CN101032754B - Method for producing nanometer metal by plasma deoxidization in low termprature - Google Patents
Method for producing nanometer metal by plasma deoxidization in low termprature Download PDFInfo
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- CN101032754B CN101032754B CN2007100571614A CN200710057161A CN101032754B CN 101032754 B CN101032754 B CN 101032754B CN 2007100571614 A CN2007100571614 A CN 2007100571614A CN 200710057161 A CN200710057161 A CN 200710057161A CN 101032754 B CN101032754 B CN 101032754B
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Abstract
The present invention relates to material technology, and is low temperature plasma reduction process for preparing nanometer metal. The production process includes: filling metal salt into vacuum chamber of plasma discharger, vacuumizing the vacuum chamber, introducing plasma discharge gas to pressure of 30-200 Pa, and applying DC or AC voltage of 200-5,000 V with a high voltage power source to discharge the gas and to form plasma reducing the metal salt for 5-120min, so as to prepare nanometer metal particle. The production process has simple equipment, easy operation, low power consumption, great metal treating amount and environment friendship; and the prepared nanometer metal particle has high purity, small size, narrow size distribution, high dispersivity, excellent performance and unique compounding performance with other material, and may find wide application foreground in molecular device, chemical/biological sensor and other fields.
Description
Technical field
The present invention relates to materials science field, especially a kind of method of producing nanometer metal by plasma deoxidization in low termprature.
Background technology
Nano material (nano material) is called the ultramicro powder material again, is made up of nano particle.Nano particle (nano particle) also be ultramicro powder, generally is meant the particle of size between 1～100nm.Nano particle has many advantages: particle diameter is little, specific area is big, catalytic efficiency is high, and the character of its optics, calorifics, electricity, magnetics, mechanics and chemical aspect has been compared significant difference with bulk solid in addition; And the magnetic Nano metallic has single domain structure, and coercivity is very high, and utilizes the electric conductivity of nano metal particles, can make electrically-conducting paint, conducting resinl etc.The potential application of nano metal particles also has a lot, for example at aspects such as rocket combustion-supporting, micropore gas separation membrane, structural material and biological engineering materials.Nano metal particles has good performance and is with a wide range of applications at numerous areas such as molecular device, chemical/biological sensors, catalysis, photoelectron materials with special performance that the other materials compound tense shows.
Current preparation metal nanoparticle method is mainly based on chemical reduction method and sol-gal process, and the both will use the chemical reagent of strong reducing property in solution, as utilizes strong reductant NaBH
4Deng metallic compound is reduced to metallic particles.The weak point of this method is: preparation process is loaded down with trivial details, complicated operation, and the condition harshness, wayward, and also above-mentioned reducing agent is huge to environmental hazard; Wherein adopt gel method in the end to need can obtain nano particle through sintering, the gained nano particle is reunited easily, and particle diameter is bigger.
The public technology the most approaching with the present invention is: (2006,11388-11394), people such as Liu disclose a kind of new method of reducing supported metal catalyst at Langmuir.This method adopts glow discharge plasma under the condition of not using chemical reducing agent, reduced noble metal on the carriers such as loading on titanium dioxide in argon gas atmosphere, its device is simple, easy to operate, saves energy consumption, environmentally friendly, have wide application prospects in the Preparation of Catalyst field.But also there is certain defective,, the nano-metal particle skewness that obtain little as the amount of metal of length consuming time, processing.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of producing nanometer metal by plasma deoxidization in low termprature is provided; This method is easy and simple to handle, and is environmentally friendly, obtained nano metal particles purity height, and granularity is little, narrow, the good dispersion of particle diameter distributed area.
The present invention is achieved through the following technical solutions:
A kind of method of producing nanometer metal by plasma deoxidization in low termprature, this production method may further comprise the steps:
(1). slaine is directly packed in the vacuum chamber of plasma discharger;
(2). vacuum chamber is vacuumized, feed plasma discharge gas then, gas pressure remains on 30～200Pa;
(3). the direct current or the alternating current that utilize high voltage source to apply 200～5000V at the electrode two ends make the discharge gas discharge, and the plasma of formation reduces slaine, and the recovery time is 5～120min, prepares nano metal particles thus.
