CN102974835B - Metal nanocapsule preparation method using metallic oxide as alternative positive pole - Google Patents
Metal nanocapsule preparation method using metallic oxide as alternative positive pole Download PDFInfo
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- CN102974835B CN102974835B CN201210466336.8A CN201210466336A CN102974835B CN 102974835 B CN102974835 B CN 102974835B CN 201210466336 A CN201210466336 A CN 201210466336A CN 102974835 B CN102974835 B CN 102974835B
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- nano capsule
- metal
- crucible
- metal oxide
- oxide
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Abstract
The invention aims to provide a metal nanocapsule preparation method which makes up defects in the prior art. The metal nanocapsule preparation method using metallic oxide as an alternative positive pole is characterized in that metal oxide powder is used as row materials and pressed into a block body which is arranged on an electric crucible and is the positive pole with the crucible together. If the crucible is made of graphite or copper, a negative pole is made of graphite or tungsten. Alcohol or alcohol and hydrogen are used as a reducing agent, a plasma body is used as a heat source, and a metal nanocapsule is prepared during processes of pyrolysis, ionization, reduction, evaporation and condensing of oxides. The material is used nanoscale metal as the core and coated with the nanocapsule made of oxides of the metal. Due to existence of shells of the oxides, oxidative resistance of the nanocapsule is effectively improved.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, provide a kind of metal oxide to be the method that alternative anode prepares metal nano capsule especially.
Background technology
Nano capsule refers to have shell-inner core, and yardstick is at the granular materials of 1 to hundreds of nanometer.When material little to nanoscale time, due to locality and the huge Surface and interface effect of its quantum effect, material, make a lot of performance generation qualitative changes of material, present and be manyly both different from macro object, be also different from the unusual appearance of single isolated atom.In atmosphere, zinc, copper, bismuth, tin and lead, its surface all forms corresponding oxide.
The shell of Nano capsule has many functions, as: protection kernel is from the destruction of environment; The stability increasing nanocluster is grown up to avoid it; Promote the dispersiveness of nano particle in different medium; Increase the activity of material; Change the optics, electricity, magnetic property etc. of kernel.
Chinese patent 200810013327.7 provides the synthetic method that metal and dissimilar metal oxide powder and micron are raw material coated dissimilar metal ' core/shell ' type nano particle; Chinese patent 20031012369.1 provides current techique prepared by a kind of nano-powder, negative oxygen balance carbon source explosive is mixed by a certain percentage with reactant, detonate by predetermined way, prepare nano-powder, United States Patent (USP) 7,422,620, provide a kind of nano particle chemically preparing copper, but these methods all directly can not be used for oxide being raw material, directly prepare the Nano capsule of copper, zinc, bismuth, tin and lead.
Summary of the invention
The object of this invention is to provide a kind of preparation method of metal nano capsule, the method compensate for the deficiency of prior art, it is characterized in that with metal oxide powder for raw material, and to be pressed on crucible that block is placed on conduction be anode together with crucible, if crucible is that graphite or copper become, negative electrode is graphite or tungsten.Alcohol or alcohol and hydrogen, as reducing agent, utilize plasma for thermal source, in the process of the pyrolysis of oxide, ionization, reduction, evaporation and condensation, prepare metal nano capsule.Resulting materials is core by nano level metal, and the Nano capsule of the oxide composition of this metal is wrapped up in outside, and the existence due to oxide shells effectively improves the oxidative resistance of Nano capsule.
It is the method that alternative anode prepares metal nano capsule that the present invention specifically provides a kind of metal oxide, it is characterized in that: the method adopting cathode and anode arc discharge under working gas to produce plasma prepares metal nano capsule, its Anodic is the block that is pressed into of metal oxide powder and crucible, and concrete technology is:
By the block be pressed into by metal oxide powder, be placed on the crucible that can conduct electricity, be first discharge between anode and negative electrode with crucible, make it to produce high-temperature electric arc, make metal oxide pyrolysis, ionization and conducting electricity, again with metal oxide block for substitute anode, and discharge between negative electrode, make metal oxide decomposition-reduction, produce metal vapors, condensation again, prepares metal nano capsule powders.
Metal oxide of the present invention is the method that alternative anode prepares metal nano capsule, it is characterized in that: described crucible is black-fead crucible or copper crucible, and negative electrode is graphite electrode or tungsten electrode, and take argon gas as working gas, operating air pressure is no more than 10
5pa, produces plasma with arc discharge, and discharge voltage is not less than 8V, and the block pyrolysis that metal oxide powder is pressed into, ionization, reduction and condensation, prepare metal nano capsule.
