CN113019468A - Copper-based Cu-Cu2Preparation method of O-CuO ternary composite core-shell material - Google Patents
Copper-based Cu-Cu2Preparation method of O-CuO ternary composite core-shell material Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 212
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 141
- 239000011206 ternary composite Substances 0.000 title claims abstract description 48
- 239000011258 core-shell material Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title abstract description 17
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000007789 gas Substances 0.000 claims abstract description 92
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000011257 shell material Substances 0.000 claims abstract description 57
- 239000012159 carrier gas Substances 0.000 claims abstract description 32
- 238000002360 preparation method Methods 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 30
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 30
- 229940112669 cuprous oxide Drugs 0.000 claims description 19
- 230000001590 oxidative effect Effects 0.000 claims description 15
- 229960004643 cupric oxide Drugs 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 10
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- 239000005751 Copper oxide Substances 0.000 abstract description 8
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
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- 239000002994 raw material Substances 0.000 description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 239000010410 layer Substances 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 16
- 238000002156 mixing Methods 0.000 description 8
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 239000005046 Chlorosilane Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J35/23—
-
- B01J35/396—
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- B01J35/40—
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- B01J35/50—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
Abstract
The invention relates to a copper-based Cu-Cu2A preparation method of an O-CuO ternary composite core-shell material belongs to the technical field of catalysts. Aiming at the practical problems that the performance is unstable due to wide particle size distribution range of catalyst particles, the catalyst is hardened due to copper oxidation and heat release, the preparation process flow is complex and not beneficial to mass production and the like, the copper-containing powder is dried and is sent into a thermal plasma torch through carrier gas, the atmosphere of the thermal plasma working gas in a reaction area is controlled to adjust the combination state of copper and oxygen, and the copper-cored Cu-cored plasma is obtained2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite core-shell material. The copper oxide shell layer of the invention has a plurality of defectsAnd the amorphous state of the disordered structure is beneficial to the material migration in the process of synthesizing the organic silicon monomer. The method has the characteristics of simple equipment requirement, short flow, high yield, easy operation and the like.
Description
Technical Field
The invention relates to a copper-based Cu-Cu2A preparation method of an O-CuO ternary composite core-shell material belongs to the technical field of catalysts.
Background
The organic silicon material is a large class of functional material compounds with semi-inorganic and semi-organic structures, has double advantages of inorganic matters and organic matters, has excellent performances of inorganic silicon dioxide such as safety, reliability, no toxicity, no pollution, no corrosion, high temperature resistance, ozone resistance, radiation resistance, aging resistance, flame resistance, electric arc resistance, corona resistance, electric leakage resistance, long service life, physiological inertia and the like, has the outstanding characteristics of organic macromolecules such as moisture resistance, hydrophobicity, easy processing, capability of being prepared into products with different performances according to different requirements, easiness in modification and the like, and is a novel macromolecular synthetic material capable of meeting the requirements of energy conservation, no pollution, safety, high reliability, multiple functions, multiple forms, high performance, high functions and compounding. With the progressive reduction in the non-renewable and recoverable quantities of petroleum resources on earth, it has been imperative that some of the traditional C-C bond resource-based functional polymeric materials have been replaced by organosiloxane-based silicone polymeric materials.
The direct method for synthesizing organic chlorosilane is a method for preparing organic halosilane by directly reacting halohydrocarbon with elemental silicon under the action of heating and a copper catalyst, and has the advantages of easily obtained raw materials, no solvent, high space-time yield and easy realization of continuous large-scale production. Copper base Cu-Cu2The O-CuO ternary catalyst has the advantages of long storage time, high activity in reaction, good M2 selectivity, short reaction induction period and the like, and can greatly reduce the production cost of the organic silicon monomer.
However, the current preparation approaches of the copper-based three-way catalyst mainly comprise a physical method (such as stirring, grinding and the like), a liquid phase synthesis method and a partial oxidation/reduction method, but the particle size distribution range of the three-way copper catalyst is wide, so that the catalytic performance is unstable; in the partial oxidation preparation, the catalyst is hardened due to the fact that copper is oxidized into a strong exothermic reaction; the process flow is complex and is not beneficial to mass production.
