CN108115148B - Method for preparing liquid nano-gold particles by adopting atmospheric pressure low-temperature plasma plume - Google Patents

Method for preparing liquid nano-gold particles by adopting atmospheric pressure low-temperature plasma plume Download PDF

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CN108115148B
CN108115148B CN201711397280.4A CN201711397280A CN108115148B CN 108115148 B CN108115148 B CN 108115148B CN 201711397280 A CN201711397280 A CN 201711397280A CN 108115148 B CN108115148 B CN 108115148B
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plasma
gold particles
atmospheric pressure
nano
pressure low
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CN108115148A (en
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王瑞雪
邵涛
张珂
高远
严萍
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Institute of Electrical Engineering of CAS
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Institute of Electrical Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The inventionRelates to a method for preparing nano gold particles, in particular to a method for preparing liquid nano gold particles by adopting an atmospheric pressure low-temperature plasma plume. A method for preparing liquid nano-gold particles by adopting an atmospheric pressure low-temperature plasma plume comprises the following steps: placing the precursor in a culture dish; placing the culture dish in a plasma discharge area; opening and adjusting the gas flowmeter to control the gas cylinder to output stable and uniform working gas into the plasma device; a high-voltage power supply is switched on to excite to generate atmospheric pressure low-temperature plasma, and plasma plume is formed on the liquid surface of the precursor by the plasma to reduce Au3+Generating nano gold particles; collecting the generated nano gold particles, measuring the particle size and testing the stability. The preparation method provided by the invention accelerates the generation speed of the nano gold particles, ensures the purity of the generated nano gold, is simple to operate, high in aging and high in purity, has high industrial feasibility, and can be used for large-scale production.

Description

Method for preparing liquid nano-gold particles by adopting atmospheric pressure low-temperature plasma plume
Technical Field
The invention relates to the field of preparation of nano-gold particles, in particular to a method for preparing liquid nano-gold particles by adopting an atmospheric pressure low-temperature plasma plume.
Background
The nano gold particles have the advantages of strong surface plasma resonance effect, good chemical stability, functional modification and the like. The nano gold particles have the advantages of strong surface plasma resonance effect, good chemical stability, functional modification and the like. The surface plasmon resonance effect of the gold nanoparticles has unique effects in immunoassay, biosensors, DNA recognition and detection, gene therapy and other aspects, including chemical sensing, biological imaging of cells and tissues, targeted delivery of antitumor drugs, immunodetection and the like. Eyes of a userPreviously, the most commonly used method for preparing gold nanoparticles was chloroauric acid (HAuCl) in the aqueous phase4) The reduction method is carried out by using sodium citrate, sodium thiocyanide, white phosphorus, sodium borohydride, ascorbic acid, tannic acid and the like as common reducing agents. In recent years, a new method for preparing gold nanoparticles by using atmospheric pressure low-temperature plasma is gradually focused because a chemical synthesis method is easy to use a toxic reducing agent and takes a long time.
Chinese patent CN106044849A discloses a process for preparing nano metal oxide powder by using a direct current plasma method. The invention firstly melts the high-purity metal, and then processes the molten metal by the direct current plasma, the process has high requirements on equipment, and if the process is used for preparing the nano gold, the pure gold is needed, the cost is high, and the dispersibility is not good. Chinese patent CN101032754B discloses a method for preparing nano metal by low temperature plasma reduction. The method comprises the steps of putting metal salt under a vacuum condition, introducing plasma discharge gas, applying 200-5000V direct current or alternating current to two ends of an electrode by using a high-voltage power supply to discharge the discharge gas, forming plasma, and reducing the metal salt for 5-120 min. This method requires vacuum conditions and requires high equipment. Compared with plasma-solid phase/gas phase reaction, the nano gold particles generated in the plasma-liquid phase interaction have better dispersity. Chinese patent CN105665740A discloses a method for synthesizing colloidal gold nanoparticles under atmospheric pressure air plasma liquid phase, which comprises placing a plasma device in a mixed solution of chloroauric acid/reducing agent, and treating for a certain time to prepare colloidal gold particles. Because the temperature of the electrode can reach thousands of degrees centigrade due to the higher temperature of the plasma discharge, the electrode material can be melted or oxidized, impurities can be introduced by the direct contact of the discharge electrode and the mixed solution, and the purity of the generated nano-gold is reduced. Chinese patent CN103008684A discloses a method for preparing liquid-phase metal nanoparticles by using microplasmas. The invention adopts micro plasma as a reduction electrode and a metal platinum electrode as an oxidation electrode to prepare the nano gold particles. Because the diameter of the micro plasma is about hundreds of microns, the liquid surface area capable of being processed is effective, and the nano gold generation rate is low.
