, and described surfactant 2 is anion surfactant, and concentration is higher than critical micelle concentration.Measure the absorption spectrum of prepared nanogold particle solution with ultraviolet/visible/near infrared spectrometer (Lambda1050) among the following embodiment, reference solution is the mixed solution of water-surfactant-organic molecule solution and chlorauric acid solution.
Embodiment 1:
With 66.14mg anion surfactant dodecyl sodium sulfate (molecular weight 272.38), 8.74mg organic molecule trans 1,2-talan (molecular weight 180.25) is put into 100mL water, carry out ultrasonic dissolution 5 minutes, and be mixed with water-surfactant-organic molecule solution.Be that 0.1% chlorauric acid solution mixes with 5mL water-surfactant-organic molecule solution and puts into the sample cell that flows with the 1mL mass fraction, wherein the amount of substance of surfactant, organic molecule and gold chloride ratio is 5: 1: 1.Pulsewidth is 8ns, and repetition rate is 10Hz, and energy is that the ps pulsed laser and ns pulsed laser of 10mW focuses on through lens, irradiation mixed solution 5-10min.Solution colour shoals redly by light blue, becomes redness at last, has generated nanogold particle.
Be illustrated in figure 2 as the uv-visible absorption spectra of the nanogold particle of embodiment 1, the absorption maximum of nanogold particle is at the 516.5nm place, reported a kind of luminosity scale of measuring the gold nano grain particle diameter in " resonance scattering spectroscopy of golden nanometer particle " paper, the maximum absorption wavelength of gold nano and the relation of particle diameter have following formula d=(260 λ
Max-1.34 * 10
5)
1/2Can know its particle size range by inference at 15-20nm according to formula.This electron microscope picture with the nanogold particle of embodiment shown in Figure 31 preparation is consistent.
Embodiment 2:
With 33.07mg anion surfactant dodecyl sodium sulfate (molecular weight 272.38), 4.37mg organic molecule trans 1,2-talan (molecular weight 180.25) is put into 100mL distilled water, carry out ultrasonic dissolution 5 minutes, and be mixed with water-surfactant-organic molecule solution.Be that 0.1% chlorauric acid solution mixes with 5mL water-surfactant-organic molecule solution and puts into the sample cell that flows with the 1mL mass fraction, wherein the amount of substance of surfactant, organic molecule and gold chloride ratio is 5: 1: 2.Pulsewidth is 8ns, and repetition rate is 10Hz, and energy is that the ps pulsed laser and ns pulsed laser of 10mW focuses on through lens, irradiation mixed solution 5-10min.Solution colour shoals redly by light blue, becomes redness at last, has generated nanogold particle.Confirm that by uv-visible absorption spectra and electron microscope picture the particle diameter of the nanogold particle of generation is 40-50nm.
Embodiment 3:
Compare with embodiment 1, except the energy of ps pulsed laser and ns pulsed laser is set to 20mW, other are identical with embodiment 1, confirm that by uv-visible absorption spectra and electron microscope picture the particle diameter of the nanogold particle that produces is 10-16nm.
Embodiment 4:
Compare with embodiment 2, except the energy of ps pulsed laser and ns pulsed laser is set to 20mW, other are identical with embodiment 2, confirm that by uv-visible absorption spectra and electron microscope picture the particle diameter of the nanogold particle that produces is 30-40nm.
Claims (5)
1. one kind generates the method that aqueous electron prepares nanogold particle by laser, it is characterized in that comprising the steps: that step 1. puts into water with surfactant, organic molecule, after carrying out ultrasonic dissolution, be mixed with water-surfactant-organic molecule solution; Step 2. is mixed with chlorauric acid solution with the gold chloride dissolution of crystals in water; Step 3. forms mixed solution in proportion with water-surfactant-organic molecule solution and chlorauric acid solution, adds in the sample cell that flows; Step 4. with pulse laser focusing after, the irradiation mixed solution, the aqueous electron of generation reduces gold chloride, the recovery time is 5-10min, prepares nanogold particle.
2. according to claim 1ly a kind ofly generate the method that aqueous electron prepares nanogold particle by laser, it is characterized in that: described surfactant is anion surfactant, forms micella in water.
3. according to claim 1ly a kind ofly generate the method that aqueous electron prepares nanogold particle by laser, it is characterized in that: described organic molecule is hydrophobic.
4. according to claim 1ly a kind ofly generate the method that aqueous electron prepares nanogold particle by laser, it is characterized in that: described pulse laser is femtosecond or ps pulsed laser and ns pulsed laser.
5. according to claim 1ly a kind ofly generate the method that aqueous electron prepares nanogold particle by laser, it is characterized in that: made nanogold particle particle diameter is in the 5-50nm scope.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868462A (en) * | 2019-03-28 | 2019-06-11 | 北京理工大学 | A method of realizing laser assisted gold ion electronation at the nanoscale |
| CN113649586A (en) * | 2021-07-12 | 2021-11-16 | 杭州苏铂科技有限公司 | Laser-assisted seedless gold nanostar synthesis method |
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| CN1431039A (en) * | 2003-02-14 | 2003-07-23 | 中国科学院上海光学精密机械研究所 | Method for preparing metal sol under super-short pulse laser inducement |
| US20060057384A1 (en) * | 2004-04-01 | 2006-03-16 | Benoit Simard | Methods for the fabrication of gold-covered magnetic nanoparticles |
| CN101090785A (en) * | 2004-11-26 | 2007-12-19 | 首尔国立大学工业基金会 | Novel methods of large scale production monodisperse nano grain |
| JP2008000654A (en) * | 2006-06-21 | 2008-01-10 | 3R Corp | Manufacturing method of nanoparticle with a particle size of 200 nm or less |
| CN102795596A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院物理研究所 | Ultrafast laser pulse method for forming nanopores with diameters of 2 nanometers |
| CN102921961A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Method for producing metallic nanomaterials through femtosecond lasers |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431039A (en) * | 2003-02-14 | 2003-07-23 | 中国科学院上海光学精密机械研究所 | Method for preparing metal sol under super-short pulse laser inducement |
| US20060057384A1 (en) * | 2004-04-01 | 2006-03-16 | Benoit Simard | Methods for the fabrication of gold-covered magnetic nanoparticles |
| CN101090785A (en) * | 2004-11-26 | 2007-12-19 | 首尔国立大学工业基金会 | Novel methods of large scale production monodisperse nano grain |
| JP2008000654A (en) * | 2006-06-21 | 2008-01-10 | 3R Corp | Manufacturing method of nanoparticle with a particle size of 200 nm or less |
| CN102795596A (en) * | 2011-05-27 | 2012-11-28 | 中国科学院物理研究所 | Ultrafast laser pulse method for forming nanopores with diameters of 2 nanometers |
| CN102921961A (en) * | 2012-11-30 | 2013-02-13 | 南京大学 | Method for producing metallic nanomaterials through femtosecond lasers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109868462A (en) * | 2019-03-28 | 2019-06-11 | 北京理工大学 | A method of realizing laser assisted gold ion electronation at the nanoscale |
| CN113649586A (en) * | 2021-07-12 | 2021-11-16 | 杭州苏铂科技有限公司 | Laser-assisted seedless gold nanostar synthesis method |
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