Disclosure of Invention
Aiming at the practical problems of unstable performance caused by wide particle size distribution range of catalyst particles, hardening of the catalyst caused by heat release of copper oxidation, complicated preparation process flow, difficulty in mass production and the like in the prior art, the invention provides the copper-based Cu-Cu2A preparation method of an O-CuO ternary composite core-shell material. The copper oxide shell layer is an amorphous state with a large number of defects and disordered structures, and is beneficial to substance migration in the synthetic process of the organic silicon monomer.
Copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material comprises the following specific steps:
drying the copper-containing powder, feeding the dried copper-containing powder into a thermal plasma torch through carrier gas, and controlling the atmosphere of thermal plasma working gas in a reaction area to adjust the combination state of copper and oxygen to obtain Cu with copper as a core2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles; according to the characteristics of a plasma reaction system, the copper-containing raw material is completely gasified or the surface layer is gasified at extremely high temperature, and is cooled along with the reduction of the temperature to obtain molten particles which form an oxide layer when contacting with gaseous oxygen atoms on the outer layer. The whole process conforms to a nucleation reaction model, and the diffusion resistance of oxygen atoms into particles is increased along with the gradual thickening of an oxidation layer, so that the inner side of the obtained shell layer is cuprous oxide in an anoxic state, and the outer side of the obtained shell layer is copper oxide in a positive enrichment state.
The copper-containing powder in the step (1) is one or more of copper powder, cuprous oxide powder and copper oxide powder, and the purity of the copper-containing powder is from industrial grade to ultra-high purity;
further, the particle size of the copper-containing powder is 0.1-500 mu m;
the feeding rate of the copper-containing powder into the thermal plasma torch through the carrier gas is 0.1-800 g/min;
selecting carrier gas according to the property of the raw material, wherein when the copper-containing powder is copper powder, the carrier gas is oxidizing gas or inert-oxidizing mixed gas; when the copper-containing powder is cuprous oxide powder, the carrier gas is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas; when the copper-containing powder is copper oxide powder, the carrier gas is reducing gas or inert-reducing mixed gas; when the copper-containing powder is copper powder, cuprous oxide powder or copper oxide powder, the carrier gas is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas;
selecting the atmosphere of a thermal plasma working gas in a system reaction region according to the properties of raw materials, wherein when the copper-containing powder is copper powder, the thermal plasma working gas is an oxidizing gas or an inert-oxidizing mixed gas; when the copper-containing powder is cuprous oxide powder, the working gas of the thermal plasma is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas; when the copper-containing powder is copper oxide powder, the working gas of the thermal plasma is reducing gas or inert-reducing mixed gas; when the copper-containing powder is copper powder, cuprous oxide powder or copper oxide powder, the working gas of the hot plasma is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas; the pressure of the working gas of the thermal plasma is 0.02-0.60 MPa;
selecting a reaction atmosphere according to the properties of raw materials: when pure copper is used as a raw material, oxidizing atmosphere is adopted, and the oxidation degree is controlled by adjusting oxygen partial pressure; when copper oxide is used as a raw material, reducing atmosphere is adopted to reduce oxygen partial pressure and realize control of oxidation degree; when cuprous oxide is used as a raw material, inert or weak oxidizing atmosphere can be adopted, and the partial pressure of oxygen is adjusted to control the copper oxidation degree; similarly, when the raw material is a mixture of three copper-containing raw materials, the reaction atmosphere is adjusted and the oxygen partial pressure is controlled according to the oxygen content of the raw materials, so that the control on the copper oxidation degree in the product is finally realized;
preferably, the inert gas is argon, the reducing gas is hydrogen, and the oxidizing gas is oxygen;
the thermal plasma torch is preferably a direct-current thermal plasma torch, and the power of a thermal plasma generator is 10-200 kW;
further, the copper-based Cu-Cu2The Cu content of the O-CuO ternary composite material is alpha and Cu2The mass content of O is b, the mass content of CuO is c, wherein a is more than 0 and less than or equal to 99 percent, b is more than 0 and less than or equal to 99 percent, c is more than 0 and less than or equal to 99 percent, and a + b + c is equal to 100 percent;
the copper-based Cu-Cu2The O-CuO ternary composite core-shell material can be used as a catalyst for synthesizing organic silicon monomers.