Metal oxide of the present invention is the method that alternative anode prepares metal nano capsule, it is characterized in that: before arc discharge, be filled with argon gas be not less than 2000Pa.
Metal oxide of the present invention is the method that alternative anode prepares metal nano capsule, it is characterized in that: adopt the gaseous mixture of alcohol or alcohol and hydrogen as reducing agent.
Metal oxide of the present invention is the method that alternative anode prepares metal nano capsule, it is characterized in that: metal oxide powder is zinc oxide ZnO, cupric oxide CuO, bismuth oxide Bi
2o
3, tin oxide SnO
2or lead oxide PbO powder.
The present invention adopts arc discharge to produce the technology of preparing of plasma, and in arc discharge process, energy U=electricity × voltage that electronics obtains in the electric field, the quantity of electric charge of electronics is e=1.6 × 10
-19coulomb, when voltage V=1 volt, thus can 1eV=1 × 1.6 × 10 be obtained
-19coulomb × volt=1.6 × 10
-19joule.Microcosmic according to temperature defines, u=3/2kT=1eV=1.6 × 10
-19joule, Boltzmann constant is substituted into and just can obtain electron temperature T, 1eV=11600K.This is only consider independent electronic behavior.Electron energy is very large, temperature is very high, but quantity is little.When plasma state becomes normal state, temperature decrease, this provides condition for metal forming core.Because the particle diameter of nano metal particles is little, specific surface large, oxidized in atmosphere, form oxide shells, i.e. said metal nano capsule.
After the block that metal oxide powder is pressed into, resistance is very large, insulator or semiconductor, in argon gas, start arc discharge and produce the electric current of plasma not by the target of metal oxide, but due to the temperature of arc-plasma at this moment very high, so metal oxide melts rapidly, pyrolysis, and pass through electric current.When with black-fead crucible, carbon electrode, is filled with argon gas or argon gas and reducing gas hydrogen and ethanol (C
2h
5oH), after metal oxide pyrolysis, just can conduct electricity, the block that metal oxide powder is pressed into then becomes anode, is then reduced into metal and evaporates, and is then condensate on water-cooling wall or in collecting chamber.
Use copper crucible by contrast, during tungsten electrode, be only filled with argon gas, be no longer filled with reducing gas hydrogen and ethanol (C
2h
5oH), be replaced by anode at metal oxide, after pyrolysis, can be reduced into metal equally and evaporate, just amount is few.This illustrates after metal oxide pyrolysis, even without carbon and hydrogen, still has ionization reduction process.
Method provided by the invention can be used for preparing a large amount of metal nano capsule, has broad application prospects in electro-magnetic wave absorption/shielding, biological medicine, photoelectric material, electro rheological fluids, functional paint etc.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of copper Nano capsule.
Fig. 2 is the transmission electron microscope photo of copper Nano capsule.
Fig. 3 is the partial enlarged drawing of copper Nano capsule.
Fig. 4 is the power spectrum of copper Nano capsule ESEM on a silicon substrate.
Fig. 5 is copper Nano capsule X-ray electron Spectrum, XPS (X-ray photoelectronspectroscopy).
Fig. 6 is the O of copper Nano capsule
1sthe X-ray electron Spectrum of electronics.
Fig. 7 is the X-ray diffracting spectrum of zinc Nano capsule.
Fig. 8 is the power spectrum of zinc Nano capsule ESEM on a silicon substrate.
Fig. 9 is the X-ray diffracting spectrum of tin Nano capsule figure.
Figure 10 is the transmission electron microscope photo of tin Nano capsule.
Figure 11 is the power spectrum of tin Nano capsule ESEM on a silicon substrate.
Figure 12 is the X-ray diffracting spectrum of bismuth Nano capsule figure.
Figure 13 is the transmission electron microscope photo of bismuth Nano capsule.
Figure 14 is the power spectrum of bismuth Nano capsule ESEM on a silicon substrate.
Figure 15 is the X-ray diffracting spectrum of plumbous Nano capsule figure.
Figure 16 is the transmission electron microscope photo of plumbous Nano capsule.
Figure 17 is the partial enlarged drawing of the transmission electron microscope photo of plumbous Nano capsule.
Figure 18 is the power spectrum of plumbous Nano capsule ESEM on a silicon substrate.
Figure 19 is plumbous Nano capsule XPS.
Figure 20 is the X-ray diffracting spectrum of zinc Nano capsule figure.
Figure 21 is the transmission electron microscope photo of zinc Nano capsule.
Figure 22 is the X-ray diffracting spectrum of zinc Nano capsule figure.
