CN110577209A - Preparation method for in-situ synthesis of carbon nano tube surface loaded copper oxide nano particles - Google Patents
Preparation method for in-situ synthesis of carbon nano tube surface loaded copper oxide nano particles Download PDFInfo
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- CN110577209A CN110577209A CN201910888901.1A CN201910888901A CN110577209A CN 110577209 A CN110577209 A CN 110577209A CN 201910888901 A CN201910888901 A CN 201910888901A CN 110577209 A CN110577209 A CN 110577209A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
Abstract
The invention relates to a method for preparing copper oxide nanoparticles loaded on the surface of a carbon nanotube by in-situ synthesis, which comprises the following steps: (1) preparing a mixed solution of the carbon nano tube and the copper sulfate crystal. (2) Chemically precipitating the surface of the carbon nano tube to obtain a copper oxide/copper hydroxide mixture: heating the mixed solution of the carbon nano tube and the copper sulfate to 90-100 ℃, dropwise adding a sodium hydroxide solution after the temperature is reached, wherein the concentration of the sodium hydroxide solution is 1-2mol/L, after the reaction is completed, carrying out suction filtration and washing on the mixed solution, and drying the mixed powder obtained by suction filtration. (3) Annealing treatment of mixed powder: and placing the dried powder in a muffle furnace for annealing treatment, wherein the annealing temperature is 300-400 ℃, the heat preservation time is 2-3h, and after the heat preservation is finished, cooling the furnace to the room temperature to obtain the CuO @ CNTs composite material.
Description
Technical Field
The invention relates to a method for in-situ synthesizing carbon nano tube surface loaded copper oxide nano particles by using a chemical precipitation method and annealing treatment, belonging to the technical field of nano material preparation.
Background
Carbon Nanotubes (CNTs) are a hollow, tubular, one-dimensional nanomaterial built from elemental carbon. Theoretically, the elastic modulus of the material can reach 1.8TPa, and the material is one of the most excellent materials found at present. In addition, since the carbon atoms in CNTs are more than SP2Hybridization and hybridization orbitals form more highly delocalized pi electrons, so that the hybrid orbitals have ultrahigh application prospect in the fields of electricity and heat. However, CNTs usually have a diameter of several to tens of nanometers, and thus can reach a micron-scale length, a high aspect ratio and strong intermolecular forces among CNTs, so that the carbon nanotubes are difficult to disperse in both liquid and solid media, and the application range of the carbon nanotubes is severely limited.
In order to overcome the defect of poor wettability of CNTs with an environmental medium, the main method at present is to modify an alloy element or a ceramic phase on the surface of CNTs. More commonly used methods include electroless plating, chemical vapor deposition, physical vapor deposition, and sol-gel techniques. The chemical plating process is complex, and the introduced heavy metal elements are not easy to completely remove, so that the chemical plating process has potential harm to the environment and the body. Other methods rely on expensive equipment, and the binding force between the metal modified layer or modified particles and the CNTs is poor, so that the coating is easy to fall off in the using process.
Disclosure of Invention
The invention aims to provide a method for preparing a CuO @ CNTs composite material by a chemical precipitation method and an annealing treatment. The method can effectively overcome the defect that the CNTs are easy to agglomerate, and enables the CNTs to have certain catalytic activity. In order to achieve the purpose, the invention is implemented by the following technical scheme:
A method for preparing copper oxide nanoparticles loaded on the surface of a carbon nanotube by in-situ synthesis comprises the following steps:
(1) Preparing mixed solution of carbon nano tube and copper sulfate crystal
The hydroxylated carbon nano tube and the copper sulfate are prepared into a mixed solution according to the mass ratio of (0.7-1.2) to 1.
(2) Chemical precipitation of carbon nanotube surface to obtain copper oxide/copper hydroxide mixture
heating the mixed solution of the carbon nano tube and the copper sulfate to 90-100 ℃, dropwise adding a sodium hydroxide solution after the temperature is reached, wherein the concentration of the sodium hydroxide solution is 1-2mol/L, after the reaction is completed, carrying out suction filtration and washing on the mixed solution, and drying the mixed powder obtained by suction filtration.