The invention has the beneficial effects that:
(1) the copper-based Cu-Cu of the invention2The O-CuO ternary composite core-shell material takes copper as a core and Cu2O is an intermediate shell layer, CuO is an outer shell layer, and Cu is an intermediate shell layer2O and the shell CuO have a large number of defects and amorphous state with disordered structure, which is beneficial to the material migration in the synthetic process of the organic silicon monomer;
(2) the invention adopts a thermal plasma system to prepare the copper-based Cu-Cu2Heating a micron-sized raw material by a thermal plasma method until the surface of the raw material is melted and gasified, and obtaining spherical micro-nano particles under a rapid cooling condition, thereby effectively avoiding agglomeration and hardening of powder particles; the method can solve the problems of wide particle size distribution and hardened catalyst, has simple process route and strong raw material compatibility, realizes one-step preparation and continuous production, does not generate harmful wastes, and is environment-friendly.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an XPS characterization of the Cu2p peak for the ternary copper catalyst of example 1;
FIG. 3 is an XPS characterization of Cu2p for the ternary copper catalyst of example 13/2Fitting by peak;
FIG. 4 is an XRD characterization of the three-way copper catalyst of example 1;
figure 5 is a TEM characterization of the three-way copper catalyst of example 2.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material (see figure 1) comprises the following specific steps:
(1) taking high-purity copper powder with the average grain diameter of 500 mu m as a copper-containing powder raw material, and placing the copper-containing powder at the temperature of 70 ℃ for vacuum drying for 0.5 h;
(2) introducing argon into the direct current thermal plasma system to exhaust air, and mixing Ar and O in a volume ratio of 90:12The mixed gas is carrier gas, the copper-containing powder raw material is fed into the thermal plasma torch at a feeding rate of 0.1g/min through the carrier gas, wherein the power of a plasma generator is 14.0kW, and the pressure of the carrier gas working gas is 0.10 MPa;
(3) ar and O in a volume mixing ratio of 90:12The mixed gas is hot plasma working gas, the working gas pressure of the hot plasma working gas is 0.10MPa, the combination state of copper and oxygen is adjusted in the atmosphere of a reaction area, the surface of high-purity copper powder is melted, gasified and condensed, and meanwhile, partial oxidation reaction is carried out to obtain copper as a core and Cu2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles;
XPS characterization of the ternary copper catalyst Cu2p peak for this example is shown in FIG. 2, and XPS characterization of the ternary copper catalyst Cu2p3/2The peak fitting is shown in FIG. 3, and it can be seen from FIGS. 2 and 3 that the Cu on the surface of the particles is Cu2O and CuO in the form of Cu2O is mainly used;
the XRD characterization pattern of the ternary copper catalyst of the embodiment is shown in FIG. 4, and it can be known that the prepared particles have crystalline metal Cu; judging that the prepared powder is crystal-form metal copper according to XRD in figure 4, and combining XPS in figures 2-3, the prepared particle surface has only cuprous oxide and cupric oxide within about 10nm thickness, which shows that the product is a core-shell structure, the inner core is crystal-form metal copper, and the outer shell is amorphous copper oxide; according to the characteristics of a plasma reaction system, the copper-containing raw material is completely gasified or the surface layer is gasified at extremely high temperature, and is cooled along with the reduction of the temperature to obtain molten particles which form an oxide layer when contacting with gaseous oxygen atoms on the outer layer. The whole process conforms to a nucleation reaction model, and the diffusion resistance of oxygen atoms into particles is increased along with the gradual thickening of an oxidation layer, so that the inner side of the obtained shell layer is cuprous oxide in an anoxic state, and the outer side of the obtained shell layer is copper oxide in a positive enrichment state.