Figure 23 is the transmission electron microscope photo of zinc Nano capsule.
Detailed description of the invention
Embodiment 1
By cupric oxide powder under 100MPa pressure, the block be pressed into, be placed in black-fead crucible as alternative anode, negative electrode is graphite, and operating room is extracted into 8 × 10
-3pa, operating room's volume 70 liters, is filled with 2 × 10
4pa argon gas, 6 × 10
3pa hydrogen, 13 milliliters of C
2h
5oH, under 20 ~ 24V voltage, under 100 ~ 120A electric current, produces plasma with arc discharge, make cupric oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 5 points of kinds that work, cool 20 minutes, extract residual gas out, then put into air, collect the copper Nano capsule on water-cooling wall.
As shown in Figure 1, the X-ray card number that collection of illustrative plates is corresponding is gained copper Nano capsule X-ray diffracting spectrum: 04-836, and principal phase is face-centred cubic copper.As shown in Figure 2, Fig. 2 shows that the size of copper Nano capsule is less than 300nm to its transmission electron microscope photo.As shown in Figure 3, copper Nano capsule superficial layer (shell) is cupric oxide to the partial enlarged drawing of gained copper Nano capsule as seen from the figure, and Nano capsule inside (core) is copper.Fig. 4 is the power spectrum of copper Nano capsule ESEM on a silicon substrate, shows that its main component is copper and a small amount of oxygen, conforms to seen by result and X-ray diffracting spectrum and transmission electron microscope.Fig. 5 is copper Nano capsule X-ray electron Spectrum, XPS (X-ray photoelectron spectroscopy).The sputter depth that in Fig. 5, three Curves are corresponding, is respectively surperficial 0nm, 2nm and 4nm.Two peaks of curve in figure, the respectively 2p of corresponding copper
3and 2p
1electronics in conjunction with energy.Fig. 6 is the O of copper Nano capsule
1sthe X-ray electron Spectrum of electronics, the sputter depth that in Fig. 6, three Curves are corresponding, is respectively surperficial 0nm, 2nm and 4nm.Be about at the atomic ratio of three different degree of depth oxygen: 1:0.45:0.31; And be about at the atomic ratio of three different degree of depth copper: 1:6.73:8.45, also illustrates that copper Nano capsule superficial layer is cupric oxide, and Nano capsule inside is copper.
Embodiment 2
By Zinc oxide powder under 200MPa pressure, the block be pressed into, is placed in black-fead crucible, makes alternative anode together with crucible, and negative electrode is graphite electrode, and operating room is extracted into 6 × 10
-3pa, is filled with 2 × 10
4pa argon gas, under 18 ~ 20V voltage, under 100 ~ 120A electric current, produce plasma with arc discharge, make zinc oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 8 points of kinds that work, cool 20 minutes, extract residual gas out, then put into air, collect the zinc Nano capsule on water-cooling wall.
As shown in Figure 7, the X-ray card number of the zinc that collection of illustrative plates is corresponding is the X-ray diffracting spectrum of gained zinc Nano capsule: 04-831, and the X-ray card number of zinc oxide is: 36-1451, principal phase is zinc.According to X-ray diffracting spectrum, with the estimation of Scherrer formula, the average-size of zinc Nano capsule is less than 100nm, and surface is zinc oxide, and kernel is zinc.Fig. 8 is the power spectrum of zinc Nano capsule ESEM on a silicon substrate, and show that its main component is zinc and a small amount of oxygen, result conforms to the result of X-ray diffracting spectrum.
Embodiment 3
By stannic oxide powder under 200MPa pressure, the block be pressed into, be placed in as alternative anode on black-fead crucible, negative electrode is graphite, and operating room is extracted into 9 × 10
-3pa, operating room's volume 70 liters, is filled with 2 × 10
4pa argon gas, hydrogen and alcohol, under 20 ~ 22V voltage, under 90 ~ 100A electric current, produce plasma with arc discharge, make tin oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 5 points of kinds that work, cool 20 minutes, extract residual gas out, put into air again, collect the tin Nano capsule on water-cooling wall.
As shown in Figure 9, the X-ray card number of the tin that collection of illustrative plates is corresponding is the X-ray diffracting spectrum of gained tin Nano capsule: 04 – 0673, and the X-ray card number of tin oxide is: 06-0395 principal phase is tin.Figure 10 is the transmission electron microscope photo of tin Nano capsule, and Figure 10 shows that the size of tin Nano capsule is less than 150nm, and kernel is tin, and surface is tin oxide.Figure 11 is the power spectrum of tin Nano capsule ESEM on a silicon substrate, shows that main component is tin and a small amount of oxygen, conforms to seen by result and X-ray diffracting spectrum and transmission electron microscope.