(3) Annealing treatment of mixed powder
And placing the dried powder in a muffle furnace for annealing treatment, wherein the annealing temperature is 300-400 ℃, the heat preservation time is 2-3h, and after the heat preservation is finished, cooling the furnace to the room temperature to obtain the CuO @ CNTs composite material.
in the invention, a chemical precipitation and annealing treatment method is adopted, hydroxylated CNTs, copper sulfate and sodium hydroxide are taken as raw materials, and copper oxide/copper hydroxide nano-particles are prepared on the surface of the hydroxylated CNTs in situ by a chemical precipitation method. And the purity of the copper oxide and the CNTs is further improved through annealing treatment. In addition, the interface bonding force of the carbon nanotube loaded copper oxide nanoparticles (CuO @ CNTs) prepared by the method is strong, and the copper oxide nanoparticles do not fall off in a large area after long-time ball milling treatment. And because the copper oxide has certain catalytic activity, the CuO @ CNTs composite material has certain research prospect in the fields of structural materials and functional materials.
Drawings
FIG. 1 shows the morphology of pristine hydroxylated carbon nanotubes
FIG. 2 shows the structure and appearance of the carbon nanotube loaded copper oxide/copper hydroxide composite powder after chemical precipitation
FIG. 3 is a structural morphology of annealed copper oxide composite powder loaded on carbon nanotubes
FIG. 4 shows the morphology of the carbon nanotube loaded copper oxide composite powder and aluminum powder after ball milling
Detailed Description
The process route of the invention is as follows:
(1) Preparing mixed solution of carbon nano tube and copper sulfate crystal
Dissolving the purchased hydroxylated CNTs and copper sulfate crystals in distilled water according to a certain proportion, and stirring for 1-2 h.
(2) Chemical precipitation of carbon nanotube surface to obtain copper oxide/copper hydroxide mixture
And heating the stirred mixed solution of the carbon nano tube and the copper sulfate to 90-100 ℃ in a water bath, and dropwise adding a sodium hydroxide solution after the mixed solution is warmed to the temperature, wherein the concentration of the sodium hydroxide solution is 1-2mol/L, and the volume of the sodium hydroxide solution is 20-40 ml. After the reaction is completed, the mixed solution is filtered and washed, and the process is repeated for 2-3 times. And (3) placing the mixed powder obtained by suction filtration into a vacuum drying oven for drying for 12-24h, wherein the drying temperature is 80-90 ℃.
(3) annealing treatment of mixed powder
And (3) placing the dried powder in a muffle furnace for annealing treatment, wherein the annealing temperature is 300-400 ℃, the heat preservation time is 2-3h, and cooling the furnace to room temperature after the heat preservation is finished. Obtaining the CuO @ CNTs composite material.
The reaction mechanism is as follows:
the purchased hydroxylated carbon nanotube and copper sulfate crystal can be dissolved in distilled water, sodium hydroxide and copper sulfate react in the process of dropwise adding sodium hydroxide solution, a reaction product nucleates at the surface defect of the hydroxylated carbon nanotube to obtain a mixture of copper oxide and copper hydroxide, and the reaction equation is as follows:
The reaction equation is as follows: CuSO4+NaOH→Na2SO4+Cu(OH)2+CuO
Cu (OH) formed during the precipitation during the annealing treatment2The decomposition occurs, and the amorphous carbon on the surface of the CNTs reacts with oxygen to generate carbon dioxide, and the reaction equation is as follows:
Cu(OH)2→CuO+H2O；
C+O2→CO2
The present invention is further illustrated by the following examples, which are intended to be illustrative only and not limiting.