Disclosure of Invention
In order to solve the above technical problems, the present invention aims to provide a method for preparing liquid gold nanoparticles by using an atmospheric pressure low temperature plasma plume, which is simple in operation, improves aging efficiency, and can be applied to large-scale production, thereby ensuring that the purity of the produced gold nanoparticles reaches the standard and accelerating the production speed of the gold nanoparticles.
The purpose of the invention is realized by the following technical scheme:
a method for preparing liquid gold nanoparticles by adopting an atmospheric pressure low-temperature plasma plume is based on an atmospheric pressure dielectric barrier discharge device and comprises the following steps:
step 1, placing the precursor in a culture dish;
step 2, placing the culture dish in a plasma discharge area; opening and adjusting a gas flowmeter, and controlling a gas cylinder to output stable and uniform working gas to the plasma discharge area through a gas inlet;
step 3, turning on a high-voltage power supply to excite a high-voltage electrode to generate atmospheric pressure low-temperature plasma, wherein the plasma forms a plasma plume on the liquid surface of the precursor; the plasma plume contains high-energy electrons, and Au is reduced by the high-energy electrons3+Generating nano gold particles; the high-energy electrons also react with H in the precursor2Ionization at O collision to generate H2O2And OH--Generation of H2O2And OH--And Au3+Carrying out reduction reaction to generate nano gold particles;
and 4, collecting the generated nano gold particles for testing, and determining the particle size and the stability by using an ultraviolet-visible absorption spectrum.
Further, the precursor is a mixed solution of a chloroauric acid solution and a stabilizer.
Further, the stabilizer is sodium citrate, polyethylene glycol or polyvinylpyrrolidone.
Further, the high-voltage power supply is selected from a pulse microsecond power supply, a pulse nanosecond power supply, a radio frequency power supply, a microwave power supply, a direct-current power supply, an alternating-current power supply or a high-frequency high-voltage power supply.
Further, the atmospheric pressure low temperature plasma generation form is flat DBD, plasma jet, dispersion discharge, arc discharge, glow discharge, sliding discharge or jet array.
Further, the plasma treatment time is determined by the concentration and volume of the precursor, and is several seconds to several hours.
Further, the distance between the plasma and the liquid surface is determined by the length of the plasma plume, and the distance is 0-5 cm.
Further, the plasma plume is magnetically stirred while passing through the culture dish in step 3 to increase the uniformity of the gold nanoparticles.
The invention has the beneficial effects that:
the invention adopts the preparation method that the high-voltage power supply excites the metal electrode to generate the atmospheric pressure low-temperature plasma, the precursor is processed under the environment of proper working gas to produce the liquid nano-gold particles with controllable particle size, the generation speed of the nano-gold particles is accelerated, the problems of secondary pollution and the like caused by the contact of the electrode and the precursor are solved, the method is stable and reliable, the operation is simple, the time efficiency is high, the low-temperature plasma device can also be in any structure and discharge form, the industrial feasibility is higher, and the method can be used for large-scale production.