Embodiment 4
By bismuth oxide powder under 200MPa pressure, the block be pressed into, be placed in black-fead crucible as alternative anode, negative electrode is graphite, and operating room is extracted into 9 × 10
-3pa, is filled with 2 × 10
4pa argon gas, hydrogen and alcohol, under 20 ~ 24V voltage, under 100 ~ 120A electric current, produce plasma with arc discharge, make bismuth oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 5 points of kinds that work, cool 20 minutes, extract residual gas out, put into air again, collect the bismuth Nano capsule on water-cooling wall.
As shown in figure 12, the X-ray card number of the bismuth that collection of illustrative plates is corresponding is the X-ray diffracting spectrum of gained bismuth Nano capsule: 44-1246, and the X-ray card number of bismuth oxide is: 47-1057, principal phase is bismuth.Figure 13 is the transmission electron microscope photo of bismuth Nano capsule, and show that the size of bismuth Nano capsule is less than 150nm, kernel is bismuth, and surface is bismuth oxide.Figure 14 is the power spectrum of bismuth Nano capsule ESEM on a silicon substrate, shows that main component is bismuth and a small amount of oxygen, conforms to seen by result and X-ray diffracting spectrum and transmission electron microscope.
Embodiment 5
By yellow lead oxide powder under 200MPa pressure, the block be pressed into, be placed in black-fead crucible as alternative anode, negative electrode is graphite, and operating room is extracted into 7 × 10
-3pa, operating room's volume 70 liters, is filled with 2 × 10
4pa argon gas, 6 × 10
3pa hydrogen, 13 milliliters of C
2h
5oH, under 22 ~ 24V voltage, under 110 ~ 120A electric current, produces plasma with arc discharge, make bismuth oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 8 points of kinds that work, cool 20 minutes, extract residual gas out, then put into air, collect the plumbous Nano capsule on water-cooling wall.
As shown in figure 15, the X-ray card number of the lead that collection of illustrative plates is corresponding is the X-ray diffracting spectrum of the plumbous Nano capsule of gained: 04-0686, and principal phase is plumbous.Figure 16 is the transmission electron microscope photo of plumbous Nano capsule, and under electron beam irradiation, because the fusing point of lead is low, plumbous Nano capsule is reunited, and granule is accumulated into bulky grain, shows that the size of plumbous Nano capsule is less than 500nm.Figure 17 is the partial enlarged drawing of the transmission electron microscope photo of plumbous Nano capsule.Kernel is plumbous, and surface is lead oxide.Figure 18 is plumbous Nano capsule XPS, matches seen by result and X-ray diffracting spectrum and transmission electron microscope.Figure 19 is the power spectrum of plumbous Nano capsule ESEM on a silicon substrate, shows that main component is plumbous and a small amount of oxygen, conforms to seen by result and X-ray diffracting spectrum and transmission electron microscope.
Embodiment 6
By Zinc oxide powder under 200MPa pressure, the block be pressed into, is placed in copper crucible, and the same anode as an alternative of crucible, and negative electrode is the tungsten bar of diameter 4 millimeters, and operating room is extracted into 8 × 10
-3pa, is filled with 2 × 10
4pa argon gas, under 14 ~ 16V voltage, under 120 ~ 130A electric current, produce plasma with arc discharge, make zinc oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 8 points of kinds that work, cool 20 minutes, extract residual gas out, then put into air, collect the zinc Nano capsule on water-cooling wall.
Compared with embodiment 2, when crucible is carbon crucible, the carbon produced in course of reaction has very strong reduction to ZnO.
As shown in figure 20, the X-ray card number of the zinc that collection of illustrative plates is corresponding is the X-ray diffracting spectrum of gained zinc Nano capsule: 04-0831, and the X-ray card number of zinc oxide is: 36-1451.From XRD result, the amount of zinc is little, is all zinc oxide substantially.Figure 21 is the transmission electron microscope photo of zinc Nano capsule, and Figure 21 shows that Nano capsule is zinc oxide, and size is less than 10nm.Because the amount of zinc is little, be difficult to find in transmission electron microscope.But from XRD statistics, the known existence having zinc.
Embodiment 7
By Zinc oxide powder under 200MPa pressure, the block be pressed into, is placed in copper crucible, and anode as an alternative together with crucible, negative electrode is the tungsten bar of diameter 4 millimeters, and operating room is extracted into 8 × 10
-3pa, is filled with 2 × 10
4pa argon gas, 10 milliliters of C
2h
5oH, under 14 ~ 16V voltage, under 120 ~ 130A electric current, produces plasma with arc discharge, make zinc oxide pyrolysis, ionization, reduce and be condensate on the water-cooling wall of operating room, after the 8 points of kinds that work, cool 20 minutes, extract residual gas out, then put into air, collect the nanometer powder on water-cooling wall.