Example 1
0.8g of hydroxylated CNTs (morphology shown in FIG. 1) and 1g of copper sulfate crystals were weighed into a beaker having a volume of 250ml, and 150ml of distilled water was added. And (3) placing the beaker in a water bath kettle, and magnetically stirring for 2 hours at room temperature to fully mix the hydroxylated CNTs and the copper sulfate in the mixed solution. The water bath is heated to 90 ℃, and 20ml of 2mol/L sodium hydroxide solution is dripped after the temperature is reached. And after the reaction is completed, carrying out suction filtration on the mixed solution, washing the powder obtained by suction filtration with distilled water, and repeatedly washing and carrying out suction filtration for 3 times. The obtained mixed powder is placed in a vacuum drying oven, the drying temperature is 80 ℃, the drying time is 12h, and the tissue morphology is shown in figure 2. It was found that the copper oxide/hydroxide nanoparticles obtained by the precipitation reaction had a diameter of about 5nm and were uniformly distributed on the surface of the CNTs. And (3) placing the dried mixed powder into a muffle furnace for annealing treatment, wherein the annealing temperature is 300 ℃, and the heat preservation time is 2 h. In the annealing process, on one hand, CNTs are purified, and amorphous carbon on the surface is removed; on the other hand, during the annealing treatment, the residual copper hydroxide in the mixed powder is decomposed into copper oxide. The morphology of the annealed CuO @ CNTs composite powder is shown in FIG. 3, which shows that copper oxide is not agglomerated or grown during annealing, and intact CNTs are remained. In order to prove that stronger binding force exists between copper oxide and the carbon nano tube and the CuO @ CNTs composite powder has good dispersibility in the metal powder, the obtained CuO @ CNTs composite powder is subjected to ball milling treatment with 19.8g of aluminum powder with the particle size of 30 mu m, the ball milling rotation speed is 200rpm, the ball milling time is 4 hours, and the ball-to-material ratio is 15: 1. The texture of the ball-milled mixed powder is shown in fig. 4, no obvious agglomeration phenomenon is observed in the CuO @ CNTs composite powder, and the CuO and CNTs are well combined and do not fall off.
Example 2
1g of hydroxylated carbon nanotubes and 1g of copper sulfate crystals were weighed into a beaker having a volume of 250ml, and 200ml of distilled water was added. And (3) placing the beaker in a water bath kettle, and stirring for 2 hours at room temperature by magnetic force to fully mix the hydroxylated carbon nanotube and the copper sulfate in the mixed solution. The water bath is heated to 90 ℃, and 20ml of 2mol/L sodium hydroxide solution is dripped after the temperature is reached. And after the reaction is completed, carrying out suction filtration on the mixed solution, washing the powder obtained by suction filtration with distilled water, and repeatedly washing and carrying out suction filtration for 3 times. And placing the obtained mixed powder in a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 12 h. And placing the dried mixed powder in a muffle furnace for annealing treatment at the annealing temperature of 300 ℃ for 2h to obtain the CuO @ CNTs composite powder.
Example 3
0.8g of hydroxylated carbon nanotubes and 1g of copper sulfate crystals were weighed into a beaker having a volume of 250ml, and 200ml of distilled water was added. And (3) placing the beaker in a water bath kettle, and stirring for 2 hours at room temperature by magnetic force to fully mix the hydroxylated carbon nanotube and the copper sulfate in the mixed solution. The water bath kettle is heated to 100 ℃, and 20ml of 2mol/L sodium hydroxide solution is dripped after the temperature is reached. And after the reaction is completed, carrying out suction filtration on the mixed solution, washing the powder obtained by suction filtration with distilled water, and repeatedly washing and carrying out suction filtration for 3 times. And placing the obtained mixed powder in a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 12 h. And (3) placing the dried mixed powder into a muffle furnace for annealing treatment, wherein the annealing temperature is 350 ℃, and the heat preservation time is 2h, so that the CuO @ CNTs composite powder is obtained.
Example 4
0.8g of hydroxylated carbon nanotubes and 1g of copper sulfate crystals were weighed into a beaker having a volume of 250ml, and 150ml of distilled water was added. And (3) placing the beaker in a water bath kettle, and stirring for 2 hours at room temperature by magnetic force to fully mix the hydroxylated carbon nanotube and the copper sulfate in the mixed solution. The water bath kettle is heated to 100 ℃, and 40ml of 2mol/L sodium hydroxide solution is dripped after the temperature is reached. And after the reaction is completed, carrying out suction filtration on the mixed solution, washing the powder obtained by suction filtration with distilled water, and repeatedly washing and carrying out suction filtration for 3 times. And placing the obtained mixed powder in a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 12 h. And (3) placing the dried mixed powder into a muffle furnace for annealing treatment, wherein the annealing temperature is 350 ℃, and the heat preservation time is 2h, so that the CuO @ CNTs composite powder is obtained.