Example 2: copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material (see figure 1) comprises the following specific steps:
(1) taking high-purity copper powder with the average grain diameter of 0.1 mu m as a copper-containing powder raw material, and placing the copper-containing powder at the temperature of 70 ℃ for vacuum drying for 24 hours;
(2) introducing argon into the direct current thermal plasma system to exhaust air, and mixing Ar and O with the volume ratio of 95:12The mixed gas is carrier gas, the copper-containing powder raw material is fed into a thermal plasma torch at a feeding rate of 800g/min through the carrier gas, wherein the power of a plasma generator is 200kW, and the pressure of the carrier gas working gas is 0.60 MPa;
(3) ar and O in a volume mixing ratio of 95:12The mixed gas is hot plasma working gas, the working gas pressure of the hot plasma working gas is 0.60MPa, the combination state of copper and oxygen is adjusted in the atmosphere of a reaction area, the surface of high-purity copper powder is melted, gasified and condensed, and meanwhile, partial oxidation reaction is carried out to obtain copper as a core and Cu2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles;
the TEM characteristic diagram of the ternary copper catalyst of this example is shown in FIG. 5, and from FIG. 5, it can be seen that the copper base Cu-Cu2The O-CuO ternary composite material is of a core-shell structure, the inner core is crystal metal copper, the outer shell is amorphous copper oxide, the particle fraction of the ternary copper composite material is uniform, and no hardening exists; according to the characteristics of a plasma reaction system, the copper-containing raw material is completely gasified or the surface layer is gasified at extremely high temperature, and is cooled along with the reduction of the temperature to obtain molten particles which form an oxide layer when contacting with gaseous oxygen atoms on the outer layer. The whole process conforms to a nuclear reaction model and followsThe oxide layer is gradually thickened, and the diffusion resistance of oxygen atoms to the particles is increased, so that the inner side of the obtained shell layer is cuprous oxide in an anoxic state, and the outer side of the shell layer is copper oxide in a positive-rich state;
in mass percent, the copper base Cu-Cu of this example2The Cu content in the O-CuO ternary composite material is 87.2 percent, and the Cu content is2The O content was 5.5% and the CuO content was 7.3%.
Example 3: copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material (see figure 1) comprises the following specific steps:
(1) placing industrial-grade copper powder and copper oxide powder in a roller ball mill for dry mixing for 8 hours to obtain a mixture with the average particle size of 3.7 mu m as a copper-containing powder raw material, and placing the copper-containing powder at the temperature of 80 ℃ for vacuum drying for 6 hours, wherein the mass ratio of the industrial-grade copper powder to the copper oxide powder is 1: 1;
(2) introducing argon into a direct current thermal plasma system to exhaust air, taking pure argon as carrier gas, and conveying a copper-containing powder raw material into a thermal plasma torch at a feeding rate of 4g/min by the carrier gas, wherein the power of a plasma generator is 14.5kW, and the pressure of carrier gas working gas is 0.16 MPa;
(3) pure argon is used as hot plasma working gas, the working gas pressure of the hot plasma working gas is 0.16MPa, the combination state of copper and oxygen is adjusted in the atmosphere of a reaction area, the surface of a copper-containing powder raw material is melted, gasified and condensed, and meanwhile, partial oxidation-reduction reaction is carried out to obtain a copper-core-Cu-oxide composite material2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles;
in mass percent, the copper base Cu-Cu of this example2The Cu content in the O-CuO ternary composite material is 62.3 percent, and the Cu content is2The O content was 11.7% and the CuO content was 26.0%.
Example 4: copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material (see figure 1) comprises the following specific steps:
(1) placing industrial-grade copper powder and cuprous oxide powder into a roller ball mill, adding deionized water, wet mixing for 72 hours to obtain a mixture with the average particle size of 6 mu m as a copper-containing powder raw material, and placing the copper-containing powder at 80 ℃ for vacuum drying for 28 hours, wherein the mass ratio of the industrial-grade copper powder to the cupric oxide powder is 1: 1;
(2) introducing argon into a direct current thermal plasma system to exhaust air, taking pure argon as carrier gas, and conveying a copper-containing powder raw material into a thermal plasma torch at a feeding rate of 4g/min by the carrier gas, wherein the power of a plasma generator is 15.5kW, and the pressure of carrier gas working gas is 0.24 MPa;
(3) pure argon is used as hot plasma working gas, the working gas pressure of the hot plasma working gas is 0.24MPa, the combination state of copper and oxygen is adjusted in the atmosphere of a reaction area, the surface of a copper-containing powder raw material is melted, gasified and condensed, and meanwhile, partial oxidation-reduction reaction is carried out to obtain a copper-core-Cu-oxide composite material2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles;
in mass percent, the copper base Cu-Cu of this example2The Cu content in the O-CuO ternary composite material is 59.4 percent, and the Cu content is2The O content was 37.8% and the CuO content was 2.8%.