Drawings
FIG. 1 is a process flow diagram of a method for preparing liquid gold nanoparticles according to the present invention;
FIG. 2 is a diagram of an atmospheric pressure dielectric barrier discharge device;
the device comprises a gas cylinder 1, a gas flowmeter 2, a high-voltage power supply 3, a high-voltage electrode 4, an upper blocking medium 5, a precursor 6, a culture dish 7, a lower blocking medium 8 and a low-voltage electrode 9;
FIG. 3 is a graph of UV-VIS lines as a function of plasma treatment time;
wherein, the change curve chart of the UV-VIS spectral line at 31-treatment time of 2min,
32-change curve chart of UV-VIS spectral line when the treatment time is 5min,
33-change curve diagram of UV-VIS spectral line when the treatment time is 7min,
34-a change curve chart of the UV-VIS spectral line when the treatment time is 8min,
35-change curve of UV-VIS line at 11min of treatment time.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method for preparing liquid gold nanoparticles by using an atmospheric pressure low-temperature plasma plume, as shown in fig. 1 and 2, comprising the following steps:
step 1, selecting a proper container culture dish 7, cleaning the culture dish, and then placing a precursor 6 formed by mixing a chloroauric acid solution and a stabilizer into the culture dish 7;
selecting a proper excitation source; among them, there can be selected: pulse power supplies (microsecond or nanosecond), direct current power supplies, alternating current power supplies, radio frequency power supplies, microwave power supplies, high-frequency high-voltage power supplies and the like;
the excitation source selects a proper discharge mode; among them, there can be selected: flat DBD, plasma jet, dispersion discharge, arc discharge, glow discharge and sliding discharge, and can also be a plasma jet array and the like;
selecting a proper working gas; wherein, argon, helium, air, oxygen or mixed gas of air and oxygen, etc. can be selected;
step 2, placing the culture dish 7 in a plasma discharge area; opening the gas flowmeter 2 to introduce stable and uniform working gas into the plasma discharge region;
step 3, turning on a high-voltage power supply 3 to excite a metal electrode high-voltage electrode 4 to generate atmospheric pressure low-temperature plasma, wherein a large amount of plasma forms a plasma plume on the liquid surface of the precursor 6; the plasma plume contains high-energy electrons, and Au is reduced by the high-energy electrons3+GeneratingGold nanoparticles; the energetic electrons also react with H in the precursor 62Ionization at O collision to generate H2O2And OH--Generation of H2O2And OH--And Au3+Carrying out reduction reaction to generate nano gold particles; regulating and controlling the grain diameter of the nano gold by regulating and controlling the concentration and proportion of the mixed solution, power supply parameters, working gas parameters, plasma processing time, plasma and liquid level spacing and other discharge conditions and parameters;
step 4, collecting the generated nano gold particles, and performing related tests by using methods such as ultraviolet-visible absorption spectroscopy, transmission electron microscopy, Zeta potential analysis and the like; the invention utilizes ultraviolet-visible absorption spectrum to determine the particle size and stability.
In this embodiment, the precursor 6 is a mixed solution of chloroauric acid solution and sodium citrate as a stabilizer, a microsecond pulse power supply is selected as an excitation source, atmospheric pressure dielectric barrier discharge is selected as a discharge mode to prepare the gold nanoparticles, and air is selected as a working gas, as shown in fig. 2, working gas air is filled in the gas cylinder 1, both the electrodes are aluminum electrodes, the diameter of the bottom surface of each electrode is 50cm, and materials such as copper or stainless steel can also be selected. The high-voltage power supply is connected to the high-voltage electrode 4, and the low-voltage electrode 9 is grounded. Upon discharge, plasma is generated between the upper barrier dielectric 5 and the lower barrier dielectric 8.
The upper blocking medium 5 and the lower blocking medium 8 are both two pieces of K9 glass with the size of 10 multiplied by 10cm and the thickness of 1mm, and materials such as polytetrafluoroethylene, organic glass and the like can also be selected. The upper blocking medium 5 is fixed and attached to the high-voltage electrode 4, and the lower blocking medium 8 is placed on the low-voltage electrode 9. The processed precursor 6 is placed in a culture dish 7, the culture dish 7 is placed on a blocking dielectric plate 8, and the blocking dielectric material, the size and the thickness can be selected and adjusted by combining the discharge power and the type of the precursor.
The nano gold particles were prepared under atmospheric pressure using the method shown in fig. 1. The microsecond power supply is set to have the repetition frequency of 1500Hz and the voltage amplitude of 10kV, and after the power supply is excited, uniform and stable plasma is generated without filaments. The culture dish 7 was filled with 3mL of the mixed solution, the ratio of chloroauric acid to sodium citrate was 1:1, and the electric discharge treatment was performed for a period of 120-. And measuring the UV-VIS ultraviolet absorption spectrum of the treated nano gold sol particles, and then storing the nano gold sol particles at the temperature of 4 ℃. As shown in FIG. 3, the absorption peak appears around 550-570nm when the UV-VIS UV absorption spectrum is observed, which indicates that the nano-gold is generated. And the absorption peak value reaches the maximum after the treatment for 5min, which indicates that the reaction is complete at the moment, the treatment time is further increased, and the absorption intensity is reduced, which indicates that the agglomeration of the nano-gold particles occurs at the moment.
