CN112439371A - Preparation method of submicron copper oxide-polymer carbon skeleton material with core-shell structure - Google Patents
Preparation method of submicron copper oxide-polymer carbon skeleton material with core-shell structure Download PDFInfo
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- CN112439371A CN112439371A CN201910819780.5A CN201910819780A CN112439371A CN 112439371 A CN112439371 A CN 112439371A CN 201910819780 A CN201910819780 A CN 201910819780A CN 112439371 A CN112439371 A CN 112439371A
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Abstract
The invention provides a preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure, belonging to a preparation method of a novel copper oxide composite material. The method comprises the following specific steps: dissolving high molecular polymer polyacrylamide in water, heating and stirring to obtain a uniform solution; firstly, adding copper salt into a polyacrylamide aqueous solution, and magnetically stirring; then quickly freezing the sample by using liquid nitrogen, and then carrying out vacuum freeze drying to obtain a white intermediate product; and finally, calcining the intermediate product to obtain the submicron copper oxide-polymer carbon skeleton material with the core-shell structure. The invention has the advantages that: the prepared material has uniform particle size, the preparation method is simple and convenient to operate, the reaction condition is mild, the production efficiency is high, no organic solvent, strong acid, strong alkali and the like are used, and the preparation process is green and environment-friendly.
Description
Technical Field
The invention relates to the field of preparation of micro/nano-scale copper oxide materials, in particular to a preparation method of a core-shell structure submicron copper oxide-polymer carbon skeleton material.
Background
Copper oxide is a black amphoteric oxide of copper, and has been widely used in the fields of catalysts, sensing materials, superconducting materials, thermoelectric materials, glass, ceramics, lithium ion batteries, and even in medicine. As a catalyst, copper oxide can increase the reaction rate of certain types of reactions, and in the selective reduction of p-nitroaniline to p-phenylenediamine, copper oxide is currently the catalyst that is the most effective catalyst in this area of research. In the core-shell structure, copper oxide is used as a core, and a porous carbon skeleton is used as a support outside, so that the dispersibility of the copper oxide can be improved, and the catalytic effect of the copper oxide can be improved.
At present, a plurality of methods for preparing the copper oxide with the core-shell structure exist, such as a precipitation method, a hydrothermal method, an alcoholic thermal method, an electrochemical method and the like. For example, CN105642286A discloses a method for preparing a nano copper oxide @ mesoporous silica core-shell structure material, which comprises dissolving a copper salt in an alcohol solution, adding a dispersing agent,Adding an alkali solution into a pore-forming agent to adjust the pH value and the like, and then carrying out a series of operations such as filtering, washing, drying, roasting and the like to obtain a final product; CN103500667B discloses a CuO-MnO2The preparation method of the core-shell structure nano material comprises the steps of dispersing copper nanowires in a strong-oxidizing potassium permanganate solution by using a hydrothermal method, and finally obtaining a target product through multi-step treatment; CN109437278A discloses a gas-sensitive nanomaterial preparation process based on a copper oxide-tin oxide core-shell nanowire structure, wherein a strong alkali sodium hydroxide solution is used in the preparation process, and a target product is finally obtained through operations such as multiple cleaning, drying, nitrogen purging and calcining; CN106561712A discloses a preparation method of nano copper oxide coated with nano zinc oxide with a core-shell structure, wherein a surfactant is used in the preparation process, and the nano copper oxide coated with nano zinc oxide with a core-shell structure are sequentially prepared in a twice calcination manner; jiangting preparation of nano copper oxide with controllable morphology and performance research thereof [ D]2016, namely synthesizing spherical Cu by using copper acetate monohydrate and sodium hydroxide as reaction raw materials and ascorbic acid as a template agent2O, and then preparing CuO @ TiO by using tetrabutyl titanate as a titanium source through annealing by using a two-step solvent synthesis process2A core-shell structure. The method generally has the following problems in the preparation process: a large amount of organic reagents are used, the preparation process is complicated, the operation difficulty coefficient is large, and the requirements of experimental conditions are strict.
Disclosure of Invention
Aiming at the problems existing at present, the invention develops a preparation method of the submicron copper oxide-polymer carbon skeleton material with the core-shell structure, the used reagents do not contain organic reagents, strong acid, strong base and the like, the operation is simple, the production efficiency is high, and the large-scale preparation is easy.