Example 5: copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material (see figure 1) comprises the following specific steps:
(1) taking high-purity copper oxide powder with the average particle size of 10 mu m as a copper-containing powder raw material, and placing the copper-containing powder at the temperature of 80 ℃ for vacuum drying for 4 hours;
(2) introducing argon into the direct current thermal plasma system to exhaust air, and mixing Ar and H in a volume ratio of 95:12The mixed gas is carrier gas, the copper-containing powder raw material is fed into a thermal plasma torch at a feeding rate of 1g/min through the carrier gas, wherein the power of a plasma generator is 13.0kW, and the pressure of the carrier gas working gas is 0.02 MPa;
(3) ar and H in a volume mixing ratio of 95:12The mixed gas being a hot plasma working gasThe pressure of working gas is 0.02MPa, the combination state of copper and oxygen is adjusted in the atmosphere of a reaction area, the surface of the copper-containing powder raw material is melted, gasified and condensed, and partial reduction reaction is carried out to obtain Cu which takes copper as a core and Cu2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles;
in mass percent, the copper base Cu-Cu of this example2The Cu content in the O-CuO ternary composite material is 8.3 percent, and the Cu content is2The O content was 18.8% and the CuO content was 72.9%.
Example 6: copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material (see figure 1) comprises the following specific steps:
(1) placing high-purity copper powder, cuprous oxide powder and cuprous oxide powder in a roller ball mill, adding absolute ethyl alcohol, wet mixing for 8 hours to obtain a mixture with the average particle size of 13 mu m as a copper-containing powder raw material, and placing the copper-containing powder at 80 ℃ for vacuum drying for 28 hours, wherein the mass ratio of the high-purity copper powder to the cuprous oxide powder is 5:3: 3;
(2) introducing argon into a direct current thermal plasma system to exhaust air, taking pure argon as carrier gas, and conveying a copper-containing powder raw material into a thermal plasma torch at a feeding rate of 5g/min by the carrier gas, wherein the power of a plasma generator is 15.0kW, and the pressure of carrier gas working gas is 0.25 MPa;
(3) pure argon is used as hot plasma working gas, the working gas pressure of the hot plasma working gas is 0.25MPa, the combination state of copper and oxygen is adjusted in the atmosphere of a reaction area, the surface of a copper-containing powder raw material is melted, gasified and condensed, and meanwhile, partial oxidation-reduction reaction is carried out to obtain a copper-core-Cu-oxide composite material2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the shell CuO contain amorphous state; copper base Cu-Cu2The O-CuO ternary composite core-shell material is spherical core-shell structure micro-nano particles;
in mass percent, the copper base Cu-Cu of this example2The Cu content in the O-CuO ternary composite material is 50.4 percent, and the Cu content is2The O content was 40.5% and the CuO content was 9.1%.
While the present invention has been described in detail with reference to the specific embodiments thereof, the present invention is not limited to the embodiments described above, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (9)
1. Copper-based Cu-Cu2The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following specific steps of:
drying the copper-containing powder, feeding the dried copper-containing powder into a thermal plasma torch through carrier gas, and controlling the atmosphere of thermal plasma working gas in a reaction area to adjust the combination state of copper and oxygen to obtain Cu with copper as a core2Copper-based Cu-Cu with O as intermediate shell and CuO as outer shell2O-CuO ternary composite nuclear shell material, intermediate shell Cu2O and the outer shell CuO contain an amorphous state.
2. Copper-based Cu-Cu according to claim 12The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: the copper-containing powder in the step (1) is one or more of copper powder, cuprous oxide powder and copper oxide powder, and the purity of the copper-containing powder is from industrial grade to ultra-high purity.
3. Copper-based Cu-Cu according to claim 22The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: the particle size of the copper-containing powder is 0.1-500 μm.
4. Copper-based Cu-Cu according to claim 12The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: the feeding rate of the copper-containing powder into the thermal plasma torch through the carrier gas is 0.1-800 g/min.
