CN107052358B - Preparation method of copper nanowire - Google Patents
Preparation method of copper nanowire Download PDFInfo
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- CN107052358B CN107052358B CN201611155853.8A CN201611155853A CN107052358B CN 107052358 B CN107052358 B CN 107052358B CN 201611155853 A CN201611155853 A CN 201611155853A CN 107052358 B CN107052358 B CN 107052358B
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Abstract
The invention provides a preparation method of a copper nanowire, which comprises the following steps: A) mixing a copper source, glucose, higher aliphatic amine and water to obtain a mixed emulsion; B) heating the mixed emulsion and reacting to obtain a first-stage product; C) heating the first-stage product and reacting to obtain a copper nanowire; the reaction temperature in the step B) is 50-90 ℃, the reaction temperature in the step C) is 80-150 ℃, and the reaction temperature in the step B) is lower than that in the step C). In the process of preparing the copper nanowire, the reaction is carried out step by step, the reaction temperature of each step is limited, the copper ions are fully reduced, and the copper nanowire with high yield is obtained.
Description
Technical Field
The invention relates to the technical field of preparation of nano materials, in particular to a preparation method of a copper nanowire.
Background
One-dimensional metal materials occupy an important position in modern nanoscience and nanotechnology due to their unique optical, electrical, thermodynamic, mechanical and catalytic properties, but the high manufacturing cost and unstable characteristics become a major bottleneck in practical applications. Copper is a highly abundant and cheap element on the earth, and is a very ideal commercial option in one-dimensional metal materials. Therefore, there is a strong need to develop one-dimensional copper nanowires with high monodispersity, good stability and oxidation resistance that can be applied to future low-cost nanomaterials and nanodevices.
The preparation method of the copper nanowire mainly comprises a solvent phase synthesis method, a vapor deposition method and a template induced electrodeposition method. At present, the vapor deposition method and the template-induced electrodeposition method are not enough to realize industrialization, but the copper nanowire prepared by the solvent phase synthesis method needs to be selected between yield and quality, and the nanowire prepared by the high-yield synthesis method is often poor in quality; high quality fabrication methods often yield nanowires that are limited by low yields and yields.
Disclosure of Invention
The invention aims to provide a method for preparing a copper nanowire, and the method can be used for massively preparing the high-quality copper nanowire.
In view of the above, the present application provides a method for preparing a copper nanowire, including the following steps:
A) mixing a copper source, glucose, higher aliphatic amine and water to obtain a mixed emulsion;
B) heating the mixed emulsion and reacting to obtain a first-stage product;
C) heating the first-stage product and reacting to obtain a copper nanowire;
the reaction temperature in the step B) is 50-90 ℃, the reaction temperature in the step C) is 80-150 ℃, and the reaction temperature in the step B) is lower than that in the step C).
Preferably, the reaction temperature in the step B) is 65-80 ℃, and the reaction temperature in the step C) is 90-120 ℃.
Preferably, in the step B), the reaction time is 12-48 h; in the step C), the reaction time is 12-48 h.
Preferably, the molar ratio of the copper source to the glucose is (1-3): 1, the molar ratio of the copper source to the higher aliphatic amine is (1-5): 1, the molar ratio of the copper source to water is (1-5): 1.
preferably, the mixing temperature is 20-50 ℃.
Preferably, in the step C), the heating is carried out under the condition of stirring, and the stirring speed is 0-250 r/min.
Preferably, the copper source is selected from copper chloride dihydrate, copper nitrate or anhydrous copper chloride; the higher fatty amine is one of hexadecylamine, octadecylamine and oleylamine.
Preferably, step C) further comprises, after the reaction:
the resulting reaction solution was centrifuged.
Preferably, the rotation speed of the centrifugal separation is 1000-5000 r/min.
The application provides a preparation method of a copper nanowire, which comprises the steps of mixing a copper source, high-grade aliphatic amine, glucose and water as raw materials to obtain a mixed emulsion, heating the mixed emulsion for reaction to obtain a first-stage product, heating the first-stage product for reaction to obtain the copper nanowire; according to the method, most of copper ions are firstly converted into the copper nanodots by means of step-by-step reaction, and then the subsequent reaction is completed on the basis of the copper nanodots, so that the yield of the copper nanowires is improved. Test results show that the preparation method of the copper nanowire can be used for preparing 50g of copper nanowire at one time, the wire diameter of the copper nanowire is uniform, the length of the copper nanowire is dozens of micrometers, and the length-diameter ratio of the copper nanowire can reach 700-1000.