And described slaine is platinum or palladium or gold or silver or ruthenium or rhodium or rhenium or the formed salt of iridium.
And described slaine is chloride or nitrate.
And described plasma discharge gas is inert gas or air or oxygen, perhaps the mixture of above-mentioned gas.
And described inert gas is argon gas or nitrogen or helium.
And the form of described gas discharge is glow discharge or dielectric barrier discharge or corona discharge.
And the particle diameter of the described nano metal particles of preparing is in 2.5～20nm scope.
Advantage of the present invention and beneficial effect are:
1. it is to utilize a large amount of high energy electrons in the plasma of HVDC or AC power discharge generation to arrive near the metallic particles at first that the plasma method that the present invention relates to is produced nano metal, wherein a part of electronics can be captured, metal is promptly reduced by static, thereby generates nano metal.Nano metal with the plasma method preparation has advantages such as output is big, granularity is controlled easily, performance is good.
2. the producing nanometer metal by plasma deoxidization in low termprature method of the present invention's employing can prepare nano metal particles fast and effectively, can at room temperature carry out, and has avoided the undesirable heat effect under the high temperature, and simple to operate, save energy consumption, the amount of metal of processing is big, do not use chemical reducing agent, environmentally friendly.
3. contain a large amount of electronics in the plasma of the present invention, make metallic compound be easy to be reduced; And this electron attachment is mutually exclusive on metallic particles, can stop the gathering of metallic particles to be grown up effectively, thereby form tiny equally distributed crystal grain, make obtained nano metal particles purity height, granularity is little, narrow, the good dispersion of particle diameter distributed area, the particle diameter of nano metal particles is in 2.5～20nm scope.
Description of drawings
Fig. 1 is the photoelectron spectroscopy figure of gold chloride after the Low Temperature Plasma Treating reduction;
Fig. 2 is the electronic diffraction spectrogram of gold chloride after the Low Temperature Plasma Treating reduction;
Fig. 3 is the high power transmission electron microscope picture of gold chloride after the Low Temperature Plasma Treating reduction.
The specific embodiment
The present invention is described in further detail in conjunction with the accompanying drawings by following examples, but the technology contents that present embodiment is narrated is illustrative, rather than determinate, should not limit to protection scope of the present invention according to this.
Embodiment 1
With gold chloride (HAuCl
4) place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into argon gas then and make discharge gas, keep the pressure of 30Pa, on electrode, apply the DC voltage of 800V, adopt glow discharge plasma reduction gold chloride (HAuCl
4), the recovery time is 100min, prepares nano Au particle, its particle diameter is 2.5～7nm.
Obtained nano Au particle can draw following analysis result through photoelectron spectroscopy, electronic diffraction and transmission electron microscope analysis:
Photoelectron spectroscopy figure as shown in Figure 1 can find out the characteristic peak that gold element only occurred from spectrum, show that gold chloride is reduced to the zero-valent state gold by the low temperature plasma method;
Electron diffraction diagram as shown in Figure 2 has only the diffraction maximum of golden simple substance among the figure, do not have other impurity diffraction maximum to exist, and shows that gold chloride is reduced fully;
Be illustrated in figure 3 as the high power transmission electron microscope picture, prepared as we can see from the figure nano Au particle, crystal grain is tiny evenly, and particle diameter is 2.5～7nm.
Embodiment 2:
With H
2PtCl
6Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into helium then and make discharge gas, keep the pressure of 50Pa, on electrode, apply the DC voltage of 200V, adopt corona discharge plasma reduction H
2PtCl
6, the recovery time is 120min, prepares the nanometer platinum particles.Confirm H through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
2PtCl
6Be reduced to simple substance platinum fully, its particle diameter is 2.5～10nm.
Embodiment 3:
With PdCl
2Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into oxygen then and make discharge gas, keep the pressure of 90Pa, on electrode, apply the alternating voltage of 1000V, adopt dielectric barrier discharge plasma reduction PdCl
2, the recovery time is 40min, prepares nanometer lead button.Confirm PdCl through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
2Be reduced to simple substance lead fully, its particle diameter is 3.0～15nm.