Example 5
0.8g of hydroxylated carbon nanotubes and 1g of copper sulfate crystals were weighed into a beaker having a volume of 250ml, and 150ml of distilled water was added. And (3) placing the beaker in a water bath kettle, and stirring for 2 hours at room temperature by magnetic force to fully mix the hydroxylated carbon nanotube and the copper sulfate in the mixed solution. The water bath kettle is heated to 100 ℃, and 40ml of 2mol/L sodium hydroxide solution is dripped after the temperature is reached. And after the reaction is completed, carrying out suction filtration on the mixed solution, washing the powder obtained by suction filtration with distilled water, and repeatedly washing and carrying out suction filtration for 3 times. And placing the obtained mixed powder in a vacuum drying oven, wherein the drying temperature is 80 ℃, and the drying time is 12 h. And (3) placing the dried mixed powder into a muffle furnace for annealing treatment, wherein the annealing temperature is 400 ℃, and the heat preservation time is 2 hours, so that the CuO @ CNTs composite powder is obtained. If the CNTs have more defects per se at 400 ℃, the quality of the mixed powder after annealing treatment is reduced.
Claims (1)
1. A method for preparing copper oxide nanoparticles loaded on the surface of a carbon nanotube by in-situ synthesis comprises the following steps:
(1) Preparing mixed solution of carbon nano tube and copper sulfate crystal
The hydroxylated carbon nano tube and the copper sulfate are prepared into a mixed solution according to the mass ratio of (0.7-1.2) to 1.
(2) Chemical precipitation of carbon nanotube surface to obtain copper oxide/copper hydroxide mixture
Heating the mixed solution of the carbon nano tube and the copper sulfate to 90-100 ℃, dropwise adding a sodium hydroxide solution after the temperature is reached, wherein the concentration of the sodium hydroxide solution is 1-2mol/L, after the reaction is completed, carrying out suction filtration and washing on the mixed solution, and drying the mixed powder obtained by suction filtration.
(3) Annealing treatment of mixed powder
and placing the dried powder in a muffle furnace for annealing treatment, wherein the annealing temperature is 300-400 ℃, the heat preservation time is 2-3h, and after the heat preservation is finished, cooling the furnace to the room temperature to obtain the CuO @ CNTs composite material.
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Cited By (4)
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| CN112837949A (en) * | 2020-12-31 | 2021-05-25 | 四川艾尔法泰克科技有限公司 | CuO-loaded carbon nanotube silver-based electric contact material and preparation method thereof |
| CN112831682A (en) * | 2020-12-31 | 2021-05-25 | 四川艾尔法泰克科技有限公司 | Composite silver-based electric contact material and preparation method thereof |
| CN112853147A (en) * | 2020-12-31 | 2021-05-28 | 四川艾尔法泰克科技有限公司 | Silver-based electric contact material and preparation method thereof |
| CN113896221A (en) * | 2021-10-28 | 2022-01-07 | 中建材蚌埠玻璃工业设计研究院有限公司 | Composite material for treating tail gas of CIGS thin-film battery and preparation method thereof |
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| CN112837949A (en) * | 2020-12-31 | 2021-05-25 | 四川艾尔法泰克科技有限公司 | CuO-loaded carbon nanotube silver-based electric contact material and preparation method thereof |
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| CN112853147A (en) * | 2020-12-31 | 2021-05-28 | 四川艾尔法泰克科技有限公司 | Silver-based electric contact material and preparation method thereof |
| CN113896221A (en) * | 2021-10-28 | 2022-01-07 | 中建材蚌埠玻璃工业设计研究院有限公司 | Composite material for treating tail gas of CIGS thin-film battery and preparation method thereof |
| CN113896221B (en) * | 2021-10-28 | 2023-12-01 | 中建材玻璃新材料研究院集团有限公司 | Composite material for CIGS thin film battery tail gas treatment and preparation method thereof |
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Application publication date: 20191217 |