The technical scheme of the invention is as follows: a preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure comprises the following steps of adding copper salt into a polyacrylamide aqueous solution, drying and calcining to obtain a final product:
1) dissolving high molecular polymer polyacrylamide in water according to a certain proportion, heating and stirring to obtain a uniform solution.
2) Adding copper salt into the polyacrylamide aqueous solution according to a certain proportion, and magnetically stirring for 1 hour at normal temperature.
3) Quickly freezing the sample by using liquid nitrogen, and then carrying out vacuum freeze drying to obtain a white intermediate product; and finally, calcining the intermediate product to obtain the submicron copper oxide-polymer carbon skeleton material with the core-shell structure.
The polyacrylamide aqueous solution in the step 1) is prepared according to the mass ratio of polyacrylamide to water of 0.25-6%, and is stirred at 80 ℃ to obtain a uniform solution.
The copper salt in the step 2) is one of copper acetate, copper chloride and copper nitrate.
The mass ratio of the anhydrous copper acetate to the polyacrylamide in the step 2) is 1:8-3: 1.
In the step 3), the calcining atmosphere is air, the heating rate is 1-5 ℃/min, the calcining temperature is 250-600 ℃, and the heat preservation time is 2-5 h.
The invention has the advantages that: 1) the used solvent is water, and reagents such as organic solvents, strong acids, strong bases and the like are not used, so that the method is environment-friendly, simple in operation flow and low in equipment requirement. 2) The prepared submicron copper oxide-polymer carbon skeleton material with the core-shell structure is not easy to agglomerate, has good dispersibility and is innovative by using polyacrylamide as a dispersing agent and a soft membrane. 3) The particle size of the prepared submicron copper oxide-polymer carbon skeleton material with the core-shell structure is 80nm-180nm, and the particle size of the core-shell material is within 1.0 mu m.
Drawings
Fig. 1 is a Transmission Electron Micrograph (TEM) of a core-shell structured submicron copper oxide-polymeric carbon skeleton material in example 1 of the present invention.
Detailed Description
The present invention is further illustrated with reference to the following specific examples, which are not intended to limit the scope of the invention.
Example 1:
a preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure comprises the following steps:
1) 1g of polyacrylamide was added to 50ml of deionized water, and magnetically stirred at 80 ℃ for 30 minutes to obtain an aqueous polyacrylamide solution.
2) Adding 1g of anhydrous copper acetate into the polyacrylamide aqueous solution, stirring for 1 hour, then quickly freezing the sample by using liquid nitrogen, and freeze-drying the sample in a vacuum freeze dryer to obtain a white intermediate product.
3) And (3) putting the white intermediate product into a muffle furnace for calcining, wherein the heating rate is 3 ℃/min, and the temperature is kept at 400 ℃ for 4 hours to obtain the core-shell structure submicron copper oxide-polymer carbon framework material.
A projection electron microscope (TEM) of the submicron copper oxide-polymer carbon skeleton material with core-shell structure prepared in this example is shown in fig. 1. As can be seen from FIG. 1, the submicron copper oxide-polymer carbon skeleton material with the core-shell structure has the copper oxide diameter of 80-180nm, the overall diameter of the core-shell structure is 1.0 μm, and the particle size distribution is uniform.
Example 2:
a preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure comprises the following steps:
1) 0.25g of polyacrylamide was added to 50ml of deionized water, and magnetically stirred at 80 ℃ for 30 minutes to obtain an aqueous polyacrylamide solution.
2) 0.75g of anhydrous copper acetate was added to the above aqueous polyacrylamide solution, stirred for 1 hour, and then the sample was rapidly frozen with liquid nitrogen, and then lyophilized in a vacuum freeze-dryer to obtain a white intermediate.
3) And (3) putting the white intermediate product into a muffle furnace for calcining, heating at a rate of 2 ℃/min, and preserving heat at the temperature of 250 ℃ for 5 hours to obtain the core-shell structure submicron copper oxide-polymer carbon framework material.
Example 3:
a preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure comprises the following steps:
1) 3g of polyacrylamide was added to 50ml of deionized water, and magnetically stirred at 80 ℃ for 30 minutes to obtain an aqueous polyacrylamide solution.