Embodiment 4:
With AgNO
3Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into nitrogen then and make discharge gas, keep the pressure of 120Pa, on electrode, apply the alternating voltage of 1500V, adopt glow discharge plasma reduction AgNO
3, the recovery time is 60min, prepares nano silver particles.Confirm AgNO through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
3Be reduced to simple substance silver fully, its particle diameter is 3.0～20nm.
Embodiment 5:
With H
2IrCl
6Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into air then and make discharge gas, keep the pressure of 150Pa, on electrode, apply the alternating voltage of 2000V, adopt glow discharge plasma reduction H
2IrCl
6, the recovery time is 80min, prepares nanometer iridium particle.Confirm H through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
2IrCl
6Be reduced to simple substance iridium fully, its particle diameter is 4.0～18nm.
Embodiment 6:
With ReCl
5Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into argon gas then and make discharge gas, keep the pressure of 180Pa, on electrode, apply the DC voltage of 3000V, adopt glow discharge plasma reduction ReCl
5, the recovery time is 20min, prepares nanometer rhenium particle.Confirm ReCl through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
5Be reduced to the simple substance rhenium fully, its particle diameter is 3.5～20nm.
Embodiment 7:
With H
3RhCl
6Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into helium then and make discharge gas, keep the pressure of 200Pa, on electrode, apply the DC voltage of 4000V, adopt glow discharge plasma reduction H
3RhCl
6, the recovery time is 10min, prepares nanometer rhodium particle.Confirm ReCl through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
5Be reduced to the simple substance rhodium fully, its particle diameter is 2.5～20nm.
Embodiment 8:
With RuCl
3Place between two battery lead plates of discharge tube in the vacuum chamber, airtight, vacuum chamber is vacuumized, charge into air then and make discharge gas, keep the pressure of 90Pa, on electrode, apply the alternating voltage of 5000V, adopt corona discharge plasma reduction RuCl
3, the recovery time is 5min, prepares nanometer ruthenium particle.Confirm RuCl through photoelectron spectroscopy, electronic diffraction and transmission electron microscope
3Be reduced to the simple substance ruthenium fully, its particle diameter is 2.5～20nm.
Claims (7)
1. the method for a producing nanometer metal by plasma deoxidization in low termprature, it is characterized in that: this production method may further comprise the steps:
(1). slaine is directly packed in the vacuum chamber of plasma discharger;
(2). vacuum chamber is vacuumized, feed plasma discharge gas then, gas pressure remains on 30～200Pa;
(3). the direct current or the alternating current that utilize high voltage source to apply 200～5000V at the electrode two ends make the discharge gas discharge, and the plasma of formation reduces slaine, and the recovery time is 5～120min, prepares nano metal particles thus.
2. the method for producing nanometer metal by plasma deoxidization in low termprature according to claim 1, it is characterized in that: described slaine is platinum or palladium or gold or silver or ruthenium or rhodium or rhenium or the formed salt of iridium.
3. the method for producing nanometer metal by plasma deoxidization in low termprature according to claim 2, it is characterized in that: described slaine is chloride or nitrate.
4. the method for producing nanometer metal by plasma deoxidization in low termprature according to claim 1, it is characterized in that: described plasma discharge gas is inert gas or air or oxygen, perhaps the mixture of above-mentioned gas.
5. the method for producing nanometer metal by plasma deoxidization in low termprature according to claim 4, it is characterized in that: described inert gas is argon gas or nitrogen or helium.
6. the method for producing nanometer metal by plasma deoxidization in low termprature according to claim 1, it is characterized in that: the form of described gas discharge is glow discharge or dielectric barrier discharge or corona discharge.
7. the method for producing nanometer metal by plasma deoxidization in low termprature according to claim 1, it is characterized in that: the particle diameter of the described nano metal particles of preparing is in 2.5～20nm scope.
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| CN112442593A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Method for recovering rhodium from waste rhodium catalyst residues |
| CN111215636B (en) * | 2020-01-17 | 2022-07-12 | 西北师范大学 | Preparation method of Ag nano particles |
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