Drawings
Fig. 1 is a scanning electron microscope photograph of copper nanowires prepared in example 1 of the present invention;
FIG. 2 is a TEM photograph of Cu nanowires prepared in example 2 of the present invention;
FIG. 3 is a TEM photograph of copper nanowires prepared in example 3 of the present invention;
FIG. 4 shows the copper nanowire stock solution in a large-capacity glass reaction kettle prepared by the method of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The embodiment of the invention discloses a preparation method of a copper nanowire, which comprises the following steps:
A) mixing a copper source, glucose, higher aliphatic amine and water to obtain a mixed emulsion;
B) heating the mixed emulsion and reacting to obtain a first-stage product;
C) heating the first-stage product and reacting to obtain a copper nanowire;
the reaction temperature in the step B) is 50-90 ℃, the reaction temperature in the step C) is 80-150 ℃, and the reaction temperature in the step B) is lower than that in the step C).
The application provides a preparation method of a copper nanowire, which can synthesize a large amount of copper nanowires at one time and has high quality.
Specifically, the raw materials are firstly mixed, namely a copper source, glucose, higher fatty amine and water are mixed to obtain a mixed emulsion; in this process, the copper source is preferably copper chloride dihydrate, copper nitrate or anhydrous copper chloride, and in certain embodiments, the copper source is preferably copper chloride dihydrate; the higher fatty amine is preferably hexadecylamine, octadecylamine or oleylamine, and in certain embodiments, the higher fatty amine is hexadecylamine. The molar ratio of the copper source to the glucose is (1-3): 1, in certain embodiments, the molar ratio of the copper source to glucose is (1-2): 1. the molar ratio of the copper source to the higher aliphatic amine is (1-5): 1, in certain embodiments, the molar ratio of the copper source to the higher aliphatic amine (2-5): 1. the molar ratio of the copper source to the water is (1-5): 1, in certain embodiments, the molar ratio of the copper source to the water is (2-5): 1. in order to uniformly mix the raw materials, the mixing is preferably carried out in a stirring and dispersing manner, and the mixing temperature is preferably 20-50 ℃.
After the raw materials are mixed, the mixed emulsion is heated to a lower temperature and reacts for a period of time to obtain a first-stage product. In the process, the reaction temperature is 50-90 ℃, in some embodiments, the reaction temperature is 65-80 ℃, and specifically, the reaction temperature can be 65 ℃, 70 ℃, 75 ℃ or 80 ℃. The reaction time is preferably 12-48 h, and in some embodiments, the reaction time is 24-36 h.
After the first reaction, the obtained first-stage product is heated and then reacts, the reaction temperature is 80-150 ℃, in certain embodiments, the reaction temperature is 90-120 ℃, specifically, the reaction temperature is 100 ℃, 110 ℃, 95 ℃ or 120 ℃. The reaction time is 12-48 h, and in some embodiments, the reaction time is 24-36 h. According to the method, the traditional preparation of the copper nanowire is carried out step by step, in the process, more than 85% of copper ions are firstly reduced to 5nm of copper nanodots, and then the subsequent reaction is completed on the basis of the copper nanodots to obtain the copper nanowire, so that the yield of the copper nanowire is improved by at least 1.6 times. In the above process, if the reaction temperature for obtaining the first stage product is too low, the conversion of the copper nanodots is insufficient, and if the reaction temperature is too high, the copper nanodots cannot be obtained. If the reaction time is too long, the copper nanodots continue to grow, and the yield of the copper nanowires is finally affected.
Finally, the obtained reaction solution is preferably subjected to centrifugal separation to remove redundant higher aliphatic amine and part of byproducts, so as to obtain the copper nanowire stock solution containing the copper nanowires. The rotational speed of the centrifugal separation is 1000-5000 r/min, and in some embodiments, the rotational speed of the centrifugal separation is 2000-4000 r/min.
The preparation method of the copper nanowire provided by the invention can prepare 50g of high-quality copper nanowire at one time, the preparation yield is the largest in the prior art, and the yield of the step-by-step stirring synthesis technology is greatly improved compared with the yield of one-step synthesis or non-stirring synthesis. Further, since the present invention uses a reactor like an industrial reaction vessel, it can be easily applied to mass production on an industrial scale. Experimental results show that the copper nanowire prepared by the method has the advantages of uniform wire diameter, length of dozens of micrometers, length-diameter ratio of 700-1000 and very good application potential.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of copper nanowires of the present invention, and the scope of the present invention is not limited by the following examples.
Example 1
Under a circulating oil bath at 50 ℃, 342g of copper chloride dihydrate, 792g of glucose and 2.7kg of hexadecylamine are stirred and dispersed in 40L of deionized water in a 50L glass reaction kettle, the obtained emulsion is heated to 75 ℃ for reaction for 24h after being dispersed, then the temperature is raised to 120 ℃ and 150rpm for stirring and reaction for 24h, finally, the reaction is centrifuged at 2000rpm, and 50g of copper nanowire product is collected.