2) Adding 1g of anhydrous copper acetate into the polyacrylamide aqueous solution, stirring for 1 hour, then quickly freezing the sample by using liquid nitrogen, and freeze-drying the sample in a vacuum freeze dryer to obtain a white intermediate product.
3) And (3) putting the white intermediate product into a muffle furnace for calcining, wherein the heating rate is 5 ℃/min, and the temperature is kept at 500 ℃ for 2 hours to obtain the core-shell structure submicron copper oxide-polymer carbon framework material.
Example 4:
a preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure comprises the following steps:
1) 1g of polyacrylamide was added to 50ml of deionized water, and magnetically stirred at 80 ℃ for 30 minutes to obtain an aqueous polyacrylamide solution.
2) 1g of anhydrous copper chloride is added into the aqueous solution of polyacrylamide, stirred for 1 hour, and then the sample is rapidly frozen by liquid nitrogen and then put into a vacuum freeze dryer for freeze-drying to obtain a white intermediate product.
3) And (3) putting the white intermediate product into a muffle furnace for calcining, wherein the heating rate is 3 ℃/min, and the temperature is kept at 600 ℃ for 2 hours to obtain the core-shell structure submicron copper oxide-polymer carbon framework material.
Claims (7)
1. A preparation method of a submicron copper oxide-polymer carbon skeleton material with a core-shell structure is characterized by comprising the following steps: dissolving copper salt in a polyacrylamide aqueous solution under a certain condition, drying to obtain an intermediate product, and calcining the intermediate product to obtain the core-shell structure submicron copper oxide-polymer carbon framework material.
2. The aqueous polyacrylamide solution of claim 1 wherein the mass ratio of polyacrylamide to water is 0.25% to 6%, preferably 1% to 4%.
3. The copper salt according to claim 1, wherein the copper salt is selected from one of copper acetate, copper chloride and copper nitrate, preferably anhydrous copper acetate.
4. The method of claim 1, wherein the mass ratio of copper acetate to polyacrylamide is 1:8 to 3:1, preferably 1:4 to 2: 1.
5. The calcined intermediate product according to claim 1, characterized in that the calcination temperature is 250-600 ℃, preferably 300-400 ℃.
6. The calcined intermediate product according to claim 1, characterized in that the temperature rise rate is 1-5 ℃/min, preferably 2-3 ℃/min, and the holding time is 2-5 h, preferably 3-4 h.
7. The core-shell structure submicron copper oxide-polymer carbon skeleton material prepared by the method of claims 1 to 6 is characterized in that the particle size of copper oxide in the prepared core-shell structure submicron copper oxide-polymer carbon skeleton material is between 80nm and 180nm, and the total particle size of the core-shell material is within 1.0 μm.
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| CN107381618A (en) * | 2017-09-01 | 2017-11-24 | 北京化工大学 | A kind of preparation method of club shaped structure nano zine oxide |
| CN107579230A (en) * | 2017-09-07 | 2018-01-12 | 江苏福瑞士电池科技有限公司 | The preparation method of zinc oxide/carbon composite and the application on lithium ion battery |
| CN107837808A (en) * | 2017-11-30 | 2018-03-27 | 上海拓径新材料科技股份有限公司 | The method that the copper-loaded method of macromolecule resin prepares copper-loaded solid carbon |
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- 2019-08-31 CN CN201910819780.5A patent/CN112439371A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102307826A (en) * | 2009-02-05 | 2012-01-04 | Lg化学株式会社 | Method for preparing carbon particles/copper composite materials |
| CN101615672A (en) * | 2009-03-03 | 2009-12-30 | 清华大学 | A kind of method for preparing lithium ion battery alloy composite anode material with nuclear shell structure |
| CN101531771A (en) * | 2009-04-02 | 2009-09-16 | 华东师范大学 | Method for using metallic copper to carry out in-situ modification on mesoporous organic polymer or carbon material |
| CN105692686A (en) * | 2016-04-28 | 2016-06-22 | 北京化工大学常州先进材料研究院 | Preparation method of nanometer zinc oxide powder |
| CN107381618A (en) * | 2017-09-01 | 2017-11-24 | 北京化工大学 | A kind of preparation method of club shaped structure nano zine oxide |
| CN107579230A (en) * | 2017-09-07 | 2018-01-12 | 江苏福瑞士电池科技有限公司 | The preparation method of zinc oxide/carbon composite and the application on lithium ion battery |
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