In the step 1, a proper container needs to be selected, and the specific selection is related to the used plasma; if the traditional medium is selected for preparing the nano gold particles, the thickness of the container is proper to not influence discharge, but the plasma jet flow is selected for preparing, so that the container is not required;
in the step 1, sodium citrate, polyvinylpyrrolidone, polyethylene glycol and other substances are selected as the stabilizing agent;
in the step 3, the discharge parameter selection standard of the excitation source is uniform and stable discharge;
in the step 3, the distance between the plasma and the liquid surface is 0-5cm, the specific selection distance depends on the length of the plasma plume, and the optimal distance is preferably the plasma plume to be contacted with the liquid surface;
in step 3, the treatment time is determined by the concentration and volume of the mixed solution, and is generally several seconds to several hours.
In step 3, the plasma plume may be introduced into the culture dish 7 and may be magnetically or ultrasonically stirred to increase the uniformity of the gold nanoparticles.
In steps 1, 2 and 3, the pressure used in the preparation method of the gold nanoparticles is atmospheric pressure, and sub-atmospheric pressure can also be used.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A method for preparing liquid gold nanoparticles by adopting an atmospheric pressure low-temperature plasma plume is based on an atmospheric pressure dielectric barrier discharge device and is characterized by comprising the following steps: step 1, placing a precursor (6) in a culture dish (7); step 2, placing the culture dish (7) in a plasma discharge area; opening and adjusting the gas flowmeter (2), and controlling the gas cylinder (1) to output stable and uniform working gas to the plasma discharge area through the gas inlet; the plasma discharge point region is positioned between a high-voltage electrode and a low-voltage electrode, an upper blocking medium is arranged on the high-voltage electrode, a lower blocking medium is arranged on the low-voltage electrode, and the culture dish is placed on the lower blocking medium; step 3, turning on a high-voltage power supply (3) to excite a high-voltage electrode (4) to generate atmospheric pressure low-temperature plasma, wherein the plasma forms a plasma plume on the liquid surface of the precursor (6); the plasma plume contains high-energy electrons, and Au is reduced by the high-energy electrons3+Generating nano gold particles; the energetic electrons also react with H in the precursor (6)2Ionization at O collision to generate H2O2And OH-Generation of H2O2And OH-And Au3+Carrying out reduction reaction to generate nano gold particles; the generation form of the atmospheric pressure low-temperature plasma is flat DBD, plasma jet, dispersion discharge, arc discharge, glow discharge, sliding discharge or jet array; the distance between the plasma and the liquid surface of the precursor (6) is determined by the length of the plasma plume, and the distance is 0-5 cm; and 4, collecting the generated nano gold particles, and measuring the particle size and the stability by using an ultraviolet-visible absorption spectrum.
2. The method for preparing liquid nano-gold particles by using an atmospheric pressure low-temperature plasma plume as claimed in claim 1, wherein the precursor (6) is a mixed solution of chloroauric acid solution and stabilizer.
3. The method for preparing liquid nano-gold particles by using the atmospheric pressure low-temperature plasma plume as claimed in claim 2, wherein the stabilizer is sodium citrate, polyethylene glycol or polyvinylpyrrolidone.
4. The method for preparing liquid nano-gold particles by using the atmospheric pressure low-temperature plasma plume as claimed in claim 1, wherein the high-voltage power supply (3) is selected from a pulsed microsecond power supply, a pulsed nanosecond power supply, a radio frequency power supply, a microwave power supply, a direct current power supply, an alternating current power supply or a high-frequency high-voltage power supply.
5. The method for preparing liquid nano-gold particles by using an atmospheric pressure low-temperature plasma plume as claimed in claim 1, wherein the plasma treatment time is determined by the concentration and volume of the precursor (6) and is several seconds to several hours.
6. The method for preparing liquid nano-gold particles by using an atmospheric pressure low temperature plasma plume as claimed in claim 1, wherein the plasma plume is passed into a culture dish (7) in step 3 and is magnetically stirred to increase the uniformity of nano-gold particles.
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