Example 2
Under a circulating oil bath at 50 ℃, 342g of copper chloride dihydrate, 396g of glucose and 2.16kg of hexadecylamine are stirred and dispersed in 40L of deionized water in a 50L glass reaction kettle, the obtained emulsion is heated to 70 ℃ for reaction for 24 hours after being dispersed, then the temperature is raised to 100 ℃ and 150rpm for stirring and reaction for 24 hours, finally, the reaction is centrifuged at 2000rpm, and 50g of copper nanowire product is collected.
Example 3
Under a circulating oil bath at 50 ℃, 85.5g of copper chloride dihydrate, 99g of glucose and 0.54kg of hexadecylamine are stirred and dispersed in 40L of deionized water in a 50L glass reaction kettle, the obtained emulsion is heated to 65 ℃ for reaction for 24 hours after being dispersed, then the temperature is raised to 110 ℃ and the stirring reaction is carried out for 36 hours at 150rpm, and finally, 20g of copper nanowire product is obtained after centrifugal collection at 2000 rpm.
Fig. 1 is a scanning electron microscope photograph of copper nanowires prepared in example 1 of the present invention; FIG. 2 is a TEM photograph of Cu nanowires prepared in example 2 of the present invention; FIG. 3 is a TEM photograph of copper nanowires prepared in example 3 of the present invention; FIG. 4 shows the copper nanowire stock solution in a large-capacity glass reaction kettle prepared by the method of the invention. As can be seen from FIGS. 1 to 3, the copper nanowires prepared by the method have uniform wire diameter, length of tens of micrometers, and length-diameter ratio of 700-1000; as can be seen from FIG. 4, since a reactor similar to an industrial reaction vessel is used, it is easy to scale up and apply to mass production on an industrial scale.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. A preparation method of copper nanowires comprises the following steps:
A) mixing a copper source, glucose, higher aliphatic amine and water to obtain a mixed emulsion;
B) heating the mixed emulsion for reaction, and reducing more than 85% of copper ions into 5nm copper nanodots to obtain a first-stage product;
C) heating the first-stage product and reacting to obtain a copper nanowire;
the temperature of the reaction in the step B) is 50-90 ℃, the temperature of the reaction in the step C) is 80-150 ℃, and the temperature of the reaction in the step B) is lower than that of the reaction in the step C); the reaction time in the step B) is 24-36 h, and the reaction time in the step C) is 24-36 h;
the molar ratio of the copper source to the glucose is (1-3): 1, the molar ratio of the copper source to the higher aliphatic amine is (1-5): 1, the molar ratio of the copper source to water is (1-5): 1.
2. the method according to claim 1, wherein the temperature of the reaction in step B) is 65 to 80 ℃ and the temperature of the reaction in step C) is 90 to 120 ℃.
3. The method according to claim 1, wherein the mixing temperature is 20 to 50 ℃.
4. The method according to claim 1, wherein the heating in step C) is performed under stirring at a speed of 0 to 250 rpm.
5. The method of claim 1, wherein the copper source is selected from copper chloride dihydrate, copper nitrate, or anhydrous copper chloride; the higher fatty amine is one of hexadecylamine, octadecylamine and oleylamine.
6. The method according to claim 1, wherein the step C) further comprises, after the reaction:
the resulting reaction solution was centrifuged.
7. The method according to claim 6, wherein the rotational speed of the centrifugal separation is 1000 to 5000 rpm.
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| CN107828080A (en) * | 2017-11-09 | 2018-03-23 | 扬州大学 | A kind of preparation method of copper nano-wire compounded latex conductive sponge |
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| CN111618315A (en) * | 2020-06-04 | 2020-09-04 | 厦门大学 | Preparation method of copper nanowire |
| CN112220130B (en) * | 2020-10-26 | 2024-02-20 | 西安工程大学 | PM 2.5-preventing copper nanowire mask and preparation method thereof |
| CN113083327B (en) * | 2021-04-06 | 2023-11-03 | 徐州瑞鑫新材料研究院有限公司 | Preparation method of copper-based heterogeneous hollow nanotube material |
| CN113707862A (en) * | 2021-08-26 | 2021-11-26 | 厦门大学 | Copper nanowire wound silicon-carbon composite material and preparation method and application thereof |
| CN113996799B (en) * | 2021-10-08 | 2024-02-02 | 郑州工程技术学院 | Preparation method of copper nanomaterial |
| CN114907805A (en) * | 2022-03-29 | 2022-08-16 | 苏州博濬新材料科技有限公司 | Low-temperature sintering conductive adhesive based on hybrid filler modification and preparation method thereof |
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