5. Copper-based Cu-Cu according to claim 22The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: when the copper-containing powder is copper powder,the carrier gas is oxidizing gas or inert-oxidizing mixed gas; when the copper-containing powder is cuprous oxide powder, the carrier gas is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas; when the copper-containing powder is copper oxide powder, the carrier gas is reducing gas or inert-reducing mixed gas; when the copper-containing powder is copper powder, cuprous oxide powder or cupric oxide powder, the carrier gas is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas.
6. Copper-based Cu-Cu according to claim 12The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: when the copper-containing powder is copper powder, the working gas of the thermal plasma is oxidizing gas or inert-oxidizing mixed gas; when the copper-containing powder is cuprous oxide powder, the working gas of the thermal plasma is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas; when the copper-containing powder is copper oxide powder, the working gas of the thermal plasma is reducing gas or inert-reducing mixed gas; when the copper-containing powder is copper powder, cuprous oxide powder or copper oxide powder, the working gas of the hot plasma is inert gas, reducing gas, oxidizing gas, inert-reducing mixed gas or inert-oxidizing mixed gas; the pressure of the working gas of the thermal plasma is 0.02-0.60 MPa.
7. Copper-based Cu-Cu according to claim 12The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: the thermal plasma torch is a direct-current thermal plasma torch, and the power of the thermal plasma generator is 10-200 kW.
8. Copper-based Cu-Cu according to claim 72The preparation method of the O-CuO ternary composite core-shell material is characterized by comprising the following steps: copper base Cu-Cu2The Cu content of the O-CuO ternary composite material is alpha and Cu2The mass content of O is b, the mass content of CuO is c, wherein a is more than 0 and less than or equal to 99 percent, b is more than 0 and less than or equal to 99 percent, c is more than 0 and less than or equal to 99 percent, and a + b + c is 100 percent.
9. Copper-based Cu-Cu according to any of claims 1 to 82Copper-based Cu-Cu prepared by preparation method of O-CuO ternary composite nuclear shell material2An O-CuO ternary composite core-shell catalyst material.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773100A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院过程工程研究所 | Ternary copper catalyst CuO-Cu2O-Cu for synthesis of dimethyldichlorosilane and its preparation method |
| CN102773099A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper-based solid solution catalyst and its preparation method |
| US20150291439A1 (en) * | 2013-06-21 | 2015-10-15 | Nisshin Engineering Inc. | Method for producing cuprous oxide fine particles, cuprous oxide fine particles and method of producing conductor film |
| CN105944722A (en) * | 2016-05-18 | 2016-09-21 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper catalyst and preparation method and application thereof |
| WO2018181482A1 (en) * | 2017-03-31 | 2018-10-04 | 三井金属鉱業株式会社 | Copper particles and manufacturing method therefor |
-
2021
- 2021-03-05 CN CN202110244288.7A patent/CN113019468A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773100A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院过程工程研究所 | Ternary copper catalyst CuO-Cu2O-Cu for synthesis of dimethyldichlorosilane and its preparation method |
| CN102773099A (en) * | 2011-05-13 | 2012-11-14 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper-based solid solution catalyst and its preparation method |
| US20150291439A1 (en) * | 2013-06-21 | 2015-10-15 | Nisshin Engineering Inc. | Method for producing cuprous oxide fine particles, cuprous oxide fine particles and method of producing conductor film |
| CN105324337A (en) * | 2013-06-21 | 2016-02-10 | 日清工程株式会社 | Process for producing fine cuprous oxide particles, fine cuprous oxide particles, and process for producing conductor film |
| CN105944722A (en) * | 2016-05-18 | 2016-09-21 | 中国科学院过程工程研究所 | Cu-Cu2O-CuO ternary copper catalyst and preparation method and application thereof |
| WO2018181482A1 (en) * | 2017-03-31 | 2018-10-04 | 三井金属鉱業株式会社 | Copper particles and manufacturing method therefor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116254567A (en) * | 2022-12-12 | 2023-06-13 | 兰州大学 | Nanocomposite and preparation method and application thereof |
| CN116254567B (en) * | 2022-12-12 | 2023-08-25 | 兰州大学 | Nanocomposite and preparation method and application thereof |
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