As shown in figure 22, the X-ray card number of the zinc that collection of illustrative plates is corresponding is the X-ray diffracting spectrum of gained zinc Nano capsule figure: 04-0831, and the X-ray card number of zinc oxide is: 36-1451.Compared with Figure 20, the amount of zinc is many, and explanation is C
2h
5oH is by zinc oxide reduction.Figure 23 is the transmission electron microscope photo of zinc Nano capsule, and Figure 23 shows that the size of zinc Nano capsule is less than 200nm, and kernel is zinc, and surface is zinc oxide.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (5)
1. one kind is the method that alternative anode prepares metal nano capsule with metal oxide, it is characterized in that: the method adopting cathode and anode arc discharge under working gas to produce plasma prepares metal nano capsule, its Anodic is the block that is pressed into of metal oxide powder and crucible, and concrete technology is:
By the block be pressed into by metal oxide powder, be placed on the crucible that can conduct electricity, be first discharge between anode and negative electrode with crucible, make it to produce high-temperature electric arc, make metal oxide pyrolysis, ionization and conducting electricity, again with metal oxide block for substitute anode, and discharge between negative electrode, make metal oxide decomposition-reduction, produce metal vapors, condensation again, prepares metal nano capsule powders.
2., by being the method that alternative anode prepares metal nano capsule with metal oxide described in claim 1, it is characterized in that: described crucible is black-fead crucible or copper crucible, and negative electrode is graphite electrode or tungsten electrode, be working gas with argon gas, operating air pressure is no more than 10
5pa, produces plasma with arc discharge, and discharge voltage is not less than 8V, and the block pyrolysis that metal oxide powder is pressed into, ionization, reduction and condensation, prepare metal nano capsule.
3. by being the method that alternative anode prepares metal nano capsule with metal oxide described in claim 1, it is characterized in that: described crucible is black-fead crucible or copper crucible, negative electrode is graphite electrode or tungsten electrode, and with argon gas and reducing agent for working gas, operating air pressure is no more than 10
5pa, produces plasma with arc discharge, and discharge voltage is not less than 8V, and the block pyrolysis that metal oxide powder is pressed into, ionization, reduction and condensation, prepare metal nano capsule; Wherein reducing agent is the gaseous mixture of alcohol or alcohol and hydrogen.
4., by being the method that alternative anode prepares metal nano capsule with metal oxide described in Claims 2 or 3, it is characterized in that: before arc discharge, be filled with argon gas be not less than 2000Pa.
5., by being the method that alternative anode prepares metal nano capsule with metal oxide described in claim 1 or 2, it is characterized in that: metal oxide powder is zinc oxide ZnO, cupric oxide CuO, bismuth oxide Bi
2o
3, tin oxide SnO
2or lead oxide PbO powder.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6320032A (en) * | 1986-07-14 | 1988-01-27 | Res Dev Corp Of Japan | Production of hyperfine particle having film |
| US6582763B1 (en) * | 1999-01-29 | 2003-06-24 | Nisshin Seifun Group Inc. | Process for producing oxide coated fine metal particles |
| CN101362200A (en) * | 2008-09-20 | 2009-02-11 | 大连理工大学 | Synthesis method of metallic oxide coated dissimilar metal 'core/shell'nano-particles |
| JP2010131558A (en) * | 2008-12-05 | 2010-06-17 | Sonac Kk | Method of manufacturing target substance-containing liquid, method of forming target substance-containing thin film, and target substance-containing liquid |
-
2012
- 2012-11-16 CN CN201210466336.8A patent/CN102974835B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6320032A (en) * | 1986-07-14 | 1988-01-27 | Res Dev Corp Of Japan | Production of hyperfine particle having film |
| US6582763B1 (en) * | 1999-01-29 | 2003-06-24 | Nisshin Seifun Group Inc. | Process for producing oxide coated fine metal particles |
| CN101362200A (en) * | 2008-09-20 | 2009-02-11 | 大连理工大学 | Synthesis method of metallic oxide coated dissimilar metal 'core/shell'nano-particles |
| JP2010131558A (en) * | 2008-12-05 | 2010-06-17 | Sonac Kk | Method of manufacturing target substance-containing liquid, method of forming target substance-containing thin film, and target substance-containing liquid |
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